Studies on Nb Microalloying of 13Cr Super Martensitic

Stainless Steel
XIAOPING MA, LIJUN WANG, SUNDARESA V. SUBRAMANIAN,
and CHUNMING LIU

The eect of Nb microalloying on microstructure, mechanical properties, and pitting corrosion

properties of quenched and tempered 13 pct Cr-5 pct Ni-0.02 pct C martensitic stainless steels
with dierent Mo and N contents was investigated. The microstructure, density, and dispersion
of high-angle boundaries, nanoscale precipitates, and amount of retained austenite were char-
acterized by using electron backscattered diraction, transmission electron microscopy, and
X-ray diraction to correlate with properties. The results show that the combined eects of
lowering nitrogen content in 13 pct Cr-5 pct Ni-1~2 pct Mo-0.02 pct C steels to 0.01 wt pct, and
adding 0.1 pct Nb are to decrease the amount of Cr-rich precipitates, as Nb preferentially
combines with residual carbon and nitrogen to form carbonitrides, suppressing the formation of
Cr2N and Cr23C6. Austenite grain renement can be achieved by Nb microalloying through
proper heat treatment. If the nitrogen content is kept high, then Cr-rich precipitates would occur
irrespective of microalloying addition. The NbN would also occur at high temperature, which
will act as substrate for nucleation of coarse precipitates during subsequent tempering,
impairing the toughness of the steel. It was shown that the addition of Nb to low interstitial
super martensitic stainless steel retards the formation of reversed austenite and results in the
formation of nanoscale precipitates (5 to 15 nm), which contribute to a signicant increase in
strength. More importantly, the pitting corrosion resistance was found to increase with Nb
addition. This is attributed to suppression of Cr-rich precipitates, which can cause local
depletion of Cr in the matrix and the initiation of pitting corrosion.

DOI: 10.1007/s11661-012-1268-4
 The Minerals, Metals & Materials Society and ASM International 2012

I. INTRODUCTION without d ferrite, and (3) the addition of Mo to improve

LOW-CARBON martensitic stainless steels, called
super martensitic stainless steels (SMSSs),[15] have been
increasingly applied to produce oil country tubular goods
(OCTG), which include seamless pipes for drilling, casing,
and tubing for the application in oil and gas elds with
severe corrosive environments. They present an econom-
ical alternative to carbon steel and duplex steels as they
oer improved corrosion resistance in relation to carbon
steels, being free from the use of coatings and inhibitors,
as well as oer lower production costs when compared
with duplex grades. They are based on the Fe-Cr-Ni-Mo
system with 13 to 16 wt pct Cr, 4 to 6 wt pct Ni, 0.5 to
2.5 wt pct Mo, low amounts of carbon, phosphorus, and
sulfur (C 0.02, P, S 0.03). The basic concept of alloy
design is (1) the increase in eective Cr content (the Cr in
solution, which can form oxide layer) by reducing C to
improve corrosion resistance and weldablity, (2) the
addition of Ni to maintain martensitic microstructure
XIAOPING MA, PhD Student, LIJUN WANG, Associate
Professor, and CHUNMING LIU, Professor, are with the Key
Laboratory for Anisotropy and Texture of Materials, Northeastern
University, Shenyang 110819, P.R. China. Contact e-mail: maxp-
neu@hotmail.com SUNDARESA V. SUBRAMANIAN, Professor, is
with the Department of Materials Science and Engineering, McMaster
University, Hamilton, ON L8S 4L7, Canada.
Manuscript submitted April 26, 2011.
the resistance to localized corrosion and sulde stress
cracking (SSC). They exhibit excellent mechanical prop-
erties as well as good corrosion resistance,[57] which
strongly depend on heat treatment history and chemical
composition. Martensite microstructure with retained
austenite occurring at martensite lath boundaries and
within laths is obtained after usual normalizing and
tempering treatment. The retained austenite has been
reported to be very eective in restoring toughness and
elongation of martensite,[812] but it lowers strength
properties. Nakamichi et al.[13] has reported that although
super martensitic stainless steel has a very low carbon
concentration, intergranular stress corrosion cracking
(IGSCC) has still been observed at heat-aected zone
because of the occurrence of Cr-depleted zones of only a
few nanometers in width caused by the precipitation of Cr
carbide. To enhance strength properties and improve
localized corrosion resistance of this type of stainless steel,
microalloying additions were adopted to stabilize residual
C as microalloying element such as Ti has higher anity
for C than Cr, forming preferentially carbides of micro-
alloying elements.[14] Ladanova et al.[15] reported that the
formation of TiC at expense of Cr23C6 in super martens-
itic stainless steel makes the steel less prone to SCC and
localized corrosion.
Recently, N as a strong austenite-forming element is
widely applied in austenitic and duplex stainless steels to
save expensive Ni and improve the resistance to localized

METALLURGICAL AND MATERIALS TRANSACTIONS A

corrosion.[16,17] There are also some commercial super
martensitic stainless steels alloyed with N.[18] The objec-
tive of the current work is to study the mechanism of Nb
microalloying in super martensitic stainless steel with
dierent N content and, more importantly, to improve
the mechanical and pitting properties of super martensitic
stainless steel by Nb microalloying, based on correlation
of microstructure with mechanical and pitting properties
of a commercial super martensitic stainless steel 13Cr-
5Ni-1Mo-0.025Nb-0.09V-0.058N. The research under-
scores the importance of balancing Nb additions with the
level of interstitial (C and N) in the alloy design of
13Cr5Ni1~2Mo stainless steels.
II. EXPERIMENTAL PROCEDURE
The chemical compositions of the commercial steel
(1MoNbVN) and the other four steels made in labora-
tory are summarized in Table I. Laboratory steel
samples were made in form of ingots, using a 100-kg
vacuum-induction furnace. The ingots of the commer-
cial steel and 1 pct Mo-bearing steels were hot rolled at
1473 K (1200 C) into plates with 12 mm thickness. The
ingots of the 2 pct Mo-bearing steels were hot rolled at
1373 K (1100 C) into plates with 12 mm thickness.
Normalizing was carried out at 1373 K (1100 C) for the
commercial steel and at 1323 K (1050 C) for the other
four steels for 0.5 hours, followed by a 2 hours of
tempering heat treatment at temperatures ranging from
823 K to 973 K (550 C to 700 C). After tempering, the
samples were quenched in oil.
The mechanical properties were evaluated by means
of tensile and impact tests. The tensile tests were
performed on a CMT5105 tensile testing machine with
a extensometer at strain rate of 0.001 s1. Cylindrical
test specimens with a uniform gauge cross section of F
5 9 25 mm and machined parallel to the plate rolling
direction were used. The impact tests were performed at
room temperature on full-size Charpy V notch impact
specimens (10 9 10 9 55 mm) with notch orientation
vertical to the rolling direction. All mechanical proper-
ties values reported in the results are the average of three
tests. All specimens for microstructure characterization
were cut from residual portion of Chary tests samples.
Thin foils for transmission electron microscopy (TEM)
analysis were prepared by mechanically grinding the
samples with initial thickness of 400 lm to the thickness
of 100 lm and electropolished with a double-jet Tenupol
Struers machine (Struers Inc., Cleveland, OH) at 233 K
(40 C), 15 V in an electrolyte containing 27 mL
perchloric acid and 273 mL alcohol. Carbon extraction
Table I. Chemical Compositions of 13 pct Cr Steels (in mass pct)
Steel Grade C Si Mn P S
1MoNbVN 0.030 0.31 0.58 0.011 0.009 12.87
1Mo 0.022 0.30 0.57 0.022 0.001 12.84
1MoNb 0.008 0.39 0.63 0.010 0.007 13.35
2Mo 0.020 0.42 0.51 0.016 0.004 12.59
2MoNb 0.022 0.41 0.48 0.016 0.006 12.91
replica were prepared on sample surfaces well polished
and lightly etched using electrolyte containing 2 mL
HCl + 4 mL HNO3 + 12 mL alcohol. The precipitate
morphology, size, and dispersion were examined using
conventional TEM (CM12 120 kV; Philips, Amsterdam,
the Netherlands) as well as a scanning transmission
electron microscope (STEM; Titan 80 to 300 kV; FEI
Company, Hillsboro, OR). The microchemical compo-
sitions of precipitates were analyzed using an energy-
dispersive X-ray spectrometer installed in TEM. The
crystallographic structures were characterized by elec-
tron backscattered diraction (EBSD). The volume
fraction of the retained austenite was measured at room
temperature by X-ray diraction using Cu-Ka radiation
on tempered specimens. The evaluation of volume
fraction was determined by measuring the integrated
intensities of (111)c and (110)a peaks of X-ray pattern,
using the procedure outlined by Leem et al.[9] The
pitting corrosion resistance of SMSSs was evaluated
electrochemically by anodic polarization experiments at
room temperature in a three-electrode polarization cell
in which the specimen as a working electrode with an
exposed area of 1 cm2, a platinum counterelectrode, and
a saturated calomel reference (SCE) electrode were used.
All electrode potentials were referred to the SCE scale.
The working electrode was cathodically cleaned by
scanning from minus 300 mV relative to open circuit
potential to remove an air formed oxide on the surface
after 15 minutes stabilization of open circuit potential,
and then its anodic polarization response to determine
pitting potential (Eb) was measured at a scan rate of
2 mV/s in aerated 3.5 pct NaCl solution.
III. RESULTS AND DISCUSSION
A. Microstructure Characterization
Not considering the eect of the other alloying
elements, the solubility product of nitrides of Nb and
V corresponding to the chemical compositions of the
investigated steels was calculated using the following
thermodynamic empirical equations[19]:
8500
lgNbN 2:89  1
T
8330
lgVN 3:40  2
T
According to the calculation, the start temperature of
thermodynamic potential for precipitation of NbN is
1493 K (1220 C), closely followed by VN at 1473 K
(1200 C) in the commercial steel, which is higher than
Cr Ni Mo N Nb V Ti
5.26 0.94 0.058 0.025 0.089 0.0100
4.44 0.69 0.010
5.10 1.08 0.010 0.11 0.0080
5.01 1.90 0.013 0.0062
5.16 2.05 0.010 0.11 0.0043
METALLURGICAL AND MATERIALS TRANSACTIONS A
the temperatures applied for hot rolling and solution
treatment of the commercial 1MoNbVN steel. Thus, the
precipitation of nitrides of microalloying elements Nb
and V would occur during cooling from melt and at the
hot rolling and solution treatment temperatures as
thermodynamic potential for precipitation increases
and the solubility product of NbN/VN decreases with
decreasing temperature. Consistent with this theoretical
calculation, globular Nb-, V-, and Ti-rich precipitates
with a diameter of 10 nm were already precipitated and
randomly distributed in the 1MoNbVN steel sample
after normalizing, as shown in Figures 1(a) and (b).
These precipitates act as substrates for the nucleation of
coarse precipitates in subsequent tempering, which
would impair the toughness of the steel. Figure 1(c)
shows the coarse-clustered carbonitrides of 50 to 60 nm
in length and 30 nm in diameter observed in the thin foil
of 1MoNbVN steel tempered at 873 K (600 C). Finer
precipitates of approximately 20 nm in length and
10 nm in diameter formed along interlath boundaries
and prior austenite grain boundaries in 1MoNbVN steel
sample tempered at 898 K (625 C), as shown in
Figure 1(d). Figure 1(e) shows coarse clustered precip-
itates and ner globular and rod-like precipitates
observed on a carbon replica of 1MoNbVN steel
tempered at 898 K (625 C) under conventional TEM.
Coarse-clustered precipitates are well aligned in arrays
and their interspacing is comparable with interlath
spacing of martensite lath. Combined with the results
shown in Figure 1(d), it is considered that the lath
boundaries and prior austenite grain boundaries are
preferable sites for nucleation of precipitates. The
energy-dispersive (ED) spectrum of these clustered
precipitates shows X-ray signals characteristic of Cr,
Mo, Nb, and V, as shown in Figure 1(f). It is suspected
that a signicant depletion of chromium in the vicinity
of the precipitates would occur, which will be detrimen-
tal to the corrosion protection. For the identication of
precipitates, high-resolution transmission electron
microscopy (HRTEM) was used. Figure 1(g) shows
rod-like and globular precipitate morphologies observed
on carbon extraction replica. The precipitates of rod
morphology were found to be enriched in Cr (spectrum 1,
Figure 1(h)). The globular precipitates are approxi-
mately 10 nm size and exhibit X-ray signals character-
istic of Ti, Nb, and V (spectrum 2, Figure 1(h)).
Actually, in this study, the content of N that can be
stabilized by precipitation of microalloying elements
calculated according to the ratio of atomic weight (x
represents mass percentage)
xTi xNb xV 15 nm observed using carbon extraction replica of
xN 3 1MoNb steel tempered at 973 K (700 C). The ED
4 7 4
is approximately 0.03 wt pct in 1MoNbVN steel. The
excess nitrogen in solution combines with Cr to cause
the occurrence of rod-like precipitates enriched in Cr
during tempering treatment at lath boundaries and prior
austenite grain boundaries. The amount of microalloy-
ing additions required to suppress Cr-rich nitride
precipitates has to increase with nitrogen content in
accordance with the equilibrium solubility product. In
METALLURGICAL AND MATERIALS TRANSACTIONS A
practice, the kinetics of precipitation determines the
degree of suppression of Cr precipitates.
From the characterization of precipitates in normal-
ized and tempered commercial 1MoNbVN steel, lower-
ing N content in super martensitic stainless steel is
necessary to decrease the amount of Cr-rich precipitates
and to obtain ner carbonitride of microalloying ele-
ments. Figure 2(a) shows the morphologies and disper-
sion of precipitates observed on the carbon extraction
replica of 1Mo steel with lowered N content of 0.01 pct
tempered at 873 K (600 C). The amount of precipitates
in 1Mo steel is signicantly decreased compared with
1MoNbVN steel. It is considered that the well-aligned
precipitates were nucleated at boundaries and the
precipitates randomly dispersed were nucleated within
martensite laths. The ED spectrum of these precipitates
shows X-ray signals characteristic of Cr, as shown in
Figure 2(b). According to the equilibrium phase dia-
gram of Fe-C-12.5Cr-4.5Ni-0.5Si-0.6Mn calculated by
Wang et al.,[20] these precipitates are probably Cr23C6.
To decrease the amount of Cr-rich precipitates in low
N super martensitic stainless steel for possible improve-
ment in corrosion resistance, 0.1 pct Nb addition to low
interstitial (C 0.02, N 0.01) 1MoNb super martens-
itic stainless steel was designed. In this case, no
precipitates were found in both thin foil and carbon
extraction replica of 1MoNb steel after hot rolling at
1473 K (1200 C) and solution treatment at 1323 K
(1050 C), as the thermodynamic potential for precipi-
tation of Nb(C, N) is signicantly decreased because of
the decreased interstitial content. Figures 3(a) and (b)
show the EBSD characterization of high-angle misori-
entation boundaries associated with band contrast map
of 1Mo and 1MoNb steel after normalizing. The prior
austenite grain boundaries are found with misorienta-
tion above 15 deg (and below 45 deg), whereas mar-
tensite lath packet boundaries exhibit misorientation
above 45 deg in both steels. Comparing the size of prior
austenite grains of 1Mo steel with that of 1MoNb steel,
austenite grains were not rened by Nb addition. This is
in agreement with said TEM observation. No precipitate
is available for pinning the austenite grain boundaries
during solution treatment after hot rolling.
Subsequent tempering above 823 K (550 C) pro-
motes the formation of retained austenite and the
occurrence of nanoscale Nb-rich precipitates of 5 to
15 nm in 1MoNb steel. It is very dicult to identify the
precipitates that occurred in samples tempered under
873 K (600 C) because of their very small size (<5 nm)
using conventional TEM. Figure 3(c) shows the
HRTEM picture of globular precipitates of 10 to
spectra analysis of the precipitate indicated in Figure 3(c)
shows X-ray signals characteristic of Nb. Almost no Cr-
rich precipitate can be found in 1MoNb steel tempered at
various temperatures. It is conrmed that the formation
of Cr-rich precipitates is eectively suppressed by the
addition of Nb. Therefore, the resistance to pitting
corrosion of 1MoNb is expected to exceed those of 1Mo
and 1MoNbVN steels. Figure 4 shows two typical X-ray
diraction patterns of 1MoNb steel normalized and
Fig. 1(a) TEM picture of extraction replica showing globular precipitates with diameter less than 10 nm. (b) ED spectrum of globular precipi-
tates showing X-ray signals characteristic of Nb, V, and Ti. (c) TEM picture of the commercial steel sample tempered at 873 K (600 C) show-
ing matrix clustered precipitates. (d) TEM picture of 1MoNbVN steel tempered at 898 K (625 C) showing austenite grain boundary and
interlath precipitates. (e) TEM picture of extraction replica of the sample tempered at 898 K (625 C) and (f) ED spectrum of clustered precipi-
tates indicated in (e) showing X-ray signals characteristic of Cr, Mo, Nb, V, and Ti. (g) HRTEM picture of extraction replica of the sample tem-
pered at 898 K (625 C). (h) ED spectrum 1 of rod-like precipitate indicated in (g) showing X-ray signals characteristic of Cr and ED spectrum 2
of globular precipitate indicated in (g) showing X-ray signals characteristic of Nb, V, and Ti.

METALLURGICAL AND MATERIALS TRANSACTIONS A

Fig. 2(a) TEM picture of extraction replica of 1Mo steel tempered at 873 K (600 C) showing globular precipitates. (b) ED spectrum of
precipitates shown in (a) showing X-ray signals characteristic of Cr. (c) HRTEM picture of an extraction replica of 1MoNb steel tempered at
973 K (700 C) showing Nb-rich precipitates of 10 nm and (d) ED spectrum of 10 nm precipitate marked in (c).

Fig. 3Comparison of EBSD characterization of high angle misorientaiton boundaries associated with band contrast map of (a) 1Mo and
(b) 1MoNb steels both hot rolled at 1473 K (1200 C) and normalized from 1323 K (1050 C) (white line is above 15 deg and below 45 deg;
yellow line is above 45 deg).

tempered at 898 K (625 C). While there is no peak of
austenite in the pattern of the specimen as normalized,
the austenite peaks are obvious in the diraction patterns
of the sample tempered at 898 K (625 C). The volume
fraction of retained austenite in specimens was calculated
by measuring the integrated intensities of (111)c and
(110)a peaks of X-ray diraction patterns. Table II
shows the volume fraction of retained austenite in 1Mo
and 1MoNb steels as a function of tempering tempera-
ture in relation to that in the commercial 1MoNbVN
steel.
Retained austenite volume fraction peaks at dierent
tempering temperature for three steel grades, being
highest at 923 K (650 C) for the 1MoNb steel. There-
fore, it approves that Nb has the eect of retarding the
formation of reversed austenite.

METALLURGICAL AND MATERIALS TRANSACTIONS A

 As 13Cr super martensite stainless steel is used in oil
and gas elds with severe corrosive environments. The
resistance to localized corrosion of this steel has been of
concern. It is well known that Mo is very eective in
improving the resistance to localized corrosion of
stainless steel. Kondo et al.[21] tested the corrosion
resistance of various low C 13Cr martensitic stainless
steels in 5 pct NaCl solution with 3.0 MPa CO2 and
0.001MPa H2S (MPa here indicates the unit of the
pressure of the gas equilibrized with the solution, which
is dierent from the MPa described in Figure 8 where
MPa represents the unit of strength) at 298 K (25 C). It
was found that the corrosion rate was remarkably
reduced with an increase in Mo content. The steel with
2 pct Mo or higher content of Mo did not suer SSC,
whereas steels with 1 pct Mo and no addition of Mo
suered SSC or pitting in exposed environment. Based
on this knowledge from the literature, low C 13 pct
Cr-5 pct Ni steel with 2 pct Mo addition (2Mo steel)
was made. Simultanenously, the low C 13 pct Cr-5 pct
Ni-2 pct Mo steel with 0.1 pct Nb addition (2MoNb
steel) was made to study the eect of Nb on the
microstructure and properties of 13 pct Cr-5 pct
Ni-2 pct Mo steel. The detailed chemical compositions
of two steels are given in Table I. The hot rolling
temperature for two steels with 2 pct Mo was decreased
from 1473 K to 1373 K (1200 C to 1100 C) to prevent
severe growth of austenite grain during processing.
Fig. 4X-ray diraction results obtained by Cu Ka radiation on
1MoNb steel samples normalized and tempered at 898 K (625 C).
Table II. Volume Fraction of Retained Austenite in Specimens Tempered at Dierent Temperatures/pct
Tempering Temperature [K (C)] 823 (550)
Volume fraction 1Mo * 4.8
of austenite, pct 1MoNb * *
1MoNbVN * *
*X-ray diraction pattern did not reveal the presence of retained austenite because of a very low volume fraction.
Figures 5(a) and (b) give the results of EBSD charac-
terization of high-angle misorientation boundaries asso-
ciated with band contrast map of two steels with 2 pct
Mo after normalizing. 2 pct Mo-bearing steels was
quenched into martensite microstructure by normalizing
from temperature of 1323 K (1050 C), with prior
austenite grains subdivided into packets of thin laths.
Prior austenite grain boundaries (white line in map) and
lath packet boundaries (yellow line in map) were found
with high-angle misorientation above 15 deg. Moreover,
obvious prior austenite grain renement is observed in
2MoNb steel after hot rolling at 1373 K (1100 C) and
solution treatment at 1323 K (1050 C) when compared
with the 2Mo steel. The carbon extraction replica of
2MoNb steel as hot rolled was prepared to nd the
precipitates which pin the austenite grain boundaries
from moving during solution treatment. Figure 5(c)
shows the precipitates observed on the carbon extrac-
tion replica of 2MoNb steel sample as hot rolled, which
was conrmed to be enriched in Ti and Nb in the ED
spectrum shown in Figure 5(d). This nding is in
agreement with thermodynamic calculation for precip-
itation. The start temperature for precipitation of
Nb(C,N) is higher than the hot-rolling temperature.
Moreover, the presence of Ti in the steel can increase the
start temperature for precipitation, as Ti(C,N) can act
as a substrate for the nucleation of Nb(C,N).[22]
Besides the retained austenite, tempering above 823 K
(550 C) also promotes the precipitation in two 13 pct
Cr-5 pct Ni-2 pct Mo steels with and without 0.1 pct Nb.
Figures 6(a) and (b) show the TEM pictures of necklace
precipitates at lath boundaries and clustered precipitates
within laths, respectively, observed in the thin foil of a
2Mo steel sample tempered at 823 K (550 C). A similar
distribution of precipitates was found in 2Mo steel
tempered at 873 K (600 C). Figure 6(c) shows the
TEM picture of clustered precipitates extracted from a
2Mo steel sample tempered at 873 K (600 C) using a
carbon replica. The ED spectrum of these clustered
precipitates shows X-ray signals characteristic of Cr and
Mo, as shown in Figure 6(d). They are probably M23C6,
where M is combination of Cr and Mo.
Figure 7(a) shows the TEM picture of globular
precipitates of 10 to 25 nm observed on carbon extrac-
tion replica of 2MoNb steel tempered at 873 K (600 C).
They are conrmed to be enriched in Ti, Nb, and small
amount of Cr from ED spectrum of these precipitates
shown in Figure 7(b). It is dicult to distinguish these
precipitates from those formed during hot rolling.
Figures 7(c) and (d) show the TEM picture of very ne
nanoscale precipitates (5 to 10 nm) pinning dislocations
848 (575) 873 (600) 898 (625) 923 (650) 973 (700)
8.9 9.3 2.5 *
4.5 7.5 11.6 4.0
5.9 11.6 9.3 <4.0
METALLURGICAL AND MATERIALS TRANSACTIONS A
Fig. 5Comparison of EBSD characterization of high-angle misorientaiton boundaries associated with band contrast map of (a) 2Mo and
(b) 2MoNb steel both hot rolled at 1373 K (1100 C) and normalized from 1323 K (1050 C) (white line is above 15 deg and below 45 deg; yel-
low line is above 45 deg). (c) TEM picture of extraction replica showing globular precipitates 0f 25 to 30 nm. (d) ED spectrum of globular pre-
cipitates showing X-ray signals characteristic of Nb and Ti.
and lath boundaries observed in the thin foil of 2MoNb
steel tempered at 898 K (625 C). They are considered
to be formed during tempering.
B. Mechanical Properties
Figure 8 shows the comparison of the room-temper-
ature mechanical properties of ve test steels after
normalizing and tempering at temperatures varied from
823 K to 973 K (550 C to 700 C) for 2 hours. The
strength properties of the commercial 1MoNbVN steel
as normalized are much higher than those of the other as
normalized test steels, whereas the Charpy toughness of
the commercial 1MoNbVN after normalizing is lower.
Associated with said microstructure characterization of
the as-normalized steels, these dierences are mainly
attributed to the solution-strengthening eect of residual
N and the precipitation strengthening of high density of
Nb- and V-rich precipitates in as normalized 1MoNbV
steel. The strength properties of the two testing steels
with Nb after normalizing are close to those of their
reference steels, although some precipitates occurred in
2MoNb steel. The toughness of 1MoNb steel is lower
than that of 1Mo steel after normalizing because of the
locking of the dislocation by Nb atoms in solution. The
higher toughness of the 2MoNb steel as normalized
METALLURGICAL AND MATERIALS TRANSACTIONS A
compared with 2Mo steel is attributed to the Nbs grain
renement eect.
The mechanical properties of the test steels after
tempering depend on the balance between the softening
eect of retained austenite, the elimination of disloca-
tion within martensite matrix, and the hardening eect
of precipitates and the retransformation of reversed
austenite to martensite. Although the relative contribu-
tion of the dierent precipitates claried previously to
strength is dicult to quantify, it is well known that the
well-dispersed, ne-scale precipitates are most eective
in contributing to the strength, although at the cost of
ductility and toughness. According to the Ashby-
Orowan model for precipitate strengthening, strength
increment in excess of 100 MPa can be obtained even at
a small precipitate fraction (<0.0005 pct) when the pre-
cipitate size is approximately 5 nm.[23] Compared with
the as-normalized state, the yield strength of 1MoNb
and 2MoNb steel is eectively increased by tempering at
823 K (550 C), whereas the yield strength of 1MoN-
bVN steel is decreased, as shown in Figure 8(a). From
the X-ray diraction measurement on volume fraction
of retained austenite, it is considered that the volume
fraction of retained austenite in all test steels is almost
equal after tempering at 823 K (550 C) because of the
low thermodynamic potential for reversed austenite
Fig. 6TEM pictures of thin foil of 2Mo steel tempered at 823 K (550 C) showing (a) interlath precipitates (b) clustered precipitates within
lath. (c) TEM pictures of extraction replica of 2Mo steel sample tempered at 873 K (600 C) showing large amount clustered precipitates. (d) ED
spectrum of clustered precipitates shown in (c) showing X-ray signals characteristic of Cr, Mo, and Fe.
formation at a lower tempering temperature. Therefore,
the dierences in the amount, size, and dispersion of the
precipitates in three steels after tempering at 823 K
(550 C) are the key to explain the dierence in change
of their yield strength. The nanoscale precipitates
(<5 nm) of high density in two low N- and Nb-bearing
steels tempered at this temperature contribute signi-
cantly to the enhanced strength. Although there are
precipitates in the other three steels after tempering at
823 K (550 C), their hardening eect is not as good as
that obtained in two low N- and Nb-bearing steels
because of their low amount, large size, and inhomo-
genous distribution. As the tempering temperature is
increased, the decrease in yield properties and the
increase in ductility and toughness are mainly attributed
to the rapid increase in volume fraction of retained
austenite. Nb retards the formation of reversed austen-
ite, thereby retarding the softening because of the
retained austenite formation. Retransformation of
reversed austenite to martensite on oil cooling after
tempering at 973 K (700 C) results in the increase in
strength properties and the decrease in elongation and
toughness. Comparing the mechanical properties of two
low N- and Nb-bearing steels with those of their
reference steels, Nb addition eectively enhances the
strength properties without much loss in elongation
and toughness. The eect of increasing the tempering
temperature is to increase the volume fraction of the
retained austenite. Among several tempering tempera-
tures, excellent mechanical properties of low N- and
Nb-bearing steels are obtained after tempering at 873 K
(600 C).
C. Pitting Corrosion Resistance
Figure 9 shows the anodic polarization curves of ve
test steels tempered at 873 K (600 C) in 3.5 wt pct
NaCl solution at room temperature. Table III shows the
pitting potential determined from these curves. It is
known that the steels with higher pitting potential oer
better corrosion resistance. By comparison, the com-
mercial 1MoNbVN steel shows the poorest pitting
resistance. The pitting corrosion resistance of 1Mo steel
is signicantly enhanced by lowering N content to
0.01 pct compared with the commercial 1MoNbVN
steel, whereas 1MoNb steel exhibits even higher pitting
potential by adding 0.1 pct Nb. According to the studies
by Gestel[24] and Nakmichi et al.[13] on super martensitic
stainless steel, it was proposed that Cr carbide occurred
along prior austenite grain boundaries causes IGSCC
because of the depletion of Cr in the vicinity of Cr-rich
precipitates. Thus, in the current study, the poor
resistance to pitting corrosion of the commercial
1MoNbVN steel is supposed to be related to the Cr
METALLURGICAL AND MATERIALS TRANSACTIONS A
Fig. 7(a) TEM picture of carbon extraction replica of 2MoNb steel sample tempered at 873 K (600 C) showing well-dispersed globular
precipitates of 10 to 25 nm. (b) ED spectrum of precipitates shown in (a) showing X-ray signals characteristic of Ti and Nb. (c) and (d) TEM
pictures of thin foil of 2MoNb steel sample tempered at 898 K (625 C) showing nanoscale precipitates (5 to 10 nm) occurred within matrix and
at lath boundaries respectively.
depletion in the vicinity of Cr-rich precipitates, espe-
cially those that occurred along prior austenite grain
boundaries and martensite lath boundaries, which is
caused by excess N content. This hypothesis needs
future atom probe work validation. The eects of
lowering N to 0.01 pct and adding 0.1 pct Nb are to
decrease the amount of Cr-rich precipitates, as Nb
preferentially combines with residual C and N to form
carbonitrides, avoiding the Cr depletion caused by the
formation of Cr2N and Cr23C6, thereby improving the
pitting corrosion resistance. It is well known that Mo is
eective in improving the resistance of stainless steel to
localized corrosion. This is also conrmed in the current
study that the pitting corrosion resistance of super
martensitic stainless steel is signicantly improved by
2 pct Mo addition. By adding 0.1 pct Nb to 2 wt pct
Mo-bearing steel, the pitting corrosion resistance is
signicantly improved over and above that obtained by
adding 0.1 pct Nb- to 1 pct Mo-bearing super martens-
itic stainless steel. The involved mechanism is still
attributed to the eect of Nb on suppressing the
formation of Cr- and Mo-rich precipitates.
In summary, adding Nb to high N martensitic
stainless steel is undesirable as the NbN would occur
at high temperature, which will act as substrate for the
nucleation of coarse precipitates during subsequent
METALLURGICAL AND MATERIALS TRANSACTIONS A
tempering, impairing the toughness of the steel, due to
the increased thermodynamic potential for precipita-
tion. As a material used in aggressive environment with
severe corrosion, resistance to pitting corrosion of super
martensitic stainless steel is concerned as much as
mechanical properties. Although the formation of
Cr-rich nitride precipitates can be suppressed by micro-
alloying elements addition in accordance with the
equilibrium solubility product, the kinetics of precipita-
tion determines the degree of suppression of Cr precip-
itates. Thus, lowering N content in super martensitic
stainless is necessary for an improvement in toughness
and pitting corrosion resistance. The eect of adding
0.1 pct Nb to low interstitial (C 0.02, N 0.01) 13 pct
Cr-5 pct Ni-1 to 2 pct Mo steel is to decrease the amount
of Cr-rich precipitates, as Nb preferentially combines
with residual C and N to form Nb carbonitrides,
suppressing the formation of Cr2N and M23C6 where
M is combination of Cr and Mo, which is schematically
illustrated by comparing 1MoNbVN steel (Figure 10(a))
and 2Mo steel (Figure 10(c)) with low N- and Nb-bearing
steels (Figures 10(b) and (d)). The increase in pitting
corrosion resistance correlates well with the signicant
decrease in amount of Cr-rich precipitates. 0.1 pct Nb
addition to low interstitial (C 0.02, N 0.01) super
martensitic stainless steel results in signicantly enhanced
Fig. 8Mechanical properties of the studied steels as a function of tempering temperature: (a) yield strength (Rp0.2); (b) ultimate tensile
strength (Rm); (c) elongation (A pct), and (d) Charpy tests (Akv).

strength properties with good pitting corrosion resistance

without much decrease in toughness.

1. Adding low Nb with high V to a commercial high
Fig. 9Eect of lowering N content and adding Nb to suppress
Cr-rich precipitates on pitting corrosion resistance of steel normal-
ized and tempered at 873 K (600 C).
IV. CONCLUSIONS
interstitial (0.06 pct N) super martensitic stainless
steel (1MoNbVN) promotes the precipitation of
carbonitrides enriched in Nb and V in as normal-
ized state because the hot rolling temperature
(1473 K [1200 C]) and solution treatment tempera-
ture (1373 K [1100 C]) is lower than the start tem-
perature of precipitation of (Nb, V)N, which would
act as substrate for nucleation of coarse-clustered
precipitates during subsequent tempering. Temper-
ing treatment promotes further ne globular
Nb- and V-rich and rod-like Cr-rich precipitates at
inter-lath boundaries and within laths. Precipitates
enriched in Cr are formed because of the excess

METALLURGICAL AND MATERIALS TRANSACTIONS A

 Table III. Pitting Potential of Test Steels in 3.5 pct NaCl Solution at Room Temperature

Steel Grade 1MoNbVN 1Mo 1MoNb 2Mo 2MoNb

Pitting potential/mV 125 50 94.5 180 264

Fig. 10Schematic diagrams showing precipitation behavior of (a) Fe-13.0Cr-5.0Ni-1.0Mo-0.025Nb-0.12V-0.06N steel in comparison with
(b) Fe-13.0Cr-5.0Ni-1.0Mo-0.1Nb-0.01N steel; (c) Fe-13.0Cr-5.0Ni-2.0Mo-0.01N in comparison with (d) Fe-13.0Cr-5.0Ni-2.0Mo-0.1Nb-0.01N.
Nb addition to low N steel suppresses Cr-rich/Cr and Mo rich precipitates, thereby enhancing the resistance to pitting corrosion.

N content, which is considered to cause the deterio-
ration of corrosion properties.
2. The eects of lowering N content to 0.01 pct and
adding 0.1 pct Nb in super martensitic stainless
steel are to decrease the amount of Cr-rich precipi-
tates, as Nb preferentially combines with residual
C and N to form nanoscale Nb carbonitrides, sup-
pressing the formation of Cr2N and M23C6 where
M is a combination of Cr and Mo. Austenite grain
renement can be obtained by Nb microalloying
through proper heat treatment, which is advanta-
geous to obtain enhanced toughness.
3. The eect of tempering is to produce the retained
austenite, which is benecial for promoting ductility
and toughness. The addition of Nb retards the for-
mation of the reversed austenite and enhances
strength through precipitation hardening. Among
several tempering treatments of low N- and
Nb-bearing steels, the one made at 873 K (600 C)
presents the best correlation between higher strength
and sucient elongation and toughness. The signi-
cant improvement in resistance to pitting corrosion
of super martensitic stainless steels is correlated well
with the decrease in amount of Cr-rich precipitates.
The involved mechanism is proposed to be the sup-
pression of Cr-depleted zone, which is caused by
Cr-rich precipitates and is the preferential site for
pit nucleation by lowering N and adding Nb.

METALLURGICAL AND MATERIALS TRANSACTIONS A

 ACKNOWLEDGMENTS
We acknowledge with grateful thanks for the award
of a scholarship by China Scholarship Council for the
student Xiaoping, Ma to do research at McMaster
University. We wish to thank sincerely Dr. Carmen
Andrie and Dr. Glynis de Silveira for helping with
TEM studies, Mr. W. Gong for the assistance with
XRD analysis, and Mariana Perez and Marcos Stuart
of CBMM for research and technical support.
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METALLURGICAL AND MATERIALS TRANSACTIONS A