Journal of Materials Processing Tech.

281 (2020) 116645

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Journal of Materials Processing Tech.

journal homepage: www.elsevier.com/locate/jmatprotec

Effects of prior deformation on precipitation behavior and mechanical T

properties of super-ferritic stainless steel
Hui-Hu Lua, Hong-Kui Guoa, Wang-Gang Zhanga, Wei Lianga,*, Yi-Ming Liua,b,**
a
College of Materials Science and Engineering, Taiyuan University of Technology, Taiyuan, 030024, PR China
b
Shanxi Academy of Analytical Sciences, Taiyuan, 030006, PR China

A R T I C LE I N FO A B S T R A C T

Associate Editor: Jian Cao The effects of the initial microstructure on the precipitation behaviors and related mechanical properties of
Keywords: 27Cr-4Mo-2Ni steel were investigated by X-ray diffraction, scanning electron microscopy, electron backscatter
Super-ferritic stainless steel diffraction (EBSD), and transmission electron microscopy techniques and tensile experiments, as well as by
Sigma precipitation kinetics Vickers hardness tests. Experimental results demonstrated the occurrence of inhomogeneous intragranular and
Rolling deformation intergranular deformation, e.g., the formation of shear bands because of differences in the grain orientations in
Laves phase the rolled specimens, especially in the specimen cold-rolled to a reduction of 70 %. EBSD revealed the presence
Embrittlement of ferritic regions with large plastic deformation around TiN particles because of stress concentration during the
rolling deformation. The sub-grain boundaries, shear bands, and regions near TiN particles formed during the
hot/cold rolling and aging processes served as additional nucleation sites and the high stored deformation en-
ergy provided a large driving force for intermetallic-phase precipitation, which caused the rolling deformation to
have an acceleration effect on the precipitation process, especially on that of the sigma phase. The sigma-phase
precipitation caused transition of the tensile fracture mode from ductile to brittle fracture and an increase in the
Vickers hardness to as high as 587 ± 7 HV. The large cooling rate during annealing process for the alloy should
be controlled to suppress the brittle phase precipitation.

1. Introduction prevent an increase in the ductile-to-brittle transition (DBT) tempera-

Super-ferritic stainless steels (SFSSs) have excellent corrosion re-
sistance, good thermal conductivity, and good mechanical properties,
and are typically employed as heat transfer materials in a Cl-rich en-
vironment, such as the condenser in coastal power station. To achieve
the above-mentioned properties of SFSSs, their chemical components
should be strictly controlled; that is, the Cr and Mo contents should be
high (25–32 wt.% Cr and 2–4 wt.% Mo) and the C and N contents
should be very low. Streicher (1974) studied the influence of the ad-
dition of C and N elements on the intergranular corrosion of Fe-28Cr-
4Mo alloy and found that the C and N additions could induce inter-
granular attack and that the total concentration of the C and N elements
should therefore be lower than 250 ppm. Thus, he proposed addition of
Ti and Nb elements to reduce the susceptibility of this alloy to inter-
granular corrosion. Fukuda (2003) investigated the effect of Ti addition
on the ductility of Fe-30Cr ferritic stainless steels with a Ti:C ratio of 1:9
(wt.%) and reported that the carbide particles should be controlled to
be coarse and globular and that they should be uniformly dispersed to
ture. The study of Pessall and Nurminen (1974), aimed at optimizing
the composition of ferritic stainless steels, revealed that the addition of
∼2 wt.% Ni to Fe-Cr alloys could improve their toughness. Streicher
(1974) developed the 28Cr-4Mo-2Ni alloy and Nichol (1977) designed
the 29Cr-4Mo-2Ni alloy, both of which contained added Ni, to optimize
the corrosion resistance and toughness of these SFSSs.
When large amounts of Cr, Mo, and Nb are added to SFSSs, some
kinds of intermetallic phases may be formed and these precipitations
make the alloy embrittlement, thus many studies were performed fo-
cusing on the precipitation behavior in SFSSs. Brown et al. (1983)
studied the precipitation phases formed in 25Cr-3Mo-4Ni SFSSs and
found that the sigma phase (σ, Fe-Cr or Fe-Cr-Mo), chi phase (χ,
Fe36Cr12Mo10), and Laves phase (η, Fe2Nb or Fe2Mo) usually pre-
cipitated in the 600–1000 °C range, and these precipitations showed a
“C” shaped temperature-time-precipitation (TTP) curves with the
“nose” temperature near 800 °C. Lu et al. (2018a) annealed the 27Cr-
4Mo-2Ni SFSS at 600–800 °C after its solution treatment at 1100 °C and
found that the Laves phase nucleated first in the grains, and the nano-

⁎
Corresponding author.
⁎⁎
Corresponding author at: College of Materials Science and Engineering, Taiyuan University of Technology, Taiyuan, 030024, PR China.
E-mail addresses: liangwei@tyut.edu.cn (W. Liang), liuym812@163.com (Y.-M. Liu).

https://doi.org/10.1016/j.jmatprotec.2020.116645
Received 19 July 2019; Received in revised form 2 February 2020; Accepted 11 February 2020
Available online 11 February 2020
0924-0136/ © 2020 Published by Elsevier B.V.
H.-H. Lu, et al.
sized chi and bulk sigma phases then precipitated at the grain bound-
aries. They also suggested that the formation of the sigma phase caused
the steel to fracture in the brittle mode during impact tests. Nichol
(1977) compared the mechanical properties of the 29Cr-4Mo-2Ni SFSS
annealed at different temperatures and reported that the precipitates
formed at 704–954 °C caused the steel to undergo precipitation em-
brittlement. Thus, the cooling rate after reheating should be strictly
controlled to go fast through this temperature range.
From an industrial point of view, the production process of SFSSs
generally comprises solution treatment, hot rolling, coiling, cold
rolling, annealing, and so on. When the cooling rate was not controlled
carefully after the hot rolling or solution annealing process, a brittle
fracture phenomenon was usually observed during the subsequent cold
rolling or the uncoiling process. The brittle fracture phenomenon ap-
peared frequently in the coiling after hot rolling process. Thus, the
rolling deformation may provide some certain effects on the brittle
phase precipitation due to their microstructural characteristic.
However, the past studies were mainly focused on the duplex, auste-
nitic, and conventional ferritic stainless steels. Mehtonen et al. (2013)
studied the hot deformation behavior of a 21 %Cr ferritic stainless steel
and found that dynamic recovery was typically induced by the high
stacking-fault energy of the ferritic steel, which resulted in the forma-
tion of numerous sub-grains. When cold-rolled sheets of SFSSs are an-
nealed, static recovery often occurs in the low-temperature range,
which results in dislocation movement and the formation of sub-grains.
Cho and Lee (2013) reported that fast precipitation of the sigma phase
in a 2205 duplex stainless steel occurred because of the high driving
force for the nucleation of intermetallic compounds and the high dif-
fusion rate of their elements that was induced by the cold rolling of the
steel. The study of Hsieh et al. (2007) on 19Cr-9Ni-2 Mn and 18Cr-
0.75Si stainless steels indicated that hot-rolling deformation caused the
sigma precipitation morphology to change from dendrite-like to glob-
ular. The fraction of the sigma phase in the steels also increased gra-
dually with an increase in the reduction from 0% to 75 %. Chandra
(1988) also observed the enhanced effect of hot working on sigma-
phase precipitation in Fe-19Cr-5Ni-2.7Mo duplex stainless steels.
Singhal et al. (1972) showed that small cold-rolling reduction had an
acceleration effect on the precipitation of the ferrite and sigma phases
in a 25Cr-24Ni austenitic stainless steel. Hsiao et al. (2017) found that
the tensile deformation increased the fraction of Laves phase, while
decreased their sizes in Crofer 22 H alloy. Lu et al. (2018b) indicated
that the hot rolling accelerated the sigma precipitation and alter their
nucleation sites, in turn, influenced the recovery of SFSSs. The above-
mentioned studies indicated that the prior deformation provided some
effects on the precipitation behavior in stainless steels. For the case in
SFSSs containing complex second phases, the effects of the rolling de-
formation on the phase precipitation behavior and sigma-precipitation
kinetics, and the influence of microstructure and precipitation on the
mechanical properties of SFSSs were required to be investigated.
In this study, SFSS specimens were solution-treated, hot-rolled, and
cold-rolled, after which all the specimens were aged at 800 °C to ex-
amine the effect the initial microstructure on the precipitation behavior
and mechanical properties during the production process and to un-
derstand the nature of precipitation embrittlement acceleration. The
aging annealing was performed at 800 °C, which located near “nose
temperature” of intermetallic precipitation curves. At 800 °C, the pre-
cipitation kinetics was fast and it is easy to investigate the precipitation
behavior.
2. Experimental procedures
Slabs of a hot-rolled 27Cr-4Mo-2Ni SFSS with a thickness of 4.1 mm
(chemical composition: Fe-27.57Cr-0.05Cu-0.23Mn-3.72Mo-0.37Nb-
1.98Ni-0.4Si-0.14Ti-0.015C-0.016N-0.022P-0.0020S, wt.%) were used
for this experimental study. First, the as-received slabs were hot-rolled
to 3.0 mm in one pass after solution treatment for 20 min at 1100 °C,
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Journal of Materials Processing Tech. 281 (2020) 116645
after which the hot-rolled slabs were rapidly quenched in water; these
slabs are hereafter referred to as hot-rolled (HR) specimens. The free
hot rolling slabs with water quenching after solution treatment for 20
min at 1100 °C (hereafter referred to as solution-treated (ST) speci-
mens) were subsequently cold-rolled to 1.2 mm in several passes
(hereafter referred to as cold-rolled (CR) specimens). Finally, the ST,
HR, and CR specimens were aged at 800 °C for 5 min, 30 min, 1 h, 2 h, 4
h, and 8 h.
The microstructure, texture, and precipitation of the specimens
were characterized by electron backscatter diffraction (EBSD) and
backscattered electron (BSE) imaging on a Tescan Mira 3 field-emission
scanning electron microscope. All the characterized positions were in
the longitudinal section (normal direction (ND) and rolling direction
(RD)) of the specimens, which were first mechanically polished and
then electrochemically polished at −30 °C with perchloric acid alcohol
solution at 25 V for 30–60 s. The scan steps in the EBSD measurement
were set between 0.3 and 2.0 μm depending on the initial grain size.
The orientation distribution function (ODF) was calculated from the
EBSD data by use of Channel 5 software. Additionally, a SmartLab X-ray
diffraction (XRD) instrument was also used to identify the precipitation.
Transmission electron microscopy (TEM; JEOL 2100 F) coupled with
selected area electron diffraction (SAED) was used to further observe
the microstructure of the specimens in detail. The thin foil specimens
were produced by double electrolytic jet processing.
Room temperature (RT) tensile experiments were carried out on an
electronic material testing machine (CMT5250) with a rate of 0.5 mm/
min controlled by an extensometer. The subsize specimens with gage
section of 25 mm (length) and 6 mm (width) were prepared according
to ASTM-E8M. Three equivalent specimens were tested under each
condition, and the standard deviation of the measured values was also
calculated. The Vickers hardness (HV) was measured using a HR-320MS
Vickers hardness tester with a load of 0.981 N for 15 s.
3. Results and discussion
3.1. Microstructure and precipitation before aging treatment
Fig. 1 shows the microstructure and texture of the ST, HR, and CR
specimens before aging treatment. It was evident that the ST specimens
were composed of equiaxed grains with an average grain size of 76 ± 6
μm and an average aspect ratio of 2.0 ± 0.3 (Fig. 1a). After hot rolling,
the equiaxed grains elongated slightly along the RD, which resulted in
an average grain size of 72 ± 7 μm and an average aspect ratio of
5.2 ± 0.8 because of the small rolling reduction ratio of ∼27 %
(Fig. 1b); these grains underwent dynamic recovery owing to the high
stacking-fault energy of ferritic stainless steels, as reported by
Mehtonen et al. (2013). In the CR specimens, the fibers elongated
drastically along the RD because of the high rolling reduction ratio of
∼70 %, which resulted in an average grain size of 70 ± 10 μm and an
average aspect ratio of 26.5 ± 1.5. In addition, the misorientation
distributions of the specimens were also plotted, as shown in Fig. 1d–1f.
The fractions of low-angle grain boundaries (LAGBs, 2°–15°) in these
specimens were ∼5%, ∼87 %, and ∼92 %, respectively indicating that
the LAGB fraction increased with increasing amount of deformation.
The LAGBs in the ST specimens were formed mainly by the quenching
stress generated during the rapid water-quenching. In addition, the ODF
calculation results indicated that weak α-fiber (< 110 > // RD) and γ-
fiber (< 111 > // ND) micro-textures were formed in the ST specimens
and that the grain orientation gradually transformed into the γ-fiber
orientation as the rolling deformation increased, as shown in Fig. 1g –
1i.
Fig. 2 shows BSE images and energy-dispersive X-ray spectroscopy
(EDS) point analysis results of the ST, HR, and CR specimens. It was
clear that only bulky TiN particles (5–10 μm in size) and fine Nb(C, N)
particles (0.2–0.5 μm in size) were observed in these three kinds of
specimens and these particles were formed in the high-temperature
H.-H. Lu, et al. Journal of Materials Processing Tech. 281 (2020) 116645

Fig. 1. EBSD images showing (a-f) the initial microstructures and (g-i) micro-texture of specimens with various conditions: (a,d,g) solution treated, (b,e,h) hot rolled
and (c,f,i) cold rolled.

Fig. 2. BSE images showing (a-c) the precipitation and (d-e) EDS point analysis results in the specimens after (a) solution treating, (b) hot rolling and (c) cold rolling.

3
H.-H. Lu, et al.
range by stabilization reactions between Ti/Nb and C/N atoms, as ex-
plained by Lu et al. (2019). The TiN particles were formed during the
solidification process and were distributed randomly. However, the Nb
(C, N) particles were distributed linearly along RD, because these par-
ticles nucleated at the initial elongated grain boundary during the
rough hot rolling process after the continuous casting, and they kept
nearly unaltered during the subsequent hot rolling and cold rolling
process in this study. In particular, the TiN particles were fragmented
during the cold-rolling process due to the large plastic deformation
(Fig. 2c).
3.2. Orientation dependent inhomogeneity deformation
Both, intragranular deformation inhomogeneity and intergranular
deformation inhomogeneity, were observed in the HR and CR speci-
mens. Some grains showed a small deformation that was characterized
by a small fraction of LAGBs (marked as green grains in Fig. 1b), and
others showed a large deformation that was characterized by a large
fraction of LAGBs (marked as blue grains in Fig. 1c). Moreover, some
shear bands were observed in the grains with the < 111 > // ND or-
ientation after the rolling deformation, and the shear bands were in-
clined at ∼30° along the RD. Experiments in some other studies, e.g.,
those conducted by Haratani et al. (1984) on silicon steels and by Ray
et al. (1994) on low-carbon steels, also revealed the presence of shear
bands after rolling deformation.
The number of in-grain shear bands in the CR specimens was much
greater than that in the HR specimens. Moreover, many LAGBs were
observed in the regions around the TiN particles (Fig. 1b and c), in-
dicating a large deformation around the TiN particles because of the
deformability difference between the ferrite matrix and the TiN parti-
cles.
The above analysis of the deformation inhomogeneity demonstrated
that it was related to grain orientation (where different orientations are
indicated in different colors in Fig. 1); the orientation dependence of
deformation inhomogeneity is usually represented by the Taylor factor
M, which was expressed by Bishop and Hill. (1951) as follows:
σij Σδ γk
M= = this finding of presence of Laves phases at sub-grain boundaries also
τc δεij (1)
where δεij is the increment in plastic strain under a stress of σij , τc is the
critical resolved shear stress, and Σδγk is the sum of shear strains on
active slip systems to achieve the strain increment δεij . The Eq. (1) also
shows that the large M values display an easily shear strain on a given
applied strain. The calculated M values for the specimens after hot/cold
rolling deformation are displayed in Fig. 3. The γ-fiber grains have the
largest M with the values of 3.5–4.0, and the α-fiber grains have larger
M with the values of 2.5–4.0, while the θ-fiber (< 001 > //ND) grains
have the smallest M with the values of ∼2.5. The larger M for the grain
orientation, the larger deformation inhomogeneity in the grain. Thus,
the inhomogeneous deformation and shear bands appear in the γ-fiber
grains easily.
3.3. Precipitation evolution during aging treatment
Fig. 4 shows the precipitation in the aged specimens characterized
by XRD, EBSD and TEM-SAED. Three kinds of intermetallics, i.e., the
chi phase, sigma phase, and Laves phase, were identified. The bulk
sigma phase was well indexed by XRD and EBSD (Fig. 4a and b) because
of its large fraction and size, whereas the fine chi and Laves phases were
well characterized by TEM-SAED, as shown in Fig. 4c and 4d. The
analysis results showed that the sigma phase precipitated along the
grain boundaries (Fig. 4b), the chi phase also precipitated along the
grain boundaries (Fig. 4b), and the Laves phase nucleated at sub-grain
boundaries and dislocations (Fig. 4c). Fig. 4b–d additionally showed
that static recovery also occurred during aging, and many sub-grains
were observed in deformed grains.
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Journal of Materials Processing Tech. 281 (2020) 116645
Fig. 5 shows BSE images depicting the microstructure and pre-
cipitation evolution in the ST, HR, and CR specimens after aging
treatment at 800 °C for various times. The sigma, chi, and Laves phases
were observed clearly in the BSE images and the BSE data were in ac-
cord with the EBSD and TEM results. The BSE images of the ST speci-
mens after aging (Fig. 5a–c) showed that first, a chi phase with a grain
size of 60–100 nm was formed along the grain boundaries, after which
it was scattered at the grain boundaries; subsequently, the sigma phase
precipitated along the chi phase around the grain boundaries. The
sigma phase gradually grew from grain boundary toward in-grain and
finally characterized by a dendritic shape. Moreover, many sigma phase
islands were also observed within the grains after prolonged aging
treatment. A Laves phase with a grain size of 50–500 nm was also
observed in grains after aging for 1 h (Fig. 5a). As the aging time in-
creased from 1 h to 4 h, the bulk sigma phase was dominant and nearly
all the grain boundaries were occupied by the sigma phase. Moreover,
microcracks were also observed within the sigma phase (marked by
blue circles in Fig. 5c–f). The EBSD analysis indicated the existence of
an orientation relationship between the sigma phase and the ferrite
matrix, i.e., (-110)σ // (1–10)α and [332]σ // [-1-1-3]α, with an average
deviation of ∼20°. The scanning electron microscopy (SEM)-EDS point
analysis showed that the main sigma-phase composition was 61.3Fe-
32.4Cr-5.5Mo, the chi-phase composition was 53.4Fe-18.6Cr-20.5Mo,
and the Laves-phase composition was 50.8Fe-19.0Cr-16.0Mo-11.2Nb
(wt. %). The microracks within sigma phase was generated by large
lattice strain induced by fast diffusion of Cr and Mo elements during the
process of sigma phase nucleation and growth, as seen the discussion in
our previous study (Lu et al., 2018a).
The presence of Laves phases at sub-grain boundaries was also ob-
served in the HR and CR specimens; additionally, the chi and sigma
phases were also found to be distributed around the TiN particles and
along the shear bands with increasing aging time, as shown in Fig. 5d–f
and Fig. 5g–i for the aged HR and CR specimens, respectively. Nano-
sized in-grain Laves phases located at sub-grain boundaries were clearly
observed in the CR specimens, as shown in Fig. 6, which is in keeping
with the TEM analysis results (Fig. 4d). The sub-grains in the CR spe-
cimens were formed by the dislocation movement during aging, and
indicated that the recovery process occurred before the precipitation of
the Laves phase. Moreover, the sigma phase in the deformed specimens
was narrow in the direction perpendicular to the grain boundaries, and
this width was smaller than that in the ST specimens; this indicates the
high nucleation rate of the sigma phase in the deformed specimens.
Specially, there were still some regions without in-grain sigma pre-
cipitation, though all the grain boundaries were occupied by sigma
phase in CR specimens after aging for 4 h. The difference in the pre-
cipitation evolution between the ST and the deformed specimens may
be related to their microstructural differences; this is discussed in
greater detail in section 3.4.
3.4. Effects of prior deformation on precipitation
In order to evaluate the effects of the microstructural state on the
precipitation behavior, the area fractions of precipitated sigma phases
in the specimens with different microstructures were measured in their
BSE images, and the results are shown in Fig. 7a. It can be seen that the
area fractions of sigma phases in the ST, HT, and CR specimens in-
creased with increasing aging time, and under the same aging condi-
tion, the area fractions in the CR and HR specimens were higher than
that in the ST specimens. For example, the area fraction of the sigma
phase in the ST specimens increased from 1.3 % ± 0.3 % after aging for
2 h to 15.7 % ± 2.5 % after aging for 8 h; the area fraction in the HR
specimens increased from 3.6 % ± 0.3 % after aging for 2 h to 35.6
% ± 2.3 % after aging for 8 h; and the content in the CR specimens
increased from 8.8 % ± 1.2 % for 0.5 h to 68.6 % ± 2.5 % for 8 h. This
phenomenon also indicated that prior deformation caused a drastic
H.-H. Lu, et al. Journal of Materials Processing Tech. 281 (2020) 116645

Fig. 3. Calculated Taylor Factor of deformed specimens: (a-c) hot rolled and (b-d) cold rolled.

reduction in the incubation period of sigma-phase precipitation. For
instance, after aging for 0.5 h, the area fraction of the sigma phase in
the CR specimens was measured to be approximately 8.8 % ± 1.2 %,
whereas the ST specimens were required to be aged for approximately 1
h for the precipitated sigma phase to become visible.
Rodrigo (2009) studied the sigma-phase precipitation in a duplex
stainless steel and found that this precipitation was controlled by the
nucleation and growth process. According to Dubiel and Cieślak (2011),
the kinetics of sigma-phase precipitation can be calculated by the
Johnson–Mehl equation:
f(t) = 1 − exp(-kt n ) (2)

Fig. 4. Identification of phases by (a) XRD, (b)EBSD and (c-d) TEM-SAED in aged specimens: (a-b) aging for 4 h after cold rolling, (c) aging for 5 min after hot rolling
and (d) aging for 30 min after hot rolling. Sub-G.B. represents sub-grain boundary.

5
H.-H. Lu, et al. Journal of Materials Processing Tech. 281 (2020) 116645

Fig. 5. BES images showing the precipitaion in aged specimens at 800 °C with different conditions: (a-c) solution treated, (d-f) hot rolled and (g-i) cold rolled. G.B.
represents grain boundary.The image j, k and l is the high resolution of image c, f and i.

where f(t) is the area fraction of the precipitated sigma phase at a
certain time t, and k and n are constants for a given material. The values
of k and n were calculated by the linear regression method by sub-
stitution of experimentally obtained values (Fig. 7a) into Eq. (2), and
the results are shown in Fig. 7b. It was evident that the CR specimens
had the fastest precipitation kinetics whereas the ST specimens had the
slowest kinetics (a higher k value represents faster kinetics). The
calculated n values ranged between 0.5 and 2.5, which indicated that
the nucleation and growth of the sigma phase were controlled mainly
by diffusion, i.e., Cr and Mo diffusion in the present study. The above-
described microstructure analysis showed that the acceleration effect of
deformation on the sigma phase was attributed to the availability of
additional nucleation sites for precipitation, such as sub-grain bound-
aries, shear bands, and the regions around TiN particles, which were

Fig. 6. High magnification of chi precipitation along shear bands and Laves precipitation within sub-grains in Fig. 5f.

6
H.-H. Lu, et al.
Fig. 7. Histograms showing (a) the effect of prior deformation on sigma precipitation and (b) the calculated dynamic equation.
formed by inhomogeneous deformation. Additionally, the high stored
plastic deformation energy may provide a large driving force for pre-
cipitation of the sigma phase.
In general, the kernel average misorientation (KAM) is sensitive to
the deformation inhomogeneity and the stored energy; Jedrychowski
et al. (2013) expressed the KAM using EBSD data as follows:
N
KAM(pointj) = (1/N)∑k = 1 ω(g i,g j)
(3)
where N is the sum of adjacent EBSD points that satisfy the threshold
misorientation value (usually 5°) and ω(g i,g j) is the difference between
the orientation of the ith neighboring point, g i , and the orientation of
point j itself, g j, i.e., the misorientation angle. The calculated KAM
Fig. 8. KAM analysis of the deformed specimens before aging: (a-c) hot rolled and (b-d) cold rolled. The black lines in image (a) and (b) represent the high angle grain
boundary with the misorientaion > 15°.
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Journal of Materials Processing Tech. 281 (2020) 116645
values of the HR and CR specimens are shown in Fig. 8; these calcu-
lation results showed that the KAM in the CR specimens was much
larger than that in the HR specimens. The average KAMs of the HR and
CR specimens were 0.90° and 1.57°, respectively. Large KAM values
were also calculated for the regions near grain boundaries (1.0°–2.0°),
sub-grain boundaries (2.5°–3.5°), shear bands (3.5°–3.8°), and TiN
particles (3.0°–4.0°), as shown in Fig. 8a–c. Thus, these regions acted as
preferential nucleation sites for precipitation because of the high in-
terfacial energy, and it was explained that some grains with uniform
deformation was free of sigma precipitation after prolonged aging.
Additionally, Liu and Hansen (1995) reported that the stored de-
formation energy is proportional to the density of geometrically ne-
cessary dislocations (ρGND). According to the study of Paula and Markus
H.-H. Lu, et al.
Fig. 9. Vickers hardness various related to (a) aging conditions and (b) sigma precipitaion.
Fig. 10. Tensile properties of the aged specimens with different initial microstructures: (a) ultimate tensile strength, (b) yield strength and (c) total elongation.
Ziehmer (2018), ρGND can be approximately calculated using KAM data
as follows:
3ϑ
ρGND=
μb
where μ is the Kernel radius or the step size when only the first nearest
neighbors are considered and b is the magnitude of the Burgers vector.
The local misorientation ϑ is the KAM obtained from EBSD data. Thus,
ρGND in the HR specimens was approximately 1.0 × 1014 m−2 and that
in the CR specimens was approximately 3.1 × 1014 m−2, which is three
times the value for the HR specimens. Thus, the stored energy in the CR
specimens was much higher than that in the HR specimens, and the
former provided a much larger driving force for precipitation of the
sigma phase. Moreover, the high density of dislocations also provided
diffusion routes for Cr and Mo, as reported by Lu et al. (2018b). Con-
sequently, the plastic deformation had an acceleration effect on sigma-
phase precipitation because of the more numerous nucleation sites and
higher stored plastic deformation energy.
Journal of Materials Processing Tech. 281 (2020) 116645
3.5. Effects of intermetallic phases on Vickers hardness
Fig. 9 shows the Vickers hardness values of the specimens under
various conditions. It can be seen that the Vickers hardness increased
(4) with increasing aging time, and a larger deformation led to higher
Vickers hardness values of the specimens under the same aging time.
For example, the Vickers hardness of the ST specimens increased from
220 ± 17 HV for 0.5-h aging to 304 ± 18 HV for 4-h aging, whereas the
Vickers hardness of the CR specimens increased remarkably from
330 ± 12 HV for 5-min aging to 606 ± 28 HV for 4-h aging (Fig. 9a).
The CR and the HR specimens showed large hardness was due to the
dislocation strengthening induced by high density dislocations. Hall
and Algie (1966) indicated that the Fe-Cr/Mo-type sigma phase was
very hard and brittle and that its hardness was as high as ∼940 HV;
during the hardness test, rupture of the phase occurred usually because
of its brittle nature. Lu et al. (2018a) reported that the Vickers hardness
increased with increasing the area fraction of the precipitated sigma
phase because of the much higher hardness of the sigma phase than of
the ferrite microstructure. Thus, in the present study, an increase in the
Vickers hardness after aging treatment was mainly caused by an
8
H.-H. Lu, et al.
increase in the sigma-phase fraction, because this fraction was much
larger than those of the chi and Laves phases, as shown in Fig. 9b.
Specifically, the Vickers hardness values of the 0.5-h-aged ST and HR
specimens were little smaller than those before their aging, whereas the
Vickers hardness value of the 0.5-h-aged CR specimens was higher than
that before their aging. The decrease in the Vickers hardness of the ST
and HR specimens upon aging for 0.5 h was due to static recovery
softening and the absence of visible sigma phases. Rapid precipitation
of the sigma phase in the CR specimens after aging for 0.5 h accounted
for the increase in the Vickers hardness, although static recovery soft-
ening also occurred in this case.
3.6. Effects of intermetallic phases on tensile properties
Fig. 10 shows the RT tensile properties of the specimens under
various conditions. It is clear that the initial state specimens before
aging possessed high ultimate tensile strength (UTS), yield strength
(i.e., 0.2 % proof strength, YS), and total elongation (TE). The UTS, YS,
and TE decreased as the aging time increased. The CR specimens
showed the highest UTS and YS, i.e., ∼975 and ∼960 MPa, whereas
the ST specimens showed the lowest UTS and YS, i.e., ∼720 and ∼490
MPa, because of the high work hardening induced by cold plastic de-
formation, which was reflected by the highest dislocation density of 3.1
× 1014 m−2 for the CR specimens and a low dislocation density of 1.0
× 1014 m−2 for the HR specimens. After short time aging, the strength
of the CR and HR specimens decreased dramatically, and these strength
decreases were mainly caused by the fast consumption of work hard-
ening after the static recovery. The HR specimens after aging showed
the smaller strength values than that for ST specimens, and this was
caused by the remarkable reduction of solution strengthening, such as
Cr and Mo, which were consumed by the much more sigma precipita-
tion in HR than that in ST specimens (Fig. 7). The relative stable YS
values for the HR specimens after prolonged aging indicated that the
sum total of the decrease in the static recovery softening and the re-
duction in solid-solution strengthening caused by the sigma-phase
precipitation during the aging process was balanced out by the
strengthening of sub-grain boundaries formed by static recovery (Fig. 4
and Fig. 11). However, ρGND of the ferrite matrix of the CR specimens
increased to 1.0 × 1015 m−2 after aging for 8 h; this finding indicated
that the rapid precipitation of the bulk sigma phase induced stress
concentration in ferrite matrix near the sigma phase, which resulted in
an increase in ρGND . As a result, the stress concentration in the ferrite
matrix led to an additional increment in the strength. Moreover, the
rapid fracture induced by sigma-phase precipitation during the tensile
experiments caused a trouble to measure YS value.
Sun et al. (2018) used the strain-hardening model to calculate the
increment in the YS induced by an increase in dislocations in ferritic
steels:
Δσ = αMGb Δρ (5)
Fig. 11. The TEM bright field image showing the dislocations and sub-grains in
HR specimens.
9
Journal of Materials Processing Tech. 281 (2020) 116645
Here, Δσ is the yield stress increment induced by work hardening and G
is ∼80 GPa at RT for stainless steels (Ratanaphan et al., 2015). The α
and M values were set as 0.5 and 3, respectively. Thus, the calculated
value of Δσ between the CR and HR specimens in consideration of
ΔρGND was approximately 228 MPa. The Δσ value measured in the
tensile test was approximately 310 MPa; the calculated value of Δσ was
slightly smaller than the measured value because others kinds of dis-
locations, such as incidental dislocation boundaries, were not con-
sidered in the calculation. From Eq. (5), the density of other kinds of
dislocations was calculated to be approximately 5.4 × 1013 m−2, which
was much lower than that of GNDs.
The TE decreased to < 5% when the aging times of the CR, HR, and
ST specimens were > 0.5 h, > 2 h, and > 3 h, respectively. The de-
crease in the TE with increasing aging time was due to the increase in
the fraction of the precipitated sigma phase, which was verified by Lu
et al. (2018b). Hall and Algie (1966) reported that the RT sigma phase
was characterized by an ordered lattice, and it was very difficult for the
sigma phase to generate dislocations during the plastic deformation,
because of which it became brittle. Thus, the formation of the sigma
phase caused a reduction in the TE of the specimens.
In a word, the effect of sigma precipitation on Vickers hardness was
conspicuous because the hard nature of sigma phase plays a major role
on the Vickers hardness measurement. While, the notable effect of
sigma precipitation on the elongation was due to its brittle nature.
Unlike the conspicuous effect of sigma-phase precipitation on the
Vickers hardness and the elongation, its effect on strength was com-
plicated because of its hard and brittle nature and many micro-cracks
within them (grain boundary weakening), as well as the Cr and Mo
exsolution from ferrite induced by sigma formation.
3.7. Ductile-to-brittle transition
Fig. 12 shows a comparison of the fracture metallography images of
the ST, HR, and CR specimens before and after aging treatment. It was
evident that the fracture surfaces of all the specimens before aging
contained fine dimples (Fig. 12a–c), which indicated the ductile frac-
ture mode although the smallest TE was measured in the CR specimens
(Fig. 10c). When intermetallic precipitation, especially sigma-phase
precipitation, occurred after aging treatment for a long time, the river
pattern and cleavage facets were visible, which were indicative of the
brittle fracture mode. It was only 0.5 h aging that was needed for CR
specimens to fracture with brittle mode, while it was about 1 h and 2 h
for HR and ST specimens. Furthermore, intergranular fracture was also
observed in the CR specimens after aging for 1 h. This phenomenon
indicated that the DBT occurred when the sigma phase was formed.
According to the Cottrell model (Petch, 1958), DBT occurs when
2
σy k y d1/2 = k y + σ0 k y d1/2 > Cμγ (6)
where σy is the brittle fracture stress or flow stress; k y is the Hall–Petch
slope; d is the average grain size; σ0 is the lattice friction stress; μ is the
shear modulus; γ is the effective surface energy of an implied crack; and
C is a constant. In this study, the d value was nearly constant. When the
bulk sigma phase and fine chi phase are formed at grain boundaries and
the Laves phase is formed at sub-grain boundaries, they can act as
strong obstacles to slip propagation across the grain boundaries, which
would further increase ky, especially in the scenario of a continuous
grain-boundary network resulting from the formation of the sigma
phase. Furthermore, Zwieten (1993) reported that microcracks within
the sigma phase can act as crack initiation sites and decrease γ. Thus,
the grain-boundary phase can induce the DBT. Fig. 12 also shows that
the rolling deformation also induced the DBT, which was reflected in
the fact that the fracture surface of the ST specimens after aging for 1 h
was characterized by dimples, while many large voids were observed in
CR specimens. This is because after hot or cold rolling, locking of dis-
locations occurred, which caused an increase in the flow stress σy .
H.-H. Lu, et al.
Fig. 12. Fracture metallographics of specimens (a-c) before and (d-f) after aging treatemt for 1 h with different initial microstructures: (a,d) solution treated, (b,e) hot
rolled and (c,f) cold rolled.
4. Conclusions
The effects of initial microstructure on the precipitation and related
mechanical properties of the 27Cr-4Mo-2Ni SFSS were investigated,
and some conclusions were drawn, as follows.
1. Equiaxed grains, dynamically recovered grains elongated along
the RD, and fiber microstructures were obtained after solution treat-
ment, hot rolling, and cold rolling processes, respectively. Orientation
dependence of deformation inhomogeneity was observed in the CR and
HR specimens, and shear bands were also observed within the γ-fiber
grains. Randomly distributed TiN and linearly distributed Nb(C, N)
particles were found in the microstructure.
2. After 800 °C aging of the CR and HR specimens, the nanosized chi
phase was first formed at the grain boundaries; then, the bulk sigma
phase precipitated near the chi phase around the grain boundaries;
synchronously, the Laves phase was formed at the sub-grain boundaries
and dislocations. The chi and sigma phases were also formed along the
shear bands and near the regions around the TiN particles because of
the high deformation at these locations. The Laves phase nucleated at
the sub-grain boundaries in the CR specimens because static recovery
occurred rapidly before precipitation of this phase during aging treat-
ment.
3. Hot and cold rolling deformation had an acceleration effect on
precipitation because of the numerous nucleation sites and high stored
plastic deformation energy generated by these processes. The pre-
cipitation of the sigma, chi, and Laves phases caused an increase in the
Vickers hardness and a marked decrease in the TE during tensile tests,
which, in turn, led to the DBT.
4. The cooling rate passing through the precipitation temperature
range of sigma phase in CR and HR specimens should be strictly con-
trolled to prevent the precipitation embrittlement.
Author Contribution Statement
The first author (Hui-Hu Lu) presented the research idea and ex-
perimental design, and wrote this manuscript. The second author
(Hong-Kui Guo) and third author (Wang-Gang Zhang) assisted to
complete the rolling and annealing experiment. The TEM analysis was
completed by the corresponding author (Wei Liang). The fifth author
(Yi-Ming Liu) put forward some instructive suggestions for the writing
of this paper and modified the language.
10
Journal of Materials Processing Tech. 281 (2020) 116645
Data availability statement
Raw data related to this study can be made available on request.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgements
This work was supported by the Projects of International
Cooperation in Shanxi, China (Grant No.: 201603D421026) and the
Innovation Project of Shanxi Province Graduate Education (Project
title: Laves phase high temperature precipitation behavior and its ef-
fects on the recrystallization texture in super-ferritic stainless steel).
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