Materials Science & Engineering A 639 (2015) 615–625

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Materials Science & Engineering A

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

A hybrid refining mechanism of microstructure of 304 stainless steel

subjected to ECAP at 500 °C
Z.J. Zheng a,b, Y. Gao a,n, J.W. Liu a, M. Zhu a
a
School of Materials Science and Engineering, South China University of Technology, Guangzhou 510641, PR China
b
School of Mechanical and Automotive Engineering, South China University of Technology, Guangzhou 510641, PR China

art ic l e i nf o a b s t r a c t

Article history: The mechanism of microstructure evolution of 304 stainless steel (SS) during equal-channel angular
Received 8 December 2014 pressing (ECAP) at 500 °C was investigated systematically by optical microscope (OM), transmission
Received in revised form electron microscope (TEM) and X-ray diffraction (XRD). The results show that the refining mechanism of
22 May 2015
microstructure of 304 SS during ECAP behaviors as a hybrid model consisting of dislocation-subdivision
Accepted 24 May 2015
mechanism and twin fragmentation mechanism, resulting in three kinds of nanostructure domains:
Available online 27 May 2015
(1) the equiaxial nano-grains with curving grain boundaries (GBs) having high angles of misorientation
Keywords: resulted from the cross-slip and movement of dislocations; (2) the equiaxial nano-grains with smooth
304 SS and distinct boundaries resulted from the intersection between primary deforming twin bundles; (3) the
ECAP
secondary nano-twins formed in the primary deforming twins. The average nano-grain size ultimately
Refining mechanism
obtained is in the range of 80 nm to 120 nm and the nano-twins have a width of 20–40 nm and a length
Hybrid model
SFE of 100 to a few hundred nm. A low content about 10% (V/V) of deformation-induced martensite (DIM) is
obtained in the first pass and remains almost constant during further passes of ECAP. The refining me-
chanism of DIM is also a hybrid model, including the refinement of banded DIM by the intersection with
slipping bands and the newly induced fine martensite in submicron and nanometer grained austenite
matrix.
& 2015 Elsevier B.V. All rights reserved.

1. Introduction successfully applied to produce UFG or NG microstructure for

Materials with ultrafine-grained (UFG) (grain size in the range
of 100 nm to 1000 nm) or nano-grained (NG) (grain size less than
100 nm) structure present unique physical and mechanical prop-
erties as compared to the conventional polycrystalline counterpart
with coarse grained (CG) structure [1]. Many methods have been
developed for producing UFG and NG materials in recent years.
Among those methods, severe plastic deformation (SPD) is the
most important one that can produce the UFG and NG micro-
structures without introducing porosity or impurities [2]. Typical
SPD techniques include high-pressure torsion (HPT), equal channel
angular pressing (ECAP), surface mechanical attrition treatment
(SMAT) and multiple forging [3–5], etc. ECAP has particularly at-
tracted a growing interest in the past decade due to its unique
capacity of processing three dimensional large scale billets for
practical application of some given materials.
There are a number of reports describing the fundamental
process of metal flow during ECAP [2,3,6]. As far as ECAP has been
n
Corresponding author. Fax: 86 20 87114484.
E-mail address: meygao@scut.edu.cn (Y. Gao).
many metals with medium or high stacking fault energy (SFE), e.g.
Al, Cu, Ni, Fe and their alloys [7–12], it is important to understand
the microstructure evolution rules of the materials with different
SFE for the development and practical application of the ECAP
process. SFE plays a very important role in the formation of de-
formation sub-structure, i.e., the density and distribution of lattice
defects, and consequently the tendency towards martensite for-
mation [13]. In general, a low SFE makes dislocation cross-slip
more difficult, resulting in lower dislocation activities, which fa-
vors more homogeneous dislocation distribution with a less ten-
dency towards the formation of dislocation cells. The case is just
opposite for a high SFE material. This influence of SFE on the
evolution of microstructure is more obvious especially for the
metals with fcc structure due to the fact that the twinning beha-
vior of fcc crystals is strongly affected by SFE [14–16].
For the fcc metals with high SFE, e.g. Al with SFE being
166 mJ/m2 [17], dislocation activities dominate the full grain re-
fining process during ECAP and consequently the mechanism of
grain refinement appears as a dislocation model. For the fcc metals
or alloys with medium SFE, e.g. Cu with SFE ¼78 mJ/m2 [17], the
dislocation cells form difficultly due to the fact that the dislocation
activities are restrained. Thus its grain refining mechanism

http://dx.doi.org/10.1016/j.msea.2015.05.085
0921-5093/& 2015 Elsevier B.V. All rights reserved.
616 Z.J. Zheng et al. / Materials Science & Engineering A 639 (2015) 615–625
behaves as a dislocation cross slipping model [8], sometime ac-
companied by a mechanical twinning model [6,18]. For the low
SFE metals or alloys, e.g. Cu–8 at% Al with SFE ¼17 mJ/m2 [19], the
mechanism of grain refinement appears mainly as a twinning
model due to the high hindering of dislocation activities.
As is well known, austenitic 304 stainless steel (SS) is a fcc
metal with low SFE (SFE ¼21 mJ/m2 [17]) in which deformation
twinning occurs readily under plastic straining [20]. Additionally,
another important characteristic of SSs is their sensitivity to de-
formation-induced martensite (DIM) transformation under plastic
deformation due to the energetic instability of the austenitic
structure [21–23], which suggests that their refining mechanism
may be different from other materials with the same low SFE (e.g.
Cu–8 at% Al). This suggestion had been confirmed by Huang et al.
[6], who investigated the refining mechanism of the ultra-low
carbon 304 SS during ECAP at room temperature and proposed a
combined mechanism of deformation twinning and DIM de-
formation. In their research, the volume fraction of а′ martensite
with a size of 74 nm increased to 83% after eight passes of ECAP
and DIM deformation mechanism was regarded to have played an
important role in the microstructure evolution of 304 SS during
ECAP. However, it is quite possible that DIM does not occur or the
content of DIM is fairly low when both the temperature and
pressing speed of ECAP are increased. This gives rise to two
questions. How will the microstructure of 304 SS evolve without
or with a little DIM during ECAP? Whether the refining mechan-
ism of 304 SS in this case is identical with Cu–8 at% Al with the
same low SFE, which presents a twinning mechanism alone?
These questions are very important for the full understanding of
the refining mechanism of SSs during ECAP with different pro-
cessing parameters and will be investigated in the present paper
through systematic observations of the microstructure evolution
in austenitic SS during ECAP from one to eight passes with high
temperature and high pressing speed.
2. Experimental procedure
The material used in this study was a commercial 304 SS with
chemical composition in Table 1. As-received 304 SS was a
Φ10  45 mm rod and was solution treated at 1050 °C for 1 h and
quenched in water to achieve homogeneity. The ECAP die used had
an angle of 90° (Ф) between the two channels and an angle of 20°
(Ψ) representing the outer arc of curvature where the two chan-
nels intersect. These angles introduce a strain of ∼100% for each
pass according to a calculating relationship [24]. The process of
ECAP was carried out for a total of eight passes at 500 °C with a
pressing speed of ∼4 mm s  1 using a MoS2 lubricant. Before the
next pressing, the samples were submitted to mechanical ma-
chining to make the surface round enough for the die channel.
Route BC was chosen where the rods were rotated by 90° around
their longitudinal axes in the same direction between each con-
secutive pass [25]. The detailed set-up and procedures of the ECAP
were described in our previous papers [26,27].
X-ray diffraction (XRD) analysis of the ECAPed specimens was
carried out on Philips X’pert with Cu-K radiation. The volume
fraction of DIM, denoted as Vа′, was calculated from the integrated
intensity of the martensitic and austenitic peaks using the fol-
lowing equation [28,29]:
Iα
Vα = ‵
‵ Iα + 1.4Iγ
‵ (1)
where Iγ is the average integrated intensity obtained at the (111)γ,
(200)γ, and (220)γ peaks, and Iа′ is that obtained at the (110)а′
peak.
Table 1
Chemical composition of the as-received 304 stainless steel.
Elements C Si Mn Cr Ni S P
Concentration (wt%) 0.056 0.44 1.54 18.0 9.82 0.02 0.016
The microstructures on the transversal plane of the ECAPed
rods were observed by optical microscope (OM) and transmission
electron microscope (TEM), respectively. The samples for OM and
TEM observations were cut from the central part of the ECAPed
rod with the observation surface perpendicular to the longitudinal
axis. For OM experiments, the specimens were ground and elec-
trochemically polished in a solution of 10% oxalic acid in water at a
voltage of 10 V. For TEM observation, slices with a thickness of
0.5 mm were manually thinned to 80 μm and then cut into discs
with a diameter of 3 mm. These discs were polished into thin foils
with a twin-jet polisher at a current of 90 mA in an electrolyte of
10% perchloric acid and ethanol at room temperature. A JEM-2100
operating at 200 kV was used for microstructure observation. The
grain size was calculated and estimated by a combination of linear
intercept method and TEM observation.
3. Experimental results
3.1. X-ray diffraction analysis
Fig. 1(a) shows the XRD profiles of the initial and ECAPed
samples (only one, four and eight passes were taken so that the
characters of the peaks can be seen more clearly). It is evident that
there are almost no martensitic peaks in the initial sample, but
after ECAP one pass both austenitic (γ phase, fcc structure) and
martensitic (α′ phase, bcc structure) peaks can be observed in the
XRD profiles. With increasing passes of ECAP, the intensity of the α
′ (110) peak does not almost fluctuate and that of the α′ (211) peak
is very weak and negligible. Apparently, the DIM transformation
via γ-α′ has taken place during ECAP and the content of α′ phase
is very low and almost constant during ECAP for all passes. It
seems that ε martensite phase, which is a transitional phase for
DIM transformation [6], is not present in this study.
Fig. 1(b) shows the volume fraction of deformation induced
martensitic phase α′ and retained austenitic phase γ during ECAP.
It can be seen that the volume fraction of the α′ phase increases
from 0% (initial state) to around 10% after the first pass, and then
keeps in the range of 9–11% with increasing passes of ECAP, while
the volume fraction of retained γ phase is in the range of 91–89%.
It is reasonable to conclude that the martensitic α′ phase has been
induced at the very beginning of ECAP with 1 pass and DIM
transformation does not take place further during the successive
ECAP straining, which is true at least with regard to the content
variety of α′ phase. This big difference from the results of Huang
et al. [6], where the volume fraction of DIM increased to 83% after
8 passes, is attributed to the different conditions of ECAP (see
Section 4 vide infra).
3.2. Microstructural evolution
3.2.1. OM observation
The optical microstructure of the as-received sample is shown
in Fig. 2(a), which is characterized by equiaxed grains with sizes of
about 50 μm together with some annealing twins. After one pass
by ECAP, most of the grains were elongated, forming many shear/
deformation bands within the elongated grains, as shown in Fig. 2
(b). An additional pass generated grains that became more
equiaxed and the size of grains further decreased in Fig. 2(c). After
 Z.J. Zheng et al. / Materials Science & Engineering A 639 (2015) 615–625
Fig. 1. (a) XRD profiles of the initial and ECAPed samples; and (b) volume fraction of γ and α′ phase vs. ECAP passes.
four passes, the grains were further refined and became nearly
equiaxed as shown in Fig. 2(d). After six and eight passes, the
grains became so refined that the initial grain boundaries (GBs)
were difficult to be identified and only deformation traces were
seen (Fig. 2(e) and (f)). Compared to the sample of four passes, the
microstructure homogeneity of the samples after both six and
eight passes was obviously improved. TEM observation was then
performed to study the more detailed microstructure of the
ECAPed 304 SS samples for one to eight passes.
3.2.2. Evolution of γ austenite matrix by TEM observation
3.2.2.1. 1 pass. Fig. 3a is a bright-field TEM micrograph of the de-
formation microstructure in the 1-pass sample. Many primary
shear slipping bands are observed, which subdivide a coarse grain
into many fine lamellae. Additionally, the intersection of slipping
bands are observed, which cuts the initial bands to some shorter
ones, as indicated by arrow 1 and 2 in Fig. 3(a). Fig. 3(b) is an
enlarged image of the white circle region in Fig. 3(a), showing the
detailed microstructure of some primary shear bands, which
consist of many finer bands with transverse dimension of tens
nanometers thick and longitudinal dimension of several micro-
meters long. It is clear that the dislocation density is quite high
inside some bands and at the band boundaries. The corresponding
selected-area electron diffraction (SAED) pattern (the inset in
Fig. 3(b)) taken from the outlined dark circle region in Fig. 3
(b) shows that the slipping bands are of relatively low mis-
orientation. In addition, SAED patterns are characterized by diffuse
and elongated diffraction spots, implying that a large portion of
boundaries of the subdivided grains in Fig. 3(b) are low angled and
that one pass is not enough to develop high angle boundaries. The
diffraction characteristic of twining deformation is not observed
from SAED pattern in Fig. 3(b).
3.2.2.2. 2-3 passes. Fig. 4(a) and (b) shows the bright-field TEM
micrographs of the 2- and 3-pass samples. The well-defined shear
bands of 1-pass sample is no longer observed but evolve into
quasi-cellar sub-grains with obscure boundaries after two passes,
where the equiaxed characteristic becomes strengthened (Fig. 4
(a)). Fig. 4b exhibits integrated cellar sub-grains with low-angle
boundaries with grain size in the range of 100–400 nm after three
passes. The dimensions of these cells are visibly shorted in the
longitudinal direction compared with that of the 2-pass sample,
but the distribution of size is still heterogeneous. From Fig. 4
(a) and (b), it is clearly seen that most grains are heavily strained,
containing high density of dislocations, and the contrasts in many
617
grains are inhomogeneous, as indicated by the arrows in Fig. 4
(a) and (b). The cellar sub-grained structure with dislocation walls
of high density from low angle to high angle grain boundaries is a
transitional structure for high SFE materials [23]. However, this
deformation mechanism is also widely observed for the low SFE SS
in the present paper. The corresponding SAED pattern (the inset in
Fig. 4(a) and (b)) shows discontinuous rings and a mixed char-
acteristic of both distinct and diffuse diffraction spots, indicating
that many different orientations exist among the fine grains and
that the microstructure in the 2- and 3-pass ECAP samples is a
transitional one with low-angle GBs to the high angle GBs.
In addition to shear bands, deformation twins are widely ob-
served in the parent austenite after two and three passes. Fig. 5
(a) is a typical bright-field TEM micrograph showing the initial
lamellae of deformation twin on {111} plane in the 2-pass sample.
Fig. 5(c) is the corresponding SAED pattern, which consists of two
sets of ⎡⎣011̄⎤⎦ twin diffraction patterns. It is clear that the width and
length dimensions of the twin lamellae are about 40 nm and
several hundred nanometers, respectively. With increasing strain,
the initially coarse twins are further refined in width via the sec-
ondary twining as shown in Fig. 5(b), which results in the average
thickness and length of twin lamellae below 20 and 300 nm, re-
spectively. This implies that the final grains resulted from the
fragmentation and interaction of twin lamellae could be very fine.
3.2.2.3. 4–6 passes. After four to six passes of ECAP, sub-grain cells
formed in former passes gradually evolve into nano-grains with
curved and ambiguous grain boundaries (CAGBs) in the size range
of 100–120 nm, marked by A as shown in Fig. 6(a) and (b), due to
the lattice distortion resulting from the high density of disloca-
tions in GBs. It is clear that the equiaxial character of grains be-
came further enhanced, but the refinement of grains is hetero-
geneous. Close examination shows that grain subdivision via dis-
location pile-up takes place near GBs and within some grains,
forming sub-grain boundaries, as indicated by the arrow-head in
Fig. 6c. Compared to the SAED patterns of 2- or 3-pass sample, it is
seen that the diffraction spots in the SAED patterns of 4- and
6-pass samples (see Fig. 6(a) and (b)) become clearer and the circle
character becomes more obvious, meanwhile the SAED patterns of
the 4- and 6-pass samples have no notable change in the angular
spread of the spots. This indicates that the nano-grains with high
angle boundaries are grandly produced after four and six passes,
and most of high angle boundaries have already been formed after
four passes, and ECAP for six passes does not obviously change the
character of GBs.
618 Z.J. Zheng et al. / Materials Science & Engineering A 639 (2015) 615–625

Fig. 2. Optical micrographs of as-received and ECAPed 304 SS after different passes: (a) as-received, (b) 1 pass, (c) 2 pass, (d) 4 passes, (e) 6 passes and (f) 8 passes.

During ECAP for four passes, especially six passes, in addition to
the refining mechanism of cutting the coarse austenitic grains by
sub-grain dislocation cells, twin cutting with each other (inter-
section of twins) as well as with austenitic matrix are observed,
resulting in two nano-crystalline structures. One consists of twin
fragmentations with width and length dimensions of 20–40 nm
and 120 nm respectively (as indicated by the white circle in
Fig. 6d). The other one is composed of some well-defined grains
with clear and smooth grain boundaries (CSGBs) with the width
and length dimensions of 100 nm and 200 nm (marked as B in
Fig. 6(a), (b) and (d)).
3.2.2.4. 8 passes. Fig. 7(a) and (b) presents respectively the typical
bright- and dark-field TEM micrographs of the 8-pass sample. It
can be observed that the initial coarse grains have been trans-
formed into ultrafine grains or nano-grains, which is confirmed by
the corresponding SAED pattern in Fig. 7(a). The GBs are not clear
because of the presence of dislocations and deformation twins
within the grains. The circular rings in SAED pattern reveal that
the misorientation of the GBs is of high angles. Fig. 7(c) shows the
nano-twin lamellae and nano-grains with CSGBs as illustrated by
alphabet A and B respectively. Generally, the grains are further
refined and the homogeneity of refinement is further improved in
the 8-pass sample.
 Z.J. Zheng et al. / Materials Science & Engineering A 639 (2015) 615–625 619

Fig. 3. (a) Bright-field TEM micrograph showing shear bands in the 1-pass sample; and (b) high magnification of the white circle region in (a).

Ultimately, three kinds of nanostructures of austenite have
been produced, including (a) nano-grains of sub-grain dislocation
cells with CAGBs resulting from dislocation subdivision mechan-
ism, the mean size of which is in the range of 80–120 nm;
(b) nano-grains of primary twin intersection in austenitic grains
with CSGBs obtained from twining mechanism, with a mean size
of around 100 nm; (c) nanoscale twin lamellae produced by the
secondary twinning inside the primary twins (twining mechan-
ism) with a dimension of 10–20 nm in width and about 60 nm in
length.
3.2.3. Evolution of strain induced α′ martensite by TEM observation
Although the DIM of 304 SS during ECAP holds only a low
content of 10% (V/V) from XRD analysis, its evolution during ECAP
was also observed and Fig. 8 shows the typical TEM micrographs
and associated SAED patterns of α′ martensite in the 1-, 4- and
8-pass samples. Fig. 8(a), (c) and (e) are the bright-field images
and Fig. 8(b), (d) and (f) are the corresponding dark-field images of
α′ martensite in the three samples respectively, where Fig. 8(b) is
taken using the (110)α′ diffraction spot as shown in Fig. 8(g), and
both Fig. 8(d) and (f) are taken using the (200)α′ diffraction spot as
indicated in Fig. 8(h) and (i).
It can be seen that deformation induced α′ martensite initially
arises along the boundaries or the intersections of micro-shear
bands after one pass, characterized by an irregular strip with the
dimension of several ten nanometers in width and several hun-
dred nanometers in length, as indicated by the arrows in Fig. 8
(a) and (b). With increasing strain, smaller and more individual α′
martensite has formed in the 4-pass sample, as indicated by A1
and A2 in Fig. 8(c) and (d), the average size of this part of α′
martensite being about 40–80 nm. Another part of DIM, however,
still remain the form of a strip (as shown by B in Fig. 8(c) and (d)),
with an analogous size to the DIM in the 1-pass sample. With
further passes of ECAP as in the 8-pass sample, the DIM with the
form of strip is no long observed, and some clearly defined α′
martensites with a size of 20–80 nm have been achieved, as shown
in Fig. 8(e) and (f).
Additionally, the corresponding SAED patterns of 1-, 4- and
8-pass samples in Fig. 8(g), (h) and (i) reveal a composite diffrac-
tion patterns of both γ phase and α′ martensite, with the intensity
of the diffraction spots of α′ martensite being very weak and the
number of spots being fairly little, implying a low content of α′

Fig. 4. Typical TEM images showing cellar sub-grained microstructure with the corresponding SAED pattern for (a) two passes, and (b) three passes.
620 Z.J. Zheng et al. / Materials Science & Engineering A 639 (2015) 615–625
Fig. 5. Typical TEM images showing (a) the initial twin microstructure after two passes, (b) the second twining microstructure after three passes and (c) is the corresponding
SAED pattern taken from the outlined circle region in (a).
martensite in the three samples.
According to the above analyses, a general description about
the evolution of DIM during ECAP can be made. Firstly, DIM forms
at the boundaries of the slipping bands like a strip in the 1 pass,
with a content of 10% (V/V). During further ECAP process, DIM
does not change obviously in content but is refined by the inter-
section with shearing bands and is ultimately evolved into nano
size of about 20–80 nm in the 8-pass sample.
4. Discussion
A large amount of microstructural observations (Figs. 2–8)
show that the predominant refining processes during the forma-
tion of nano-grains are the successive dislocation- and/or twin-
subdivision in grains with sizes ranging from microns to nan-
ometers and consequently three kinds of nanostructures of aus-
tenite and two kinds of nanocrystalline DIM are achieved in 304 SS
after ECAP deformation for eight passes. Based on the above ob-
servations and analyses, a hybrid mechanism of microstructure of
austenite as well as DIM in 304 SS subjected to ECAP can be de-
picted as following, which is schematically shown in Fig. 9.
4.1. Evolution model of UFG or NG austenite during ECAP
The as-received sample, far from strain deformation, maintains
intact as shown in Fig. 9(a). Once it is subjected to ECAP for one
pass, the coarse grains are subdivided into many lamellae with a
dimension of 80–500 nm in width and 10–80 μm in length, ac-
companied by some intersection with each other, as shown
schematically in Fig. 9(b). Deformation twins are not observed
during ECAP for one pass, but are widely obtained after more
passes in this study, which had also been observed in the literature
[6], as a critical dislocation density is required for forming de-
formation twins during severe plastic deformation [30]. In the
sample processed by ECAP for one pass, the density of dislocation
obtained may be lower than the critical value, due to the relatively
high processing temperature (500 °C) of ECAP in this study.
However, the processing temperature in the literature [6] is room
temperature, much lower than that in the present case, thus the
critical dislocation density is easier to be obtained.
After further straining, e.g. ECAP for two passes, the elongated
bands produced in 1-pass sample are cut short in length, whereas
the width of the bands does not change. After three passes, a fully
developed dislocation cell structure starts to form as schematically
shown in Fig. 9(c1). The dislocation cells, with a broad cell size
 Z.J. Zheng et al. / Materials Science & Engineering A 639 (2015) 615–625 621

Fig. 6. Typical bright-field TEM images with corresponding SAED patterns showing the microstructures of two types of nano-grains in the (a) 4- and (b) 6-pass sample;
(c) the bright-field TEM micrograph showing the detailed microstructure of  100 nm grains indicated by the red outlined area in (a); and (d) nano-twin lamellae in the
6-pass sample. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

varying from 80 nm to 400 nm, do not show any preferred or-
ientation and remain roughly isotropic. At the same time, de-
formation twins and secondary twinning are widely observed in
the austenite matrix in both two-pass and three-pass samples,
which is characterized by many fine fragments of twin lamellae as
schematically illustrated in Fig. 9(c2).
As discussed in Section 3.2 for 4-pass and 6-pass samples, sub-
grains with low-angle boundaries are further evolved into nano-
grains with high-angle boundaries, where two types of nano-
grains are formed. One type with CAGBs is formed from the dis-
location cells as schematically shown in Fig. 9(d1). The other type
with CSGBs is produced from the intersections of primary twins as
schematically shown in Fig. 9(d2). Additionally, the nano-scale
twin lamellae are also observed in the 4-pass and 6-pass samples,
as schematically shown in Fig. 9(d2). Tao et al. [31] and Wang et al.
[32] have shown the micro-mechanism of twin fragmentation
during the nanostructure formation on the top surface layer of
Inconel 600 alloy and Cu samples subjected to SMAT. Their ob-
servations demonstrated that a lot of dislocations and/or
dislocation walls rather than micro-twins were introduced into the
thin twin-matrix lamellae in order to accommodate plastic de-
formation. These dislocation walls were eventually developed into
GBs, cutting the two-dimensional twin-matrix lamellae into three-
dimensional equiaxed nano-grains. In the present case of ECAP,
part of nano-grains is also achieved via the twin fragmentation
mechanism. After ECAP for eight passes, equiaxed nano-grains
with uniform distribution are obtained, as schematically shown in
Fig. 9(e).
Based on the above comprehensive analyses, the hybrid refin-
ing model proposed in the present paper is reasonable, including
dislocation-subdivision mechanism and the twin fragmentation
mechanism. Accordingly, the uniform nanostructure is composed
of nano-grains with CAGBs (as indicated by the black polygons in
Fig. 9e) evolved from dislocation model and nano-grains with
CSGBs (as indicated by the green polygons in Fig. 9(e)) produced
from the intersection of primary twins. Besides, some nano-twin
lamellae are also included, which are evolved from the secondary
twining inside the primary twins (as indicated by the blue parallel
622 Z.J. Zheng et al. / Materials Science & Engineering A 639 (2015) 615–625

Fig. 7. (a) Bright-field and (b) dark-field TEM micrographs showing very fine and equiaxed nanocrystalline grains with uniform distribution, and (c) Bright-field TEM
micrograph showing the nano-twin lamellae and nano-grains with smooth and distinct boundaries as illustrated by A and B, respectively.

lines in Fig. 9(e)).
4.2. The issue of deformation-induced martensite during ECAP
Austenitic SS is susceptible to martensite transformation under
plastic deformation at low temperature, which can be regarded as
an additional deformation mechanism to accommodate plastic
strain in addition to dislocation mechanism and deformation
twinning. In comparison with conventional deformation pro-
cesses, the effect of ECAP on DIM transformation is obvious. For
example, Huang et al. [6] recently measured the amount of the
transformed martensite in 304 SS deformed by ECAP and found
that shear deformation achieved by ECAP was the most effective
route to trigger DIM transformation, where the content of DIM was
up to 83%.
According to the results in Section 3.1 in the present study,
however, the content of DIM in 1-pass to 8-pass samples is only
about 10% (V/V), which is much lower than that in the literature
[6]. This low content of DIM can be attributed to relatively high
pressing temperature (500 °C) in the present case. The
investigations [33,34] indicated that after annealing treatment at
853 K to 893 K (580 °C to 620 °C) for 60 min, the ultrafine mar-
tensite grains are converted into ultrafine austenite grains via the
martensite reversion process, forming a fully austenitic micro-
structure. Hence, it is not difficult to understand that most of DIM
was subjected to a reverse transformation (α-γ) during the high
processing temperature of ECAP, and consequently a relatively low
content of DIM was obtained in the present study. Thus, the DIM
finally obtained with the content of 10% (V/V) should be the
completing result between the formation of new DIM during the
successive ECAP and the reversion from martensite to austenite at
high temperature.
Although the content of the surviving DIM is much lower than
that of austenite matrix, its evolution during ECAP is not ignored.
At low plastic strain (e.g. 1 pass), α′ martensite nucleates at the
boundaries or the intersections of micro-shear bands with high
strain, which are favorable nucleation sites [35,36], and forms
banded DIM with the dimension of several ten nanometers in
width and several hundred nanometers in length. This evolution
process is shown schematically in Fig. 9b. At intermediate plastic
 Z.J. Zheng et al. / Materials Science & Engineering A 639 (2015) 615–625 623

Fig. 8. Typical TEM micrographs showing the deformation induced α′ martensite in the 1-, 4- and 8-pass samples: (a) bright-field image after 1 pass, (b) dark-field image
after 1 pass, (c) bright-field image after 4 passes, (d) dark-field image after 4 passes, (e) bright-field image after 8 passes, (f) dark-field image after 8 passes, together with the
associated SAED patterns of (g) 1 pass, (h) 4 passes and (i) 8 passes.

strain (e.g. 4 passes), some banded martensites gradually become
more granulated through the intersection with slipping bands, as
indicated by A1 and A2 in Fig. 8(c) and (d). However, some mar-
tensites remain the strip shape, as shown by B in Fig. 8(c) and (d).
This evolution process is shown schematically in Fig. 9(c1) and
(d1). As increasing passes of ECAP to higher plastic strain (e.g.
8 passes), most of the banded martensites have refined ultimately
into the clearly defined α′ martensites with a size of 20–80 nm, as
schematically shown in Fig. 9(e).
Besides the formation of nanocrystalline DIM by the intersec-
tion with slipping bands mentioned above, other nanocrystalline
DIM may be directly produced from the martensite transformation
taking place in submicron and nanometer γ grains according to the
researching results in the literature [6]. In this study, however, the
refining mechanism of DIM by dislocation subdivision of large
grains is not present due to the relatively high pressing tempera-
ture. Therefore, the refining mechanism of DIM consists of both
the refinement of banded DIM by the intersection of slipping
bands and the newly induced fine martensite in submicron and
nanometer grained austenite matrix.
5. Conclusions
Investigations on microstructural evolution reveal that three
kinds of nanostructures are achieved in 304 austenitic SS after
ECAP deformation for eight passes and a hybrid refining me-
chanism is proposed:
(1) A hybrid refining mechanism, which is composited of
624 Z.J. Zheng et al. / Materials Science & Engineering A 639 (2015) 615–625

Fig. 9. Schematics of microstructural evolution in 304 austenitic SS during 1–8 passes of ECAP.

dislocation-subdivision mechanism as well as twin fragmen-
tation mechanism, has been proposed. Three types of nano-
crystalline grain microstructures have been successfully
achieved: (i) The equiaxed nano-grains with CAGBs and a size
of 80–120 nm from dislocation-subdivision mechanism, (ii)
The equiaxed nano-grains with CSGBs and a size of 100 nm
from twin intersection mechanism, and (iii) the nano-twin
lamellae with a dimension of 10–20 nm in width and about
60 nm in length from secondary twinning mechanism.
(2) More ECAP extrusions (beyond 4–6) do not contribute to fur-
ther grain refinement, but primarily serve to increase mis-
orientation between neighboring structures, to create high-
angle sub-grain boundaries, and to assist in achieving a more
homogeneous distribution of the fine sub-grains.
(3) The content of DIM is 10% (V/V) and has almost no fluctuation
in all passes of ECAP. The refining mechanism of DIM is also a
hybrid model, including the refinement of banded DIM by the
intersection with slipping bands and the newly induced fine
martensite in submicron and nanometer grained austenite
matrix. The grain size of DIM obtained after ECAP for eight
passes is in the range of 20–80 nm.
Acknowledgments
This work was financially supported by the National Natural
Science Foundation of China (NSFC) under Grant nos. 50871041
and 51471072, the Fundamental Research Funds for the Central
Universities under Grant no. 20112M0064 and the Key Laboratory
of Clean Energy Materials of Guangdong Higher Education In-
stitute under Grant no. KLB11003.
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