NiTiHf-based shape memory alloys

H. E. Karaca*, E. Acar, H. Tobe and S. M. Saghaian

NiTiHf-based shape memory alloys have been receiving considerable attention for high
temperature, high strength and two-way shape memory applications since they could have
transformation temperatures above 100uC, shape memory effect under high stress (above
500 MPa) and superelasticity above 100uC. Moreover, their shape memory properties can be
tailored by microstructural engineering. However, NiTiHf-based alloys have some drawbacks
such as low ductility and high slope in stress induced martensite transformation region. In order to
overcome these limitations, studies have been focused on microstructural engineering by aging,
alloying and processing. It has been revealed that microstructural control is crucial to govern the
shape memory properties (e.g. transformation temperatures, matrix strength, shape recovery
strain, twinning type, etc.) of NiTiHf-based alloys. A summary of the most recent improvements on
selected NiTiHf-based systems is presented to point out their significant shape memory
properties, effects of alloying, aging and microstructure of transforming phases and precipitates.
Keywords: NiTiHf, High temperature shape memory alloys, Microstructure control, Precipitation hardening, Superelasticity, Work output

This paper is part of a special issue on Smart Materials

Introduction
Shape memory alloys (SMAs) are a unique class of
smart materials with the ability of changing their shapes
depending on the applied temperature, stress and in special case of ferromagnetic alloys, magnetic field. Shape
memory alloys can produce very high actuation strains,
stresses and work outputs as they undergo reversible
martensitic phase transformation.1 In addition to their
remarkable properties in actuation, vibration damping,
noise reduction and sensing, they are compact, robust,
lightweight, frictionless, quiet, environment-friendly (no
hydraulic liquids), easy to inspect and have low aftermarket costs for inspection and maintenance.24 Shape
memory alloys are playing a growing role in supplying key
actuation forces and sealing functions in oil and gas,
automotive, aerospace and biomedical industries.24 The
ability to remain elastic under very large deformation
makes SMAs potential candidates for superelastic devices
for civil structures.5,6 Moreover, their superelasticity, good
corrosion resistance, biological and magnetic resonance
compatibility and high bending resistance resulted in their
employment as the biomedical devices in the orthodontic,
orthopaedic, vascular, neurosurgical fields.7,8
Among the various SMA systems, NiTi alloys have
good dimensional stability, shape memory properties,
ductility and workability. Currently, NiTi alloys are the
most commercially viable SMAs and practically being
used in various medical and engineering applications
where the operating temperature is below 100uC.9 It has
been found that the transformation temperatures (TTs)
Department of Mechanical Engineering, University of Kentucky, Lexington,
KY 40506, USA
*Corresponding author, email karacahaluk@uky.edu

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2014 Institute of Materials, Minerals and Mining

Published by Maney on behalf of the Institute
Received 1 November 2013; accepted 23 June 2014
DOI 10.1179/1743284714Y.0000000598

of NiTi can be adjusted by tailoring the stoichiometry or

formation of precipitates.10,11 However, the TTs of
binary NiTi cannot be increased above 120uC. The
development of a shape memory material with properties similar to those of near equiatomic NiTi, but with
higher strength and TTs, especially above 100uC, is
urgently needed for a broad range of applications in the
aerospace, automotive and oil and gas industries to serve
as compact actuators for flow and clearance controls,
actuation tubes for rotors, moving or morphing surfaces
as well as inlet/exhaust configurations, linear actuators
and sealants.24
Ternary element addition to NiTi alloys is the most
promising method to obtain commercially available high
temperature shape memory alloys (HTSMAs) in the
near future.12 Ternary element addition should not only
increase the TTs, but also help to maintain the good
mechanical and shape memory properties of NiTi alloys.
It has been found that the addition of Hf, Zr, Pd, Pt and
Au elements to NiTi increases its TTs.2,9 Among those
elements, Pd, Pt and Au are very expensive and will limit
the use of their respective ternary alloys to some critical
applications only (i.e. aerospace), while Zr is associated
with high oxygen affinity.2,9,13 Among the potential
HTSMAs, due to its low cost, medium ductility and high
work output NiTiHf seems to be the most encouraging
HTSMA for a wide range of applications in the critical
100300uC temperature range.12
The TTs of NiTiHf alloys do not increase much up to
10 at-% Hf content, however, at chemical concentrations
higher than 10 at-%, they tend to increase linearly up to
525uC for 30 at-% Hf when Hf is added at the expense of
Ti.1416 Transformation temperatures of NiTiHf alloys
are not notably affected by a change in Ni composition as
long as the alloys are Ni-lean, but dropped steeply when

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Ni content is increased beyond the equiatomic (50 at-%)

composition, consistent with the behaviour of NiTi
alloys.1517
The main disadvantages of Ni-lean NiTiHf alloys are
their large hysteresis (.50uC), poor ductility at room
temperature, lack of cyclic stability due to the high stress
for the reorientation of martensite and detwinning, the
low strength for slip and poor formability.2,18 It should
be noted that Wojcik19 studied the possibility of the
commercialisation of the NiTiHf (Hf content less than
10 at-%) alloys and showed that hot rolling can be
successfully utilised to produce thin sheets. Another
drawback of the alloy is the absence of stress plateau
during phase transformation that results in the lack of
superelasticity. This behaviour has been attributed to the
simultaneous occurrence of stress induced martensite
(SIM) and dislocation slip.20,21 To increase the strength
for slip, NiTiHf alloys were severely deformed that resulted
in increased recoverable transformation strain, decreased
irrecoverable strain levels and thermal hysteresis under
constant stress experiments, as well as improved cyclic
stability.18 However, no superelasticity was observed due
to large hysteresis and low material strength.
Precipitation strengthening has been used to improve
the mechanical properties of NiTiHf alloys as a successful
method. Meng et al.22,23 revealed that it is possible to form
precipitates in Ni-rich NiTiHf alloys and TTs can be
increased drastically to temperatures above 100uC. They
have also reported that coherent precipitates increase the
matrix strength and enhance the thermal stability.22 If
the chemical composition is slightly Ni-rich with high Hf
content (15 to 20 at-% Hf), fine nanometer size precipitates which are face centred orthorhombic structure,
simply referred to as the H-phase,24,25 are formed upon
aging treatments. The formation of fine precipitates
provides high resistance to dislocation motion resulting
in exceptional strength and stability limiting residual
strain during transformation under isothermal and isobaric conditions.2628
Quaternary alloying and precipitation strengthening
have also been used to improve the overall behaviour of
NiTiHf polycrystalline and single crystal alloys. The shape
memory properties of heat treated Ni45?3Ti29?7Hf20Pd5 (at%) alloys in single crystalline and polycrystalline forms
have been reported.2933 The replacement of 5% Pd with
Ni of Ni50?3Ti29?7Hf20 alloy resulted in a very high strength
alloy that has high damping capacity of 35 J cm23
in polycrystalline form and 44 J cm23 in [111] oriented
single crystals.32-33 Transformation strain of 2% was
observed in aged [111] oriented Ni45?3Ti29?7Hf20Pd5 single
crystals under a compressive biasing stress of 1500 MPa.31
Moreover, perfect superelastic behaviour with recoverable
strain of 4?2% was observed in the solutionized condition
even when compressive stress levels as high as 2?5 GPa
were applied.32 However, it is also known that
Ni45?3Ti29?7Hf20Pd5 alloys are brittle, since they generally
fail after limited plastic deformation in compression and
during phase transformation in tension in superelasticity
experiments.34
It has been considered that low workability is one of
the main problems with NiTiHf alloys for practical use.
Kim et al.35 reported that an addition of Nb to NiTiHf
alloys caused the formation of a soft Nb-rich b phase
and improved the cold workability, although the TTs
and plastic strain in thermal cycling experiments under

NiTiHf-based shape memory alloys

stress were decreased. Cu has been another alloying

element to NiTiHf systems where, in general, it improved
the glass forming ability and thermal stability of NiTiHf
alloys while decreasing their TTs.36,37 NiTiHfCu alloys
have also demonstrated two-way shape memory effect.38
It has recently reported that Ni45?3Ti29?7Hf20Cu5 alloys
have the capability to recover compressive strains of 2%
above 100uC and two-way shape memory strain of 0?8%
above 80uC.39
Hsieh and Wu40 investigated the TTs and hardness
values of Ti50?52xNi49?5Zrx/2Hfx/2 (x5020 at-%)40 and
revealed that TTs can be increased from 50 to 323uC
with increased Zr and Hf contents. Their shape memory
responses under stress (e.g. constant stress thermal cycling,
superelasticity) have not been reported yet.
This article reviews the effects of alloying, aging and
processing on the shape memory properties and microstructure of NiTiHf-based alloys. Special attention is
given to recently developed Ni-rich NiTiHf-based alloys.

Transformation temperatures of NiTiHfbased shape memory alloys

Many studies have been conducted in order to gain the
fundamental understanding on how to change the TTs
of SMAs.41 It is known that chemical composition
alteration is very effective to change the properties such
as TTs, transformation strain and matrix strength of
SMAs. Figure 1a shows the effects of Ni content on the
Mp (martensite peak temperature) of NixTi902xHf10.16
It is clear that Mp is insensitive up to 50 at-% Ni and
then suddenly decreases to below 0uC with increased Ni
content.
Figure 1b shows the change in Mp as a function of
Hf.1416,42 It is clear that Mp does not change up to 3%
of Hf and then increases after 5%. Up to 10% Hf, the
increase of Mp is about 5uC/at-% Hf. As the Hf increases
beyond 10%, there is an abrupt increase of Mp by almost
20uC/at-% Hf in NiTiHf alloys and Mp reaches up to
400uC for 25% Hf.
Figure 2a shows the differential scanning calorimetry
responses of the Ni50?3Ti29?7Hf20 alloys after heat treatment at selected temperatures from 300 to 900uC for
3 h.27 Initially, TTs slightly decreased compared to the as
extruded (extruded at 900uC) material when aged at 300
and 400uC. Then, TTs increased with heat treatment
temperature up to 700uC and then TTs decreased. The
maximum Af (austenite finish temperature) was revealed
to be 210uC in Ni50?3Ti29?7Hf20 alloys aged for 3 h at
600uC. Figure 2b shows the change in TTs for Ni45?3
Ti29?7Hf20Pd5 polycrystalline specimens aged for 3 h at
temperatures between 400 and 900uC.33 The trend in TTs
with heat treatment temperature was similar to that
of Fig. 2a. The maximum Af was about 150uC in
Ni45?3Ti29?7Hf20Pd5 after aging at 600uC for 3 h. The
main reason for the TTs change with aging in the both
alloys could be attributed to the change in the chemical
composition of matrix33 due to the formation of precipitates that will be discussed in details in the microstructure part.
Zarinejad et al.41 revealed a practical relationship
between the chemical composition and TTs by considering the number (ev/a) and concentration (cv) of valence
electrons in NiTi-based alloys. The number of d and s
electrons is accepted as the number of valence electrons

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1 Mp temperature as a function a Ni and b Hf contents in NiTiHf alloys1416,42 (chemical compositions are in at-%)

for an atom in transition metals while the number of

valence electrons is considered to be p and s electrons for
an atom in non-transition metals.43 The number of
valence electrons of alloys can be calculated with the
following equation44
ev
B
C :::
(1)
~fA eA
v zfB ev zfC ev z
a
where fA, fB and fC are atomic fractions of A, B and C
B C
elements, eA
v ,ev ,ev are the related valence electrons for
the elements in an alloy system.
The following equation can be used to determine the
average concentration of valence electrons44
cv ~

B
C
:::
ev
fA eA
v zfB ev zfC ev z
~
et fA ZA zfB ZB zfC ZC z:::

(2)

where ZA, ZB and ZC are the atomic numbers of

elements A, B and C, respectively.
Figure 3 shows the relationships between the Ms
(martensite start temperature) (or Mp) and ev/a and cv in
NiTiHf-based SMAs.30,35,37,40,41,44,45 It is clear that the

TTs do not have a clear trend with ev/a while they

generally decrease with increasing cv. It is commonly
agreed that higher electron concentration results in
higher bulk (resistance to volume change) and shear
(resistance to shape change) moduli.44,46 Thus, the
concentration of the electrons may affect the strength
of atomic bonds in metallic materials. In general, as the
concentration of valence electrons increases, the resistance to shear also increases. Thus, further energy
provided by undercooling is necessary for the martensitic transformation resulting in decreased TTs.
As stated above, even though there are some guidelines
in predicting the TTs of NiTiHf-based alloys, the
relationship between the nominal chemical composition
and TTs is not completely established since there are
many other factors that may alter TTs such as precipitation and grain size effects.37,4345 For instance, if the
precipitates are fine and interparticle distances are small,
nucleation of martensite could be more difficult and
require additional undercooling, resulting in decreased
TTs. Transformation temperatures are also sensitive to

2 Transformation temperatures of a Ni50?3Ti29?7Hf20 and b Ni45?3Ti29?7Hf20Pd5 alloys after heat treatment of 3 h at selected
temperatures27,33

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NiTiHf-based shape memory alloys

3 Ms as a function of a ev/a and b cv in NiTiHf-based shape memory alloys30,35,37,40,41,44,45

local chemical composition changes due to formation of

precipitates. Moreover, it is known that internal stress
fields increase the TTs in SMAs.37,4345

Crystal structure and microstructure of

NiTiHf-based alloys
The shape memory and superelastic properties of NiTibased alloys are significantly influenced by the microstructure, such as the precipitation size, interparticle
distance and martensite morphology. In order to obtain
good shape memory and superelastic properties, it is
important to strengthen the matrix to prevent the introduction of dislocations during the martensitic transformation. One of the well-known procedures to improve the
strength of the matrix is the precipitation hardening.
Aging of NiTiHf alloys produces several precipitates that
affect the martensite morphology that will be discussed in
details.

Crystal structure of NiTiHf alloys

In general, the crystal structures of austenite and
martensite phases in NiTiHf alloys are cubic (B2) and
monoclinic (B199), respectively, which are similar to those
in NiTi binary alloys. Zarinejad et al.47 investigated
the effect of Hf on the lattice parameters of the B199
martensite in NiTiHf alloys. The lattice parameters a, b, c
and b angle of the martensite are plotted in Fig. 4 as
a function of Hf content for Ni(1002x)/2Ti(1002x)/2Hfx,
Ni502xTi50Hfx and Ni50Ti502xHfx (x5520 at-%) alloys.
The addition of Hf increased all the lattice parameters for
the Ni(1002x)/2Ti(1002x)/2Hfx and Ni502xTi50Hfx alloys. On
the other hand, when Ni is constant, the increase in Hf in
the Ni50Ti502xHfx alloy increased a, c and b but decreased
b. Potapov et al.45 also observed a similar dependence of
lattice parameters on the Hf content for Ni49?8Ti50?22xHfx
(x5825 at-%) alloys where the increase in Hf while Ni
was kept constant to 49?8% slightly decreased the lattice
parameter b, while it increased a, c and b of B199
martensite. It was also reported that the addition of Hf
increased the lattice parameter of B2 austenite.45 The
volume change during transformation was smaller than
0?5% which was similar to that in NiTi binary alloys
(y0?3% or less).48,49 It should be noted that in some
studies, NiTiHf alloys with more than 15 at-% Hf in

Ni48?5(Ti51?52xHfx)50 and between 20 and 30 at-% Hf of

Ni50(Ti502xHfx)51 were reported to have orthorhombic
B19 martensite.

Precipitation characteristics and their effects on

martensite morphology
Ni-lean NiTiHf-based alloys

Konig et al.52 fabricated NiTiHf thin films with a wide

composition range by magnetron sputtering method and
investigated their TTs, precipitate structure and thermal
cycling properties. Multilayer thin films (individual layers
y15 nm thick) were sputtered from elemental targets
and annealed at 550uC for 1 h in order to transform their
multilayer structure into alloys. Figure 5 depicts the
composition regions in which different precipitates are
formed.52 The relative intensity of one characteristic Xray diffraction peak belonging to the phase of interest was
plotted colour-coded within a section of the NiTiHf
ternary phase diagram. Four different precipitates, i.e.
HfNi(Ti), Ti2Ni(Hf), Hf2Ni(Ti) and Laves phase, were
confirmed in Ni-lean composition regions. They concluded that the observation of reversible phase transformation was limited by the formation of Ti2Ni(Hf),
HfNi(Ti) and/or Hf2Ni(Ti) precipitates. These precipitates restricted the transforming region to compositions
with Ni contents above y40 at-% and Hf contents below
y30 at-%.
The Ti2Ni(Hf) precipitates have also been observed by
many other researchers in Ni-lean NiTiHf alloys.17,36,5355
It has been reported that the volume fraction of the
Ti2Ni(Hf) precipitates decreased with increasing the Ni
content, although the Ti2Ni(Hf) precipitates were still
observed in slightly Ni-rich compositions.17,23 Fine Ti2
Ni(Hf) precipitates strengthen the matrix and improve
shape memory and superelastic properties of NiTiHfbased alloys.36,53 The effects of aging temperature and time
on the formation of Ti2Ni(Hf) precipitates were investigated by Meng et al. in Ni49Ti36Hf1553 and Ni44Ti36
Hf15Cu536 alloys. The size of the precipitates increased with
increasing aging temperature and time. Figure 6a and b
shows the bright-field transmission electron microscopy
(TEM) images of the Ni44Ti36Hf15Cu5 ribbons annealed
at 500 and 700uC for 1 h, respectively.36 According to the
selected area diffraction (SAD) pattern (Fig. 6c) taken
from the specimen annealed at 500uC, the precipitate was

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4 Lattice parameters a a, b b, c c and d b of B199 martensite as a function of Hf in NiTiHf alloys47

confirmed to be Ti2Ni(Hf). The diameter of the precipitates was estimated to be 2040 nm when the annealing
temperature was 500uC. After annealing at 700uC, the
size of the precipitates increased to y150 nm. The fine
precipitates formed in the ribbon after annealing at 500uC
strengthened the matrix and prohibited plastic deformation, which resulted in a perfect superelastic shape recovery
after deformation to 3?5% strain. On the other hand, the
ribbon annealed at 700uC showed an incomplete shape
recovery due to the lower strength of the matrix with large
precipitates.
It is important to note that the size of the Ti2Ni(Hf)
precipitates are very effective to control the martensite
morphology. It was found that (001)B199 compound
twins were dominant when the material contained
homogeneously distributed Ti2Ni(Hf) precipitates with
2040 nm in diameter (Fig. 6a). Similar martensite
morphology has been observed in a Ti-rich NiTi thin
film with a homogeneous distribution of fine Ti2Ni
precipitates.56 When the annealing temperature was
700uC, {011}B199 type I twins became dominant and
the martensite variants showed mainly spear-like and
mosaic-like morphologies as shown in Fig. 6b. Martensite domains with (001)B199 compound twins were also
observed around the coarse Ti2Ni(Hf) precipitates. The
spear-like and mosaic-like morphologies have been
reported as typical morphologies of the martensite in
Hf-added NiTi alloys.57,58

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Ni-rich NiTiHf-based alloys

Meng et al.23,59 have reported that Ni4(Ti, Hf)3 precipitates were formed in Ni-rich NiTiHf alloys similar to
the Ni4Ti3 precipitation in NiTi binary alloys. However,
recently, it has been reported that a new precipitate which
has a more complicated structure than that of Ni4(Ti,Hf)3
forms in Ni-rich NiTiHf alloys24,25,60 and improves
their shape memory and superelastic properties due to
precipitation strengthening.26,27,33 Initially, Han et al.61
reported a precipitate with a face-centred orthorhombic
lattice with a space group of F 2/d 2/d 2/d in an aged
Ni48?5Ti36?5Hf15. There are six different variants in this
orthorhombic precipitate with habit planes of (100)P//
{001}B2 and long axes of [001]P//,1- 10.B2. However, they
did not provide an atomic structure model for the
observed precipitate.
Recently, Yang et al.25 proposed an atomic structure
model which contains of 192 atoms in an orthorhombic
unit cell for the observed precipitate in Ni-rich NiTiHf
alloys. The orthorhombic precipitate phase was named
as H-phase and Fig. 7a shows the unit cell of this
precipitate.25 In order to refine the structure model, ab
initio density functional theory calculations have also
been performed to relax the structure model.24,25 Selected
area diffraction patterns obtained from a single large Hphase precipitate in a Ni52Ti28Hf20 alloy are shown in
Fig. 7bd.25 All the SAD patterns revealed the orientation dependence between the precipitate and austenite B2

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NiTiHf-based shape memory alloys

5 Composition regions in which different precipitate phases exist. The relative intensity of an X-ray diffraction peak for
each phase is plotted colour-coded within a section of the ternary NiTiHf diagram for a HfNi(Ti), b Ti2Ni(Hf), c
Hf2Ni(Ti), and d Laves phase (colour code: red5high; green5medium; blue5low intensity)52 Figure 5 will be reproduced to be mono on the printed version

phase (the diffraction spots are indexed according to the

austenite phase). There were additional reflections at 1/3
positions along ,110.B2* in reciprocal space as shown
by arrows, which was a characteristic of the H-phase. The
composition of the proposed H-phase was Ni50Ti16?7
Hf33?3, whereas it has been indicated by energy dispersive
spectroscopy analysis that the Ni content of the H-phase
precipitate was always slightly richer than that of the
nominal composition of Ni-rich NiTiHf alloys in contrast
to the proposed Ni content of 50 at-% .24,25,62 Therefore
the formation of H-phase precipitates depleted Ni from
the matrix and increased TTs as shown in Fig. 2. Yang
et al.25 observed anti-site defects within the precipitate which may slightly change the composition of the
precipitate, and proposed that the H-phase did not have

a unique composition. The effects of the alloy composition on the H-phase precipitation were investigated by
Santamarta et al.24 They concluded that the H-phase
precipitates grew faster in alloys with higher Ni content
since the precipitates were richer in Ni content compared
to the nominal composition of the alloys. Similarly, for a
fixed Ni content, the growth of the H-phase became faster
when the Hf content was increased.
The control of the size and interparticle distance of Hphase precipitates is important to obtain good shape
memory and superelastic responses. It has been reported
that the aging temperature and time significantly affected
the size and interparticle distance of the precipitates
formed in Ni-rich NiTiHf-based alloys.23,24,33 Figure 8ac
illustrates the representative microstructure of Ni50?3Ti29?7

6 a typical bright-eld image of martensite in Ni44Ti36Hf15Cu5 ribbon annealed at 500uC for 1 h and SAD pattern taken
from region W, electron beam//[1-10]M,T; b typical martensite structure in the ribbon annealed at 700uC for 1 h and the
SAD pattern taken from region D, electron beam//[2 -11]M1,M2//[ -2 -11]M3; c SAD pattern obtained from Ti2Ni(Hf) type precipitates formed in ribbon annealed at 500uC for 1 h, electron beam//[110]Ti2Ni(Hf)36

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7 a unit cell of unrelaxed orthorhombic model of the H-phase.25 SAD patterns of the b [001]B2, c [1-11]B2, d [1-10]B2 and e
[110]B2 zone axes obtained from a single large particle in a Ni52Ti28Hf20 alloy.24 The small arrows and circles mark the
additional reections arising from the precipitate

8 Bright-eld images of the Ni50?3Ti29?7Hf20 alloy a extruded at 900uC, b aged at 550uC for 3 h and c aged at 650uC for
3 h.27 Bright-eld images of the Ni45?3Ti29?7Hf20Pd5 alloy aged at d 550uC and e 650uC for 3 h.33 Inset in d is the enlargement of area D. The SAD patterns shown in d and e were taken from the area D and E, respectively

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9 a bright-eld image of Ni45?3Ti39?7Hf10Pd5 alloy homogenised at 900uC followed by furnace cooling, b SAD pattern taken
from B2 austenite phase and c SAD pattern taken from martensite phase indicating B199 monoclinic structure30

Hf20 alloys in as extruded and aged conditions.27 The

bright-field image of the as extruded Ni50?3Ti29?7Hf20
alloy is shown in Fig. 8a. Precipitate formation was not
confirmed in the as extruded condition. Figure 8b and c
shows TEM micrographs of the extruded Ni50?3Ti29?7Hf20
alloy aged at 550 and 650uC for 3 h, respectively. Fine and
coherent H-phase precipitates were formed in the 550uC
aged specimen. When the aging temperature increased
from 550 to 650uC, the precipitate size increased from
about 20 to 4060 nm. The interparticle distance also
increased after aging at 650uC for 3 h compared with the
550uC for 3 h case. Figure 8d and e shows the H-phase
precipitates and B199 martensite in slightly (NizPd)-rich
Ni45?3Ti29?7Hf20Pd5 alloys in aged conditions.33 The size
of the spindle-shaped H-phase was increased when the
aging temperature was increased from 550 to 650uC.
The fine and coherent H-phase precipitates in the Ni50?3
Ti29?7Hf20 and Ni45?3Ti29?7Hf20Pd5 alloys aged at 550uC
improved the shape memory and superelastic properties
due to precipitation strengthening. However, the alloys
aged at 650uC exhibited relatively poor shape memory
and superelastic properties due to large precipitate sizes.
The martensite morphology in Ni-rich NiTiHf-based
alloys is affected by the size and interparticle distance of
H-phase precipitates. The martensite variants in the as
extruded Ni50?3Ti29?7Hf20 alloy show spear-like morphology and high density of twins can be seen inside the
martensite plates (Fig. 8a). Han et al.57,58 have reported
two types of martensite morphologies; spear-like and
mosaic-like in NiTiHf alloys and they also revealed that
each martensite lath is consisted of (001)B199 compound
twins. If the precipitates were small and interparticle
distance was short, the growing martensite plates can
absorb all the precipitates during growth as it can be
seen in the 550uC aged Ni50?3Ti29?7Hf20 alloys (Fig. 8b).
The large martensite plates were related by the {011}B199
type I twinning mode, which was confirmed by the SAD
pattern shown in Fig. 8b taken at the interface of the
plates. It should be noted that no internal twins were
observed in the large martensite plates in the 550uC aged
specimen. On the other hand, when the precipitates were
big and interparticle distance was large, martensite
plates can be formed between the precipitates and the
thickness of the plates was controlled by the interparticle
distance of the precipitates (Figs. 8ce). In Ni45?3Ti29?7
Hf20Pd5, the SAD patterns were taken from the area D
for the 550uC aged specimen (Fig. 8d) and from the area
E for the 650uC aged specimen (Fig. 8e). It was revealed

that the main twinning mode observed in the martensite

was (001)B199 compound twin in both aging conditions.
It was suggested that the internal twinning type was not
affected by the size of the H-phase precipitates if the
martensite plates are formed between the precipitates.
Addition of Nb and Pd to NiTiHf alloys

In NiTiHf-based alloys, the lattice invariant shear (LIS)

of the martensitic transformation depends on the alloy
composition. The (001)B199 compound twins have been
frequently observed in martensite plates and considered
as the LIS in NiTiHf alloys.57,58 However, recently, it was
found that the ,011.B199 type II twin was the LIS in a
(NizPd)-rich Ni45?3Ti39?7Hf10Pd5 alloy which was homogenised at 900uC followed by furnace cooling.30 The
Ni45?3Ti39?7Hf10Pd5 alloy exhibited less hardening during
transformation compared to a Ni45?3Ti29?7Hf20Pd5 alloy
which has (001)B199 compound twins.
Figure 9a shows a bright-field TEM image for the
Ni45?3Ti39?7Hf10Pd5 alloy30 which consisted of two phases,
B2 austenite and B199 martensite at room temperature. In
the SAD pattern taken from the austenite phase (Fig. 9b),
there were diffuse streaks along the ,110.B2* directions
in reciprocal space. The diffuse streaks could be attributed
to the formation of very small precipitates during the slow
furnace cooling process from the homogenisation temperature. Sandu et al.63 also observed similar diffuse
streaks in an aged Ni-rich NiTiZr alloy. The SAD pattern
taken from the martensite phase (Fig. 9c) indicated that
the internal twins formed in the martensite variants were
the ,011.B199 type II twins. Compared to the (001)B199
compound twin, lower density of twins is found when the
LIS is the ,011.B199 type II twin. It is noted that the LIS
in NiTi binary alloys is known as the ,011.B199 type II
twin and the (001)B199 compound twin has been observed
in NiTi alloys as a deformation twin.64 The (001)B199
compound twin has been also found in nanocrystalline
NiTi alloys65 and in aged Ni-rich NiTi alloys with fine
Ni4Ti3 precipitates.66 These results suggested that the LIS
in NiTiHf-based alloys depends on the alloy composition
and the size and interparticle distance of precipitates.
Kim et al.35 reported that addition of Nb to NiTiHf
alloys causes the formation of a soft Nb-rich b phase and
improves the cold workability. The stability of shape
memory properties is improved by the precipitation of the
b phase, although the shape recovery strain decreases by
the addition of Nb. Figure 10 shows the back-scattered
scanning electron images of (Ni49?5Ti35?5Hf15)Nb alloys.35

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10 Back-scattered scanning electron images of a Ni49?5Ti35?5Hf15, b (Ni49?5Ti35?5Hf15)Nb1 and c (Ni49?5Ti35?5Hf15)Nb15 alloys35

In Fig. 10a, the Ti2Ni type precipitate can be seen in the

Ni49?5Ti35?5Hf15 ternary alloy with a slightly dark contrast.
The b phase, which appears white on the images, was
observed even after 1% Nb addition (Fig. 10b), indicating
that the solubility limit of Nb in the matrix was less than
1%. The amount of the b phase increased with increasing
Nb content. When 15% Nb was added, it exhibited a fully
lamellar microstructure as shown in Fig. 10c, which is a

characteristic of eutectic solidification. This fine lamellar

structure strengthened the matrix and prohibited plastic
deformation during transformation.

Morphologies of reoriented martensite and

stress induced martensite
Acar et al.67 have reported the morphology of the
reoriented martensite in a Ni45?3Ti34?7Hf15Pd5 alloy.

11 Bright-eld image (TEM) of a as homogenised Ni45?3Ti34?7Hf15Pd5 and b 8% deformed alloy with corresponding SAD
pattern.67 Bright-eld image of Ni49Ti36Hf15 c deformed to 8% at 250uC and d deformed to 16% at 250uC.21 The SAD
pattern shown in c was taken from area II

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12 a effect of aging time on yield strength and elongation of Ni49Ti36Hf1553 and b hardness values of Ni50?3Ti29?7Hf20 and
Ni45?3Ti29?7Hf20Pd5 alloys as a function of aging temperature

Transmission electron microscopy observation was carried on a homogenised sample after 8% compressive
deformation at 15uC (below martensite finish temperature, Mf). Figure 11a and b shows the TEM micrographs
obtained from the as homogenised and deformed samples,
respectively. There are fine twins in the martensite plates
in the as homogenised sample (Fig. 11a). In the deformed
sample (Fig. 11b), thicker martensite plates were formed
by the reorientation of martensite variants as compared to
the as homogenised sample. The thick martensite plates
are considered to be favourable martensite variants under
stress. The inset in Fig. 11b is an SAD pattern taken from
the interface between the martensite plates A and B. It was
revealed that the fine twins in the martensite plates are
(001)B199 compound twins and the boundary between the
plates A and B is close to the {111}B199 type I twin plane
(so called {111}B199-type boundary).36 It is considered
that the {111}B199-type boundary can move under stress
without significant detwinning of fine (001)B199 compound
twins in martensite plates.
Dalle et al.68 investigated the morphology of reoriented
martensite of annealed (800uC for 1 h) Ni49?8Ti42?2Hf8
after 10% tensile deformation. They observed finer
(001)B199 compound twins in the deformed material compared to the as annealed material with self-accommodated martensite. They suggested that the detwinning of
the (001)B199 compound twins is difficult and proposed
that, instead of the detwinning, a supplementary (001)B199
mechanical twinning could take place during deformation
by a mechanism of the repetition of the dislocation slip on
the (001)B199 plane.
Meng et al.20,21 investigated the morphologies of the
SIM in Ni49Ti36Hf15 which were solution treated at 1000uC
for 1 h and deformed in tension at 250uC. Figure 11c
shows the typical morphology of the preferentially
oriented SIM variants and the SAD pattern taken from
the area II for the 8% deformed Ni49Ti36Hf15.21 (001)B199
compound twins were mainly observed in the SIM plates.
The SAD pattern revealed that the SIM plates were twinrelated with {011}B199 type I mode, which was similar to
the thermally transformed martensite.57,58 The preferentially oriented SIM variants were disappeared and several
martensite variants were intersected into each other after

deformation. Figure 11d shows the variant-crashed/variant-intersected morphology after deformation of 16%.
The interfaces of the martensite variants are blurred in the
variant-crashed/variant-intersected morphology. They noted
that the stress induced martensitic transformation and
dislocation slip occurred simultaneously during loading
and suggested that the introduction of dislocations increases the martensite variants with the variant-crashed/
variant-intersected morphology.

Mechanical behaviour of NiTiHf-based

shape memory alloys
The relatively high degree of brittleness or poor cyclic
stability in NiTiHf alloys are the main obstacles for
their commercial high temperature applications. It has
been observed that ductility of NiTiHf alloys could be
improved by deformation at higher temperatures in Nilean NiTiHf alloys. Ni49Ti36Hf15 alloys failed after 7% of
bending deformation at room temperature while they did
not fracture until 30% tensile strain at 260uC.42,69
Material properties of NiTiHf-based alloys can be
controlled by aging at different temperatures and time as
illustrated in Fig. 12. Meng et al.53 illustrated that yield
strength of Ni49Ti36Hf15 can be adjusted by aging at
700uC while ductility was constant as shown in Fig. 12a.
The strength of matrix was improved after 20 h but
further increase in aging time decreased the strength of
alloy which can be related to the size, interparticle
distance and volume fraction of Ti2Ni(Hf) precipitates.
Figure 12b shows the hardness (HV) of Ni50?3Ti29?7Hf20
and Ni45?3Ti29?7Hf20Pd5 alloys as a function of aging
temperature for 3 h aging. The increase in the hardness in
the both alloys can be attributed to formation of nanosize coherent precipitates that minimises the dislocation
motion. The decrease in hardness at high aging temperatures in the both alloy systems can be linked to formation
of semi-/non-coherent precipitates and larger interparticle
distance due to over-aging and thus the lack of precipitation strengthening which was also demonstrated in Fig. 8.
It is also clear that Ni45?3Ti29?7Hf20Pd5 is harder in nature
when is compared to Ni50?3Ti29?7Hf20.
Initially, SMA properties of Ni-lean NiTiHf alloys
were mainly investigated due to low TTs of Ni-rich

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13 a thermal cycling under stress response of Ni-rich Ni50?3Ti29?7Hf20,26 b superelastic behaviour of hot rolled Ni-lean
Ni49Ti36Hf1520 and c superelastic behaviour of Ni-rich Ni50?3Ti29?7Hf2027

NiTiHf alloys.23,59 Shape memory effect with 3% recoverable strain or 80% recovery of 6% applied strain is
observed in compression and bending while 80% recovery of 2?5% applied tensile strain is observed in
Ni49Ti36Hf15.20,69 The poor shape memory effect is
attributed to high stress (y500 MPa) for martensite
reorientation and high slope in SIM transformation region
(no plateau region observed) confirmed by tensile experiments.69,70 Although no superelasticity is observed in Nilean NiTiHf alloys,21,23 0?88% strain for two-way shape
memory effect has been observed.71 Unstable cyclic
behaviour is a major problem in Ni-lean NiTiHf alloys
where it has been observed that TTs were decreased by
40uC during stress free thermal cycling of Ni49Ti41Hf10
after 20 cycles.14
In Ni-rich NiTiHf alloys, almost perfect dimensional
stability with 3% strain under a compressive stress of
500 MPa was observed as illustrated in Fig. 13a.26 It can
be seen from Fig. 13b that the stressstrain curve of
solutionised Ni-lean Ni49Ti36Hf15 at temperature above
Af showed high slope in SIM transformation region and
deformation was not fully recovered upon unloading
which was similar to that in cold worked TiNi,72 TiPd73
and as extruded or overaged Ni-rich NiTiHf27 alloys.
Aging can improve the shape memory and material
properties of Ni-rich NiTiHf alloys. Figure 13c shows
the superelasticity responses of as extruded and aged
Ni50?3Ti29?7Hf20 alloys.27 Perfect superelastic behaviour
with 4% recoverable strain was revealed at 240uC after
aging at 550uC for 3 h in Ni50?3Ti29?7Hf20. The improvement in superelastic behaviour with aging can be attributed
to the presence of coherent and fine H-phase precipitates
(as discussed in the microstructure part and shown in
Fig. 8), which strengthen the matrix. Poor superelastic
response after aging at 650uC for 3 h can be attributed to
loss of the coherency of the coarsened precipitates. It is
worth to note that beside the fully recoverable strain, Nirich NiTiHf exhibited high yield strength at high
temperature and the ClausiusClapeyron (CC) slopes
were between 7 and 13 MPa uC21. It should also be noted
that almost fully recoverable strain with small amount of
plastic deformation under 1000 MPa with low plastic and
perfect superelastic behaviour was obtained in Ni-rich
Ni50?3Ti29?7Hf20 along the [111] orientation.28

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Another method to improve the shape memory

properties of NiTiHf has been the quaternary alloying.
Recently, several studies29,3133 have revealed the effects
of Pd addition on the mechanical properties of Ni50?3
Ti29?7Hf20. It was shown that perfect superelastic curves
(with negligible plastic strain) at stress levels as high as
2 GPa were possible for aged polycrystalline Ni45?3Ti29?7
Hf20Pd533 for a temperature window of 50130uC as
illustrated in Fig. 14a. However, full strain recovery was
not observed in over aged materials due to the formation
of large precipitates as shown in Fig. 8 and high degree of
hardening was observed during transformation. When
the Hf content was decreased to 10% in Ni45?3Ti39?7
Hf10Pd5, high slope in SIM transformation region was
not observed that can be attributed to the formation of
different type and density of twinning as discussed in the
microstructure section (see Fig. 9). It was mentioned
before that the ,011.B199 type II twin was the LIS in
a (NizPd)-rich Ni45?3Ti39?7Hf10Pd5 alloy30 in contrast
to the (001)B199 compound twin in Ni45?3Ti29?7Hf20Pd5
alloys.33 Type II twins could be held responsible for the
lack of hardening in the transformation region of Ni45?3
Ti39?7Hf10Pd5 alloys containing 10% Hf compared to
Ni45?3Ti29?7Hf20Pd5 alloys that has (001)B199 compound
twins. The growth of martensite variants with thin (001)B199
compound twins is more difficult in contrast to ,011.B199

14 Stressstrain responses of a Ni45?3Ti29?7Hf20Pd533 and

b Ni45?3Ti39?7Hf10Pd530 at temperatures above Af

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NiTiHf-based shape memory alloys

Ni-rich NiTiHf. Also, as the Nb content was increased

the TTs were decreased and the shape memory properties
of (Ni49?5Ti30?5Hf15)Nb5 alloys became more stable as the
plastic strain was decreased due to the fine lamellar
structure that strengthen the matrix as shown in Fig. 10.
Moreover, the shape recovery ratio was increased as Nb
content increased. Addition of Pd to Ni50?3Ti29?7Hf20
decreased the TTs and transformation strain while it
improved the strength of the alloy.
Cycling instability is a major concern of the NiTiHf
alloys for high temperature applications. Figure 16 shows
the thermal cycling under 200 MPa experiments of Ni49?8
Ti42?2Hf8 in homogenised and equal channel angular
extruded at 650uC conditions.18 It is clear that severe
plastic deformation improved the thermal cyclic stability
and decreased the thermal hysteresis of Ni-lean Ni49?8
Ti42?2Hf8 alloys. Moreover recoverable strain increases
and irrecoverable strain decreases. Formation of precipitates influences the cyclic degradation resistance in
NiTiHf27 where small coherent precipitates generally
improve the thermal cyclic stability while larger precipitates do not affect the stability.
15 Thermal cycling under constant compressive stress of
500 MPa results for NiTiHf-based SMAs27,33,35

type II twins. Thus, the required energy to complete the

SIM transformation increased and resulted in high slope
in SIM transformation region.
Another alloying addition to NiTiHf alloys has been
Cu where it generally improved the two-way shape
memory effect and thermal stability of NiTiHf alloys
while decreased their TTs.3638 It has been reported that
Ni45?3Ti29?7Hf20Cu5 can recover compressive strains of
y2?2% under 700 MPa at temperature above 100uC and
can produce 0?8% two-way shape memory strain at
temperature above 80uC.39 Perfect superelasticity response
was not observed in Ni45?3Ti29?7Hf20Cu5 due to its high C
C slope (about 1425 MPa uC21) and work hardening
coefficient in addition to low yield stress for plastic
deformation.39
It can be seen from Fig. 15 that the Ni-rich Ni50?3Ti29?7
Hf20 alloys had higher TTs and strength than the Ni-lean
Ni49?5Ti35?5Hf15 alloys. This can be attributed to the
difference in precipitates types where H-phase particles
were observed in Ni-rich and Ti2Ni(Hf) precipitates were
formed in Ni-lean NiTiHf after aging. NiTiHfNb has
higher transformation strain but lower strength than

Work output, damping capacity and

potential applications of NiTiHf-based
alloys
Shape memory alloy based actuators can be employed as
light weight and energy efficient alternatives of hydraulic
or pneumatic systems2 in automotive, aerospace and
down-hole energy exploration industries. Alloys with
higher work output values can be used to decrease the
required weight or size of actuators.
The maximum work output levels of various NiTiHfbased SMAs as a function of their average operating
temperature range are shown in Fig. 17a. Work output
can be calculated as the mathematical multiplication of
reversible transformation strain and applied stress in
constant-stress thermal cycling experiments. NiTi alloys
have work output densities of about 1218 J cm23,74 while
NiTiPd and NiTiPt alloys have work output capabilities of
69 and 13 J cm23 respectively75 at temperatures above
150uC. The work output of Ni-rich NiTiHf polycrystalline
alloys was found to be 1820 J cm23.27 Ni45?3Ti29?7Hf20
Cu5 alloys can generate work outputs of around 14
15 J cm23 while NiTiHfNb alloys have work output levels

16 Straintemperature response of Ni49?8Ti42?2Hf8 under 200 MPa a homogenised and b equal channel angular extruded
at 650uC using route 2C under 200 MPa18

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17 Comparisons of a work outputs and b damping capacities for typical NiTi-based SMAs

of 1718 J cm23 above 100uC and 150uC, respectively.35,39

On the other hand, Ni45?3Ti29?7Hf20Pd5 alloys can generate
higher work outputs of 3235 J cm23 (up to 120uC)
compared to other NiTiHf-based SMAs, while upper
temperature capability is somewhat limited compared to
the above mentioned NiTiHf-based alloys.33
Figure 17b shows the damping capacities/absorbed
energies of NiTi-based alloys as a function of transformation stress. Damping capacities can be calculated
from the area between the loading and unloading curves
in a superelastic cycle and can be explained as the ability
to repeatedly dissipate unwanted energy from a system.
SMA based mechanisms could be employed under high
number of cycles in real practical applications. Thus,
stability of a superelastic curve is essential for damping
applications. A HTSMA that could absorb large energy
will be very appealing for high temperature damping
devices. In addition to the high work output, NiTiHfbased SMAs have high damping capacities. They could
be employed in aircraft engines as a damper for acoustic
energy and construction for countering seismic movements in impact damping devices.
The damping capacity of Ni45?3Ti29?7Hf20Pd5 alloys is
3034 J cm23 stemming from its outstanding mechanical
hysteresis (around 900 MPa) and good superelastic strain
of 4%.33 In related systems, the damping capacity is 16,
1820, 38, and 54 J cm23 for NiTi, NiTiHf, NiTiNb and
NbTi/NiTi nanocomposites, respectively.7678 The Ni45?3
Ti29?7Hf20Pd5 alloy has similar damping capability to
NiTiNb alloys that are often used in coupling applications. However, it should be noted that Ni45?3Ti29?7
Hf20Pd5 alloys have the ability to operate at much higher
stresses (y2 GPa) than the NiTiNb systems. Damping
capacities of NiTiHfCu and NiTiHfNb were not compared since full recoverable superelastic cycles have not
been reported in literature.

Conclusions
From the present review of NiTiHf-based alloys, it is clear
that NiTiHf-based alloys are attractive candidates for
high temperature, high strength and damping applications.
Their TTs and strength can be adjusted by heat treatments.
They could show perfect superelasticity above 100uC and
shape memory effect under high stress levels. However,
some of their drawbacks such as low ductility, high slope in

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SIM transformation region and low cyclic stability are still

remained to be improved.
It has been shown that microstructural control by
composition alteration and aging is essential in tailoring
shape memory and mechanical properties (e.g. TTs,
strain, hysteresis and strength) in NiTiHf-based alloys.
Based on the composition and precipitation characteristics (e.g. precipitate size and interparticle distance), the
main microstructural features such as twin type, martensite morphology can be adjusted that would affect the
shape memory and mechanical properties. In Ni-lean
NiTiHf-based alloys, the size of the Ti2Ni(Hf) precipitates are effective to control the martensite morphology.
(001)B199 compound twins are dominant when Ti2Ni(Hf)
precipitates are small (about 2040 nm) and homogeneously distributed while {011}B199 type I twins become
dominant with increasing the size of Ti2Ni(Hf) precipitates. The martensite morphology in Ni-rich NiTiHfbased alloys is affected by the size and interparticle
distance of H-phase precipitates. When the precipitates
are small and interparticle distance is short, martensite
plates can absorb the precipitates during their growth and
they are mainly twin-related with the {011}B199 type I
mode. On the other hand, when the precipitates are big
and interparticle distance is large, martensite plates can
be formed between the precipitates. The thickness of the
plates is governed by the interparticle distance of the
precipitates. The formation of fine H-phase precipitates
significantly improves the shape memory and superelastic
properties due to precipitation strengthening.
Pd addition decreases the TTs of NiTiHf alloys while the
matrix strength was increased by solid solution strengthening. Ni45?3Ti29?7Hf20Pd5 alloys can show perfect superelastic
response under extremely high compressive stress levels of
2 GPa with negligible plastic deformation. NiTiHf(Pd)
alloys have high work outputs and damping capacities
reaching up to 3035 J cm23 owing to their good strain,
high strength and large mechanical hysteresis. Nb addition
to NiTiHf alloys improves the cold workability and the
stability of shape memory properties while decreases the
shape recovery strain by the precipitation of the b phase.
Detailed studies are needed to gain the fundamental
understanding on processingcompositionmicrostructureproperty relationships and reveal the true potential
of NiTiHf-based alloys. Currently, they are the most

Karaca et al.

promising alloys for high temperature and strength

applications.

Acknowledgement
This work was supported by the NASA EPSCOR
program under grant no. NNX11AQ31A.

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