Intermetallics 85 (2017) 163e169

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Intermetallics
journal homepage: www.elsevier.com/locate/intermet

Multiple-stage transformation behavior of Ti49.2Ni50.8 alloy with

different initial microstructure processed by equal channel angular
pressing
Y.X. Tong a, *, K.P. Hu a, F. Chen a, B. Tian a, L. Li a, Y.F. Zheng b
a
Institute of Materials Processing and Intelligent Manufacturing, College of Materials Science and Chemical Engineering, Harbin Engineering University,
Harbin, 150001, China
b
Department of Materials Science and Engineering, College of Engineering, Peking University, Beijing, 100871, China

a r t i c l e i n f o a b s t r a c t

Article history: Multiple-stage transformation of Ti49.2Ni50.8 alloy processed by equal channel angular pressing (ECAP)
Received 23 May 2016 was investigated as a function of pass number and aging treatment before ECAP. When the pass number
Received in revised form is no more than four passes, three stage transformation, namely A/R, R1/M1 and R2/M2, occurs in the
13 September 2016
as-ECAP processed alloy initially aged at 450
C for 60 min. Only the A/R/M forward transformation
Accepted 23 January 2017
Available online 24 February 2017
occurs provided that the aging duration was decreased/increased to 10/600min. The transformation
sequence was discussed based on the microstructure evolution of as-ECAP processed alloy with different
initial microstructure and pass number.
Keywords:
Shape-memory alloys
2017 Elsevier Ltd. All rights reserved.
Equal channel angular pressing
Martensitic transformation
Microstructure

1. Introduction
TiNi-based shape memory alloys (SMAs) have attracted much
attention in many engineering and biomedical applications due to
their superior functional properties, including large work output
force per unit volume, large displacement generated during shape
recovery and the excellent biocompatibility [1]. In order to further
enhance the properties of TiNi-based SMAs, equal channel angular
pressing (ECAP), a several plastic deformation technique, has been
employed to rene the microstructure of TiNi-based SMAs [2e4].
For example, the ultrane grained microstructure, with a grain size
of 0.2e0.3 mm, can be obtained in bulk samples of Ti49.4Ni50.6 and
Ti49.8Ni50.2 as a result of ECAP [2]. As compared to the coarse-
grained counterpart, the ultrane grained TiNi-based alloys show
several advantages, including improved shape recovery stress and
strain [5], enhanced cycling stability [6e9], and biocompatibility
[10].
Microstructure of the as-ECAP processed TiNi-based alloy can be
naturally affected by processing conditions, including processing
temperature [7] and pass number [11] etc. Very recently, our works
* Corresponding author.
E-mail address: tongyx@hrbeu.edu.cn (Y.X. Tong).
[8,12] indicate that the second phase also greatly inuences the
microstructure of as-ECAP processed TiNi-based SMAs. To be more
specic, Ti3Ni4 precipitate is benecial to rening the nal micro-
structure of as-ECAP processed Ti49.2Ni50.8 alloy when processed by
ECAP [8], but b-Nb particles retard the grain renement of
Ti44Ni47Nb9 alloy [12]. During ECAP, shear plastic deformation is
also applied on the Ti3Ni4 phase besides the matrix which may
cause the re-dissolution of second phase [8,13,14]. In the coarse-
grained Ni-rich TiNi alloys, the Ti3Ni4 phase as a result of aging
can cause the multiple-stage transformation [15e17]. It is generally
accepted that the as-ECAP processed TiNi alloys usually show a
two-stage A(B2 parent phase)/R/M(B190 martensite) trans-
formation upon cooling resulting from the rened microstructure
and dislocations [8,11,18]. However, as yet, a comprehensive un-
derstanding of the effect of initial microstructure on martensitic
transformation of as-ECAP processed TiNi SMAs is still missing;
knowledge of how the re-dissolution of precipitates inuence the
transformation behavior is lacking.
In the present work, the initial microstructure with Ti3Ni4 pre-
cipitates having different sizes was obtained in Ti49.2Ni50.8 alloy by
aging at 450
C for different durations. The samples were processed
by ECAP for different passes to obtain the various states of Ti3Ni4
precipitates. The multiple-stage transformation was paid particular
attention and correlated with the microstructure evolution. This

http://dx.doi.org/10.1016/j.intermet.2017.01.017
0966-9795/ 2017 Elsevier Ltd. All rights reserved.
164 Y.X. Tong et al. / Intermetallics 85 (2017) 163e169
understanding may allow optimization of transformation behavior
through control of the initial microstructure and the processing
condition.
2. Experimental procedure
A commercial TiNi alloy with a nominal composition of
Ti49.2Ni50.8 (at.%) was studied. Before processing, the alloy was
solution-treated in a vacuum furnace at 900
C for 1 h, and then
quenched into water. The as-quenched alloy has the microstructure
with an average grain size of 70 mm. In order to obtain the pre-
cipitate with different sizes, the solution-treated alloys were aged
at 450
C for 10 min, 60 min and 600 min, respectively. The samples
were sealed in the evacuated quartz tubes for heat-treatments.
Hereafter, the aged samples were represented by A10, A60 and
A600 for simplicity, respectively. After aging, the grain size keeps
almost constant, as conrmed by optical microscopy observation.
The samples, in the form of 10 mm in diameter and 60 mm in length
rods, were processed by ECAP at a temperature of 450
C for up to 8
passes using a die with a channel-intersection angle of 120
.
The rod was kept at 450
C for 10 min in a furnace prior to each
pass, transferred to the pre-heated ECAP die as quickly as possible
and then extruded at a rate of 15 mm/s. The pressing route Bc was
used in which the sample was rotated by 90
in the same sense,
since it is the optimum one for producing the ultra-ne structure
[19].
Thermal cycling was performed on a Perkin-Elmer Diamond
differential scanning calorimeter (DSC) at a constant heating/
Fig. 1. TEM bright eld images of the aged samples, (a) A10, (b) A60 and (c) A600. Diffraction patterns corresponding to the [111]B2 were also inserted, respectively. DSC curves of
the solution-treated and aged samples are shown in (d). The transformation sequences are also indicated.
cooling rate of 20
C/min. DSC samples have a mass between 10 and
35 mg. Microstructure was carefully observed on a JEOL 2010
transmission electron microscopy (TEM) which was operated at
200 kV with a double-tilt sample stage. The samples were cut by a
low-speed diamond saw to avoid any change of microstructure. The
TEM foils were prepared by mechanical grinding, followed by twin-
jet electropolishing using an electrolyte solution consisting of 95%
acetic acid and 5% perchloric acid by volume.
3. Results and discussion
The microstructure of aged samples were observed by TEM at
room temperature. Fig. 1 (a), (b) and (c) show the bright eld im-
ages of the microstructure of A10, A60 and A600, respectively. As
expected, numerous thin precipitates with a lens shape present in
the samples, as indicated by the arrows. The selected area electron
diffraction (SAED) patterns is characterized by the 1/7 superlattice
spot in the 213 direction, indicating that the precipitates are Ti3Ni4
phase. The diffraction spots corresponding to R-phase are also
revealed. For the A10 sample, the Ti3Ni4 precipitates are sur-
rounded by strong stress-eld, which means that the precipitates
are coherent with the matrix. With increasing aging duration from
10 to 60 and 600 min, the average size of Ti3Ni4 precipitate in-
creases from about 20 to 38 and 108 nm, respectively. The obser-
vation area is in the grain interior. It should be mentioned that the
distribution of Ti3Ni4 precipitate is uniform across the sample. Fig. 1
(d) shows the DSC curves of the solution-treated and aged samples.
It is seen that upon cooling, all of the three samples show a two-
 Y.X. Tong et al. / Intermetallics 85 (2017) 163e169 165

stage A/R/M forward martensitic transformation. Upon heating,
the A10 and A60 samples show the two-stage M/R/A reverse
transformation, and the A600 sample shows the single-stage M/A
reverse transformation. The transformation sequence was deter-
mined by the partial DSC cycling method [15]. The above results are
consistent with the reported results on the effect of aging on
martensitic transformation of Ti49.2Ni50.8 alloy [16,20,21]. It has
been reported by Karbakhsh et al. that Ti49.2Ni50.8 alloy was aged at
450
C after sealing into an evaluated quartz tube, then the aged
sample shows normal two-stage transformation upon cooling [16].
According to their work [16], the two-stage transformation is
possibly related to the higher degree of Ni supersaturation in the
sample aged at 450
C which may result in the uniform distribution
of Ti3Ni4 phase. Therefore, the normal two-stage transformation
are expected.
Fig. 2(a) shows the TEM bright eld image of the microstructure
of A10 sample processed for one pass. After the shear deformation
imposed by the one pass ECAP, the initially equiaxed and coarse
grains were greatly elongated and rened. A large number of dis-
locations can be observed in the grains having widths of about
1 mm. The SAED pattern does not show any superlattice spots
related to Ti3Ni4 precipitates, implying that the precipitates have
re-dissolved into the matrix due to the plastic deformation. This is
consistent with the reported results [8,13,14]. The brightly spherical

Fig. 2. TEM bright eld images of the initially aged samples processed for different passes, (a) A10, 1 pass, (b) A10, 8 passes, (c) A60, 1 pass, (d) A60, 8 passes, (e) A600, 1 pass and (f)
A600, 8 passes. Diffraction patterns corresponding to the [111]B2 were also inserted, respectively.
166 Y.X. Tong et al. / Intermetallics 85 (2017) 163e169
phase is Ti4Ni2O which formed during melting [22]. This phase does
not dissolve into the matrix [14] and will not be discussed hereafter.
After processed for eight passes, the elongated grains turned into
the equiaxed shape with an ultrane grain size of about 0.4 mm, as
shown in Fig. 2(b). The evolution of grain morphology with pass
number is a general tendency observed in the as-ECAP processed
TiNi alloys [11,14] and other alloys [19,23]. The Ti3Ni4 precipitates
were not found in the matrix.
Fig. 2(c) and (d) show the bright eld images of the micro-
structure of the A60 samples processed for one pass and eight
passes, respectively. After eight passes, the grain size was reduced
to about 0.3 mm. From the inserted SAED pattern, it is seen that the
Ti3Ni4 precipitates exist after one pass, but re-dissolve into the
matrix after eight passes. Fig. 2(e) and (f) show the bright eld
images of the microstructure of the A600 sample processed for one
and eight passes, respectively. It is seen that the Ti3Ni4 precipitates
exist even after eight passes, as conrmed by the SAED pattern.
According to the results shown in Fig. 2, it is proposed that the
degree of redissolution of Ti3Ni4 phase is controlled by the plastic
deformation strain and initial size of precipitate.
Fig. 3(a) and (b) show the DSC curves of the A10 samples pro-
cessed for different passes. Upon cooling, as compared to the results
Fig. 3. DSC curves of the initially aged samples processed for different passes, (a) A10, 1 pass, (b) A10, 8 passes, (c) A60, 1 pass, (d) A60, 8 passes, (e) A600, 1 pass and (f) A600, 8
passes.
shown in Fig. 1(d), the transformation sequence does not change,
the transformation temperatures are reduced and the trans-
formation peaks become diffused. The reduced transformation
temperatures can be attributed to the suppression of rened grain
and dislocations introduced during ECAP [11,12,18]. The diffused
transformation peak is possibly related to the large number of
dislocations [24]. Upon heating, after one pass, the as-ECAP pro-
cessed A10 sample shows the single-stage M/A reverse trans-
formation, which is different from that of the A10 sample.
Fig. 3(c) and (d) show the DSC curves of the A60 samples pro-
cessed for one and eight passes, respectively. Upon cooling, the
samples processed for less than 4 passes show three-stage forward
transformation. The sample processed for eight pass shows the
A/R/M transformation, same as that of A10 sample. Upon
heating, after one pass, the as-ECAP processed sample shows three-
stage reverse transformation. After two or four passes, the DSC
curves of as-ECAP processed samples are characterized by the two-
stage reverse transformation. The sample processed for eight
passes show the two-stage M/R/A reverse transformation.
Fig. 3(e) and (f) show the DSC curves of the A600 samples processed
for different passes. The transformation sequence is the same as
that of the aged one, irrespective of pass number.
 Y.X. Tong et al. / Intermetallics 85 (2017) 163e169 167

In order to identify the transformation peaks of the A60 samples

Fig. 4. Partial DSC curves of the A60 sample processed for one pass. The original full
DSC curves of this sample has been shown in (a).
processed by ECAP, the partial DSC cycling method was used [15].
The results of the sample processed by one pass are shown in Fig. 4,
as an example. The full cycle DSC curves were also shown in
Fig. 4(a) for the comparison purpose. First, the sample was cooled to
a temperature between peaks 1 and 2. It is seen from Fig. 4(b) that
the peak 1 corresponds to the peak 5, the transformation hysteresis
between peaks 1 and 5 is about 3.6
C. Therefore, this pair results
from the R-phase transformation, which is characterized by a small
hysteresis due to its small lattice deformation [25]. When cooled to
a temperature between peaks 2 and 3, the heating DSC curve shows
the peak 6 besides the peak 5 which are overlapped. This suggests
that the peak 2 corresponds to the peak 6. It is found that upon
heating during the second partial cycle (Fig. 4(c)), the size of peak 5
is reduced as compared to that in the rst partial cycle (Fig. 4(b)).
This implies that R phase partially transformed to another phase
(M1) during the second cooling, which is quite similar to the pre-
vious reported results [26]. In addition, the peak 6 locates at the
higher temperature side of peak 5. Therefore, peaks 2 and 6 are
identied to be R1/M1 and M1/A, respectively. When further
cooling from the cool end temperature of second partial cycle, the
residual R phase transformed to martensite (R2/M2), corre-
sponding to peak 3. During heating, M2 transformed to R phase,

Fig. 5. Schematic illustration of microstructure evolution and corresponding transformation sequence for the as-ECAP processed samples with different initial microstructure, h and
c represent heating and cooling, respectively. A and B present precipitate-dissolved and precipitate-rich regions, respectively.
168 Y.X. Tong et al. / Intermetallics 85 (2017) 163e169
resulting in the presence of peak 4. The detailed transformation
sequence was also marked in Fig. 3(c). It should be mentioned that
the subscripts 1 and 2 does not mean that there are two kinds of R
phase or B190 martensite. Using the same method, the reverse
transformation sequence of the A60 samples processed for two or
four passes was determined to be M1/A and M2/A.
Fig. 5 schematically illustrates the microstructure evolution and
the induced transformation sequence in the as-ECAP processed
samples with different initial microstructure. It is generally
accepted that the multiple-transformation of the aged Ni-rich TiNi
alloys results from the inhomogeneous distribution of Ti3Ni4 phase
[15]. However, in the case of A10 sample, this mechanism is not
applicable since the Ti3Ni4 phase re-dissolves into the matrix even
after one pass due to the severe plastic deformation, as shown in
Fig. 5(a). With increasing the pass number, the microstructure was
greatly rened and the dislocation density increase. This is
responsible for the two-stage transformation in the as-ECAP pro-
cessed A10 sample.
Once the initial aging duration was increased to 60 min, the
average size of Ti3Ni4 precipitates increases, as shown in Fig. 5(b).
Based on the results shown in Fig. 2(a) and (c), it is reasonably
suggested that there is a critical size of Ti3Ni4 precipitates between
20 nm and 38 nm for the present ECAP conditions. The precipitates
having a size below this critical value may completely re-dissolve
into the matrix after one pass ECAP. The precipitates having a size
above this value may fracture or partially re-dissolve into the ma-
trix, which requires further investigation. The microstructure of
part region is similar to that the as-ECAP processed A10 sample and
characterized by the full re-dissolution of Ti3Ni4 phase and high
density dislocations. Correspondingly, martensitic transformation
occurs in the two-stage A/R(R1)/M1 manner. The microstructure
of other region is characterized by the residual Ti3Ni4 phase and
high density dislocations. This should be responsible for the
A/R(R2)/M2 transformation. After eight passes, the residual
Ti3Ni4 phase disappeared. The microstructure of as-ECAP processed
A60 sample is quite similar to that of A10 sample other than the
slightly different grain size, as shown in Fig. 2(b) and (d). Therefore,
martensitic transformation occurs in the same manner with that of
as-ECAP processed A10 sample.
In the case of A600 sample, after eight passes, the Ti3Ni4 phase is
still visible, as conrmed by the TEM results shown in Fig. 2 (f),
because that the precipitate size is much larger than the proposed
critical value of re-dissolution. The overlarge precipitates also
retard the grain renement, as demonstrated by the elongated
grains of A600 sample. The precipitate size even increases possibly
due to the interpass annealing. This is supported by the increased
transformation temperatures with the increase of pass number. The
microstructure of as-ECAP processed A600 sample is still charac-
terized by Ti3Ni4 precipitates and high density dislocations intro-
duced by ECAP. This gives rise to the two-stage A/R/M
transformation shown in Fig. 3(e) and (f).
4. Conclusions
The transformation behavior of Ti49.2Ni50.8 alloy with different
initial microstructure processed by ECAP depends on the pass
number and initial aging treatment. When the alloy was initially
aged at 450
C for 10 min/600 min, the as-ECAP processed alloy
shows the A/R/M forward transformation. When the alloy was
initially aged at 450
C for 60 min, if the pass number is no more
than four, the forward transformation occurs in the three-stage
manner, namely, A/R, R1/M1 and R2/M2. This can be ascribed
to the partial re-dissolution of Ti3Ni4 phase. If the pass number is
eight, the forward transformation occurs in the two-stage
A/R/M sequence.
Acknowledgments
This work was supported by Natural Science Foundation of
China (51671064), Harbin City Innovative Talents Research Special
Program (2015RAXXJ033) and Postdoctoral Funds for Scientic
Research Initiation of Heilongjiang Province (LBH-Q14035).
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