Materials Science & Engineering A 560 (2013) 653–666

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Materials Science & Engineering A

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

The effect of training on two-way shape memory effect of binary NiTi

and NiTi based ternary high temperature shape memory alloys
K.C. Atli a, I. Karaman a,b,n, R.D. Noebe c, D. Gaydosh c
a
Department of Mechanical Engineering, Texas A&M University, College Station, TX 77843, USA
b
Materials Science and Engineering Program, Texas A&M University, College Station, TX 77843, USA
c
NASA Glenn Research Center, Structures & Materials Division, Cleveland, OH 44135, USA

a r t i c l e i n f o abstract

Article history: The propensity for various high-temperature shape memory alloys (HTSMA), i.e., Ni28.5Ti50.5Pt21,
Received 3 August 2012 Ni24.5Ti50.5Pd25 and Ni24.5Ti50Pd25Sc0.5, to exhibit two-way shape memory effect (TWSME) was
Received in revised form compared to that of a conventional binary Ni49.9Ti50.1 shape memory alloy (SMA). Thermomechanical
2 October 2012
training in the form of thermal cycling under constant stress levels was employed to induce two-way
Accepted 4 October 2012
shape memory behavior in the various materials. The resulting TWSME was characterized for its
Available online 12 October 2012
magnitude and stability under stress-free conditions, while parameters such as training stress and
Keywords: upper cycle temperature during training were investigated for their influence on this phenomenon. For
Shape memory alloys Ni49.9Ti50.1, a negative correlation was found between an increasing training stress, from 80 MPa to
Martensitic transformation
200 MPa, and the magnitude of the resulting TWSM strain, while a positive correlation was observed
Thermomechanical training
for Ni24.5Ti50.5Pd25 and Ni24.5Ti50Pd25Sc0.5. The stability of the TWSME for the Ni49.9Ti50.1, measured by
Two-way shape memory effect
Thermal stability the strain evolution of the cold (martensitic) and hot (austenitic) shapes of the samples upon stress-free
thermal cycling, was found to depend on the stress and temperature interval during training.
Conversely, the stability of the NiTiPd based HTSMAs was much greater and less sensitive to these
parameters over the stress and temperature intervals investigated. No TWSME was seen in
Ni28.5Ti50.5Pt21 due to the higher upper cycle temperatures required during thermal cycling, which
resulted in the recovery of any favorable dislocation structures generated during training.
& 2012 Elsevier B.V. All rights reserved.

1. Introduction actuator to remember both its low-temperature and high-

NiTi based shape memory alloys (SMAs) have been exploited
in a wide range of product forms such as eyeglass frames,
orthodontic wires, valves, pipe couplings, and switches due to
their unique functional properties [1]. In addition, the fact that
the shape memory effect can be used to do work against a load
has led to the development of SMAs as compact, solid-state
actuators. Compared to D.C. motors or their pneumatic counter-
parts, these actuators have several advantages such as light
weight, reduction in total part count, ease of inspection and
higher energy densities [2]. SMA actuators mostly operate based
on the one-way shape memory effect (OWSME) combined with a
biasing force to reset the SMA after each actuation cycle. How-
ever, it would be advantageous in many designs to eliminate the
need to mechanically reset the actuator. In this respect, the two-
way shape memory effect (TWSME) renders it possible for an
n
Corresponding author at: Department of Mechanical Engineering, Texas A&M
University, College Station, TX 77843, USA. Fax: þ1 979 862 2418.
E-mail address: ikaraman@tamu.edu (I. Karaman).
temperature shapes without the need for a re-biasing force.
Unlike OWSME, TWSME is not an inherent characteristic of SMAs,
but rather it is obtained after thermomechanical treatments
(training), such as stress or temperature cycling.
Recently, a need for compact, high-temperature actuation
sources has emerged in several aerospace, oil exploration, and
automotive applications. One drawback of NiTi based binary SMAs
is the relatively low transformation temperatures (o100 1C), limit-
ing their use when high temperature actuation is required.
To overcome this restriction, NiTi can be alloyed with Pd, Pt, Au,
Hf and Zr, to raise transformation temperatures [3]. Among these
ternary NiTi based high-temperature SMAs (HTSMAs), the NiTiPd
system has recently attracted considerable attention due to its
adequate workability, low thermal hysteresis, and good strain
recovery under constrained and stress-free conditions [4–11].
Early studies on the TWSME mostly concentrated on conventional
Cu-based [12–20] and binary NiTi SMAs [21–38]. These studies
focused on the explanation of the TWSME mechanisms, generation
of TWSME using different training procedures, and the effects of
training parameters on the magnitude and stability of the TWSME.
Similar studies were also conducted on ternary NiTi based SMAs, such

0921-5093/$ - see front matter & 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.msea.2012.10.009
654 K.C. Atli et al. / Materials Science & Engineering A 560 (2013) 653–666
as NiTiCu [38–41], NiTiFe [35], and NiTiNb [42,43]. However, there is
very limited data on the TWSME characterization of HTSMAs. The
only studies in this area for NiTi based HTSMAs were performed on
NiTiHf alloys [44,45]. In the first study [44], Ni49Ti36Hf15 (at%) plates
were trained via bending in martensite followed by unconstrained
recovery for up to 30 cycles at different temperatures. The highest
two-way shape memory (TWSM) strain of only 0.88% was achieved
after a bending strain of 7.1% at room temperature. But even at this
limited strain level, the stability of the TWSME was poor. This was
attributed to the low strength of the martensite, which permitted the
introduction of dislocations during the TWSME cycles, relaxing the
oriented stress fields. Furthermore, the already limited TWSM strain
decreased by 50% in just 10 stress-free cycles. In an effort to improve
the stability of the TWSME, the same training procedure was applied
to a precipitation-hardened Ni50.6Ti29.4Hf20 (at%) HTSMA [45]. While
the stability of the TWSME improved, the alloy still exhibited a 20%
decrease in the TWSM strain after 30 stress-free cycles and the
magnitude of the initial TWSM strain was only slightly increased
compared to the solutionized material.
To the authors’ knowledge, there has not been a systematic
study on the TWSME of promising HTSMA systems such as NiTiPd
and NiTiPt. In this study, a series of NiTi based HTSMAs are
compared to a conventional binary Ni49.9Ti50.1 SMA in terms of
the magnitude and stability of the TWSME as a result of a 100-
cycle thermomechanical training procedure. The effects of Sc
microalloying to NiTiPd are also investigated in an effort to
enhance the TWSME. The effects of training parameters on the
resulting TWSME, such as training stress and the upper cycle
temperature (UCT) are also considered. Since most of the emer-
ging actuator applications require the SMA to do work against a
load, it is also useful to characterize the work output capability of
the TWSME and its stability during actuation, which initially has
been addressed for a Ni24.5Ti50.5Pd25 HTSMA [46]. However, this
broader study is focused on optimization of the TWSME and thus
characterization of this phenomenon under stress-free conditions
is sufficient and will provide direction for the selection, proces-
sing, and design of HTSMA actuators exploiting the TWSME.
1.1. Origin of TWSME
Two mechanisms for the TWSME have been proposed in the
literature. The first mechanism attributes the TWSME to the oriented
residual stress fields of the dislocation arrays generated during
thermomechanical training [12]. These residual stress fields are able
to induce the same variants of martensite in the absence of an
external stress as the ones that are generated by the external training
stress, thus resulting in the TWSME [20]. The magnitude and stability
of the TWSME depends to a great extent on the magnitude of these
stress fields and how they can be maintained through repeated
thermal cycling. The same mechanism has also been explained from a
thermodynamics point of view [15]. According to this view, the
dislocation arrays generated during thermomechanical training create
low energy configurations in the repeatedly induced martensite
variants, while a relatively higher energy configuration is induced in
the less frequently induced variants. As a result, the growth of
martensite variants with the low energy configuration is favored
even when the external stress is removed, resulting in TWSME.
The second mechanism is based on the local stabilization of
martensite, retained above the austenite finish (Af) temperature.
Similar to the residual stress fields in the first mechanism,
retained martensite plates are attributed with influencing the
nucleation of certain preferred martensite variants during the
transformation process, resulting in TWSME [12].
Common to these two mechanisms is the prerequisite for
some amount of plasticity to occur in the material during training,
which manifests itself as residual strain [12]. However, it has also
been shown that excessive residual strain in the form of generalized
plastic deformation and the subsequent formation of retained
martensite have undesirable effects on the TWSME [14]. Thus, the
approach for obtaining maximum TWSM strain is to induce just
enough localized plasticity that will yield the highest magnitude of
stable oriented stress fields for nucleation of single variant marten-
site [28].
1.2. Thermomechanical training procedures to obtain TWSME
Different training techniques have successfully been imple-
mented to obtain TWSME in various SMA systems. The most
common training techniques are: deformation in martensite
followed by constrained or unconstrained recovery (OWSME
cycling) [24,26,37,40,42,44]; stress cycling above the Af tempera-
ture (superelastic cycling) [12]; temperature cycling through the
martensitic transformation under a constant stress level (isobaric
thermal cycling) [13,14,20,23–25,27,28,32,36] or a combination
of the latter two methods [29]. Common to all these techniques is
the repeated growth and shrinkage of particular martensitic
variants, which is responsible for the generation of stable dis-
location arrays [47–49]. Another technique, which is different in
principle than the aforementioned techniques, is aging under
constraint. This method has been used to obtain TWSME in
Ni-rich NiTi SMAs. With this method, coherent precipitates are
formed in preferred orientations under applied stress, resulting in
oriented internal stress fields that bias the formation of single-
variant martensite [30].
Among the training procedures mentioned above, thermal
cycling through the martensitic transformation under a constant
stress level has been shown to yield satisfactory results in terms
of the magnitude and stability of the TWSME generated. This
method has been proven to be an efficient procedure, and
depending on how it is implemented, can involve relatively low
stresses, which can result in minimal plastic deformation com-
pared to other training procedures [28]. Consequently, this
approach was adopted in the current study.
2. Experimental procedures
2.1. Materials
Four different material compositions were chosen for this study:
conventional binary Ni49.9Ti50.1, Ni24.5Ti50.5Pd25, Ni24.5Ti50Pd25Sc0.5
and Ni28.5Ti50.5Pt21 (all in at%). It should be noted that all composi-
tions fall on the Ti-rich side of stoichiometry so that precipitation is
not a complicating factor in any of the materials in this study. Binary
Ni49.9Ti50.1 (at%) was acquired from Special Metals, New Hartford, NY.
in the form of 10 mm diameter rods in the hot-rolled and hot-
straightened condition. This lot of material has been characterized in
some detail and properties as diverse as thermal expansion [50],
elastic moduli [51], basic shape memory behavior [52,53] and
textural evolution during thermomechanical testing are available in
the literature [52,54].
Ingots of the high-temperature ternary and quaternary alloys
were prepared by vacuum induction melting of high-purity elemental
constituents (99.95% Ti, 99.98% Ni, 99.995% Pd, 99.995% Pt and
99.95% Sc). Each ingot was homogenized at 1050 1C for 72 h under
vacuum and allowed to furnace cool. Subsequent to the homogeniza-
tion, ingots were placed in mild-steel extrusion cans and extruded at
900 1C with an area reduction ratio of 7:1. Rectangular and cylindrical
dog-bone shaped tension specimens with gage dimensions of
8 mm  3 mm  1.5 mm and 3.81 mm Ø  16.4 mm, respectively,
were cut from the hot-rolled and hot-extruded rods for thermome-
chanical training and TWSME characterization.
 K.C. Atli et al. / Materials Science & Engineering A 560 (2013) 653–666 655

Binary Ni49.9Ti50.1 was chosen to represent the baseline of a 7.5 kW induction heater. Temperature was measured with a
behavior of a conventional SMA without complications from K-type thermocouple, which was spot-welded to the middle of
off-stoichiometry strengthening and precipitation, as occurs in the gage section. Samples were heated and cooled at rates of
Ni-rich compositions. Ni24.5Ti50.5Pd25 was selected as an HTSMA 30 72 1C/min and 2072 1C/min, respectively. Additional experi-
appealing to applications requiring intermediate transformation mental details related to this test setup can be found in [8].
temperatures of around 200 1C [3,5,7–10]. Ni24.5Ti50Pd25Sc0.5 has
transformation temperatures about 10 1C lower compared to the
ternary alloy. However, as shown in a previous study [4], this 3. Results and discussion
HTSMA displays slightly improved functional behavior in the
form of better dimensional stability and smaller thermal hyster- Fig. 1a illustrates a typical strain vs. temperature evolution
esis during isobaric thermal cycling compared to the ternary during the 100-cycle thermomechanical training procedure
alloy. One question to be answered is whether these improve- employed in this study. The results are for the binary Ni49.9Ti50.1
ments will also extend to the TWSME response. Ni28.5Ti50.5Pt21 trained under 150 MPa. Training is initiated by loading the
was chosen as a representative alloy for high-temperature appli- sample at room temperature in martensite and subsequently
cations, capable of actuation around 350 1C. Constant stress heating above the Af temperature to the upper cycle temperature
thermal cycling behavior of a similar composition, Ni30Ti50Pt20 (UCT), which in this example was 165 1C, to obtain austenite
has previously been studied by Noebe et al. [55,56] and this under the applied load. The first complete and all subsequent
material exhibited good work output and dimensional stability thermal cycles are comprised of cooling from the UCT to the lower
with transformation temperatures around 300 1C. cycle temperature (LCT) and heating of the sample back to the
UCT, e.g., through the forward and reverse transformations,
2.2. Thermomechanical training and TWSME characterization respectively. A common characteristic for all these materials is
that the 1st training cycle was completed with a relatively high
The choice of training procedure to induce the TWSME in the value of residual strain, eres , as compared to subsequent cycles.
currently studied materials was thermal cycling under constant We use the term eres for residual strain per cycle to denote that it
stress for 100 cycles. Training was carried out under tensile is strain that was not recovered during a given thermal cycle and
stresses of 80 MPa, 150 MPa and 200 MPa for all alloys. One- not to imply any given mechanism for the strain generation. With
hundred thermal cycles was selected, since it was expected to increasing number of cycles, the material obtains an almost stable
yield a reasonably stabilized material response with minimal shape memory response, demonstrating a subtly different strain
changes in shape and transformation temperatures upon further
thermal cycling [8,9].
For the Ni24.5Ti50.5Pd25 and Ni24.5Ti50Pd25Sc0.5 HTSMAs, train-
ing was carried out on a custom-built constant-load testing frame
using the small rectangular tensile samples. Heating and cooling
was done at a rate of 571 1C/min. Samples were heated by
conduction from the grips, which were in turn heated by radiation
through the use of an environmental furnace equipped with four
1 kW halogen lamps. For cooling, water was circulated around the
grips flowing through copper tubing. Temperature was controlled
with a K-Type thermocouple attached to the middle of the sample
gage section. To minimize the radiation heat transfer on the
sample surface (which will lead to erroneous temperature
readings that are not representative of the bulk specimen), the
sample was shielded with a 1 mm thick reflective aluminum foil.
A capacitive displacement probe (Capacitecs HPC-75) with a
linear range of 0–1.5 mm was attached to the grips to measure
the displacements during the training process. Axial strain was
calculated by dividing the change in length to the initial gage
section length.
Following thermomechanical training, samples were unloaded
and TWSME was characterized using a separate MTS testing
frame for 10 stress-free cycles to assess its magnitude and
stability. Strain was measured using an MTS high-temperature
extensometer with a gage length of 12.7 mm and a  20/þ20%
strain range. Samples were heated through conduction from
the grips with heating bands. Cooling was achieved through
conduction by flowing liquid nitrogen in copper tubes wrapped
around the grips. Heating and cooling rate of the samples was
10 72 1C/min. Similar to the training procedure, temperature was
measured using a K-type thermocouple attached to the middle of
Fig. 1. (a) An example of the thermomechanical training procedure used and the
the sample gage section. resulting strain evolution due to repeated isobaric thermal cycling. Data is for the
For the Ni49.9Ti50.1 and Ni28.5Ti50.5Pt21 samples, both training Ni49.9Ti50.1 alloy at 150 MPa. The 1st and the 100th cycles are highlighted. Total
and TWSME characterization were performed on an MTS servo- residual strain,etotal
res , was measured as the cumulative residual strain per cycle, eres,

hydraulic load frame using the cylindrical dog-bone samples.
Strain was measured using an MTS high-temperature extens-
ometer with a gage-length of 12.7 mm and a strain range of
10/ þ20%. Heating of the samples was achieved through the use
after 100 cycles. (b) 10 stress-free TWSME cycles following the training regimen
shown in (a). TWSM strain, eTWSM, was calculated as the strain difference between
the cold and hot shapes for a given thermal cycle. Note that the stress-free strain–
temperature cycles were rezeroed for easier comparison between conditions and
various materials.
656 K.C. Atli et al. / Materials Science & Engineering A 560 (2013) 653–666

vs. temperature curve at the end of the 100th cycle that has a extracted from the 80 MPa data along with 150 MPa and 200 MPa
nearly negligible eres per cycle. During the course of training, the training results and summarized in Table 1.
material accumulates a total residual strain, etotal
res , which is the The 80 MPa training results, shown in Fig. 2, reveal that all
total strain increase in the sample after 100 isobaric thermal materials exhibited a relatively small transient response during
cycles, measured in the austenite state at the UCT. the very first heating cycle. After this initial transient response, a
Following training, the sample is unloaded at room tempera- more consistent erec was observed that evolved much more subtly
ture and heated above the stress-free Af temperature before the during the course of training. The highest erec values were seen in
1st stress-free TWSME cycle, recovering a fraction of the strain
associated with the detwinned, post-trained microstructure
Table 1
(Fig. 1b). During TWSME cycling, degradation in stability of the A summary of recovered transformation strain, erec, during the 1st and 100th
TWSME is encountered, evidenced by a decrease in cold and hot- training cycles and total accumulated strain, etotal after 100 cycles, determined
res
shape strains (Fig. 1b). This is the opposite behavior of what is from thermomechanical training tests conducted under different stress levels and
observed in Fig. 1a during training, where both the cold and hot- upper cycle temperatures (UCTs).
shape strains increase with training cycles. In this study, the
Material (at%) Training Training Rec strain Rec strain Total
stability of the TWSME is also quantified by the change in the stress UCT (1C) (erec) 1st (erec) residual
two-way shape memory strain, eTWSM, which is calculated as the (MPa) cycle (%) 100th strain,
difference between the cold and hot-shape strains for a given cycle (%) (etotal
res ) (%)
stress-free cycle, as demonstrated in Fig. 1b.
Ni49.9Ti50.1 80 165 2.04 3.68 4.29
150 165 3.62 3.39 7.15
150 200 3.82 3.76 12.38
3.1. Thermomechanical training and the evolution of shape memory 200 165 3.76 3.44 10.11
behavior Ni24.5Ti50.5Pd25 80 280 1.68 2.40 1.10
150 280 2.28 2.55 2.26
150 320 2.43 2.73 2.36
Fig. 2 is a compilation of the strain vs. temperature response
200 280 2.71 2.69 3.00
for binary Ni49.9Ti50.1, Ni24.5Ti50.5Pd25, Ni24.5Ti50Pd25Sc0.5 and Ni28.5Ti50.5Pt21 80 500 0.32 0.55 1.17
Ni28.5Ti50.5Pt21 during the 100-cycle training process at 80 MPa. 150 500 1.34 2.24 4.53
To better understand the generation of TWSM behavior in each 200 500 2.09
trained material, pertinent information such as etotal and the Ni24.5Ti50Pd25Sc0.5 80 280 1.80 2.41 1.12
res
150 280 2.49 2.74 1.74
recovered transformation strain, erec for the 1st and 100th train- 200 280 2.73 2.75 2.80
ing cycles, measured during the reverse transformation, were

Fig. 2. 80 MPa, 100-cycle thermomechanical training results for (a) Ni49.9Ti50.1, (b) Ni24.5Ti50.5Pd25, (c) Ni24.5Ti50Pd25Sc0.5 and (e) Ni28.5Ti50.5Pt21.
 K.C. Atli et al. / Materials Science & Engineering A 560 (2013) 653–666
Ni49.9Ti50.1 at all stress levels investigated, while Ni28.5Ti50.5Pt21
had the lowest values, which was attributed to a higher stress
needed to reorient martensitic variants in this material [55].
All samples accumulated strain during the thermomechanical
training procedure. At the end of the 80 MPa, 100-cycle training,
the lowest etotal res levels occurred in the Ni24.5Ti50.5Pd25 and
Ni24.5Ti50Pd25Sc0.5 HTSMAs, while Ni49.9Ti50.1 exhibited the high-
est values (Table 1).
As expected, an increasing training stress led to an increased
value of etotal
res for all materials, though for a given stress level, the
values were always larger for binary Ni49.9Ti50.1 (Table 1 and
Fig. 3). It is also interesting to see that Ni28.5Ti50.5Pt21 accumu-
lated a relatively higher value of etotal
res under 150 MPa compared to
Ni24.5Ti50.5Pd25 and Ni24.5Ti50Pd25Sc0.5, while it had almost the
same etotal
res at 80 MPa. This is most likely the result of creep
deformation due to the increased stress level and the need to
cycle to a much higher UCT than the other materials, which was
necessary to complete the reverse transformation. For this same
reason, Ni28.5Ti50.5Pt21 could not endure 100 thermal cycles under
200 MPa and failed at the 60th cycle generating a etotal res of 8.3%.
Fig. 4 illustrates the evolution of the TWSME during the subse-
quent 10 stress-free cycles after training at 80 MPa (Fig. 4a, c, e and g),
as well as the changes in eTWSM as a function of cycle count after
training at all three stress levels (Fig. 4b, d, f and h). Table 2 lists 1st
and 10th cycle eTWSM values; efficiency factor for each trained
material, defined as the ratio of the 1st cycle eTWSM and the erec of
the 100th training cycle; the amount of degradation in eTWSM as well
as the cold and hot-shape strain values during 10 TWSME cycles.
With the exception of Ni28.5Ti50.5Pt21, efficiency factors for materials
trained under 80 MPa were found to be quite similar, around 0.8,
which indicated that the 1st cycle eTWSM values were only  20% less
than the erec values of the 100th training cycle (an efficiency factor of
1 indicates that 1st cycle eTWSM is equal to the erec of the 100th
training cycle). In terms of TWSME stability, Ni49.9Ti50.1 demonstrated
poor performance with large degradations in eTWSM (10%) and cold
and hot-shape strains (a decrease in strain of 0.6% and 0.3%,
respectively) during TWSME cycling. Ni24.5Ti50.5Pd25 and Ni24.5Ti50
Pd25Sc0.5 HTSMAs exhibited superior stability with less degradation in
eTWSM and cold and hot-shape strains.
3.2. Effect of training stress on the TWSME
As mentioned previously, TWSME arises from the presence of
oriented internal stress fields, which bias the formation of specific
Fig. 3. Total residual strain (etotal
res ), measured in the austenite, after 100 thermo-
mechanical cycles as a function of stress level for the different SMA systems.
657
martensite variants during the martensitic transformation, while
actually inhibiting the formation of non-favorable variants [15].
The oriented stress fields are usually imposed in the material
through the presence of defects such as dislocations that are
generated during thermomechanical training. Thus, some amount
of residual strain is expected during training; yet overstressing
the material might result in an increase in the plastic deformation
and facilitate the formation of retained martensite. This in turn,
would result in a decrease in the TWSME due to a decrease in the
amount of transforming volume. Thus, it would be anticipated
that there is an ideal stress or range of stresses for optimizing
TWSME through thermomechanical training.
3.2.1. Ni49.9Ti50.1
For Ni49.9Ti50.1, training stress had a complex effect on the
magnitude and stability of the TWSME. The magnitude of the
10th cycle eTWSM varied inversely proportional to the training
stress, with increasing training stress resulting in lower 10th
cycle eTWSM (Fig. 5). However, while the magnitude of the eTWSM
decreased with increasing training stress, the stability of the
eTWSM increased as evident from the smaller changes between
successive cycles (Fig. 4b). For instance, upon unloading the
80 MPa-trained material and heating above the Af temperature,
more than 4% strain was recovered (Fig. 4a). Only 73% of this
value, or about 3% strain, was carried over to the 1st TWSME cycle
and the eTWSM degraded by a further 10% in 10 thermal cycles
(Table 2). The eTWSM for the 150 MPa-trained material decreased
from 2.6% to 2.5% in 10 cycles, while the eTWSM for the 200 MPa-
trained material was found to be very stable during cycling, and
may have actually increased slightly by the end of the 10th cycle
(Fig. 4b). At this point, it should be noted that a stable eTWSM is not
necessarily a sign of a stable TWSME. eTWSM might be quite stable
while there is a significant change in overall dimensions of the
sample due to an almost equal amount of degradation in cold and
hot-shape strains. On the other hand, minimal changes in cold
and hot-shape strains will by definition result in a stable eTWSM.
NiTi was found to display poor TWSME stability by exhibiting
large changes in cold and hot-shape strains upon TWSME cycling
even though the changes in eTWSM were sometimes very minor
(Table 2). For example, after 10 cycles, the hot shape of the
200 MPa-trained material changed by 0.7% strain even though the
magnitude of eTWSM changed by only 0.1% strain.
For the 150 MPa-trained Ni49.9Ti50.1, etotalres was around 7%
(Fig. 3). Stress-free thermal cycling altered the post-trained
dislocation structure in a way that each cycle caused a progres-
sive relaxation of the oriented internal stresses. This inevitably
caused a decrease in the cold-shape strain due to the formation of
more self-accommodated martensite instead of heterogeneously
nucleated single-variant martensite (Fig. 4a). At the end of each
cycle, it was noticed that the hot-shape strain did not match the
strain value of the previous cycle, i.e., there was also a decrease in
the hot-shape strain. The primary reason for the decrease in hot-
shape strain upon stress-free thermal cycling is that after a total
deformation of 7%, there is probably retained martensite in the
material at the UCT [54]. But upon stress-free thermal cycling and
gradual relaxation of the internal stresses some of this oriented
retained martensite is able to transform back to austenite result-
ing in a decrease in the hot-shape strain as well. It is also possible
that back stresses due to the dislocation structures developed
during training were relaxed, which would also result in a slight
strain recovery. TWSM behaviors of 80 MPa and 200 MPa-trained
NiTi can be described based on the same scenarios. The notable
difference between these conditions is the amount of etotal res
generation during training. This variation could result in different
amounts of retained martensite and dislocation densities in the
658 K.C. Atli et al. / Materials Science & Engineering A 560 (2013) 653–666

Fig. 4. The evolution of strain vs. temperature behavior during no-load thermomechanical cycling used to determine TWSME after training at 80 MPa for (a) Ni49.9Ti50.1,
(c) Ni24.5Ti50.5Pd25, (e) Ni24.5Ti50Pd25Sc0.5 and (g) Ni28.5Ti50.5Pt21. Note that the strain–temperature cycles were rezeroed after training for easy comparison. The variation of
the TWSM strain during stress-free thermal cycling for (b) Ni49.9Ti50.1, (d) Ni24.5Ti50.5Pd25, (f) Ni24.5Ti50Pd25Sc0.5 and (h) Ni28.5Ti50.5Pt21 after training at various stress levels.

trained materials, which alter the volume fraction of oriented stable eTWSM but unstable axial dimension upon cycling, can be
martensite variants that cause the TWSME. For instance, the attributed to a recovery of a large volume fraction of retained
peculiar TWSM behavior of the 200 MPa-trained material, i.e., martensite. For this material, the decrease in the hot-shape strain
 K.C. Atli et al. / Materials Science & Engineering A 560 (2013) 653–666 659

Table 2
Magnitude and stability of the TWSME for the various SMA systems after thermomechanical training under different stress levels and upper cycle temperatures (UCTs).

Training Training TWSME 1st cycle TWSM 10th cycle TWSM Efficiency TWSM strain Hot-shape strain Cold-shape
stress UCT (1C) UCT (1C) strain (eTWSM) (%) strain (eTWSM) (%) factora degradationb degradationc strain
(MPa) degradationc

Ni49.9Ti50.1 80 165 165 3.06 2.75 0.83 0.10 0.33 0.60

150 165 165 2.60 2.53 0.77 0.03 0.68 0.64
200 165 2.95 2.82 0.78 0.04 0.46 0.49
200 2.43 2.09 0.65 0.14 0.64 0.91
200 165 165 2.34 2.36 0.68 -0.01 0.69 0.58
Ni24.5Ti50.5Pd25 80 280 280 2.12 1.99 0.88 0.06 0.10 0.24
150 280 280 2.41 2.28 0.95 0.05 0.17 0.31
320 280 2.34 2.20 0.86 0.06 0.13 0.27
200 280 280 2.58 2.46 0.96 0.05 0.08 0.23
Ni28.5Ti50.5Pt21 80 500 500 -0.04 -0.08 -0.08 -1.00 0.04 0.09
150 500 500 0.13 0.00 0.06 1.00 0.03 0.09
200 500
Ni24.5Ti50Pd25Sc0.5 80 280 280 2.11 2.04 0.88 0.03 0.20 0.26
150 280 280 2.46 2.38 0.90 0.03 0.13 0.22
200 280 280 2.56 2.46 0.93 0.04 0.10 0.22

a
Efficiency factor was calculated as the ratio of the two-way shape memory strain (eTWSM) of the 1st stress-free cycle to the recoverable transformation strain (erec)
of the 100th training cycle, i.e., (1st cycle eTWSM/100th cycle erec).
b
Degradation in eTWSM upon stress-free thermal cycling was calculated as the ratio of the difference between the 1st and 10th stress-free cycle eTWSM values to the
eTWSM of the 1st stress-free cycle, i.e., ((1st cycle eTWSM – 10th cycle eTWSM)/(1st cycle eTWSM)).
c
Degradations in cold and hot-shape strains were calculated as the difference between the percent shape strain values of the 1st and 10th stress-free cycles.

Fig. 5. (a) TWSM strain values after 10 stress-free cycles for the tested materials as a function of training stress. The 10th no-load thermal cycles for (b) Ni49.9Ti50.1
and (c) Ni24.5Ti50.5Pd25 after training under 80 MPa, 150 MPa and 200 MPa.

was very similar, if not larger, than the decrease in the cold-shape 3.2.2. Ni24.5Ti50.5Pd25 and Ni24.5Ti50Pd25Sc0.5
strain, resulting in a very stable or even slightly increasing eTWSM, Compared to Ni49.9Ti50.1, much lower etotal res values were
while resulting in a significant change in the axial dimension of recorded at all training stress levels for both Ni24.5Ti50.5Pd25 and
the sample. Ni24.5Ti50Pd25Sc0.5 HTSMAs (Fig. 3). While etotalres was 1.1% for
660 K.C. Atli et al. / Materials Science & Engineering A 560 (2013) 653–666
training at 80 MPa for Ni24.5Ti50.5Pd25, it doubled to 2.3% when the
stress was increased to 150 MPa and at 200 MPa, etotal res was 3.0%.
Marginally smaller values for etotalres were observed at each stress
level for Ni24.5Ti50Pd25Sc0.5 (Table 1). These values were much less
than that observed for Ni49.9Ti50.1. Thus the NiTiPd(Sc) HTMSAs
were much more resistant to the development of plastic deforma-
tion at the stress levels investigated than Ni49.9Ti50.1, even though
the NiTiPd(Sc) HTSMAs were thermally cycled to much higher
temperatures. In addition, the transformation strain for the
NiTiPd(Sc) HTSMAs increased with training stress. Thus an
increasing transformation strain with increasing training stress
naturally led to an increasing eTWSM with training stress.
Furthermore, eTWSM of the trained NiTiPd(Sc) HTSMAs were
found to be very close to the maximum recoverable strain levels
under stress, resulting in high training efficiencies (Table 2),
which actually increased with increasing training stress level
(Fig. 5), while the opposite behavior was observed in binary
Ni49.9Ti50.1. For example, the strain recovered during the initial
heating of the 150 MPa-trained material above the Af temperature
was very close to the 1st cycle eTWSM. Out of the 2.55% strain
recovered during the last training cycle, 95%, or 2.4% strain, was
carried over to the subsequent TWSME cycle and only degraded
by about 5% at the end of 10 stress-free thermal cycles for all
training stress levels.
In terms of TWSME stability, cold and hot-shape strains of
Ni24.5Ti50.5Pd25 were very stable and changed much less upon
stress-free thermal cycling than Ni49.9Ti50.1 (Fig. 4c and Table 2).
The hot-shape strain change was less than 30% of that observed in
Ni49.9Ti50.1 for a given stress level while the change in cold-shape
dimensions was less than half of that observed in the binary alloy.
This would indicate that the dislocation structures developed in
Ni24.5Ti50.5Pd25 during training were more resistant to relaxation
and recovery of the internal stresses than in Ni49.9Ti50.1, in spite of
cycling to higher temperatures. But there was also a consistent
anisotropy in the cold versus hot-shape strain change, which can be
seen in Fig. 4c and quantified in Table 2. In general, the hot-shape
strain change was about half of that observed for the change in cold
shape strain during the ten stress-free thermal cycles. As discussed
above, the change in shape of the sample measured at the LCT in the
martensite phase is due to a slight reversion of oriented martensite
back to self-accommodated martensite. The change in hot-shape
dimensions measured at the UCT is presumably due to reversion of
retained martensite to austenite. This would indicate that in
Ni24.5Ti50.5Pd25 either very little retained martensite was generated
during training or the retained martensite that was formed was
very stable. Ni24.5Ti50Pd25Sc0.5 displayed very similar results to
Ni24.5Ti50.5Pd25, with similar or slightly improved eTWSM and cold
and hot-shape strain stability (Table 2).
3.2.3. Ni28.5Ti50.5Pt21
The high transformation temperatures of Ni28.5Ti50.5Pt21
necessitated thermal cycling to much higher temperatures during
the training process, i.e., 500 1C compared to just 280 1C for the
NiTiPd(Sc) HTSMAs. Heating of the 80 MPa-trained sample above
the Af temperature resulted in a strain recovery of 0.5% (Fig. 4g),
which is almost the same as the erec of the last training cycle
(Table 2). Further stress-free cycling, however, did not yield any
useful eTWSM. At the end of 10 stress-free thermal cycles, the
eTWSM of Ni28.5Ti50.5Pt21 was almost non-existent regardless of the
training stress.
Although Ni28.5Ti50.5Pt21 exhibited reasonable recoverable and
residual strains during training for an alloy with such high
transformation temperatures [57], it did not show significant
evidence of TWSME. This can be attributed to the high UCT
required for thermal cycling. Therefore, regardless of the training
stress used, the first stress-free cycle at 500 1C relaxed any
beneficial dislocation structure that might have developed during
training [56], eliminating the driving force for the TWSME (Fig. 4g
and h).
3.3. Effects of composition on the TWSME
The most obvious change in the TWSME characteristics
between the various SMA systems is the basic effect of composi-
tion on transformation temperatures and the role that cycling
above the various transformation temperatures plays on subse-
quent microstructural development. Fig. 6 shows the 10th
TWSME cycles for all materials previously trained under
150 MPa. The substitution of 25 at% Pd for Ni in NiTi results in
an increase in the transformation temperatures of Ni24.5Ti50.5Pd25
to around 200 1C. The small quaternary alloying addition of Sc to
Ni24.5Ti50.5Pd25 subsequently decreased the resulting transforma-
tion temperatures slightly, by about 10 1C, consistent with the
isobaric thermal cycling results and differential scanning calori-
metry (DSC) analysis reported previously [4]. Pt has a greater
effect per unit of alloying addition on transformation tempera-
tures than Pd, such that the addition of 21% Pt to NiTi raised the
transformation temperatures of Ni28.5Ti50.5Pt21 to between 350 1C
and 400 1C. Thus cycling above this temperature to ensure
complete transformation under stress, i.e., 500 1C, was high
enough to allow complete recovery of any dislocation structure
that may have developed during training, removing any driving
force for subsequent TWSME. Noebe et al. [56] have previously
shown that recovery processes begin at approximately 450 1C in a
Ni29.5Ti50.5Pt20 HTSMA. It thus remains a technological challenge
to obtain stable TWSME response in HTSMAs when transforma-
tion temperatures are close to the recovery/recrystallization
temperatures of the particular alloy.
Substitution of Pd with Ni not only increases the transformation
temperatures, but also acts as a solid-solution strengthener and
results in a change in the martensite structure from monoclinic B19’,
to orthorhombic B19, resulting in improved compatibility [4]
between transforming phases (cubic, B2 austenite transforming to
orthorhombic martensite instead of monoclinic martensite). This
improved crystallographic compatibility coupled with increased
strength levels, results in a much more stable thermomechanical
cycling response compared to that of Ni49.9Ti50.1. This is evidenced
by smaller etotal
res values during training under all stress levels (Fig. 3)
and smaller changes in cold and hot-shape strains during TWSME
Fig. 6. Effect of composition on the TWSME for materials previously trained at
150 MPa for 100 thermal cycles. The strain–temperature curves represent the
TWSM response for the 10th load-free thermal cycle. The right axis represents the
efficiency of the eTWSM compared to the erec during training.
 K.C. Atli et al. / Materials Science & Engineering A 560 (2013) 653–666
cycles (Fig. 4c), even though the sample was cycled to a higher UCT.
For these same reasons, there was also a decrease in energy
dissipation during transformation, contributing to a significant
reduction of the thermal hysteresis during both training and the
TWSME cycles.
Microalloying with Sc further improved the compatibility of
the transforming phases in Ni24.5Ti50.5Pd25 and increased the
material strength due to solid-solution strengthening [4]. As a
result, Ni24.5Ti50Pd25Sc0.5 had slightly smaller thermal hysteresis
compared to Ni24.5Ti50.5Pd25 during both training and TWSME
cycles. Recently, the second eigenvalue, l2, of the transformation
stretch tensor that maps the austenite lattice to the martensite
lattice, has been related to the thermal hysteresis associated with
the martensitic transformation [58]. It has been shown that as the
l2 value gets closer to 1, compatibility between transforming
phases increases, leading to a smaller thermal hysteresis. Current
results for the l2 of binary NiTi (0.9663) [59], Ni24.5Ti50.5Pd25
(1.0171) [4] and Ni24.5Ti50Pd25Sc0.5 (1.0158) [4] are consistent
with this finding for the thermal hysteresis associated with the
TWSME, as well.
In terms of eTWSM, Ni49.9Ti50.1 exhibited a higher absolute value
at the end of 10 TWSME cycles compared to Ni24.5Ti50.5Pd25 and
Ni24.5Ti50Pd25Sc0.5 (Fig. 6). However, when the TWSM values were
normalized with respect to the highest amount of recoverable
strain that could be obtained from each material at a stress level
of 150 MPa, it was observed that Ni24.5Ti50.5Pd25 and Ni24.5Ti50
Pd25Sc0.5 HTSMAs outperformed Ni49.9Ti50.1 with values very
close to 1 (Fig. 6). This indicates that for a specific thermomecha-
nical treatment, the NiTiPd(Sc) HTMSAs responded to training
more efficiently and have nearly perfect TWSME relative to their
load-biased behavior during training. A high value of training
efficiency indicates that dislocation structures and local stress
fields generated by cycling are very effective in biasing the
same martensite variants that were formed through load-biased
thermal cycling, during the subsequent thermal cycling under
zero stress [28]. On the other hand, Ni28.5Ti50.5Pt21 had a value
close to 0, indicating that this material is not suitable for TWSME
applications.
3.4. Effect of training upper cycle temperature (UCT) on the TWSME
It is commonly accepted that for a chosen SMA system,
transformation strains generated during thermomechanical train-
ing will be representative of the resultant eTWSM. This is the case
for the Ni49.9Ti50.1 SMA and NiTiPd(Sc) HTSMAs studied here.
Thus, any training parameter that can potentially increase the
erec of the last training cycle will most likely increase the eTWSM of
the following stress-free cycles. While erec is a function of applied
stress, it also can be affected by the UCT the material is exposed to
during cycling [53]. While a high UCT is more likely to trigger
global plasticity due to the decrease in critical shear stress (CSS)
for slip, it is also possible that higher UCT values may reduce the
amount of retained martensite present in the alloy by heating
further above the Af temperature.
The initial choice of UCT for thermomechanical training was
made to ensure complete transformation of martensite to auste-
nite under the applied stress. Since all materials have different
transformation temperatures, different UCTs were used during
training. Ni49.9Ti50.1 was thermally cycled to 165 1C, whereas
NiTiPd(Sc) HTSMAs were cycled to 280 1C and Ni28.5Ti50.5Pt21
was heated to 500 1C. Padula et al. [53] have already demon-
strated that UCT affects the thermomechanical response of the
Ni49.9Ti50.1 SMA used in this study, at least for a relatively low
number of thermal cycles. They have shown that the material
cycled using a higher UCT, up to some maximum value depending
on the stress level, exhibited higher transformation strains
661
reaching a maximum erec at a UCT of around 250 1C under
200 MPa [60]. It is of interest to determine whether similar trends
will be seen after a relatively high number of thermal cycles and
how this may affect the resulting TWSME. Consequently,
Ni49.9Ti50.1 and Ni24.5Ti50.5Pd25 were trained using two different
UCT values under 150 MPa. Ni49.9Ti50.1 was cycled to UCTs of
165 1C and 200 1C, while the Ni24.5Ti50.5Pd25 was cycled using
UCTs of 280 1C and 320 1C.
3.4.1. Ni49.9Ti50.1
The strain vs. temperature response of the Ni49.9Ti50.1 during
thermomechanical training under 150 MPa is shown in Fig. 7a
and b with UCTs of 165 1C and 200 1C, respectively. At a first
glance, it is clear that etotal
res generated during training increased
from 7.2% to 12.4% due to an increase of UCT from 165 1C to
200 1C. In spite of the large difference in etotal res there are also
similarities in the strain vs. temperature evolution for these two
cases. For both materials, the 1st training cycle is characterized by
a relatively large eres and thermal hysteresis. However, during the
course of training, the materials started to show a more stable
behavior characterized by smaller shifts in transformation tem-
peratures during cycling and smaller values of eres per cycle. Also,
a smaller thermal hysteresis was observed, indicative of slightly
less dissipation of elastic stored energy during later transforma-
tion cycles, which could be due to a reduced interaction between
martensite variant pairs or to the development of low energy
dislocation structures with cycling.
There are also obvious differences between these two condi-
tions in terms of erec . Compared to the 165 1C-UCT trained
material, the 100th cycle of the 200 1C-UCT trained material had
a noticeably higher erec (3.8% vs. 3.4%) and higher transformation
temperatures. For the 165 1C-UCT trained material erec decreased
from 3.6% to 3.4% after 100 thermal cycles at 150 MPa. For the
200 1C-UCT trained material, erec remained quite stable at around
3.8% during the entire 100 cycle training regime. As plasticity was
more prominent at the higher UCT value (Fig. 7a vs. b), one would
anticipate a reduced transforming volume. Regardless, the higher
transformation strain of the 200 1C-UCT trained material can be
explained by a retained martensite argument. While a higher UCT
results in higher values of etotal res during training, the amount of
retained martensite is probably diminished compared to the
lower UCT case, as evidenced by the increased erec . In addition,
while plasticity was greater in the 200 1C-UCT trained material as
measured by etotal
res , it is possible that the transforming volume was
actually relatively unchanged or even greater than that for the
165 1C-UCT trained material, because excess dislocations could
have been annihilated during cycling or rearranged into low
energy networks, given the additional thermal energy introduced
by cycling to 200 1C.
The resultant TWSME obtained from these two cases is also
different in terms of stability and magnitude. While a UCT of
200 1C during thermomechanical training resulted in a higher
value of etotal
res , it also yielded a higher initial eTWSM of around 3.0%
(compared to 2.6% when a UCT of 165 1C was used). The
degradation levels associated with cold and hot-shape strains
are also different. After 10 TWSME cycles, the material trained
with a UCT of 165 1C exhibited a eTWSM of around 2.5% (Fig. 7e)
with about 0.7% decrease in both cold and hot-shape strains
(Fig. 7c). Fig. 7d illustrates the TWSM response of the same
material trained with a UCT of 200 1C. Compared to the material
trained with a UCT of 165 1C, the decrease in both cold and hot-
shape strains are less by about 0.2% and the resulting eTWSM was
2.8% at the end of 10 TWSME cycles. The larger decrease in the
cold-shape strain, in the material trained with a UCT of 165 1C, is
probably due to a larger relaxation of internal stresses, and thus
662 K.C. Atli et al. / Materials Science & Engineering A 560 (2013) 653–666

Fig. 7. The evolution of strain vs. temperature response of Ni49.9Ti50.1 trained under 150 MPa using a UCT of (a) 165 1C and (b) 200 1C. The evolution of the TWSME during
the subsequent 10 stress-free cycles for the material trained with UCT of (c) 165 1C and (d) 200 1C. (e) A comparison of 10th TWSME cycles for the Ni49.9Ti50.1 alloy trained
with different UCTs.

the formation of more self-accommodated martensite at the
expense of the preferred oriented martensite. The larger etotal
res of
12.4% in the 200 1C-UCT trained material is likely to have
produced a more stable, lower energy dislocation network, which
would be more resistant to relaxation of internal stresses in this
material, leading to an improved TWSME stability. Finally, the
smaller degradation in the hot-shape strain of the same material
is possibly associated with smaller amounts of retained martensite
present in the microstructure that reverts back to austenite during
stress-free cycling.
3.4.2. Ni24.5Ti50.5Pd25
In contrast to Ni49.9Ti50.1, a 40 1C increase in the UCT used
during training of Ni24.5Ti50.5Pd25 resulted in no significant
difference in etotal
res levels (Table 1). The sample, which was
thermally cycled under 150 MPa using a UCT of 280 1C had a
etotal
res of 2.3% (Fig. 8a), while the same thermomechanical training
with a UCT of 320 1C resulted in a etotal res value of 2.4% (Fig. 8b).
When the 1st and 100th cycles are inspected for both cases, it is
clear that the evolution in strain vs. temperature responses are
unaffected by the choice of UCT. Unlike Ni49.9Ti50.1, the 1st and
100th cycles for Ni24.5Ti50.5Pd25 are very comparable in terms of
erec and the shape of the hysteresis loops. These are all indications
of a shape memory response that is not affected by the choice of
UCT, at least over the temperature range investigated. In addition,
cycling to either UCT resulted in an approximately 16 1C shift in
transformation temperatures during the course of training com-
pared to a 7 1C shift in Ni49.9Ti50.1. This is an indication that larger
residual stresses are generated in the Ni24.5Ti50.5Pd25 alloy,
assisting the transformation.
The initial stress-free heating curves after the training procedure
follow almost the same strain–temperature path for the two cases
(Fig. 8c and d) indicating similar values of internal stresses in both
materials regardless of the UCT used. Consequently, the changes in
cold and hot-shape strains are indistinguishable and are minimal
 K.C. Atli et al. / Materials Science & Engineering A 560 (2013) 653–666 663

Fig. 8. The evolution of strain vs. temperature response of Ni24.5Ti50.5Pd25 trained under 150 MPa using a UCT of (a) 280 1C and (b) 320 1C. The evolution of the TWSME
during the subsequent 10 stress-free cycles for the material trained with UCT of (c) 280 1C and (d) 320 1C. (e) A comparison of 10th TWSME cycles for the Ni24.5Ti50.5Pd25
alloy trained with different UCTs.

compared to Ni49.9Ti50.1. The 10th TWSME cycle for each case is
shown in Fig. 8e. The two strain vs. temperature curves are nearly
identical with similar transformation strain, hysteresis, and trans-
formation temperatures. The 0.1% difference in eTWSM for the 10th
stress-free cycle (Fig. 8e) is essentially within the uncertainty of the
strain measurements and is hardly significant.
3.5. Effect of TWSME cycling upper cycle temperature (UCT2W) on
the TWSME
In the previous section, the significance of the UCT used for
thermomechanical training cycles was demonstrated for the
binary Ni49.9Ti50.1 alloy (while the Ni24.5Ti50.5Pd25 alloy was
insensitive to this effect over the narrow range of temperatures
investigated). Consequently, the selection of UCT for the TWSME
cycles also deserves attention. To avoid any confusion with the
UCT used during the training process, the UCT used during the
TWSME cycles will be denoted as UCT2W. To show the effect of
UCT2W on the stability and magnitude of TWSME, the binary
Ni49.9Ti50.1 alloy, trained under 150 MPa using a UCT of 200 1C,
was thermally cycled stress-free using a UCT2W of 165 1C and
200 1C. As expected for this alloy, a higher UCT2W used during
stress-free cycling severely affected both the magnitude and
stability of TWSME. Out of the 3.8% erec for the last training cycle,
only 2.4% (vs. 3.0% with a UCT2W of 165 1C) could be carried over
to the 1st TWSME cycle (Table 2). The eTWSM decreased by 0.3%
(vs. 0.1% with a UCT2W of 165 1C) in 10 cycles and the largest
decrease in cold-shape strain was observed for this condition.
This increased degradation in stability is undoubtedly due to the
rapid relaxation of oriented internal stresses at this higher cycling
temperature.
3.6. Factors that affect the magnitude and stability of TWSME
For a review of the factors that can affect the magnitude and
stability of TWSME, the schematic in Fig. 9 is introduced.
664 K.C. Atli et al. / Materials Science & Engineering A 560 (2013) 653–666
Fig. 9. Schematic showing the parameters involved in the generation of TWSME, its magnitude and stability. See text for details. (?: dislocations, s: applied stress during
training, UCT: upper cycle temperature during either training or TWSME cycles, TRIP: transformation-induced plasticity, RM: retained martensite, etotal res : total residual
strain measured in the austenite state at the UCT, OM: oriented martensite (responsible for the TWSME), SAM: self-accommodated martensite.).
The figure is divided into five main parts, each summarizing
relevant microstructural parameters, mechanisms, or testing
conditions that can directly or indirectly influence the magnitude
and stability of the TWSME.
Part I illustrates the key parameters that are likely to affect the
microstructural evolution during thermomechanical training: the
applied stress (s), the choice of UCT, and the number of cycles.
In this study, only s and UCT were chosen as variables. The most
evident effect of an increase in either s (Fig. 3) or UCT (Figs. 7 and 8)
was an increase in etotal
res generated during training. The effect of the
number of cycles on the TWSME was not directly investigated in
this study, with the number of cycles being kept constant at 100. But
it is clear from the data that etotal
res increases with cycle count, in a
manner that appears to saturate at some higher number of cycles.
Though the effect of cycle count on the TWSME was not directly
investigated, it can be postulated that as the cycle count increases
and the strain–temperature response saturates with cycling, a more
stable TWSME should be developed.
In addition to the martensitic phase transformation in SMAs it
is possible for a number of additional inelastic and predominantly
non-recoverable deformation processes to occur concurrently, as
illustrated in Part II of Fig. 9. These are what give rise to the major
component of the etotal res generated during thermomechanical
cycling or training. Depending on the temperature and applied
stress under which the transformation occurs, several deforma-
tion mechanisms can come into play. The most critical, because it
will occur regardless of the stress–temperature conditions, is
accommodation of the volume mismatch during the martensitic
transformation by dislocation generation at austenite/martensite
interfaces, a process also known as transformation-induced plas-
ticity (TRIP). Evidence for this behavior in NiTi, through detailed
TEM studies, has been presented by a number of investigators
[47,49,61]. In addition, general plasticity is also likely as internal
stresses or stress concentrations in the material reach the critical
resolved shear stress for slip at first locally [52] and then more or
less generally throughout the material [62–65]. Finally, the effects
dislocation relaxation, recovery and even creep deformation
cannot be ignored during thermal cycling under stress at even
moderate temperatures [66] as seen in the Ni28.5Ti50.5Pt21 case.
Consequently, thermomechanical cycling during the training
process results in an accumulation of defects in the microstruc-
ture. These defects are usually either dislocations or deformation
twins [47–49,61–65,67] generated due to the mechanisms sum-
marized in Part II. In addition to their contribution to plasticity,
and potentially acting as a source for preferred nucleation of
oriented martensite (OM), these defects also form a barrier
against reverse transformation, stabilizing some of the martensi-
tic variants such that they cannot revert back to austenite during
transformation.
Part III of Fig. 9 represents the formation of dislocations (?)
and retained martensite (RM) as a result of training. The hor-
izontal arrow is used between ? and RM to represent the inter-
play between dislocation structures and martensite stabilization.
A consequence of both dislocation generation and to a much
lesser extent the formation of RM is an increase in the etotal
res and
change in the hot-shape strain of the sample, which can be
quantified from the thermomechanical testing results (Fig. 3).
Some amount of etotalres is probably necessary for the generation of
TWSME, yet excessive deformation leads to a decrease in the
TWSME, as seen in binary Ni49.9Ti50.1 (Fig. 5b). Although there is
no unique relationship between etotal res and the TWSME, dislocation
structures and RM determine the amount of transforming volume
available after training. Since it is not exactly known how disloca-
tion structures contribute to the amount of transforming volume,
the connection between ? and transforming volume has been
indicated with a dashed arrow. Due to the presence of oriented
internal stresses induced during training, a fraction of the trans-
forming volume will be comprised of OM, which is responsible
for the TWSME and directly controls the magnitude of the eTWSM.
The remainder will transform into self-accommodated martensite
 K.C. Atli et al. / Materials Science & Engineering A 560 (2013) 653–666
(SAM). The difference between the observed eTWSM and the
theoretical maximum transformation strain for the polycrystal-
line aggregate is then due to this SAM and any RM, which does
not participate in the transformation process.
Obviously, microstructural features such as crystallographic
compatibility between transforming phases, texture, grain size
and the initial dislocation density also affect microstructural
evolution during training (Part IV of Fig. 9). Higher strength levels
through finer grain size, higher initial dislocation density, pre-
cipitate strengthening, or preferred textures/orientations where
slip is severely restricted, as well as improved compatibility
between the transforming phases through compositional changes
should decrease defect generation during training, resulting in a
relatively lower dislocation density and possibly less RM. Other
than improved compatibility between transforming phases as
exemplified by comparing the response of the binary NiTi and
NiTiPd(Sc) systems [4], the effects of these microstructural para-
meters on the TWSME were beyond the scope of this study, but
are included in Part IV of Fig. 9 for completeness.
The actual stress-free cycling of the trained material, used to
investigate the stability of the TWSME, can cause additional
microstructural evolution. First, a higher UCT2W will tend to cause
rearrangement and annihilation of the dislocation structures
generated during training, relaxing the internal stress fields and
affecting the proportion of OM that is formed. Furthermore, it
may assist in destabilization of any RM in the structure.
The magnitude of the eTWSM and the stability of the TWSME
depend directly on the relative amounts of all types of martensite
structures (SAM, OM and RM) during stress-free cycling. Thus
relaxation of the dislocation structures that affect the volume
fractions of OM and the fraction of SAM retained during the
transformation process will result in a change in eTWSM and
instability of the TWSME due to changes in cold and hot-shape
strains of the sample (Fig. 7c and d). Hence the selection of UCT
during the TWSME cycling, as well as the other microstructural
parameters mentioned above (Part IV of Fig. 9), will have a strong
influence on the magnitude and stability of the TWSME.
4. Summary and conclusions
In this study, a binary Ni49.9Ti50.1 SMA and Ni28.5Ti50.5Pt21,
Ni24.5Ti50.5Pd25 and Ni24.5Ti50Pd25Sc0.5 HTSMAs were character-
ized in terms of the stability and magnitude of the two-way shape
memory effect (TWSME). The TWSME was induced in these
materials through a thermo-mechanical training procedure con-
sisting of 100 thermal cycles under various stress levels with
different upper cycle temperatures (UCTs). In the process of
training, the evolutionary behavior of the strain–temperature
response of the materials as a function of stress was also
determined. Subsequently, the stability and magnitude of the
TWSME was assessed by running 10 stress-free thermal cycles
following the training cycles.
A summary of the results and conclusions that could be
derived from this study are:
1. In general Ni49.9Ti50.1 exhibited poor TWSME stability evi-
denced by large degradations in cold (martensite) and hot
(austenite) shape strains upon stress-free thermal cycling.
Ni24.5Ti50.5Pd25 and Ni24.5Ti50Pd25Sc0.5 had superior stability
characterized by minimal shape changes.
2. After training at 150 MPa, Ni49.9Ti50.1 exhibited a eTWSM of 2.5%
at the end of 10 stress-free cycles. This value was about 60% of
the recoverable strain level for the material under biased
conditions at the end of training. On the other hand, NiTiPd(Sc)
HTSMAs had much more efficient responses to training. These
665
alloys had eTWSM values around 2.4%, which corresponded to
almost 90% of the recoverable strain that could be obtained
from these materials during 150 MPa thermal cycling. Due to
the inherently high transformation temperatures of the
Ni28.5Ti50.5Pt21, stress-free thermal cycling was performed at
temperatures above the recovery range for the alloy, relaxing
or recovering any dislocation structures in the material. Con-
sequently, no significant TWSME was observed.
3. Both the stress level and UCT used during thermo-mechanical
training have significant but varied effects on the magnitude
and the stability of the resulting TWSME. UCT2W, the upper
cycle temperature selected for stress-free thermal cycling
during measurement of the TWSM response, was equally
important for the stability of the TWSME. A higher UCT2W
was found to result in a faster degradation of the TWSME in
Ni49.9Ti50.1.
4. NiTiPd(Sc) HTSMAs have been shown to be attractive candi-
dates for TWSME applications and are the only currently viable
option for use at higher temperatures (to about 200 1C). These
alloys generated relatively small amounts of residual strain
during thermomechanical training, over the range of UCTs and
stress levels investigated. The resultant TWSME was shown to
have excellent stability, including relatively stable cold and
hot-shape strains, and adequate eTWSM.
Acknowledgments
The authors gratefully acknowledge insightful discussions
with Ji Ma (Graduate research assistant at Texas A&M University)
and the Shape Memory Alloy and Active Structures Group at
NASA Glenn Research Center. Particular thanks to Brian E. Franco
(Graduate research assistant at Texas A&M University) for his
help with the construction of the thermomechanical test setup
and training of samples. This study has been supported by the
NASA Fundamental Aeronautics Program, Subsonic Fixed Wing
Project through Cooperative Agreement No. NNX07AB56A, with
additional support from the Aeronautical Sciences Project. IK also
acknowledges the support from the US Air Force Office of
Scientific Research, Grant No. FA9550-12-1-0218.
References
[1] K.N. Melton, in: T.W. Duerig, K.N. Melton, D. Stockel, C.M. Wayman (Eds.),
Engineering Aspects of Shape Memory Alloys, Butterworth-Heinemann, New
York, 1990, pp. 21–35.
[2] C. Mavroidis, Res. Nondestr. Eval. 14 (2002) 1–32.
[3] J. Ma, I. Karaman, R.D. Noebe, Int. Mater. Rev. 55 (2010) 257–315.
[4] K.C. Atli, I. Karaman, R.D. Noebe, A. Garg, Y. Chumlyakov, I. Kireeva, Metall.
Mater. Trans. A 41 (2010) 2485–2497.
[5] K.C. Atli, I. Karaman, R.D. Noebe, H.J. Maier, Scr. Mater. 64 (2011) 315–318.
[6] K.C. Atli, I. Karaman, R.D. Noebe, A. Garg, Y. Chumlyakov, I. Kireeva, Acta
Mater. 59 (2011) 4747–4760.
[7] G. Bigelow, R.D. Noebe, S.A. Padula, A. Garg, in: B. Berg, M.R. Mitchell, J. Proft
(Eds.), Proceedings of the International Conference on Shape Memory and
Superelastic Technologies, 2006, pp. 113–132.
[8] G. Bigelow, S.A. Padula, A. Garg, D. Gaydosh, R.D. Noebe, Metall. Mater. Trans.
A 41 (2010) 3065–3079.
[9] G. Bigelow, D. Gaydosh, A. Garg, S.A. Padula, R.D. Noebe, in: S. Miyazaki (Ed.),
Proceedings of the International Conference on Shape Memory and Super-
elastic Technologies, 2007, pp. 83–92.
[10] G. Bigelow, S.A. Padula, A. Garg, R.D. Noebe, in: M.J. Dapino (Ed.), Proceedings
of SPIE: Behavior and Mechanics of Multifunctional and Composite Materials,
2007, pp. 2B1-2B12.
[11] B. Kockar, K.C. Atli, J. Ma, M. Haouaoui, I. Karaman, M. Nagasako, R. Kainuma,
Acta Mater. 58 (2010) 6411–6420.
[12] J. Perkins, R.O. Sponholz, Metall. Trans. A 15 (1984) 313–321.
[13] R. Stalmans, J.V. Humbeeck, L. Delaey, Acta Metall. Mater. 40 (1992) 501–511.
[14] R. Stalmans, J.V. Humbeeck, L. Delaey, J. Phys. IV 1 (1991) 403–408.
[15] R. Stalmans, J.V. Humbeeck, L. Delaey, Acta Metall. Mater. 40 (1992) 2921–2931.
[16] R. Stalmans, J.V. Humbeeck, L. Delaey, in: R. Yamamoto, E. Furubayashi, Y.
Doi, R. Fang, B. Liu (Eds.), Advanced Materials ‘93, Vol. V: Pt. A: Ecomaterials;
Pt. B: Shape Memory Materials and Hydrides, 1994, pp. 927–930.
666 K.C. Atli et al. / Materials Science & Engineering A 560 (2013) 653–666
[17] R. Stalmans, J.V. Humbeeck, L. Delaey, Scr. Metall. Mater. 31 (1994) 1573–1576.
[18] E. Cingolani, M. Ahlers, Mater. Sci. Eng., A 273 (1999) 595–599.
[19] R. Rapacioli, V. Torra, E. Cesari, J.M. Guilemany, J.R. Miguel, Scr. Metall. 22
(1988) 261–264.
[20] L. Contardo, G. Guénin, Acta Metall. Mater. 38 (1990) 1267–1272.
[21] J. Perkins, Scr. Metall. 8 (1974) 1469–1476.
[22] K. Escher, Metal. Wiss. Tech. 44 (1990) 23–28.
[23] D.A. Hebda, S.R. White, Smart Mater. Struct. 4 (1995) 298–304.
[24] R. Lahoz, L. Gracia-Villa, J.A. Puertolas, J. Eng. Mater. Technol.-ASME. 124
(2002) 397–401.
[25] R. Lahoz, J.A. Puértolas, J. Alloys Compd. 381 (2004) 130–136.
[26] Y. Liu, Y. Liu, J. Van Humbeeck, Acta Mater. 47 (1998) 199–209.
[27] Y. Liu, P.G. McCormick, Scr. Metall. 22 (1988) 1327–1330.
[28] Y. Liu, P.G. McCormick, Acta Metall. Mater. 38 (1990) 1321–1326.
[29] H.Y. Luo, E.W. Abel, Smart Mater. Struct. 16 (2007) 2543–2549.
[30] M. Nishida, T. Honma, Scr. Metall. 18 (1984) 1293–1298.
[31] E. Quandt, C. Halene, H. Holleck, K. Feit, M. Kohl, P. Schlomacher, A. Skokan,
K.D. Skrobanck, Sens. Actuators, A 53 (1996) 434–439.
[32] H. Scherngell, A.C. Kneissl, Scr. Mater. 39 (1998) 205–212.
[33] H. Scherngell, A.C. Kneissl, Acta Mater. 50 (2002) 327–341.
[34] K. Wada, Y. Liu, J. Alloys Compd. 449 (2008) 125–128.
[35] J.J. Wang, T. Omori, Y. Sutou, R. Kainuma, K. Ishida, Scr. Mater. 52 (2005)
311–316.
[36] L.M. Wang, Y.F. Zheng, W. Cai, X.L. Meng, L.C. Zhao, J. Mater. Sci. Technol. 17
(2001) 263–266.
[37] Z. Wang, X. Zu, X. Feng, J. Dai, Mater. Lett. 54 (2002) 55–61.
[38] Z.G. Wang, X.T. Zu, J.Y. Dai, P. Fu, X.D. Feng, Mater. Lett. 57 (2003) 1501–1507.
[39] L.P. Chen, N.C. Si, J. Alloys Compd. 448 (2008) 219–222.
[40] A.V. Shelyakov, Y.A. Bykovsky, N.M. Matveeva, Y.K. Kovneristy, J. Phys. IV 5
(1995) 713–716.
[41] Z.G. Wang, X.T. Zu, X.D. Feng, S. Zhu, J.Y. Dai, L.B. Lin, L.M. Wang, Mater. Lett.
56 (2002) 284–288.
[42] X.L. Meng, F. Chen, W. Cai, L.M. Wang, L.C. Zhao, Mater. Trans. 47 (2006)
724–727.
[43] L.M. Wang, X.L. Meng, W. Cai, L.C. Zhao, J. Mater. Sci. Technol. 17 (2001)
13–14.
[44] X.L. Meng, Y.F. Zheng, W. Cai, L.C. Zhao, J. Alloys Compd. 372 (2004) 180–186.
[45] X.L. Meng, W. Cai, Y.D. Fu, Q.F. Li, J.X. Zhang, L.C. Zhao, Intermetallics 16
(2008) 698–705.
[46] K.C. Atli, I. Karaman, R.D. Noebe, Scr. Mater. 65 (2011) 903–906.
[47] D.M. Norfleet, P.M. Sarosi, S. Manchiraju, M.F.X. Wagner, M.D. Uchic,
P.M. Anderson, M.J. Mills, Acta Mater. 57 (2009) 3549–3561.
[48] R. Delville, B. Malard, J. Pilch, P. Sittner, D. Schryvers, Int. J. Plast. 27 (2011)
282–297.
[49] T. Simon, A. Kröger, C. Somsen, A. Dlouhy, G. Eggeler, Acta Mater. 58 (2010)
1850–1860.
[50] S. Qiu, V.B. Krishnan, S.A. Padula, R.D. Noebe, D.W. Brown, B. Clausen,
R. Vaidyanathan, Appl. Phys. Lett. 95 (2009) 141906–141906-3.
[51] S. Qiu, B. Clausen, S.A. Padula, R.D. Noebe, R. Vaidyanathan, Acta Mater. 59
(2011) 5055–5066.
[52] S. Manchiraju, D. Gaydosh, O. Benafan, R.D. Noebe, R. Vaidyanathan,
P.M. Anderson, Acta Mater. 59 (2011) 5238–5249.
[53] S.A. Padula, D. Gaydosh, R.D. Noebe, G. Bigelow, A. Garg, D.C. Lagoudas,
I. Karaman, K.C. Atli, in: M.J. Dapino, Z. Ounaies (Eds.), Proceedings of SPIE:
Behavior and Mechanics of Multifunctional and Composite Materials, 2008,
pp. 692912–692912-11.
[54] S. Qiu, PhD Thesis, University of Central Florida, 2011.
[55] R.D. Noebe, D. Gaydosh, S.A. Padula, A. Garg, T. Biles, M. Nathal, in:
W.D. Armstrong (Ed.), Proceedings of SPIE: Behavior and Mechanics of
Multifunctional and Composite Materials, 2005, pp. 364–375.
[56] R.D. Noebe, S. Draper, D. Gaydosh, A. Garg, B. Lerch, N. Penney, G. Bigelow,
S.A. Padula, in: B. Berg, M.R. Mitchell, J. Proft (Eds.), Proceedings of the
International Conference on Shape Memory and Superelastic Technologies,
2006, pp. 409–426.
[57] S.A. Padula, G. Bigelow, R.D. Noebe, D. Gaydosh, A. Garg, in: B. Berg,
M.R. Mitchell, J. Proft (Eds.), Proceedings of the International Conference on
Shape Memory and Superelastic Technologies, 2007, pp. 787–802.
[58] J. Cui, Y.S. Chu, O.O. Famodu, Y. Furuya, J. Hattrick-Simpers, R.D. James,
A. Ludwig, S. Thienhaus, M. Wuttig, Z.Y. Zhang, I. Takeuchi, Nat. Mater. 5
(2006) 286–290.
[59] K.F. Hane, T.W. Shield, Acta Mater. 47 (1999) 2603–2617.
[60] S.A. Padula, R. Vaidyanathan, D. Gaydosh, S. Qiu, R.D. Noebe, G. Bigelow,
A. Garg, Metall. Mater. Trans. 43A (2012) 4610–4621.
[61] A. Pelton, J. Mater. Eng. Perform. 20 (2011) 613–617.
[62] K. Gall, M.L. Dunn, Y. Liu, P. Labossiere, H. Sehitoglu, Y. Chumlyakov, J. Eng.
Mater. Technol.- ASME. 124 (2002) 238–245.
[63] G. Kang, Q. Kan, L. Qian, Y. Liu, Mech. Mater. 41 (2009) 139–153.
[64] H. Sehitoglu, R. Anderson, I. Karaman, K. Gall, Y. Chumlyakov, Mater. Sci. Eng.,
A 314 (2001) 67–74.
[65] X. Wang, B. Xu, Z. Yue, J. Alloys Compd. 463 (2008) 417–422.
[66] P.K. Kumar, U. Desai, J.A. Monroe, D.C. Lagoudas, I. Karaman, G. Bigelow,
R.D. Noebe, Mater. Sci. Eng., A 530 (2011) 117–127.
[67] W.J. Moberly, J.L. Proft, T.W. Duerig, R. Sinclair, Acta Metall. Mater. 38 (1990)
2601–2612.