Materials Science and Engineering A251 (1998) 192 – 199

Alloying and aging effects on the fatigue crack growth of duplex

stainless steels
T.H. Kang a, D.M. Li a, Y.D. Lee b, C.S. Lee a,*
a
Center for Ad6anced Aerospace Materials, Pohang Uni6ersity of Science and Technology, Pohang 790 -784, South Korea
b
Stainless Steel Research Team, POSCO Technical Research Laboratory, Pohang 790 -785, South Korea

Received 9 September 1997; received in revised form 26 February 1998

Abstract

The effect of the addition of W instead of Mo on fatigue crack growth (FCG) behavior has been studied for duplex
(ferritic–austenitic) stainless steels. The microstructure and the FCG properties of the homogenized alloys are basically insensitive
to the variation of W content. For the alloys aged at 900°C for 30 min after homogenization, however, the apparent FCG
resistance is significantly increased and is attributed principally to the roughness-induced crack closure due to the existence of
brittle secondary phases precipitated during aging. With an increase in W content, the quantity and size of the brittle s and x
precipitates decrease and the ductility of the aged alloys increases. In accordance, the intrinsic FCG resistance of the aged alloys
is improved with increasing W content. © 1998 Elsevier Science S.A. All rights reserved.

Keywords: Aging; Duplex stainless steels; Fatigue crack growth

1. Introduction which depends on the nature and extent of the phase,

Ferritic–austenitic duplex stainless steel (DSS),
which usually has approximately equal volume frac-
tions of ferrite and austenite [1], is becoming increas-
ingly popular for its good combination of properties
that cannot be achieved by either fully austenitic or
fully ferritic stainless steel. In particular, the content of
expensive nickel is lower in the DSS than in the
austenitic steels with which it competes. This increasing
popularity of duplex stainless steels has pushed materi-
als researchers to further improve the strength, tough-
ness and resistance to stress corrosion cracking [2].
Also, more efforts have been made to develop the
super-DSS [3], i.e. the DSS with a value of pitting
resistance equivalent (PRE) [4] higher than 40.
However, problems may arise as a large amount of
undesirable secondary phases may form in the DSS
during isothermal aging or exposure to temperatures
between 300 and 1000°C due to the instability of the
ferrite. The formation of these secondary phases can
lead to the embrittlement of the DSS, the degree of
* Corresponding author. Tel.: + 82 562 2792141; fax: + 82 562
2792399; e-mail: cslee@postech.ac.kr
and on the temperature and time of exposure. A typical
example is the ‘475°C embrittlement’ due to the decom-
position to the a%-phase below about 500°C [5], which
can be critical to the potential long-term operation of
the DSS [6,7]. Another example is the higher tempera-
ture embrittlement due to the precipitates of s, x, Cr2N,
secondary austenite, etc. [8], which can be a problem in
large castings and weldments. It is generally known that
an increase in Cr and Mo contents would intensify the
embrittlement due to the precipitation of intermetallic
phases such as s and x. Like Mo, W is known to
improve the resistance to localized corrosion [9], but
unlike Mo, W tends to retard the precipitation of the
intermetallic phases and, hence, to improve ductility
and corrosion resistance [1,4]. While these alloying
effects provide a general guidance to the improvement
of ductility and corrosion resistance, a detailed ap-
proach to the alloying dependence of the fatigue crack
growth (FCG) behavior of the DSS is still lacking.
In the present investigation, the DSSs containing
different amounts of W while maintaining the same
PRE value are prepared, and the FCG behavior is
investigated in relation to the influence of alloying.
Since the alloying influence is especially sensitive to

0921-5093/98/$19.00 © 1998 Elsevier Science S.A. All rights reserved.

PII S0921-5093(98)00587-5
 T.H. Kang et al. / Materials Science and Engineering A251 (1998) 192–199 193

Table 1
Chemical composition (wt.%) of the DSSs

Phase Cr Ni Mo W Fe, etc.

3.5Mo – 0W a/g 26.59/24.25 6.94/7.43 3.97/2.78 —/— Balance

2.5Mo – 1.5W a/g 27.02/24.12 4.80/7.42 2.99/1.37 2.10/1.27 Balance
1.5Mo – 3W a/g 25.95/24.38 4.35/7.38 2.12/1.05 4.35/2.42 Balance
1Mo – 3.6W a/g 27.11/24.04 4.50/7.22 2.01/0.86 4.52/3.57 Balance

specific heat treatments, the effect of isothermal aging transverse (T) direction (L–T orientation). The geome-
on the microstructure and the FCG behavior is also try of the CT specimens for the FCG tests is shown in
investigated for purposes of comparison with the ho- Fig. 1. The crack length was monitored with a traveling
mogenization treatment. microscope. The precracking was conducted at a fre-
quency of 12 Hz and a load ratio (R) of 0.1 using an
Instron servohydraulic testing machine. All the speci-
mens were precracked to a depth of at least 2 mm from
2. Experimental procedure the crack tip and were subsequently tested at a constant
load amplitude with a sinusoidal waveform. Fractogra-
Four different alloys with the base composition of phy of fatigue failed specimens was performed in a
25.5Cr–6Ni–3.5Mo were used in this study. While the JEOL scanning electron microscope (SEM). To observe
PRE value was fixed at 41, i.e. Mo+0.69W =3.5, Mo the microstructure under the transmission electron mi-
was substituted for W at different contents as 3.5Mo– croscope (TEM), the thinned discs were electropolished
0W, 2.5Mo–1.5W, 1.5Mo – 3W and 1Mo – 3.6W, re- in a twin jet electropolisher using a solution of 75 ml
spectively. A detailed description of chemical perchloric acid and 925 ml acetic acid. Optimum polish-
compositions in different phases of the DSSs studied is ing conditions were obtained between 30 and 40 V at
given in Table 1. room temperature. The thin foils were examined in a
After hot rolling the ingots at 1100°C, 12 mm thick Philips EM400 microscope operated at 200 kV.
plates with microstructures of nearly equal volume
fractions of ferrite and austenite [10] were produced.
Solution treatment was carried out at 1100°C for 10
min to dissolve secondary phases, followed by water
quenching. Island-like austenite grains were found in
the ferritic matrix, while no precipitates could be ob-
served by light microscopy. The volume fractions of
austenite (g) and ferrite (a) were determined with image
analysis application software on representative micro-
graphs. The results are shown in Table 2 for different
compositions. Isothermal aging treatment at 900°C for
30 min, corresponding to the ‘nose’ of the C-curve for
s transformation, was performed to evaluate the mi-
crostructural effects resulting from the alloy composi-
tion. To get good contrast, a color etching technique
was applied to the specimens.
Tensile specimens were oriented with the tensile axis
parallel to the longitudinal (L) direction, and compact
tension (CT) specimens were oriented with the crack
plane normal to the L direction, propagating in the

Table 2
Volume fractions of the a- and g-phases in the DSSs

3.5Mo – 0W 2.5Mo–1.5W 1.5Mo–3W 1Mo– 3.6W

a/g 0.479/0.521 0.505/0.495 0.541/0.459 0.549/0.441

Fig. 1. Geometry of the CT specimen for the FCG test.
194 T.H. Kang et al. / Materials Science and Engineering A251 (1998) 192–199

results are summarized in Table 3. Both the s- and

x-phases are Cr- and Mo-rich phases. However, the
x-phase is richer in Mo and poorer in Cr as compared
with the s-phase [12]. In the 2.5Mo–1.5W composition
(Table 3), W is found to be more enriched in x than in
s. For a given alloy, the ‘nose’ of the C-curve for the
x-phase usually shifts to a lower temperature and a
shorter time than for the s-phase [13]. With the increase
in W content, as in the 1.5Mo–3.6W alloy, W is more

Fig. 2. TEM photographs showing microstructure and diffraction

pattern of the aged 3.5Mo–0W alloy.

3. Results and discussion

3.1. Microstructures

The homogenized microstructure consists of g- and

a-phases (the phase ratio of a and g is roughly one to
one), with the volume fraction of g decreasing slightly
with increasing W content (Table 2). The grains of both
phases were severely elongated in the rolling direction
and no precipitates were observed in the light and
transmission electron microscopy for all homogenized
specimens. However, the microstructure changes notice-
ably after the isothermal aging treatment. In the alloy of
3.5Mo–0W composition, a large amount of s-phase
precipitates at a/g grain boundaries, extending to the side
of the a-phase, as shown in Fig. 2. The formation of the
s-phase has been recognized to be the result of a
eutectoid decomposition (a “g2 +s). A pre-existing x-
phase could not be detected, presumably due to the
transformation of the x-phase to s-phase on aging [11].
When W is added, as in the 2.5Mo – 1.5W alloy, the
s-phase precipitates in the same manner as in the
3.5Mo–0W alloy but its amount is decreased. Besides,
the x phase can be occasionally found at the a/a grain
boundaries or the a/g boundaries, as indicated in Fig. 3.
As the W content increases, as in the 1Mo – 3.6W alloy,
a lot of x-phase precipitates can be observed (Fig. 4)
while the s-phase is hardly detectable at a/a or a/g
boundaries. In addition, secondary austenite forms, not
by eutectoid reaction but by decomposition, due to
instability of the ferrite at 900°C. Consequently, the
addition of W retards the formation of intermetallic
s-phase by shifting the ‘nose’ of the C-curve towards a
longer formation time. As a result, an increase in W
content decreases appreciably the total amount of sec-
ondary phases precipitated.
The composition of each secondary phase in the aged
alloys has been analyzed by means of energy-dispersive Fig. 3. TEM photographs showing microstructure and diffraction
X-ray microanalysis (EDX) using the TEM, and the patterns of the aged 2.5Mo – 1.5W alloy.
 flT.H. Kang et al. / Materials Science and Engineering A251 (1998) 192–199 195

(0W, Fig. 5(b)), the elongation decreases steeply with

increasing aging time and reaches a value as low as 10%
after 30 min aging treatment. However, with an increase
in W content, this decreasing trend becomes gradually
moderated and finally, in the 3.6%W alloy, the decrease
of the elongation is quite insignificant even after aging
for 30 min.
In view of the microstructural characteristics described
in the preceding sections, the variation of the tensile
properties with alloying composition and aging time is
considered reasonable. Because the a/g ratio is not
significantly changed (Table 2) by the alloying (i.e.
substitution of Mo for W), the tensile strength and
ductility should not be much influenced by the variation
in W content. Now that the secondary phases are mainly
precipitated at grain boundaries, the change of sy and
Fig. 4. TEM photographs showing microstructure and diffraction UTS due to aging should also be minimal, since sy and
patterns of the aged 1Mo–3.6W alloy. UTS depend chiefly on the interior of the grain at
ambient temperatures. The elongation, which is a ductil-
enriched in the x-phase up to an amount exceeding 50% ity index at tensile fracture, is expected to correspond to
(Table 3). As confirmed by the diffraction pattern in Fig. the extent of grain-boundary fracture due to the brittle
4, the x-phase has a cubic crystal structure with a lattice secondary phases precipitated during aging.
parameter almost three times that of ferrite [14], while the
s-phase has a tetragonal structure. Hence, the x-phase 3.3. FCG beha6ior
has a low interfacial energy and easily nucleates at the
a/a and a/g boundaries. Thus, it is understood that the Fig. 6 shows the FCG rate versus apparent stress
retardation in the precipitation of the intermetallic phase intensity range (da/dN –DK) curves for both the homog-
due to the substitution of Mo for W has an evidently enized and the aged alloys under different alloying
stronger influence on the formation of the s-phase than conditions. For the homogenized alloys, it is found that
on that of the x-phase. the apparent FCG resistance (as indicated by DK) is
almost independent of the alloy composition, i.e. the
3.2. Tensile properties substitution of Mo for W. This is in accordance with the
tensile test result that both the strength and the ductility
Fig. 5 shows the effects of aging time on the tensile of the as-homogenized alloys are insensitive to the alloy
properties of the specimens with different compositions. composition (Fig. 5). To investigate the effect of aging
For the as-homogenized alloys (i.e. zero aging time in treatment on fatigue properties for different W contents,
Fig. 5), the yield strength (sy) and the ultimate tensile isothermal aging has been performed at 900°C for 30 min
strength (UTS) are basically independent of the W and the FCG results of the aged alloys are compared with
content. Even after aging for 30 min, the increase of sy the homogenized alloys in Fig. 6.
and UTS are rather insignificant. On the other hand, the Fig. 6 shows that the aged alloys exhibit a noticeable
variation of ductility with aging time is quite different difference in their FCG properties as compared to the
and is very sensitive to alloy composition. For the homogenized alloys. The apparent FCG resistance, espe-
as-homogenized alloys, the elongation is almost indepen- cially in the early stage of the crack growth regime, of
dent of alloy composition, with a range of 41 –44%. By the aged microstructure is much higher than that of
contrast, the elongation of the aged microstructures homogenized microstructures, and the enhancement of
shows a remarkable variation. In the alloy without W FCG resistance varies with the W contents of the alloys.
While there has been a slight increase in the FCG
Table 3 resistance of the aged 3.5Mo–0W alloy, the FCG resis-
Chemical composition (wt.%) of s- and x-phases in the aged alloys
(EDX results)
tance of the 1Mo–3.6W alloy has been considerably
enhanced. For the 3.5Mo–0W alloy, the variation of the
Phase Cr Ni Mo W Fe, etc. apparent FCG resistance in the aged state can be
interpreted by the microstructural characteristics in view
3.5Mo – 0W s 32.10 3.65 8.09 — Balance of the fact that brittle s precipitates weaken the grain
2.5Mo – 1.5W s 31.98 3.22 8.90 4.29 Balance
x 24.87 2.45 14.69 12.75 Balance
boundaries, along which the failure may constitute at
1Mo – 3.6W x 12.27 1.04 7.00 52.83 Balance least part of the fatigue fracture surface. This is confi-
rmed by the fractographic observations shown in Fig. 7
196 T.H. Kang et al. / Materials Science and Engineering A251 (1998) 192–199
Fig. 5. (a) Yield strength (sy) and ultimate tensile strength (UTS), and (b) elongation as a function of aging time for various compositions.
which contrast the fatigue fracture surfaces of the ho-
mogenized and the aged alloys. It is found that the
fracture surface of the homogenized alloy is basically
transgranular but that of the aged alloy contains consid-
Fig. 6. The da/dN– DK curves for the homogenized and aged alloys
with various compositions.
erable areas of intergranular failure and becomes much
rougher. The roughness analysis of the fatigue fractured
surfaces corresponding to Fig. 7 has been made and the
results are plotted for different profiles, as shown in Fig.
8. As expected, the fracture surface roughness of the
aged alloy is evidently greater than that of the homoge-
nized alloy. It is then inferred that the slight increase in
the apparent FCG resistance of the aged 3.5Mo–0W
alloy is attributed to the roughness-induced crack clo-
sure effect due to the intergranular failure via grain
boundaries weakened by the secondary phase (s) precip-
itation. Intergranular cracking mainly occurs along s or
x interfaces. This type of crack closure effect should
decrease as the brittle precipitates diminish in quantity;
however, the apparent FCG resistance of the aged
1Mo–3.6W alloy containing the smallest amounts of
brittle precipitates is significantly improved. To account
for the fatigue behavior in this alloy, which has smaller
roughness-induced crack closure but exhibits higher
FCG resistance compared with the 3.5Mo–0W alloy,
intrinsic and extrinsic contributions have been separately
considered, as stated below.
 T.H. Kang et al. / Materials Science and Engineering A251 (1998) 192–199
Fig. 7. SEM fractography for fatigue failed specimens of: (a) homogenized, and (b) aged alloys (3.5Mo – 0W composition); CPD, crack
propagation direction.
3.4. Extrinsic 6ersus intrinsic FCG resistance
To distinguish between extrinsic and intrinsic contri-
butions to the FCG behavior, the crack closure load
has been measured in order to calculate the effective
stress intensity range, DKeff ( : Kmax −Kcl), so that the
intrinsic FCG resistance can be evaluated. Although
there are several other extrinsic effects induced by crack
branching and crack deflection [15,16], it is assumed
here that only the crack closure has a major role in the
extrinsic effects. The normalized crack closure levels
(Kcl/Kmax), plotted as a function of DK for the homoge-
nized and aged microstructures, are shown in Fig. 9. It
is observed that the crack closure levels of aged mi-
crostructures are much higher than those of homoge-
nized microstructures, which is in good agreement with
Figs. 7 and 8. However, a variation of crack closure
levels for the alloys with different W contents is not
significant in either homogenized or aged
microstructures.
After subtracting this crack closure effect from the
apparent FCG rate, the intrinsic FCG rate is plotted
against DKeff to obtain the effect of alloy composition
for both the homogenized and the aged alloys (Fig. 10).
As indicated in Fig. 10, the intrinsic FCG behavior of
the homogenized alloys is nearly insensitive to the
variation of the alloy composition, in agreement with
the fact that the microstructure in these alloys does not
change much by alloying. It is noted that the intrinsic
FCG resistance of the homogenized alloys is obviously
superior to (for the 3.5Mo – 0W composition) or no
worse than (for the 2.5Mo – 1.5W and 1Mo – 3.6W com-
positions) that of the aged alloys. Moreover, with the
197
increase in W content, the intrinsic FCG resistance of
the aged alloys increases accordingly. This implies that
the intrinsic FCG resistance is remarkably decreased,
by the aging treatment, in the 3.5Mo–0W alloy, but is
not much influenced in the alloys containing W con-
tents. In view of the microstructural change during
aging (Figs. 2–4), it has been clarified that the quantity
and the size of the brittle s-phase become smaller as
the W content increases, and finally (as in the 1Mo–
3.6W alloy) the precipitation of the s-phase is halted
and replaced by that of the tougher x-phase. As a
result, the ductility in tensile tests gets improved as the
W content increases (Fig. 5(b)). It is then inferred that
this improvement in ductility contributes to the intrinsic
FCG resistance in the aged alloys (Fig. 10).
Considering the above extrinsic and intrinsic contri-
butions, the apparent FCG behavior of the aged alloys
regarding the compositional effect (Fig. 6) can be inter-
preted as follows. For the 3.5Mo–0W alloy, its FCG
resistance is counterbalanced by two factors, i.e. the
large amounts of crack closure mainly due to the rough
surface, and the inferior intrinsic FCG resistance due to
the precipitation of the brittle s-phase upon aging. For
the 2.5Mo–1.5W alloy, while the crack closure contri-
bution does not change much (Fig. 9), the intrinsic
(ductility-facilitating) contribution resulting from the
suppression of s precipitation takes effect (Fig. 10). The
net result is the improvement in the apparent FCG
resistance of the 2.5Mo–1.5W alloy compared with the
3.5Mo–0W alloy. For the 1Mo–3.6W alloy, although
the crack closure effect is minimized due to the disap-
pearance of the brittle s-phase, the intrinsic contribu-
tion predominates in the overall FCG resistance. As to
198 T.H. Kang et al. / Materials Science and Engineering A251 (1998) 192–199
Fig. 8. Relative surface roughness of: (a) homogenized, and (b) aged
microstructures (3.5Mo–0W composition).
the role of the x-phase in the fatigue properties, it
has not been clarified yet. It is of great interest to
Fig. 9. Normalized crack closure plotted as a function of DK.
Fig. 10. The da/dN– DKeff curves for the homogenized and aged
alloys with various compositions.
know whether the x precipitates play a role similar to
that of the s precipitates when the x precipitates are
present solely in the microstructure. This requires fur-
ther investigation.
4. Conclusions
The fatigue crack growth resistance of duplex stain-
less steels has been investigated in relation to the
variation of W contents and heat treatment, and the
following conclusions have been drawn.
(1) Both the apparent (da/dN –DK) and the intrin-
sic (da/dN –DKeff) FCG behavior of the homogenized
alloys is basically insensitive to the compositional
variation (the substitution of Mo for W).
(2) The improvement of the apparent FCG resis-
tance of the aged alloys compared to the homoge-
nized alloys is attributed to the roughness-induced
crack closure caused by intergranular failure due to
the precipitation of the brittle secondary phases.
(3) With the increase in W content, the ductility of
the aged alloys increases and, consequently, the in-
trinsic FCG resistance of the aged alloys also in-
creases with increasing amounts of W.
Acknowledgements
This work was financially supported by Pohang
Iron and Steel Co. Ltd. (POSCO) under contract No.
96Y075. The authors are grateful to Mr H.J. Ko for
his help in TEM work and to Mr J.S. Park for his
assistance in preparing the manuscript.
 T.H. Kang et al. / Materials Science and Engineering A251 (1998) 192–199
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