Materials Science & Engineering A 705 (2017) 273281

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Materials Science & Engineering A

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

Inuence of strongly textured microstructure on the all-round shape MARK

memory eect of rapidly solidied Ni51Ti49 alloy

Y.Y. Li, S.S. Cao, X. Ma, C.B. Ke, X.P. Zhang
School of Materials Science and Engineering, South China University of Technology, Guangzhou 510640, China

A R T I C L E I N F O A B S T R A C T

Keywords: Ni51Ti49 alloy strip with all-round shape memory eect (ARSME) was obtained through rapid solidication
NiTi alloy followed by constraint-aging treatment. The high cooling rate and large temperature gradient along the thick-
Texture ness direction of Ni51Ti49 alloy strip yield ne columnar grains and strong ber texture of < 100 > B2 during
Rapid solidication rapid solidication. Such ne-grained and strongly textured microstructure increases the nucleation, limits the
All-round shape memory eect
orientation and restricts the growth of Ni4Ti3 precipitates during constraint-aging treatment. The ne and well-
Ni4Ti3 precipitate
aligned Ni4Ti3 precipitates with dispersive distribution introduce strong coherent stress eld and numerous
interfaces between the matrix and precipitates in the rapidly solidied and constraint-aged Ni51Ti49 alloy.
Homogeneous composition and massive interfaces in the B2 matrix promote the simultaneity of local phase
transformations. The strong coherent stress eld and the excellent deformability of < 100 > B2-oriented grains
contribute to large deformation and high recovery ratio of the alloy during phase transformation. Thus, the
strongly textured microstructure formed during rapid solidication allows the constraint-aged NiTi alloy to
possess superior ARSME with narrow phase transformation temperature range.

1. Introduction
NiTi-based shape memory alloys (SMAs) have been widely used in
elds such as aerospace, mechanical engineering, biomedical en-
gineering and so forth for their unique shape memory eect (SME) and
super-elasticity (SE) as well as excellent mechanical properties [1,2].
The SME of NiTi alloys originates from a thermo-elastic martensitic
transformation [3] and can be classied into two major types: one-way
shape memory eect (OWSME) and two-way shape memory eect
(TWSME). The former is the intrinsic property of near equi-atomic NiTi
alloys while the latter is a result of training treatment. Notably, the so-
called all-round shape memory eect (ARSME), as a special kind of
TWSME, features large recovery ratio and can only be obtained through
constraint-aging treatment [4]. As a crucial thermo-mechanical training
method, constraint-aging treatment can provide the near equi-atomic
Ni-rich NiTi alloys with ARSME of excellent thermal cycling stability
[5], which is crucial in long-term use [6]. The mechanism of ARSME
has been well studied over the past few decades. It is found that both
the grain orientation [710] and the stress eld induced by coherent
Ni4Ti3 precipitates [1113] play a key role in determining the de-
formation and recovery ratio of NiTi alloys. On the one hand, it was
shown that the texture in the NiTi rolling plate results in ARSMEs of
dierent levels between the rolling direction and the transverse
direction [7]. Also, it has been proved that the recovery strain strongly
depends on the texture and martensite symmetry in polycrystalline
SMAs [8]. Besides, the tension-compression asymmetry was demon-
strated to bring about dierent eects on the deformation behavior of
NiTi alloys with dierent grain orientations [9]. Moreover, the con-
tribution of [100]-orientation to the increase of recovery strain of NiTi
single crystal was investigated [10]. On the other hand, ne and well-
aligned precipitates with dispersive distribution help generate the en-
hanced coherent stress eld, which is in proportion to the extent of
ARSME [1113]. Indeed, the above mentioned studies do oer ex-
tensive understandings in the individual eects of the inuential factors
including grain orientation and precipitation of Ni4Ti3 particles on the
SME of NiTi alloys. However, due to the coherency relationship be-
tween the matrix and Ni4Ti3 precipitates, the texture of NiTi alloys also
restricts the orientation of Ni4Ti3 precipitates and thereby aects the
ARSME. Moreover, other original microstructure characteristics of as-
cast NiTi alloys, including composition, grain size and grain mor-
phology, also lead to dierent precipitation behaviors of Ni4Ti3 parti-
cles during constraint-aging treatment and thus aect the ARSME. For
example, little segregation and high solid solubility promote the nu-
cleation of Ni4Ti3 precipitates [14,15] and the rened grains can re-
strict the growth of Ni4Ti3 precipitates [16]. Heretofore, the relation-
ship among grain orientation, constraint stress direction and coherent

Corresponding author.
E-mail address: mexzhang@scut.edu.cn (X.P. Zhang).

http://dx.doi.org/10.1016/j.msea.2017.08.090
Received 28 April 2017; Received in revised form 24 August 2017; Accepted 26 August 2017
Available online 30 August 2017
0921-5093/ 2017 Elsevier B.V. All rights reserved.
Y.Y. Li et al.
Ni4Ti3 precipitate orientation remains unclear. More importantly, the
integrate eect of the composition, grain size, grain morphology and
grain orientation on the SME, especially ARSME, of constraint-aged
NiTi alloys has not been suciently studied yet, neither have the roles
of Ni4Ti3 precipitates and the coherent stress eld during the process
been ascertained clearly.
As can be seen above, the textured microstructures are benecial to
the SME of NiTi alloys. At present, the commonly used method for
producing NiTi SMAs with textured microstructure is rapid solidica-
tion technology (RST), which is a near net-shape technique. The RST
usually used today includes melt spinning, twin-roll casting, laser
melting, suction casting and so forth [1720]. Among them, melt
spinning and twin-roll casting are only applied to fabricating ribbon-
type NiTi alloys, whose geometries and dimensions are limited. How-
ever, it is worth indicating that due to the excessively high cooling rate
during melt spinning and twin-roll casting processes, amorphous
structure is introduced in so-obtained alloys, which is unfavorable for
the precipitation of Ni4Ti3 particles. Dierently, laser melting and
suction casting can be used to produce not only strip-type SMAs but also
bulk ones of complex geometries and dierent dimensions. However,
laser melting, which is more often used in selective melting and surface
treatment processes, is time consuming and costly compared with
suction casting. Therefore, rapid solidication through suction casting
is an economic and eective method to fabricate textured NiTi alloys
with desirable size and geometry. Recently, a Ni51Ti49 alloy was pre-
pared through rapid solidication followed by dierent aging pro-
cesses, which exhibited tunable two-way shape memory eect suitable
for making a specially designed bio-actuator [21].
In the present study, a high cooling rate was adopted during suction
casting process so as to acquire the Ni51Ti49 alloy strip with strongly
textured microstructure, and subsequent constraint- aging treatment
was applied to securing the ARSEM. The focus is placed on character-
izing the transformation behavior and recovery ratio of the rapidly
solidied and constraint-aged Ni51Ti49 alloy, and revealing the inu-
ential mechanism of the microstructure of the so-obtained alloy on the
ARSME.
2. Materials and experiments
Suction-cast and conventional cast Ni51Ti49 alloys were prepared for
comparative study. Both types of samples are made from electrolytic
nickel (purity > 99.9%) and sponge titanium (purity > 99.7%) with a
nominal composition of Ti-51 at.%Ni. Firstly, button-type ingots were
prepared through smelting in a non-consumable vacuum arc melting
furnace (WK- mode). The smelting process was repeated for six times
to reach homogeneity and each ingot weighs about 25 g. Afterwards, a
NiTi alloy strip was produced by sucking the molten master alloy into a
water-cooled thick copper mold (VSC-CM) under vacuum condition,
which was solidied at a high cooling rate of about 1 104 C/s. The
suction-cast NiTi alloy strip has a dimension of 20 8 0.48 (length
width thickness, mm), as shown in Fig. 1. For a comparison, the
smelted ingot was cut by electric discharge machining from the center
part to prepare the conventional cast strip sample having the same
geometry and dimension as the suction-cast strip. Finally, after solution
Fig. 1. Schematic of characterization positions and directions in the Ni51Ti49 alloy strip.
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Materials Science & Engineering A 705 (2017) 273281
treatment at 850 C for 3 h followed by water quenching, both suction-
cast and conventional cast NiTi alloy strips were placed in a specially-
designed arch-shaped steel mold with a diameter of 48 mm and then
subjected to constraint-aging at 450 C for 10 h to obtain the ARSME.
Microstructures of as-cast alloy samples were observed on optical
microscope (OM, DM 2500 P Leica). Samples for OM observation were
prepared by etching with a mixed solution of 2 ml HF, 8 ml HNO3 and
10 ml H2O after mechanical grinding and polishing. Phase constituents
were characterized by X-Ray diraction (XRD, Xpert Philips) with
CuK radiation at a scanning step of 0.01. The grain orientation was
determined using the scanning electron microscope (SEM, Nova
NanoSEM 430 FEI) equipped with an electron backscattered diraction
(EBSD) Nordlys detector. The EBSD results were analyzed through HKL
Channel 5 package software. The sample for EBSD measurement was
prepared by electropolishing at 5 C using 20 vol% H2SO4 and 80 vol%
methanol solution. Microstructure observation of constraint-aged sam-
ples was performed on SEM (Merlin Zeiss). Samples for SEM observa-
tion were also prepared by electropolishing using the same electrolyte
as that in preparation of EBSD sample.
The phase transformation behavior and recovery ratio of the NiTi
alloy strip were characterized to evaluate the ARSME. The phase
transformation behavior was analyzed by dierential scanning calori-
meter (DSC, Q200 TA) from 80 to 80 C with a heating/cooling rate
of 5 C/min. The recovery ratio, r(x), of the NiTi alloy strip between
high temperature and low temperature states was calculated using Eq.
(1) as follows [22]:
p x
r(x ) = 100%
d (1)
where p and x are arc angles of the NiTi alloy strip at high tem-
perature and low temperature respectively, d is the arc angle in the
constraint state, as illustrated in Fig. 2. The arc angles were acquired
through immersing the constraint-aged NiTi alloy strips in liquids with
dierent temperatures of 100, 25, 0 and 196 C, in which p was
obtained at 100 C, x was obtained at low temperatures of 25, 0 and
196 C, respectively, marked as r, i and m correspondingly. In
detail, images of the deformed strips at 100 C (in boiling water), 25 C
(in water at ambient temperature), 0 C (in ice water) and 196 C (in
liquid nitrogen) were successively captured by a high denition
camera. Then the corresponding arc angles of deformed strips were
measured by using AutoCAD software.
OM, XRD, EBSD and SEM analyses were all performed under am-
bient temperature. The OM observation was performed in both long-
itudinal and transverse cross-sections of NiTi alloy strips while XRD,
EBSD and SEM characterizations were conducted only in the long-
itudinal cross-section. The characterization positions and directions in
the NiTi alloy strip are illustrated in Fig. 1, where LD, TD and ThD
represent the longitudinal direction, transverse direction and thickness
direction, respectively.
3. Results
3.1. Microstructures in the as-cast state
Optical micrographs taken from both longitudinal and transverse
Fig. 2. Illustration of the recovery ratio calculation dened by Eq. (1).
Y.Y. Li et al.
Fig. 4. Statistical analysis of the size, geometry and distribution of grains in suction-cast
and conventional cast Ni51Ti49 alloy strips.
cross-sections of the suction-cast and conventional cast Ni51Ti49 alloy
strips in the as-cast state are shown in Fig. 3. According to Fig. 3(a) and
(b), clearly, grains in both samples exhibit nearly equiaxed shape in the
longitudinal cross-section. However, from the viewpoint of transverse
cross-section, grains in the suction-cast sample exhibit columnar shape
along ThD, whereas those in the conventional cast one are still
equiaxed, as shown in Fig. 3(c) and (d). To quantify such micro-
structural dierence between suction-cast and conventional cast sam-
ples, the grain size, grain geometry and grain distribution were
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Materials Science & Engineering A 705 (2017) 273281
Fig. 3. Optical micrographs of two types of Ni51Ti49
alloy strips in the as-cast state taken from the long-
itudinal cross-sections of (a) suction-cast and (b)
conventional cast samples, and from the transverse
cross-sections of (c) suction-cast and (d) conven-
tional cast samples.
statistically analyzed by using Image Pro Plus software and the corre-
sponding results were recorded as diameter, aspect ratio and box ThD/
TD value respectively, as shown in Fig. 4. The grain diameter of the
suction-cast sample refers to the average radial diameter of columnar
grains; the grain aspect ratio represents the average ratio of the max-
imum grain diameter to the minimum grain diameter; the box ThD/TD
value is the average ratio of the grain length along ThD to the grain
length along TD. Clearly, the suction-cast sample consists of ner grains
with an average radial diameter of 3.9 0.7 m, much smaller than the
average grain diameter of 28.5 9.4 m in the conventional cast one.
Furthermore, the grains in the suction-cast sample have an average
aspect ratio of 4.2 1.5 and box ThD/TD value of 3.4 1.0, indicating
that the length of columnar grains along ThD is more than three times of
that along TD. Comparatively, the average aspect ratio and box ThD/TD
value of grains in the conventional cast sample are 1.6 0.4 and
1.1 0.3, respectively. Although grains in the conventional cast
sample are slightly non-equiaxed, they still distribute homogeneously
along ThD and TD. In addition, it is worth noting that besides the dif-
ference in grain size, grain geometry and grain distribution between
two types of samples, there is also a clear dierence in amount of
precipitate phases between two samples, that is, there are many pre-
cipitates, indicated by massive coarse etching pits in Fig. 3(b) and (d),
at grain boundaries of the conventional cast sample; by contrast, grain
boundaries of the suction-cast sample are very clean and smooth,
meaning that there is a slight segregation during rapid solidication. As
a consequence, the as-cast suction-cast Ni51Ti49 alloy strip possesses
homogeneous composition and consists of ne columnar grains along
the direction of thickness.
Y.Y. Li et al. Materials Science & Engineering A 705 (2017) 273281

Fig. 5. XRD patterns of two types of Ni51Ti49 alloy samples in the as-cast state of (a) suction-cast and (b) conventional cast strips, and in the constraint-aged state of (c) suction-cast and
(d) conventional cast strips.

Fig. 6. EBSD results of the as-cast suction-cast

Ni51Ti49 alloy strip: (a) orientation map, (b) {100}
pole gure and (c) ThD inverse pole gure with re-
ference to LD, TD and ThD.

3.2. Phase constituents
XRD patterns of suction-cast and conventional cast Ni51Ti49 alloy
strips in both as-cast and constraint-aged states are shown in Fig. 5.
Comparing Fig. 5(a) with (b), the matrix of the suction-cast alloy is
supersaturated Ni1.02Ti0.98 of austenite phase while that of the con-
ventional cast one is austenitic NiTi with a small amount of NiTi2
precipitates. Besides, the intensity distribution of diraction peaks in
the suction-cast alloy is obviously dierent from that of the conven-
tional cast one. The strongest diraction peak of the former is (200)

276
Y.Y. Li et al.
while that of the later is (110). Since matrices of both alloy samples are
of body-centered cubic (BCC) structure, whose structure factor de-
termines that the strongest diraction peak should be (110) for iso-
tropic materials, the shift of the strongest diraction peak of the suc-
tion-cast sample is due to the grain orientation preference. Grains with
preferred orientation largely increase the relative intensity of (200)
diraction peak, thus it is dicult to identify the NiTi2 precipitates in
the suction-cast sample. Therefore, the high cooling rate leads to high
solid solubility and grain orientation preference in the suction-cast
alloy during rapid solidication. Furthermore, after undergoing solu-
tion and constraint-aging treatment, R-phase and Ni4Ti3 precipitates
occur in matrices of both types of alloy samples and the grain or-
ientation preference in the suction-cast alloy sample still exists, as
shown in Fig. 5(c) and (d).
3.3. Texture
In order to further determine the grain orientation preference in the
suction-cast Ni51Ti49 alloy strip, EBSD analysis was performed and the
corresponding results are shown in Fig. 6, which gives orientation map,
pole gure and inverse pole gure. In the orientation map, the red
color, which represents < 100 > directions, is given to the vast ma-
jority of grains in the suction-cast sample, as shown in Fig. 6(a). The
{100} pole gure shows axis density distribution around ThD, sug-
gesting that < 100 > directions of most grains in the suction-cast
sample are toward ThD, as shown in Fig. 6(b). Similarly, the ThD inverse
pole gure indicates that the lattice planes perpendicular to ThD are
mainly around {100}, as shown in Fig. 6(c). Thus, it is conrmed that
the suction-cast strip has strong ber texture with < 100 > B2//ThD.
3.4. Microstructures after constraint-aging
Microstructures of constraint-aged suction-cast and conventional
cast Ni51Ti49 alloy strips were characterized by SEM and the results are
shown in Figs. 7 and 8, which include backscattered electron (BSE)
images and statistical analyses of the precipitation behavior of Ni4Ti3
particles. As the outer part of bent NiTi alloy strip is in the tensile stress
state and the inner part is in the compressive stress state, BSE images in
both stress states are displayed in Fig. 7(a)(b) and Fig. 8(a)(b), where
the directions of the constraint stress are indicated by the black arrows
in bottom left corners. According to BSE images, in both suction-cast
and conventional cast samples after constraint-aging treatment, mas-
sive lenticular particles, which have been proved to be Ni4Ti3 pre-
cipitates [17], distribute homogeneously in and at grain boundaries
with strong orientation nearly parallel to the tensile stress direction or
the direction perpendicular to the compressive stress direction. Further,
the size (L) and inter-particle distance (D) of Ni4Ti3 precipitates in both
types of alloy samples were statistically analyzed to evaluate the pre-
cipitation behavior, as shown in Fig. 7(c)(d) and Fig. 8(c)(d). Results
show that Ni4Ti3 precipitates in the suction-cast sample have an
average size of 306.7 145.5 nm and distribute with an average inter-
particle distance of 166.5 71.8 nm, as shown in Fig. 7(c) and (d).
Comparatively, the average precipitate size and inter-particle distance
of Ni4Ti3 precipitates in the conventional cast sample are
342.6 171.5 nm and 198.7 93.6 nm, respectively, as shown in
Fig. 8(c) and (d). Notably, Ni4Ti3 precipitates with size in the range of
100300 nm account for 56.5% in the suction-cast sample and those in
the conventional cast one account for 51.5%. Similarly, 16.8% of Ni4Ti3
precipitates in the suction-cast sample and 10.1% of Ni4Ti3 precipitates
in the conventional cast one show inter-particle distance in the range of
0150 nm.
Hence, comparing with conventional casting, rapid solidication
enables the Ni51Ti49 alloy to have ner Ni4Ti3 precipitates with more
dispersive distribution during constraint-aging treatment. Additionally,
it can also be seen from the BSE images that ner NiTi2 particles pre-
cipitate at grain boundaries of the suction-cast sample compared with
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Materials Science & Engineering A 705 (2017) 273281
the conventional-cast one, which is consistent with the morphology of
the clean and smooth grain boundaries of the suction-cast sample under
OM observation.
3.5. Phase transformation and deformation
The ARSME of the constraint-aged Ni51Ti49 alloy strip can be
comprehensively evaluated by the phase transformation behavior and
recovery ratio. DSC curves of suction-cast and conventional cast
Ni51Ti49 alloy strips after constraint-aging treatment are shown in
Fig. 9, where Rs and Rf as well as Ms and Mf denote the starting and
nishing temperatures of R-phase transformation and martensitic
transformation, respectively; As and Af represent the starting and n-
ishing temperatures of austenitic transformation. Specic phase trans-
formation temperatures and temperature ranges (T) are listed in
Table 1. Clearly, both types of alloy samples have the same phase
transformation path, namely R-phase transformation and martensitic
transformation on cooling while austenitic transformation on heating.
However, the suction-cast alloy sample exhibits slightly lower Rs but
much higher Ms and As compared with the conventional cast one.
Moreover, the DSC curve of the suction-cast alloy sample shows sharper
transformation peaks with narrower phase transformation temperature
ranges compared with the conventional cast one.
Table 2 gives the measurement results of arc angles and recovery
ratios of suction-cast and conventional cast Ni51Ti49 alloy strips after
constraint-aging treatment, where the negative values of x (x = r, i, m)
signify the occurrence of ARSME. The higher p value and lower x
value indicate higher recovery ratio and more excellent ARSME. It can
be seen from Table 2 that after being heated to 100 C, NiTi alloy strips
change their geometries to the high temperature shape; then during the
subsequent cooling process, the ARSME appears in both types of sam-
ples when cooling to 25 C and becomes stronger with the decrease of
temperature. Meanwhile, the recovery ratio of the suction-cast sample
is higher than that of the conventional cast one whenever cooling to
25 C, 0 C or 196 C, indicating the superior ARSME of the alloy
induced by rapid solidication and constraint-aging.
4. Discussion
4.1. Grain growth in rapidly solidied Ni51Ti49 alloy
Based on a comprehensive characterization by OM, XRD and EBSD
analyses, it is clear that the suction-cast Ni51Ti49 alloy strip has high
solid solubility, slight segregation, ne columnar grains and strong ber
texture of < 100 > B2//ThD, which are mainly caused by the high
cooling rate during rapid solidication. It is well known that the cooling
rate during solidication is inversely proportional to the dimension of
casting product [23]. As the conventional cast strip is a part cut from
the smelted NiTi ingot, the nearly spherical shape of the ingot enables
similar cooling rates in all directions and thus results in equiaxed
grains, as shown in Fig. 3(b) and (d). In contrast, the suction-cast strip is
the direct product of rapid solidication and has the maximum cooling
rate along the thickness direction. Besides, due to the smaller dimension
of the suction-cast strip than the smelted ingot, the cooling rate during
suction casting is much higher than that during conventional casting.
Inevitably, the maximum cooling rate along ThD triggers directional
solidication in the suction-cast sample. On the one hand, grains in the
suction-cast sample grow preferentially along the maximum tempera-
ture gradient direction during rapid solidication and nally develop
into columnar shape along the direction of thickness, as shown in
Fig. 3(c). On the other hand, as < 100 > B2 is the typical and preferred
orientation during grain growth in cubic systems [24], the great ma-
jority of grains are well-oriented with < 100 > B2 along the direction of
the maximum cooling rate, leading to the formation of strong < 100
> B2 ber texture along thickness direction, as shown in Fig. 6.
Moreover, the high cooling rate during rapid solidication brings about
Y.Y. Li et al.
Fig. 7. Backscattered electron (BSE) images in (a) the tensile stress state and (b) the compressive stress state of the constraint-aged suction-cast Ni51Ti49 alloy strip and the corresponding
statistical analyses of (c) size and (d) inter-particle distance of Ni4Ti3 precipitates.
restriction to grain growth and the increased Ni solid solubility and
high Ni diusion velocity in the suction-cast sample, consequently re-
sulting in ne-grained and supersaturated NiTi alloy with homogeneous
composition.
4.2. Precipitation of Ni4Ti3 particles during constraint-aging
As mentioned above, the composition and microstructure of as-cast
Ni51Ti49 alloys have a great inuence on the precipitation behavior of
Ni4Ti3 particles during constraint-aging treatment, which can be sum-
marized into three aspects. Firstly, ne columnar grains in the suction-
cast sample provide numerous grain boundaries as nucleation sites for
Ni4Ti3 precipitates and simultaneously restrict the growth of pre-
cipitates. Secondly, the high cooling rate during rapid solidication
leads to relatively high solid solubility of Ni in the matrix of the suction-
cast sample, which increases the Ni diusion velocity and thus pro-
motes the nucleation of Ni4Ti3 precipitates during constraint-aging
treatment. Thirdly, according to a previous study [25], Ni4Ti3 pre-
cipitates have a coherency relationship of (001)h//(111)B2, so there are
eight Ni4Ti3 variants in the B2 matrix and every two of the variants are
conjugate. In order to simplify the analytical process, four typical var-
iants, which are marked as V1, V2, V3 and V4, are considered and the
orientation relationship between the matrix and Ni4Ti3 variants is
shown in Fig. 10(a) and (b). As is well-known, Ni4Ti3 precipitates prefer
to grow along the tensile stress direction or the direction perpendicular
to the compressive stress direction during constraint-aging treatment
[26,27]. However, due to the restriction of the coherency relationship
between the matrix and Ni4Ti3 precipitates, only the Ni4Ti3 variant,
whose orientation is closest to the preferential orientation, can
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Materials Science & Engineering A 705 (2017) 273281
precipitate. In the suction-cast Ni51Ti49 alloy strip with strong ber
texture of < 100 > B2//ThD, the constraint stress is always parallel to
{100}B2 lattice planes. Therefore, when grains have orientation with
(001)B2//ThD, the direction of constraint stress can be recorded as
[uv0], as indicated in Fig. 10(a). Assuming that the index of the central
plane of lenticular Ni4Ti3 precipitates is (hkl), which belongs to {111}B2
lattice planes, the angle () between the Ni4Ti3 precipitates and con-
straint-stress can be calculated through Eq. (2) as follows:
hu + kv
= arcsin
3 u2 + v 2 (2)
Taking tensile stress state as an example, when u and v have the
same parity, V3 and V4 variants precipitate; when u and v have dif-
ferent parities, V1 and V2 variants precipitate; when the tensile stress is
parallel to [100]B2 or [010]B2, all Ni4Ti3 variants have the equal pos-
sibility to precipitate, as shown in Fig. 10(c). In this manner, the
probability distribution of the precipitation of Ni4Ti3 variants in the
compressive stress state is shown in Fig. 10(d). Therefore, in the suc-
tion-cast Ni51Ti49 alloy with strong texture of (001)B2//ThD, the ma-
jority of Ni4Ti3 precipitates are restricted to be V1 and V2 variants or
V3 and V4 variants. For the case of (010)B2//ThD and (100)B2//ThD, the
probability distribution of the precipitation of Ni4Ti3 variants is similar,
that is, the precipitation of Ni4Ti3 variants mainly contains two possi-
bilities. Conversely, since the relative direction of constraint stress to
grain orientation in the conventional cast alloy is absolutely random
any one or more of Ni4Ti3 variants have opportunity to precipitate. In
other words, the Ni4Ti3 precipitates are better aligned in the suction-
cast alloy than in the conventional cast one. In summary, the ne grains
with homogeneous composition and the strong texture formed during
Y.Y. Li et al. Materials Science & Engineering A 705 (2017) 273281

Fig. 8. Backscattered electron (BSE) images in (a) the tensile stress state and (b) the compressive stress state of the constraint-aged conventional cast Ni51Ti49 alloy strip and the
corresponding statistical analyses of (c) size and (d) inter-particle distance of Ni4Ti3 precipitates.

Table 2
Arc angles and recovery ratios of suction-cast and conventional cast Ni51Ti49 alloy strips
after constraint-aging treatment.

Samples Arc angles () Recovery ratios (%)

p r i m r (r) r (i) r (m)

Suction-cast 4.68 0.64 4.03 5.79 44.5 73.0 87.7

Conventional cast 3.96 0.81 1.67 4.63 39.9 47.1 71.9

rapid solidication facilitate the precipitation of ne and well-aligned

Ni4Ti3 precipitates with dispersive distribution in the suction-cast
Ni51Ti49 alloy strip during constraint-aging treatment.

4.3. Eect of strongly textured microstructure on the ARSME

The inuence of the strongly textured microstructure on the ARSME

Fig. 9. DSC curves of suction-cast and conventional cast Ni51Ti49 alloy strips after con- of Ni51Ti49 alloy is mainly embodied in changes of the phase transfor-
straint-aging treatment. mation behavior and recovery ratio, in which the phase transformation
behavior is largely aected by the matrix composition and the

Table 1
Phase transformation temperatures and temperature ranges of suction-cast and conventional cast Ni51Ti49 alloy strips after constraint-aging treatment.

Samples Phase transformation temperatures (C) Phase transformation temperature ranges (C)

Rs Rf Ms Mf As Af TR TM TA

Suction-cast 39.4 30.7 5.7 13.5 37.6 42.9 8.7 7.8 5.3
Conventional cast 41.9 31.3 7.4 21.9 34.1 42.6 10.6 14.5 8.5

279
Y.Y. Li et al.
precipitation of Ni4Ti3 particles. Normally, the high Ni solid solubility
in the matrix ought to decrease the R-phase transformation and mar-
tensitic transformation temperatures [24]. However, the precipitation
of coherent Ni4Ti3 particles during aging process leads to the decrease
of Ni concentration dierence between two types of alloy samples, re-
sulting in the decrease of phase transformation temperature dierences.
Since martensitic transformation is more sensitive to the size and dis-
tribution of Ni4Ti3 precipitates than R-phase transformation, ne and
dispersively distributed Ni4Ti3 precipitates reduce the resistance of
martensitic transformation and Ms of the suction-cast alloy thus in-
creases. Further, massive interfaces between the parent phase and
Ni4Ti3 precipitates in the suction-cast alloy provide large amounts of
nucleation sites for phase transformations, which eectively accelerates
phase transformation processes. Besides, the homogeneous composition
in the suction-cast alloy increases the simultaneity of local phase
transformations. Therefore, massive interfaces between the parent
phase and Ni4Ti3 precipitates, together with the homogeneous com-
position in the suction-cast alloy, contribute to narrow phase transfor-
mation temperature ranges, as shown in Fig. 9 and Table 1. As is well-
known, the acute deformation of NiTi SMAs on heating and cooling
originates from the corresponding phase transformation, so the narrow
phase transformation temperature range means that NiTi SMAs can
deform in a small temperature range rapidly. Such property is called
fast response property, which is important for producing NiTi SMA
actuators.
Since the recovery ratio directly reects the deformability and re-
coverability of NiTi alloys, the higher recovery ratio of the suction-cast
alloy over the conventional cast one means that the rapid solidication
enables the NiTi alloy to possess the superior ARSME after constraint-
aging treatment. The mechanism of ARSME has been well investigated
in previous studies [1113]. During constraint-aging treatment, the
outer part of bent NiTi alloy strip is in the tensile stress state and the
inner part is in the compressive stress state, Ni4Ti3 precipitates tend to
grow along the tensile stress direction or the direction perpendicular to
280
Materials Science & Engineering A 705 (2017) 273281
Fig. 10. Illustration of the interrelationship of grain orientation,
constraint stress and Ni4Ti3 variants: (a) 3D illustration of four
Ni4Ti3 variants with dierent orientations in cubic system, (b) the
coherency relationship between B2 austenite and Ni4Ti3 variants,
(c) probability distribution of the precipitation of Ni4Ti3 variants
in the tensile stress state and (d) that in the compressive stress
state.
the compressive stress direction. Simultaneously, the so-obtained co-
herent stress eld around Ni4Ti3 precipitates in the tensile stress state is
in the opposite direction to that in the compressive stress state, leading
to the formation of ARSME. Therefore, the recovery ratio of Ni51Ti49
alloy strip is in proportion to the coherent stress eld induced by Ni4Ti3
precipitates. On the one hand, massive ne and dispersively distributed
Ni4Ti3 particles precipitate in the suction-cast alloy and thus generate
increased coherent stress eld. On the other hand, due to the constraint
from the strong < 100 > B2 ber texture, Ni4Ti3 precipitates in the
suction-cast alloy are well-aligned, leading to the further increase of
coherent stress eld. Moreover, it has been proved that the [100]-or-
iented single crystal has excellent deformability and can lead to en-
hanced SME [8,10]. As a consequence, the increased coherent stress
eld in the suction-cast alloy, together with the excellent deformability
of < 100 > B2-oriented grains, contributes to superior ARSME com-
pared with the conventional cast one.
5. Conclusions
1) Rapidly solidied Ni51Ti49 alloy strip consists of ne columnar
grains with strong ber texture of < 100 > B2 along the direction of
thickness.
2) The ne-grained and strongly textured microstructure of the
Ni51Ti49 alloy increases the nucleation, limits the orientation and
restricts the growth of Ni4Ti3 precipitates during constraint-aging
treatment.
3) Rapidly solidied and constraint-aged Ni51Ti49 alloy strip possesses
superior all-round shape memory eect in narrow phase transfor-
mation temperature range.
4) Homogeneous composition due to rapid solidication and numerous
interfaces between the parent phase and Ni4Ti3 precipitates formed
during constraint-aging contribute to the narrow phase transfor-
mation temperature range.
5) The enhanced coherent stress eld induced by ne, well-aligned and
Y.Y. Li et al.
dispersively distributed Ni4Ti3 precipitates, together with excellent
deformability of < 100 > B2-oriented grains, leads to high recovery
ratio of the rapidly solidied and constraint-aged Ni51Ti49 alloy
strip.
Acknowledgements
This research was supported by Key Project Program of Guangdong
Provincial Natural Science Foundation under Grant No.
S2013020012805 and the Natural Science Foundation of China under
Grant Nos. 51401081 and 51205135.
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