Intermetallics 107 (2019) 24–33

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

Correlation between the thermal and superelastic behavior of Ni50- T

xTi35Zr15Cux shape memory alloys

W.C. Kima, Y.J. Kima, J.S. Kima, Y.S. Kima, M.Y. Nab, W.T. Kimc, D.H. Kima,∗
a
Department of Materials Science and Engineering, Yonsei University, Seoul, 03722, South Korea
b
Advanced Analysis Center, Korea Institute of Science and Technology, Seoul, 02792, South Korea
c
Department of Optical Engineering, Cheongju University, Cheongju, 28503, South Korea

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

Keywords: The alloying effect of Cu on thermal and mechanical behavior in Ni50-xTi35Zr15Cux (x = 0, 3, 5, 10, 15 at.%)
Shape-memory alloys shape memory alloys has been systematically investigated in the present study. The addition of Cu changes the
Thermal properties lattice parameters and expands the unit cell volume of B2 austenite and B19' martensite. With alloying Cu, the
Martensitic transformation temperature for austenite ↔ martensite transformation tends to decrease, and the transformation from B2
Mechanical properties
austenite to B19' martensite occurs in a single step mode. The decrease of transformation temperature with
Superelasticity
alloying Cu is attributed to the chemical stabilization of B2 (destabilization B19') which is reflected by the
decrease of the transformation enthalpy. The stabilization of B2 comes along with the increase of valence
electron concentration and non-basal shear modulus resisting to transformation into B19' . While, the destabi-
lization of B19' structure is represented by the increase of monoclinic angle. When compared to the ternary
Ni49.5Ti50.5-xZrx (x = 0, 3, 5, 10, 15, 18, 20 at. %) and Ni50-xTi50Cux (x = 0, 2.5, 5, 7.5, 10 at. %) alloys, the
stabilization of B2 (destabilization B19') is more pronounced in the NieTieZreCu alloys investigated in the
present study. Due to the change of thermal and structural properties with alloying Cu, the temperature de-
pendence of stress for inducing martensitic transformation gradually decreases and the superelastic window is
enlarged. As a result, the superelastic recovery is enhanced with alloying Cu.

1. Introduction induced martensite (Md). The stress-induced martensitic transformation

Among various shape memory alloys (SMAs), NieTi alloy is the
most preferred SMA for many fields of application due to its stability,
feasibility and better thermomechanical properties [1–4]. One of the
unique features for the NiTi alloy is that it can recover back to its ori-
ginal shape from the deformed state based on the thermoelastic mar-
tensitic transformation. The recovery back to the original shape can be
proceeded by heating or releasing stress, which is called as shape
memory effect (SME) or superelasticity (SE), respectively [5–8]. In
general, SME starts from the form of thermally induced twinned mar-
tensite which forms by self-accommodation of martensitic variants
below the martensite finish temperature (Mf). When the twinned mar-
tensite is deformed, macroscopic shape change is accompanied with
detwinning process. Subsequent heating above the austenite finish
temperature (Af) results in a reverse transformation from martensite to
austenite, leading to shape recovery to its pre-deformed state. On the
other hand, SE is manifested in the state of austenite at the temperature
range between Af and the upper limit temperature for deformation
gives rise to a large reversible strain up to ∼8% and recovers back to its
initial austenite state after unloading due to thermodynamic destabili-
zation of martensite. By using such unique properties, the SMAs can be
applied to extensive industrial fields such as aerospace, automotive,
MEMS and biomedical industries which require various operating
conditions from cryogenic to high temperature range [9–12]. Thus, it is
of importance to have a clear understanding on the thermal properties
including transformation temperature, hysteresis and transformation
path in NiTi-based SMAs.
There are two typical ways to tune the transformation behavior: 1)
by microstructural control via thermomechanical treatment [13,14];
and 2) by tailoring chemical composition by adding proper alloying
elements [15,16]. For instance, grain refinement by cold working sta-
bilizes the austenite structure [17], limiting the space for formation of
martensite variant, and thereby decreasing the transformation tem-
perature in NieTi and Cu based SMAs [13,18,19]. Ni4Ti3 precipitates
which appear depending on the various aging conditions in Ni-rich
NieTi alloys cause local strain field around them [20], changing the

∗
Corresponding author.
E-mail address: dohkim@yonsei.ac.kr (D.H. Kim).

https://doi.org/10.1016/j.intermet.2019.01.005
Received 7 December 2018; Received in revised form 4 January 2019; Accepted 4 January 2019
Available online 12 January 2019
0966-9795/ © 2019 Elsevier Ltd. All rights reserved.
W.C. Kim et al.
transformation path from B2→B19' to B2→R→B19' [21,22]. The effect
of alloying element on the thermal behavior of NieTi based SMAs have
been demonstrated experimentally in the past. In ternary alloy systems,
all but a few elements such as Zr, Hf, Pd, Pt and Au [15], most of the
micro-alloying elements are known to decrease the transformation
temperature [23]. Due to the limitation of temperature, below 373 K, in
binary NieTi SMAs, Zr addition replacing Ti-site has received an at-
tention because of potential applicability as high temperature SMAs as
well as cost-effectiveness in raw material price [24]. In addition, it has
been reported that substituting Cu for Ni enhances the SME by reducing
the transformation hysteresis and the dependence of transformation
temperatures on chemical composition. Such advantages are attributed
to the change of transformation path from single-step transformation
(B2→B19') to two-step transformation (B2→B19→B19') when the Cu
content is higher than 7.5 at.% [25]. Since the transformation tem-
perature and path are sensitively affected by even slight change of the
alloy composition [5], the thermal properties of NieTi based SMAs can
be more effectively tuned by tailoring alloy composition rather than
thermomechanical treatment.
The thermal properties of NieTi based SMAs depending on alloying
elements can be estimated by the relative stability of austenite and
martensite [26,27], i.e. the transformation from B2 austenite to B19'
martensite is thermodynamically possible below the temperature when
the chemical Gibbs free energy of martensite is lower than that of
austenite [28]. The driving force for austenite → martensite transfor-
mation is given by the chemical enthalpy change (ΔHchem), representing
the difference of structural stability as the sum of interatomic binding
energy of each phase. Therefore, ΔHchem can be reflected by the para-
meters such as nonbasal shear modulus (C44) of B2 austenite, valence
electron concentration (Cv) and the monoclinic angle (β) of B19' mar-
tensite. The addition of Zr in binary NieTi alloy decreases C44 and Cv,
while and increases β [24,28], implying the destabilization of B2. While
the addition of Cu increases C44 and Cv, and decreases β [21,30], im-
plying the stabilizaition of B2. However, in order to induce the nu-
cleation of martensite, additional driving force is required to overcome
the non-chemical energy barrier [28]. The non-chemical energy barrier
is affected by two factors, i.e. stored elastic energy and frictional work,
which can be estimated by considering the microstructural or crystal-
lographic factors. For instance, with decreasing grain size, the inter-
facial motion of the martensite variants is limited (i.e. increase in
frictional work) due to high fraction of grain boundary and the self-
accommodation of martensite variants becomes difficult (i.e. increase
in stored elastic energy) [13]. The precipitates which can be formed
during casting or annealing treatment constrain the martensite growth
and increase the frictional work [31]. Besides, the geometrical simi-
larity reflected by the parameters such as β or lattice compatibility
indicator (λ 2) influences on the non-chemical energy. With increasing
the geometrical similarity (i.e. decrease in β and λ 2 close to 1), both the
stored elastic energy and the frictional work can be decreased.
On the other hand, the mechanical behavior of NiTi-based SMAs are
also affected by the thermal and structural properties. The stress for
inducing martensitic transformation (σ 1) follows the thermodynamic
Clausius-Clapeyron relationship [5,32]. According to the relation, it can
be varied with the operating temperature, thermodynamic parameters
and transformation shear strain (ε tr). The effect of Cu addition on the
temperature dependence of σ 1 has been studied in NieTieCu system
showing the B2↔B19 transformation [25], while the effect of Zr has not
been investigated in detail due to low slip stress at high operating
temperature [33]. In addition, the recovery strain by SE is an important
factor in evaluating the actual applicability of NieTi based alloy
system. SE is influenced by the parameters mentioned above, since it
results from the competitive interaction between reversible martensitic
transformation and irreversible slip deformation.
So far, many research works on ternary element addition have led to
a great improvement in SMA technology. However, in order to meet the
recent requirement for more enhanced properties of SMAs, there is a
25
Intermetallics 107 (2019) 24–33
great demand for the development of new multicomponent SMAs
overcoming the limit of existing NiTi-based ternary alloy systems.
Recently, D. Canadinc et al. have found an ultra-high temperature SMA
in quinary (Ni,Pd)50(Ti,Hf,Zr)50 alloy showing Af higher than 973 K due
to the effect of high configurational entropy [34]. SMA with near-zero
hysteresis by doping a small amount of Pd in NiTiCu ternary alloy have
been developed [35,36]. However, to the best of authors’ knowledge,
despite the attractive effect of Cu on the transformation behavior in
NieTi alloys, the alloying effect of Cu in quaternary NiTiZrCu SMA has
not been systematically explored before.
In this paper, we demonstrate the variation of shape memory
characteristics, especially focused on the thermal and mechanical be-
havior, when substituting Cu for Ni in NiTiZr alloy. With increasing Cu
content, the quaternary Ni50-xTi35Zr15Cux (x = 0, 3, 5, 10, 15 at. %)
alloys show a sharp decline in the transformation temperature ex-
hibiting a single-step transformation from B2 to B19'. Furthermore, it is
revealed that the superelastic window between Af and Md increases
with the addition of Cu. In order to reveal the origin of the variation in
transformation temperature and superelastic behavior, structural and
thermodynamic parameters of B2 and B19' phases have been in-
vestigated in detail. To discuss the compositional dependence of Ms,
ΔH, β and λ 2 were evaluated for the Ni50-xTi35Zr15Cux alloys. For sys-
tematic explanation, these parameters were compared with parameters
estimated from the previously reports on ternary Ni49.5Ti50.5-xZrx
(x = 0, 3, 5, 10, 15, 18, 20 at. %) and Ni50-xTi50Cux (x = 0, 2.5, 5, 7.5,
10 at. %) alloys.
2. Experimental
The quaternary alloy ingots with nominal composition of Ni50-
xTi35Zr15Cux (x = 0, 3, 5, 10, 15 at.%) were produced by plasma arc
melting under a Ti-gettered high purity argon atmosphere. Each ingot
was re-melted for five times to achieve chemical homogeneity. After
that, cylindrical specimens with 2 mm diameter were obtained by
suction casting into a water-cooled copper mold. In order to remove
segregation during casting process, each specimen was sealed with
argon-filled quartz tube, homogenized at 1223 K for 72 h and then
subsequently quenched into water. In order to evaluate the thermal
properties of the alloys, differential scanning calorimetry (DSC, Netzsch
DSC 200F) analysis was performed in the temperature range between
123 K and 483 K. In addition, to evaluate the temperature dependence
of the lattice parameters of the crystal, high temperature X-ray dif-
fraction (XRD, Bruker D8 advance) with Cu Kα (λ = 1.5405 Å) for a
range of 2θ = 20° ∼ 80° was performed at room temperature, 503 K,
533 K and 563 K. The microstructure was investigated using a scanning
electron microscope (SEM, JEOL JSM 7100F) equipped with an energy
dispersive X-ray spectrometer (EDS, EDAX). The compressive test was
performed using a thermo cyclic tester (MTDI) at a strain rate of 1 ×
10−4 s−1. The superelastic response was investigated by cyclic loading/
unloading up to 8% strain level at Af +30 K (for Ni35Ti35Zr15Cu15: Af
+50 K) .
3. Results
The crystal structure of as-homogenized Ni50-xTi35Zr15Cux (x = 0, 3,
5, 10, 15 at.%) quaternary alloys was identified by XRD at room tem-
perature, as shown in Fig. 1. With increasing Cu content, it is clearly
observed that the fraction of B19' martensite decreases, while that of B2
austenite increases. Ni50Ti35Zr15, Ni47Ti35Zr15Cu3 and Ni45Ti35Zr15Cu5
alloys exhibit the diffraction pattern from monoclinic B19', while
Ni40Ti35Zr15Cu10 alloy shows the pattern from cubic B2 with minor
fraction of B19'. When Cu content reaches 15 at.%, the peaks from
B19'martensite completely disappears. Instead, the diffraction peaks
from B2 together with weak intensity peaks from (Ti,Zr)2(Ni,Cu) phase
are observed. The XRD result indicates that the stability of B2 increases,
i.e. austenite↔martensite transformation temperature decreases with
W.C. Kim et al.
Fig. 1. Room temperature XRD patterns obtained from the as-homogenized
Ni50-xTi35Zr15Cux (x = 0, 3, 5, 10, 15 at.%) alloys.
increasing Cu content. Here, it is worth to mention that B19 martensite
which has been reported to be present in ternary NieTieCu alloys [25]
is not observed in the present alloys. It can be attributed to more strong
resistance to transformation into B19 indicated by the variation of shear
modulus. This will be further discussed in the following discussion
section. In order to get more information on the effect of Cu addition on
crystal structure, lattice parameters of B2 and B19' were calculated
from the XRD results and summarized in Table 1. Since the thermal
expansion influences on the change of lattice parameter at high tem-
perature, the lattice parameter of B2 was measured at three different
temperatures and was fit to Gaussian function. Considering that the Af
temperature of Ni50Ti35Zr15 is ∼456 K (Table 2), the operating tem-
perature of high temperature X-ray diffraction was set to 503 K, 533 K
and 563 K to guarantee the austenite state. As shown in Fig. 2(a),
(110)B2 diffraction peak in the patterns obtained from the Ni50Ti35Zr15,
Ni47Ti35Zr15Cu3 and Ni45Ti35Zr15Cu5 alloys shifts toward lower angle-
side with increasing temperature due to the thermal expansion, as ex-
pected. It can be further noticed that the 2θ value for (110)B2 diffraction
peak decreases slightly with increase of Cu content at the same mea-
suring temperature, for example, at 563 K, 2θ is 41.131° for
Ni50Ti35Zr15, 41.102° for Ni47Ti35Zr15Cu3 and 41.080° for
Ni45Ti35Zr15Cu5 alloys, respectively. Although the diffraction pattern
from B19' in Ni40Ti35Zr15Cu10 and Ni35Ti35Zr15Cu15 alloys could be
obtained from low temperature XRD, it was not sufficient to calculate
the lattice parameter of the low symmetric monoclinic phase. As an
alternative, the lattice parameter of the martensite in Ni40Ti35Zr15Cu10
and Ni35Ti35Zr15Cu15 alloys were obtained by linear regression of the
date from the Ni50Ti35Zr15, Ni47Ti35Zr15Cu3 and Ni45Ti35Zr15Cu5 alloys,
referring to the previous cases reported in NieTi based ternary and
quaternary alloys [37,38]. The lattice parameters for B2 and B19’ ob-
tained in the present alloys are listed in Table 1. As shown schemati-
cally in Fig. 2 (b), it is clear that the cubic lattice parameters ao and the
Table 1
Lattice parameters of B2 austenite and B19' martensite of the as-homogenized Ni50-xTi35Zr15Cux (x = 0, 3, 5, 10, 15 at.%) alloys. And the corresponding eigenvalues
(λ 1, λ 2 and λ 3). of the deformation matrix and volume change (ΔV/2*VB2) accompanied with martensitic transformation.
ao (Å ) a(Å ) b(Å ) c(Å )
Ni50Ti35Zr15 3.094 3.055 4.117 4.890
Ni47Ti35Zr15Cu3 3.097 3.062 4.123 4.862
Ni45Ti35Zr15Cu5 3.099 3.066 4.128 4.844
Ni40Ti35Zr15Cu10 3.105 3.075 4.138 4.801
Ni35Ti35Zr15Cu15 3.110 3.084 4.148 4.757
26
Intermetallics 107 (2019) 24–33
martensite lattice parameter a increase significantly (the martensite
lattice parameter b increase only slightly), while the martensite lattice
parameter c and β decrease with the addition of Cu. Using the data of
lattice parameters, unit cell volume and transformational volume ratio
(V19'/2*VB2) were calculated, as shown in Fig. 2 (c). Firstly, it can be
noticed that the unit cell volume of B19' and B2 expands with in-
creasing Cu content. Considering that the atomic radius of Cu is almost
similar to that of Ni (Ni: 125 p.m., Cu: 128 p.m.), the lattice expansion
with increasing Cu content can be ascribed to the lower interatomic
bond strength between Cu and the constitute elements than Ni, which
can be verified from the mixing enthalpy values shown in Fig. 2(d), i.e.
CueTi: 9 kJ/mol, CueZr: 23 kJ/mol, NieTi: 35 kJ/mol and NieZr:
49 kJ/mol. The similar trend has been reported in ternary NieTieCu
SMAs [31]. Secondly, it can be noticed that the volume difference be-
tween the two phases gradually decreases with Cu content increase.
This result implies that lower interfacial energy would be introduced
with alloying Cu during the transformation.
The thermal behavior of the alloys was investigated using a DSC in
the range from 123 K to 483 K, as shown in Fig. 3 (a). The transfor-
mation temperatures including martensite finish temperature (Mf),
martensite peak temperature (Mp), martensite start temperature (Ms),
austenite start temperature (As), austenite peak temperature (Ap) and Af
obtained from the DSC analysis are listed in Table 2. During heating and
cooling process, all the alloys show only a single transformation peak.
Furthermore, it is clear that all the transformation temperatures in-
cluding Ms, Mf, As and Af decrease with increasing Cu content. Fig. 3(b)
shows the compositional dependence of the peak temperatures (Ap and
Mp). The slope of the compositional dependence for Ap and Mp calcu-
lated using linear regression method was −15.15 K/(1 at.% Cu) and
−15.53 K/(1 at.% Cu), respectively. It is noticeable that the slopes for
Ap and Mp are almost identical, implying that the thermal hysteresis
(ΔTH) difference is not large with the variation of alloy composition.
The ΔTH for each alloy (ΔTH =Af−Ms) is included in Table 2. In addi-
tion, the transformation enthalpy from austenite to martensite (ΔH AM)
and from martensite to austenite (ΔH MA) was calculated from DSC
traces shown in Fig. 2 (a). As listed in Table 2, both the ΔH AM and ΔH MA
decrease with increasing Cu content. The transformation enthalpy is not
only associated with the relative stability of martensite and austenite
but also the transformation strain during martensitic transformation.
Thus, this result implies that the Cu addition decreases the lattice dis-
tortion accompanied with martensitic transformation.
In order to compare the microstructure of the alloys, back scattered
electron (BSE) SEM images were obtained from the central region of the
as-homogenized rod specimens. As shown in Fig. 4, Ni50Ti35Zr15,
Ni47Ti35Zr15Cu3 and Ni45Ti35Zr15Cu5 alloys consist of two types of
matrix phases; B2 austenite showing gray contrast and B19' martensite
showing same gray contrast as B2 austenite, but stepped surface due to
the formation of thermally induced martensite during cooling. While,
Ni40Ti35Zr15Cu10 and Ni35Ti35Zr15Cu15 alloys consist of single B2 aus-
tenite matrix, as expected from the XRD result. In all SEM images,
submicron-sized particles with black contrast are present rather
homogeneously. The particles were identified as (Ti,Zr)2(Ni,Cu) by EDS
analysis (the average composition by EDS: 49.89 at.% Ti, 15.17 at% Zr,
32.75 at. % Ni, 2.2 at.% Cu). The volume fraction of (Ti,Zr)2(Ni,Cu) in
the alloys investigated in the present study was similar.
β (°) λ1 λ2 λ3 Δ V/2*VB2(%)
102.31 0.9407 0.9163 1.1764 1.40
101.10 0.9414 0.9263 1.1625 1.37
100.55 0.9418 0.9304 1.1550 1.20
98.79 0.9423 0.9438 1.1336 0.82
97.09 0.9430 0.9562 1.1128 0.34
W.C. Kim et al. Intermetallics 107 (2019) 24–33

Table 2
Thermal properties related to forward/reverse martensitic transformation of the as-homogenized Ni50-xTi35Zr15Cux (x = 0, 3, 5, 10, 15 at.%) alloys.
Composition Mf(K) Mp(K) Ms(K) As(K) Ap(K) Af(K) ΔTH To(K) ΔH AM(J/g) ΔH MA(J/g) ΔS AM(mJ/g) ΔG AM(J/g)

Ni50Ti35Zr15 385.8 405.6 414 438.5 452 458.8 44.8 436.4 −25.52 24.62 −58.5 −1.31
Ni47Ti35Zr15Cu3 333.1 358.1 370.9 402.9 417.2 429.7 58.8 400.3 −19.23 18.09 −48.0 −1.41
Ni45Ti35Zr15Cu5 323.8 337.7 352 379.7 390.2 407 55.0 379.5 −15.59 15.08 −41.1 −1.13
Ni40Ti35Zr15Cu10 245.8 256.7 267 298.4 310.4 319.4 52.4 293.2 −10.02 10.58 −34.2 −0.90
Ni35Ti35Zr15Cu15 143.3 171.5 189.1 208.5 228 246.1 57.0 217.6 −5.17 6.64 −23.8 −0.68

Fig. 5 shows the results of compression test and 8% cyclic loading/
unloading test performed at Af+30 K (Ni35Ti15Zr35Cu15: at Af+50 K).
The measured mechanical properties including σ 1, martensite yield
stress (σ 2), residual strain after cyclic deformation (ε r) are listed in
Table 3. Ni45Ti35Zr20 and Ni40Ti35Zr17Cu3 alloys exhibit conventional
deformation behavior; yielding-plastic deformation-fail with showing
little sign of superelastic effect, however Ni45Ti35Zr15Cu5
Ni40Ti35Zr15Cu10 and Ni35Ti35Zr15Cu15 alloys show typical 4-stage de-
formation behavior which is typical for superelastic alloys; elastic de-
formation of austenite (stage I), stress induced martensitic transfor-
mation (stage II), elastic deformation of martensite (stage III) and
plastic deformation of martensite (stage IV). As shown in Table 3, σ 1
decreases from 1136 MPa to 640 MPa with increasing Cu content from 0
to 15 at.%, while ε r decreases from 2.25% to 0.44%. Therefore,
Ni35Ti35Zr15Cu15 alloy exhibit the best superelastic property among the
alloys investigated in the present study.
4. Discussion
4.1. Variation of Ms with Cu content
The transformation temperatures of SMAs can be determined by
relative thermodynamic stability of B2 austenite and B19' martensite
[26,27]. Thus, the effect of Cu content on the transformation tem-
peratures is considered using the thermodynamic parameters which can
be achieved from the DSC result in Fig. 3(a). The chemical equilibrium
temperature (To) between B2 austenite and B19' martensite can be
obtained by following equation:
To= (Ms + Af)/2 (1)

Fig. 2. (a) High temperature XRD patterns obtained from the as-homogenized Ni50Ti35Zr15, Ni47Ti35Zr15Cu3 and Ni45Ti35Zr15Cu5 alloys measured at 503 K, 533 K and
563 K. The peak near 2θ = 41° is indexed to (110) plane of B2 austenite; (b) calculated room temperature lattice parameters of B2 austenite and B19' martensite as a
function of Cu content; (c) variation of unit cell volume of B2 austenite and B19' martensite and their ratio depending of Cu content; and (d) heat of mixing among the
constituent elements in the NieTieZreCu alloy system.

27
W.C. Kim et al.
Fig. 3. (a) DSC traces obtained from the as-homogenized Ni50-xTi35Zr15Cux (x = 0, 3, 5, 10, 15 at.%) alloys; and (b) the dependence of transformation peak tem-
peratures (Ap and Mp) on Cu content in the as-homogenized Ni50-xTi35Zr15Cux (x = 0, 3, 5, 10, 15 at.%) alloys.
Then, the entropy change for forward martensitic transformation
(Δ SAM) can be calculated by the equation:
ΔSAM=(ΔHAM)/To
As shown in Table 2, both the values of |ΔH AM| and |ΔSAM| decrease
with increasing Cu content. According to Cohen and Salzbrenner [28],
the total enthalpy change (ΔH total), corresponding to the area below the
peaks from DSC analysis, can be expressed as the sum of ΔH chem, stored
elastic energy (ΔH elast) and frictional work (ΔH fric):
ΔHtotal = ΔHchem + ΔHelast + ΔHfric (3)
H chem is, in principle, determined by chemical structural difference
between austenite and martensite which depends on chemical compo-
sition and crystal structure. It works as a driving force in the forward
martensitic transformation (i.e. negative value). By contrast, ΔH elast
and ΔH fric act as a barrier for nucleation and growth of martensite
variants during forward martensitic transformation (i.e. positive va-
lues). Since ΔH elast, is the reversible energy which is stored during the
forward martensitic transformation and released during the reverse
transformation, it actually can be determined by the volume change
during transformation. On the other hand, ΔH fric is the irreversible
energy which is dissipated during the forward or reverse transforma-
tion, actually signifying internal resistance and contributing to the
Fig. 4. The back-scattered SEM images obtained from the as-homogenized Ni50-xTi35Zr15Cux (x = 0, 3, 5, 10, 15 at.%) alloys: (a) Ni50Ti35Zr15; (b) Ni47Ti35Zr15Cu3; (c)
Ni45Ti35Zr15Cu5; (d) Ni45Ti35Zr15Cu10; and (e) Ni35Ti35Zr15Cu15.
Intermetallics 107 (2019) 24–33
hysteresis during thermal cycling.
The transformation volume change (Δ V/2*VB2) was calculated
using the lattice parameters listed in Table 1. The calculation result for
(2)
each alloy is listed in Table 1, indicating that Δ V/2*VB2 decreases with
increasing Cu content; from 1.4% for Ni50Ti35Zr15 alloy to 0.34% for
Ni35Ti35Zr15Cu15 alloy. Thus, it can be inferred from the Δ V/2*VB2 data
that the contribution of ΔH elast to ΔH total should decrease with in-
creasing Cu content. Moreover, since the contribution of ΔH fric on total
enthalpy change is small enough to be negligible [28] as well as the
difference in Δ TH (listed in Table 2) for each alloy is not so large, it can
be concluded that the decrease in |ΔH AM| comes from the lowered
|ΔH chem| resulting from the decrease of chemical driving force,
|ΔH chem|. On the other hand, the total entropy change (ΔS total) can be
expressed as a sum of vibrational (ΔSvib), configurational (ΔSconfig),
electrical (ΔSelec) and magnetic (ΔS mag) entropy change [39–41]:
ΔStotal = ΔSvib + ΔSconfig + ΔSelec + ΔSmag (4)
Since the martensitic transformation takes place in a diffusionless
manner, the contribution of ΔS config is zero. ΔSmag also can be dis-
regarded, because the present alloys show no magnetic behavior. ΔS elec
is associated with the valence electron concentration and its contribu-
tion is usually quite small to be ignored [39]. Thus, the decrease of
28
W.C. Kim et al.
Fig. 5. The compressive stress-strain curves and superelastic responses of the
as-homogenized Ni50-xTi35Zr15Cux (x = 0, 3, 5, 10, 15 at.%) alloys performed at
Af+30 K (for Ni35Ti35Zr15Cu15 alloy, Af+50 K).
ΔS total with increasing Cu content results from the decrease of ΔS vib by
substituting low density Ni (8.908 g/cm3) with high density Cu (8.96 g/
cm3) [41].
The effect of such change in thermodynamic parameters on the
transformation temperature can be visualized by illustrating the dif-
ference in Gibbs free energy curves of B2 austenite and B19'martensite,
as shown in Fig. 6. Based on J. Frenzel's report [42], the compositional
dependence of Ms can be described schematically by plotting Gibbs free
energy - temperature curves. Assuming the entropy of B2 and B19'
phases is constant regardless of the alloy composition, the To shifts to
lower value (from To To') by decreasing the |Δ HAM| (from Δ H to ΔH'),
as shown in Fig. 6(a). By contrast, when the Δ HAM is constant, the To
shifts to higher value by decreasing the |ΔSAM| (from Δ S to ΔS' ), as
shown in Fig. 6(b). If only the ΔSAM is considered for Ms change, Ms
should increase with Cu content (|Δ SAM| decreases with Cu content, in
Table 2), however, the result is opposite (Ms decreases with Cu content,
in Table 2). Therefore, it can be concluded that the variation of the
transformation temperature depending Cu content in the present study
is attributed to the |Δ HAM| during transformation.
Fig. 7 schematically shows the effect of Cu content on Ms, β, Δ HAM
and λ 2 in Ni50-xTi35Zr15Cux alloys. For comparison, the parameters for
the effect of Zr in Ni49.5Ti50.5-xZrx alloys and Cu in Ni50Ti50-xCux alloys
are also included by calculating from the previously reported results
[24,31,41–43]. As shown in Fig. 7(a), the addition of Zr increases Ms in
NieTieZr alloys, while Cu decreases in both NieTieCu and Nie-
TieZreCu alloys. In particular, Ms of NieTieZr alloys increases sharply
when Zr content is above 10 at.%. In order to compare the role of Cu in
NieTieCu and NieTieZreCu alloys, the slope of Ms vs xCu was cal-
culated using linear regression method. The result shows that the de-
pendence of the slope on Cu content appears more sharply in
Table 3
Mechanical properties of the as-homogenized Ni50-xTi35Zr15Cux (x = 0, 3, 5, 10, 15 at.%) alloys: stress for inducing martensitic transformation (σ 1), martensite yield
stress (σ 2), residual strain after cyclic deformation (ε r), maximum transformation strain (ε max), theoretical density (ρ t) and the slope (dσ/dT) .
Ni50Ti35Zr15 Ni47Ti35Zr15Cu3
σ1 (MPa) 1136±14 1105±11
σ2 (MPa) 1548±19 1612±12
εr (%) 2.25 2.0
εmax 0.174 0.160
ρt (g/cm3) 6.703 6.701
(dσ / dT ) 2.25 2.01
Intermetallics 107 (2019) 24–33
NieTieZreCu alloy, −15.1 °C /(1 at.% Cu) than in NieTieCu alloy,
−6.6 °C/(1 at.% Cu). In addition, the transformation path of the
ternary alloys changes from single-step (B2→B19') to double-step (B2→
B19→B19') above 7.5 at.% Cu [25], while the quaternary alloys in-
vestigated in the present study show single-step martensitic transfor-
mation (B2→B19'). The different transformation temperature and path
can be explained by the shear softening phenomenon [44]. For the
intermediate transformation into B19 to take place, the softening in
basal plane shear {110 } < 11̄0 > of B2 austenite should occur. More-
over, the transformation into B19' requires additional softening in non-
basal plane shear {001} < 11̄0 > . Such martensitic transformation can
take place when the elastic modulus of basal shear (C') or non-basal
shear (C44) of B2 austenite reaches a critical value which is not sensitive
to alloy composition, and only can be reached by decreasing tempera-
ture [45]. In addition, the transformation path is determined by the
anisotropy factor (A) defined by the ratio of C44 to C' [21]. When C44 is
softened more quickly than C' with decreasing temperature, i.e. when
the A value decreases, the B19' martensitic transformation takes place,
while in the opposite case the B19 martensitic transformation occurs.
Since the elastic modulus of alloy can be varied by composition and
temperature, the alloying element can change the transformation path
and temperature. It has been reported that the substitution of Zr for Ti
in NieTi alloys increases C', while decreases C44 [29]. Thus, with al-
loying Zr, the B19' martensitic transformation tends to take place. By
contrast, the substitution of Cu for Ni in NieTi alloys increases C44,
while decreases C' [21]. Consequently, with alloying Cu, the B19
transformation takes place more easily than B19' transformation due to
the increase of A value. In quaternary NieTieZreCu alloys, however,
since the pre-alloyed 15 at. % Zr already increase the C' value by ∼15%
in comparison with the binary Ni50Ti50 alloy [29], the addition of Cu is
not sufficient to increase the A value with decreasing temperature and
therefore the B19 transformation is suppressed. On the other hand, as
mentioned above, the Δ HAM effect can be coupled with Ms. Fig. 7(b)
shows the variation ofΔ HAM with Cu content in ternary and quaternary
alloys. It can be noticed that quaternary NieTieZreCu alloy shows
much more steep dependence on Cu addition than ternary NieTieCu
alloys, which is analogous to the trend of Ms, confirming the dominant
role of ΔH AM on Ms. This implies that the chemical driving force for
martensitic transformation, i.e. ΔH chem, is more significantly reduced in
the quaternary alloy due to the effect of strong stabilization of B2
(destabilization of B19') with alloying Cu.
The β of B19' martensite can be an indicator which represents the
crystallographic stability of the phase [42]. As the β comes closer to 90°,
the geometry of the B19' lattice becomes closer to that of B2 lattice,
implying that the crystallographic destabilization of B19' martensite
occurs. As shown in Fig. 7(c), the addition of Zr in NieTieZr alloys
increases the β away from 90°, while the Cu addition in NieTieCu and
NieTieZreCu gradually decrease the β close to 90°. Moreover, the
addition of Cu in the quaternary alloys show steeper decline of β than
the ternary alloys (NieTieCu: 0.2°/(1 at.% Cu), NieTieZreCu: 0.35°/
(1 at.% Cu)), indicating more powerful effect in destabilizing B19'
martensite.
In addition to the geometrical similarity of austenite and martensite,
the lattice compatibility also can be characterized by λ 2, the middle
Ni45Ti35Zr15Cu5 Ni40Ti35Zr15Cu10 Ni35Ti35Zr15Cu15 (Af +50)
839± 18 723± 9 640± 13
1785±20 1830± 15 1574±11
1.83 0.98 0.44
0.153 0.131 0.110
6.698 6.690 6.681
1.80 1.75 1.44
29
W.C. Kim et al. Intermetallics 107 (2019) 24–33

Fig. 6. Schematic illustrations of the effect of ΔH and ΔS variation on transformation temperature. (a) ΔH effect; (b) ΔS effect; and (c) dependence of |ΔHAM|, |ΔSAM|
and Ms on Cu content of the as-homogenized Ni50-xTi35Zr15Cux (x = 0, 3, 5, 10, 15 at.%) alloys during forward martensitic transformation.

eigenvalue of the deformation matrix converting the austenite lattice to
the martensite lattice [46]. The lattice deformation matrix, U, is de-
termined from the lattice parameters of B2 austenite and B19' mar-
tensite. The detailed calculations can be found in Ref. [46]. As λ 2 ap-
proaches to 1, the interfacial misfit of martensite and austenite
decreases, resulting in the reduction of elastic and interfacial energy
[31,47]. Furthermore, the nucleation of martensite becomes more easy
with lowering thermal hysteresis. It has been reported that as λ 2 is close
to 1, the thermal hysteresis is predicted to be smaller in NieTieCu and
NieTieZr alloys [48,49]. As can be seen in Fig. 7(d), in addition to the
correlation with thermal hysteresis, the λ 2 also can be coupled with Ms.
That is, Ms decreases with increasing lattice compatibility. Specifically,
λ 2 moves away from 1 with alloying Zr (i.e. increasing Ms) in ternary
NieTieZr alloys, but on the contrary it comes closer to 1 with alloying
Cu (i.e. decreasing Ms) in ternary NieTieCu and quaternary Nie-
TieZreCu alloys. Besides, the compositional dependence of λ 2 is re-
flected more sensitively in the quaternary alloys than in the ternary
alloys with the variation of Cu content.

Fig. 7. Thermal and geometrical parameters dependence on the content of alloying element in the Ni49.5Ti50.5-xZrx (x = 0, 3, 5, 10, 15, 18, 20 at. %), Ni50-xTi50Cux
(x = 0, 2.5, 5, 7.5, 10 at. %) and Ni50-xTi35Zr15Cux (x = 0, 3, 5, 10, 15 at.%) alloys. (a) Ms dependence on alloying element Cu and Zr; (b) ΔHAM dependence on
alloying element Cu and Zr; (c) β dependence on alloying element Cu and Zr; and (d) λ 2 dependence on alloying element Cu and Zr.

30
W.C. Kim et al.
Fig. 8. Relationship between Ms and Cv values of the Ni49.5Ti50.5-xZrx (x = 0, 3,
5, 10, 15, 18, 20 at. %) Ni50-xTi50Cux (x = 0, 2.5, 5, 7.5, 10 at. %) and Ni50-
xTi35Zr15Cux (x = 0, 3, 5, 10, 15 at.%) alloys.
The electronic structure of SMAs is concerned with transformation
temperature, because it determines the bond strength and elastic
properties [50,51]. With increasing the Cv, which participate in the
metallic bonds, the higher elastic modulus is expected. It is consistent
with the results of M. Zarinejad et al. [52], showing the decreasing
trends of Ms with increasing Cv in NieTi based SMAs. As shown in
Fig. 8(a), the ternary NieTieZr and NieTieCu alloys and the present
quaternary NieTieZreCu alloys follow the same trend. However, it is
noticeable that the sensitivity of Ms dependence on Cv is different be-
tween alloy systems. Especially, in spite of the same alloying element,
the quaternary NieTieZreCu alloys show a much steeper Ms depen-
dence on Cv than ternary Ni50-xTi50Cux alloys. It can be inferred that the
reinforcement in C44 modulus resisting against the B19' transformation
is greater in the quaternary alloys, implying the stabilization of B2
phase.
As can be seen the above results, the Ms is highly correlated with
ΔH AM, β, λ 2 and Cv. With decreasing Ms, the value of |ΔH AM| decreases,
the values of β and λ 2 approach to 90° and 1, respectively, and the Cv
value increases. The decrease of Ms means the stabilization of B2 aus-
tenite and/or the destabilization of B19' martensite. In thermo-
dynamics, since the ΔH indicates the driving force of a transformation,
the decrease of the driving force corresponds to the decrease of Ms. The
destabilization of B19' is elucidated by the geometrical parameter, β
and λ 2. As the β value comes closer to 90°, not only the structural de-
stabilization of B19' occurs more intensively, but also the geometrical
similarity between B2 and B19' increases. Though the geometrical si-
milarity helps the martensitic transformation by decreasing interfacial
misfit between the two phases, the structural destabilization has more
dominant effect on determining the Ms. It can be further identified from
the dominant effect of ΔH chem on ΔH AM. As the lattice compatibility is
improved with the increase of geometrical similarity, the λ 2 value close
to 1 can be coupled with the decrease of Ms. Along with the structural
destabilization of B19', the stabilization of B2 structure can be ex-
plained by the Cv value. Since the increased Cv value is attributed to the
increased shear modulus indicating the greater resistance to martensitic
transformation, the increased Cv indicates the structural stabilization of
B2 phase and contributes to the decrease of Ms. On the other hand,
though these parameters follow the common trends with Ms, the com-
positional sensitivity of these parameters differ in each alloy system. In
particular, when the same amount of Cu added, the more drastic var-
iation of these parameters can be observed in the quaternary
NieTieZreCu alloy than in the ternary NieTieCu alloy. This implies
31
Intermetallics 107 (2019) 24–33
Fig. 9. Schematic illustration of the effect of the decrease in Ms on the super-
elastic temperature window.
that the alloying effect of Cu on stabilizing B2 and destabilizing B19' is
greater in the quaternary NieTieZreCu alloy than in the ternary
NieTieCu alloy.
4.2. Superelastic behavior
The superelastic behavior of SMAs is a result of competitive inter-
action between irreversible slip deformation and reversible martensitic
transformation. The schematic illustration for the temperature depen-
dence of critical slip stress (σ s) and martensitic transformation stress
(σ m) of austenite phase is shown in Fig. 9. It has been well known that
the σ s of austenite gradually decreases with increasing operating tem-
perature [33]. Although it can be increased by substituting alloying
elements, in the present alloys, however, it is expected that no dramatic
effect would occur, since the difference in atomic radius of Ni and Cu is
not sufficiently large to arise matrix strengthening. The stress required
to induce martensitic transformation shows a linear variation as a
function of temperature, and it can be described as the Clausius-Cla-
peyron equation as follows [5,32]:
dσm/dT=(-ρΔHAM)/εtrTo=(-ρΔSAM)/εtr (5)
where the ρ is density of B2 austenite. Based on the equation, the
martensitic transformation requires higher stress with increasing op-
erating temperature. The slope of dσ/dT which depends on the alloy
composition can be determined by using equation (5). The thermo-
dynamic parameters such as ΔH AM, ΔSAM and T o can be obtained from
the DSC analysis shown in Table 2. The values of ε tr and ρ of the alloys
can be calculated from lattice parameters shown in Table 1. Assuming
that the Ti and Zr occupy the Ti-site, and Cu, and Ni occupy the Ni-site
of B2 austenite unit cell, respectively, the theoretical density (ρt ) is
simply given as follows:
ρt = ( ∑ ni wi )/(VB2NA) (6)
where ni is the number of i atoms in the B2 austenite unit cell, wi is
molar weight of i atom, V B2 is unit cell volume of B2 and N A is Avo-
gadro constant. In addition, by using the U, which is derived from
lattice parameters, the calculation of transformation strain is possible.
The matrix product of U and lattice vector of B2 austenite [uvw] results
in a lattice vector of B19' martensite [UVW]. From these two lattice
vector, ε tr is given as follows [53]:
εtr = (U 2 + V 2 + W 2)
(u2 + v 2 + w 2) − 1 (7)
Since the ε tr values differ from each lattice vector of cubic basis, the
W.C. Kim et al.
maximum transformation strain (ε max) value is considered to be able to
calculate dσ/dT of the present alloys. The calculated ρt , ε max and dσ/dT
are listed in Table 3. As shown in the table, with increasing Cu content,
the slope, dσ/dT decreases gradually from 2.25 MPa/K for Ni50Ti35Zr15
alloy to 1.44 MPa/K for Ni35Ti35Zr15Cu15 alloy. Therefore, the decrease
of σ 1 with alloying Cu in Fig. 5 & Table 2 can be described by the
smaller rate in changing of the slope, dσ/dT . Meanwhile, the tem-
perature for superelastic behavior, i.e. the superelastic window, is given
as a range from Af to Md, where the intersection point of σ s and σ m lines
as shown in Fig. 9. With increasing Cu content in the alloys, the wider
superelastic window is allowed due to high σ s and smaller slope of
dσ/dT . Furthermore, since the wider the superelastic window is, the less
slip deformation is involved in the total strain, it is reasonable that the
improvement in the superelastic recovery appears in high content Cu
alloys.
5. Conclusions
In the present study, the effects of Cu on the thermal and mechan-
ical behavior of quaternary Ni50-xTi35Zr15Cux (x = 0, 3, 5, 10, 15 at.%)
have been investigated. Based on the XRD and DSC analyses, the
structural and thermal parameters are deduced and it is found that
strong correlation exists among those parameters. The transformation
behavior and superelastic recovery depending on the Cu addition are
examined and the following important conclusions can be drawn:
(1) The addition of Cu in ternary NieTieZr alloy results in an expan-
sion of both the B2 austenite and B19' martensite unit cell. It leads
to the decrease of β and ΔV/VB2 and reduction of the geometrical
difference between B2 austenite and B19' martensite, indicating the
destabilization of monoclinic structure.
(2) The transformation temperatures (Mf, Ms, As and Af) and the ab-
solute value of transformation enthalpy (|ΔHAM|, |ΔHMA|) con-
tinuously decrease by alloying Cu. The forward/reverse martensitic
transformation occurs in a single-step mode. The absence of the B19
intermediate phase is due to the greater resistance to basal shear
softening, i.e. increased C' by 15 at.% Zr already present in the
quaternary Ni50-xTi35Zr15Cux alloy.
(3) The decrease in |ΔHAM| dominantly results from the reduction of
chemical driving force, ΔHchem, implying the structural stabilization
of B2 and destabilization of B19'. The increase of Cv results in an
increase of shear modulus, indicating the stabilization of B2 phase.
In addition, the destabilization of B19' is accompanied with the
enhancement in geometrical similarity, represented by the values of
β and λ 2 approaching to 90° and 1, respectively.
(4) Though the improvement in geometrical similarity helps the for-
mation of martensitic by reducing the elastic misfit and interfacial
energy, the contribution of these effects to the variation of Ms is
marginal. The result corresponds to the insignificant contribution of
ΔHelast and ΔHfric to ΔH.
(5) The degree of stabilization of B2/destabilization of B19' differ de-
pending on the alloy system, i.e. ternary NieTieZr and NieTieCu,
and quaternary NieTieZreCu alloy systems. When the addition of
Cu is considered, the values of Ms, ΔH, β, λ 2 and Cv show more
steeper dependence in the quaternary NieTieZreCu than in the
ternary NieTieCu alloys, implying greater effect in stabilization of
B2 (destabilization of B19') .
(6) The value of σ 1 for inducing martensitic transformation decreases
and the superelastic recovery is enhanced with the addition of Cu.
The decrease of σ 1 results from the smaller rate in change of the
slope, dσ/dT . The decrease of ε r is attributed to enlarged super-
elastic temperature window, resulting from the high σ s and the
lower slope of dσ/dT by alloying Cu.
32
Intermetallics 107 (2019) 24–33
Acknowledgements
This work was supported by the Samsung Science & Technology
Foundation.
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