Stimulus Responsive Shape Memory Materials A Review

Materials and Design 33 (2012) 577640
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Materials and Design

journal homepage: www.elsevier.com/locate/matdes
Review
Stimulus-responsive shape memory materials: A review

L. Sun a, W.M. Huang b,, Z. Ding b, Y. Zhao b, C.C. Wang b, H. Purnawali b, C. Tang b
a
b
School of Civil Engineering, Shenyang Jianzhu University, Shenyang 110168, PR China

School of Mechanical and Aerospace Engineering, Nanyang Technological University, Singapore 639798, Singapore
a r t i c l e
i n f o
Article history:
Received 14 March 2011
Accepted 30 April 2011
Available online 8 May 2011
Keywords:
A. Multi-materials
E. Mechanical
E. Thermal
a b s t r a c t
Stimulus-responsive materials are able to response to a particular stimulus, such as, heat, chemical, and
light. As such, they are smarter and more intelligent than ordinary materials. While in most stimulusresponsive materials, the result is limited to a change in their certain physical/chemical properties,
stimulus-responsive shape memory materials (SMMs) are able to recover their original shape, after being
quasi-plastically distorted. SMMs are ideal for an integrated intelligent system, in which The material is
the machine that can sense and then generate reactive motion as pre-programmed.
This paper presents a brief review on the current progress in stimuli-responsive SMMs, from recent
development in traditional shape memory alloys (SMAs) and shape memory polymers (SMPs) to newly
emerged shape memory hybrids (SMHs), which open the door for ordinary people to design their own
SMMs in a do-it-yourself (DIY) manner.
The focus of this review is on twofold, namely phenomena, in particular those newly observed ones,
and novel applications with great potential at present and in near future.
2011 Elsevier Ltd. All rights reserved.
1. Introduction
Driven by the needs from engineering applications, new
materials are kept on being developed for enhanced performance
and/or new functions. Among them, there is a group of materials
which are able to respond to a particular stimulus by means of altering their physical and/or chemical properties. Such stimuli include
heat (thermo-responsive materials), stress/pressure (mechanoresponsive materials), electrical current/voltage (electro-responsive
materials), magnetic eld (magneto-responsive materials), pHchange/solvent/moisture (chemo-responsive materials) and light
(photo-responsive materials), etc. Technically speaking, these materials are known as the stimulus-responsive materials (SRMs) (Fig. 1).
SRMs (in particular, polymers) and their composites, have
become a very hot topic in recent years due to a wide range of potential applications, from functional nanocomposites to controlled/
targeted drug/gene delivery [115]. Among them, one group of
SRMs is able to change their shape at the presence of the right
stimulus [16]. If the shape change is spontaneous and instant in
the presence of the right stimulus, this is the shape change material (SCM). Among others, electro-active polymer (EAP) and piezoelectrical material (such as PZT) are two typical examples of SCM
[1719]. Liquid crystal is a family of fantastic material, which has
numerous attractive features and great potentials for a wide range
of engineering applications. Some liquid crystals (nematic liquid
Corresponding author. Tel.: +65 67904859; fax: +65 67924062.
E-mail address: mwmhuang@ntu.edu.sg (W.M. Huang).
0261-3069/$ - see front matter 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.matdes.2011.04.065
crystal) do have the ability for shape change at the presence of a

particular stimulus by means of arrangement of the long axes of
the molecules in parallel lines [20]. Of course, any material under
elastic deformation can be called stress-responsive SCM.
In the other group, which is known as the shape memory materials (SMMs), the temporary shape can be virtually held forever unless the right stimulus is applied to trigger the shape recovery. All
SMMs are characterized by the shape memory effect (SME), which
is dened as the ability to recover the original shape at the presence of the right stimulus, after being severely and quasi-plastically distorted [21].
There are a number of types of SMMs, which have been developed so far. Among them, shape memory alloys (SMAs) and shape
memory polymers (SMPs) are the most important ones at present
[2225]. While the mechanism behind the SME in SMAs is the
reversible martensitic transformation, the dual-segment/domain
system is the mechanism for the SME in SMPs [2628]. Probably
the newest type of SMM, i.e., shape memory hybrid (SMH), which
is made of at least two components but without any SME as an
individual, shares the same mechanism as SMPs [21,29]. Shape
memory ceramic (SMC) may have the same working principle as
that of SMA, i.e., reversible phase transformation, or have a multi-phase system which is thus similar to that of SMP [3032]. It
should be pointed out that although due to the swelling effect
and/or electrical charge, gels are normally considered as a typical
SCM and can be used to develop novel functional materials, such
as light-triggered swelling in [33] and wet shrinkable material reported in [34], some gels do have the SME due to, for instance, a
578
L. Sun et al. / Materials and Design 33 (2012) 577640
Materials
Stimulus-responsive material (SRM)
Change in ?
Physical properties
Chemical properties
Shape
d
t an
tan ous
Ins tane
n
spo
Shape change
material (SCM)
Shape
memory
alloy
(SMA)
Me
mo
ry t
ype
Shape memory
material (SMM)
Shape
memory
polymer
(SMP)
Shape
memory
hybrid
(SMH)
Shape
memory
ceramic
(SMC)
Shape
memory
gel (SMG)
Shape memory
composite (SMc)
Fig. 1. Location of various types of SMMs within the world of materials.
reversible orderdisorder transition [13,3537]. Recently the

swelling effect has been utilized for activating SMPs as reported
in [38]. It should be pointed out that shape memory composite
(SMc) is dened as a composite with at least one SMM (most likely,
SMA or SMP) as its component [22,3941]. From this point of view,
SMc is not an independent subgroup of SMM. Shape memory bulk
metallic glass composite is actually one of SMcs [42].
Although there are a couple of versions, it seems that the nding of the SME can be well traced back to as early as 1932 in an
AuCd alloy. However, only until 1971 when signicant recoverable
strain was observed in a NiTi alloy at the Naval Ordnance Laboratories, USA, this phenomenon started to attract real attention for
engineering applications [26,43]. Right now, a few SMA systems
have been developed and commercially available in the market
[44]. One interesting research direction at present is thin lm NiTi
based SMA, which, as an actuation material, has great potential in
microelectromechanical system (MEMS) [11].
If heat shrinkable polymer (HSP) is considered under the category of SMP, we can trace the history of SMPs back to as early as
1906 [25], even earlier than SMAs. Water shrinkable polymer
(WSP) is another example [45]. Heat-shrink tubing made of polyethylene (PE) and ethylenevinyl acetate (EVA) has been widely
used to protect conductors, connections, joins and terminals in
electrical engineering. However, technically speaking, according
to [39], we normally regard the polynorbornene-based SMP invented in 1984 by Nippon Zeon Co. in Japan as the rst generation
of real SMP. This SMP and the other two invented right after it, one
is trans-isopolyprene-based developed by Kuraray Company (Japan) and the other is styrenebutadiene-based developed by Asahi
Company (Japan), all have limited processability. The thermoplastic polyurethane (PU) SMP invented by Hayashi does not have this
problem at all [46] and has been developed into a full range of
products with a wide range of transition temperature in various

forms, i.e., pellets/solution and solid/foam, which are commercially
available in the market right now. Another relatively recently but
also successfully marketed SMP is thermo-set polystyrene based
from Cornerstone Research Group, USA [47].
Although relatively much newer, SMH is more attractive since it
is easily accessible to ordinary people (instead of professionals) to
design his/her own SMM even without much background knowledge of materials and materials processing [21]. SMHs share the similar working principle as that of SMPs. However, SMHs can be easily
designed to have a much wider range of tailored functions and features to meet the requirements in engineering applications [29].
This paper presents an extensive review on three major SMMs,
namely SMA, SMP and SMH. It covers not only from phenomena to
mechanisms, but also from fundamentals to engineering applications. Since there are some previous excellent review papers and
books, in particular about the fundamentals of SMAs and SMPs
(e.g., [11,16,26,4852]), the focus of this review paper is more on
new phenomena, novel engineering applications and concerns in
engineering design and practice.
Sections 24 discuss SMAs, SMPs and SMHs, respectively, while
Section 5 focuses on modeling of them. Conclusions are presented
in Section 6.
2. Shape memory alloys

According to the type of stimulus, SMAs fall in two categories,
one is thermo-responsive, and the other is magneto-responsive
(i.e., ferromagnetic SMA). As such, the former can only be activated
thermally by heating, while the latter can also be activated by
applying a static magnetic eld (magneto-responsive) or an alter-
579
nating magnetic eld (inductive heating) to trigger the SME

[53,54]. In both types, the reversible martensitic transformation
is the underlying driving mechanism. Although we have seen good
progress in developing ferromagnetic SMAs and some applications
(e.g., [55,56]), thermo-responsive SMA has matured much more
from the real engineering application point of view and many commercial applications have, so far, been realized [11,26,5760].
Therefore, we will only focus on thermo-responsive SMAs in this
section.
There are three major types of SMA systems at present, namely
Cu-based (mainly CuAlNi and CuZnAl), NiTi-based, and Fe-based
(e.g., FeMnSi, FeNiC and FeNiCoTi). The rst two are more suitable
for engineering applications, while the last one is traditionally seldom used (a high performance Fe-based SMA, Fe28Ni17Co
11.5Al2.5Ta0.05B (atomic percentage, at.%) has been developed
recently by [61]). NiTi-based SMAs are more reliable and can be
highly biocompatible [62]. Although they are difcult to handle
by conventional machining techniques, various advanced technologies, for instance, wire cutting (electrical discharge machining),
waterjet cutting and laser cutting [6365] have been developed
(refer to Fig. 2 for typical examples). Furthermore, thin lms can
be fabricated by means of, for instance, pulse laser deposition
and sputter deposition etc. [11,6671]. On the other hand, resistance welding, laser welding and ultrasonic bonding have been
mature for some years, which are also applicable to SMA thin lms.
In addition, high actuation stress (up to 500 MPa) and large recoverable strain (about 7%) are two advantages of NiTi based SMAs. As
such, if price is not an extremely important concern, they are the
rst choice, in particular in biomedical and MEMS applications
[60]. As proved in [72], down to submicron thickness, sputterdeposited NiTi thin lm SMA still has excellent SME.
A systematical comparison of NiTi, CuAlNi and CuZnAl in terms
of various important properties presented by means of perfor-
mance index and Ashbys Chart [73] for engineering applications

can be found in [44].
2.1. Phenomenon and mechanism
Thermo-responsive SMAs are featured by the four characteristic
temperatures, namely austenite start temperature (As), austenite
nish temperature (Af), martensite start temperature (Ms) and
martensite nish temperature (Mf). Upon cooling from high temperature austenite phase, the martensitic transformation starts at
Ms and nishes at Mf. Upon heating from low temperature martensite phase, the reverse martensitic transformation starts at As
and nishes at Af.
While at low temperatures, SMAs have the SME (Fig. 3a), at high
temperatures, recovery can be achieved instantly and simultaneously upon releasing the applied load, just like rubber band. This
is called the super-elasticity (SE) (Fig. 3b). According to the denition above, the SME is the characteristic of the SMM, while the SE is
that of the SCM.
The underlying mechanism behind the SME in SMAs is the diffusionless solid phase transformation between the high temperature austenite phase and low temperature martensite phase.
However, as compared with the conventional martensitic transformation in, for instance, steels [74], the transformation in SMAs is
within around room temperature and also fully reversible [26].
Since the austenitemartensite inter-phase is fully coherent to ensure high reversibility during transformation, there is a denite
relationship between the orientation of an austenite crystal and
that of a neighboring martensite crystal. In addition, as the order
of symmetry of martensite is lower than that of austenite, corresponding to one austenite grain, up to 24 martensite variants,
which are crystallographically equivalent, but have different orientation and different planes of shearing, may be developed. Due to
Fig. 2. Machining using advanced technologies. (a) Two 2.1 mm diameter holes produced by waterjet on a NiTi plate; (b) AVIA laser cutting of a sputter deposited NiTi thin
lm.
Heating
Stress
Loading
Unload
ing
Stress
Loading
Unloadin
Strain
Strain
(a) Shape Memory Effect
(b) Superelasticity
Fig. 3. SME (a) and SE (b) in SMA. (Reproduced from Ref. [44], with permission.)
580
symmetry, group theory can be applied to conveniently describe

the relationship among these variants [75]. For instance, Fig. 4
reveals the distribution of 48 normal directions of martensite
habit plane variants in DO3 austenite to 18R martensite
transformation.
It should be pointed out that different martensite variants arrange themselves into twinned groups to minimize the internal
stress [76]. All transformations, free from external stress, tend to
be self-accommodating since the shape change in any groups will
produce stress elds favoring the formation of some particular
variants [77]. In thermally induced martensite, which is twinned,
macroscopically there is no shape change, but surface relief [78]
(Fig. 5a). In addition to surface relief, reversible wrinkling due to
the buckling of top surface TiO2 thin layer has been observed in
both fully and partially crystallized sputter deposited NiTi based
thin lms (Fig. 5b and c).
These reversible surface features have been utilized to determine the real transformation temperatures of SMAs based on the
evolution of surface roughness or light reection upon thermal cycling (e.g., Fig. 6) [8183]. This technique is particularly useful for
real time monitoring the transformation process in small sized
SMA samples, in which conventional characterization techniques,
such as differential scanning calorimeter (DSC), have many difculties to cope with.
Other non-conventional techniques to characterize the transformation process include bulging test, curvature method,
indentation test and photoelectron emission test, etc.
[11,71,8590]. As a matter of fact, due to its convenience for
in situ materials characterization [91,92], curvature method has
been widely adopted in investigating the thermomechanical
behavior of SMA thin lms deposited atop an elastic substrate
(e.g., in [79]).
Depending on the thermal-stress history, a SMA might be austenite (A), twinned martensite (TM) or detwinned martensite
(DM). A and TM may co-exist during stress free thermal cycling.
The relationships among these three phases and six possible transformations among them are illustrated in Fig. 7.
These six transformations are [94],
(1) Austenite transforms into detwinned martensite upon loading A ) DM.
(2) Detwinned martensite transforms back to austenite upon
unloading at high temperatures or upon heating without
any applied load or with a very small applied load DM ) A.
(3) Detwinned martensite (variant k) transforms into another

detwinned
martensite
(variant
l)
upon
loading
DMk ) DM l .
(4) Twinned martensite transforms into detwinned martensite
upon loading TM ) DM.
(5) Austenite transforms into twinned martensite upon cooling
A ) TM.
(6) Twinned martensite transforms into austenite upon heating
TM ) A.
The change in lattice structures corresponding to the individual
transformation is schematically illustrated in Fig. 8. For simplicity,
transformation (3) is omitted. The last two transformations, i.e.,
A ) TM and TM ) A, are thermally induced without any macroscopic shape change, but with signicant surface relief. As such, a
at surface in austenite becomes rough upon cooling to twinned
martensite, and vice versa (Fig. 5a).
It should be pointed out that due to the difference in crystal
structure and/or orientation, the properties of a SMA of different
phases (for polycrystal) or orientations (for single crystal) might
differ remarkably [44,95]. Apart from those well known ones, such
as the Youngs modulus, electrical resistivity, thermal conductivity
and coefcient of thermal expansion, as reported in [96], martensite NiTi wire has much higher plastic energy and tearing energy
than that of austenite NiTi wire.
As we can see, fundamentally, there are two types of transformations in SMAs, one is between austenite and martensite, and
the other is among martensite variants. The thermo-mechanical
behavior of SMAs is complicated and is not only stressstrain-temperature dependent [97], but also phase dependent. For instance,
according to the ClausiusClapeyron equation, in uniaxial stretching a piece of SMA, the transformation start stress should roughly
be a linear function of the temperature. However, as observed in
not only NiTi based but also copper based SMAs, the start stress
does not decrease monotonically with the decrease in temperature.
It may increase to form virtually a V-shape and/or keep almost
constant at below a certain temperature [98101]. According to
the simulation by Gao and Huang [102], the V-shape of the transformation start stress against temperature relationship occurs only
in the cooling process (Fig. 9).
Theoretically, in order to induce the austenite to martensite
transformation, the chemical free energy of martensite phase must
be lower than that of austenite phase. However, since the transformation requires also non-chemical free energy, such as transformation strain energy and friction energy, the transformation can
Fig. 4. Distribution of 48 normal directions of martensite habit plane variants in DO3 austenite to 18R martensite transformation. (a) Overall view; (b) top view; (c) bottom
view. (Reproduced from Ref. [75], with permission.)
581
Fig. 5. Evolution of surface morphology upon thermal cycling in sputter deposited NiTi based thin lms. (a) Surface relief at low temperature due to the martensitic
transformation (scanned by atomic force microscope, AFM) (Reproduced from Ref. [79], with permission); (b) wrinkling in fully annealed thin lm (AFM scanning)
(Reproduced from Wu et al. [79], with permission); (c) wrinkling in partially crystallized thin lm (image of optical microscope). (Reproduced from Fu et al. [80], with
permission.)
happen only when the difference between the chemical free energies of the two phases is greater than the necessary non-chemical
free energy. Similarly, the transformation from martensite to austenite will occur when the difference between the above energies,
with their signs reversed, is sufciently large [103105]. Thus, another distinguishing characteristic of SMAs is hysteresis [106,107],
i.e., there is a difference between the forward and reverse transformation paths, which is only ignorable in deforming along some
certain orientations in some single crystal SMAs [95].
In real experiments, we often observe the so called phase transformation front propagation, in particular in uniaxial stretching
[108110]. This is a phenomenon similar to the well-known Luders
bands in the yielding of polycrystalline metals, such as aged low
carbon steel in uniaxial tension [111], in which yielding begins at
a point where there is an initial defect (such as stress concentration
due to dislocation, or geometrical imperfection) and then propagates along the specimen. It is usually argued that the region near
a Luders band is softer than the rest of the material and hence fur-
ther plastic deformation occurs at the boundary between the initial

band and the unyielded part [112].
Instead of yielding, here we have the stress induced martensitic
transformation, which is exothermal, in stretching a piece of SMA
as shown in Fig. 10. As we can see, at a low strain rate, phase transformation starts at the top clamping point (very likely due to additional stress from the clamp) and moves downwards gradually.
However, at higher strain rates, more phase transformation start
points occur. It should be pointed out that in all these tests, one
same piece of 1 mm diameter NiTi SMA wire was used (even without re-clamping). Apparently, both initial imperfection and strain
rate have inuence on the initialization and propagation of the
front. This phenomenon has been investigated and numerically
simulated [113115]. Furthermore, in uniaxial stretching of ribbon-like SMA samples, there is a constant angle between the transformation front and the applied tensile stress [110]. It was found
that this angle can be predicted based on the exact SMA and type
of transformation [116].
582
1
0.9
120
Heating
Cooling
0.8
Reflection
Rms
100
Fraction ()
Fraction ()
0.7
0.6
0.5
0.4
80
60
cooling
40
0.3
20
0.2
0.1
heating
0
0
20
40
60
80
100
120
20
40
60
80
100
Temperature (C)
Temperature (C)
(a)
(b)
Fig. 6. Comparison of the martensite fraction (n) vs. temperature relationship. (a) Between DSC (black line) and AFM (surface roughness, symbols) (reproduced from He et al.
[81], with permission); (b) between AFM (surface roughness, Rms) and reection measurement. (Reproduced from Ref. [84], with permission.)
Austenite
(2) Unloading
Heating
(6
)H
ea
tin
(5
g
)C
oo
lin
g
/
ng
di
oa
nl ng
i
) U at
/
(2 He
ng
di
oa ng
) L li
(1 Coo
DM
TM
(6)
Heating
(3)
Stress
DM
(4)
Loading
(5)
Cooling
DM
(1) Loading
Cooling
(4) Loading
Fig. 7. Three phases and six transformations. Subscripts l and k stand for different
martensite variants. (Reproduced from Ref. [93], with permission.)
Instead of stretching at a constant strain rate, a quasi-constant

load may be applied to a SMA. Fig. 11 reveals the evolution of
stress, temperature (measured at two points, bottom and middle)
and strain in a 0.5 mm diameter, 112 mm long NiTi wire when a
deadweight of 21.1 N (corresponding to a stress about 110 MPa,
which is well over the transformation start stress of this SMA at
the testing temperature, which was slightly over 22 C) was instantly applied. As we can see, the temperature at both points is
about the same (this is because the applied stress is well over
the transformation start stress), and almost instantly reaches the
maximum right after the deadweight is applied. Subsequently,
the measured temperature decreases gradually. On the other hand,
the strain increases in a much gradual manner, which is due to the
inuence of heat generated during the stress induced martensitic
transformation.
In another group of tests, a deadweight (W) (which is always
lower than the required transformation start stress at the testing
temperature) was dropped from the top end of the SMA wire to apply an impact (refer to Fig. 12d for an illustration of the experimental set-up). An infrared camera was used to record the temperature
distribution along the wire. As we can see, the phase transformation always starts at both ends of the wires (at the clamping
Twinned
Martensite
Detwinned
Martensite
Fig. 8. Change in lattice structure. (Reproduced from Ref. [93], with permission.)
points) and moves toward the middle. The heavier the deadweight,
the higher the recorded temperature and the longer the area in
which the transformation passes through.
More fascinatingly, in NiTi microtubing under complex stress
states, spiral shaped propagation front has been observed
[117,118].
In the case of joule heating for actuation, which is most welcomed by many engineering applications, we have to bear in mind
the inuence of non-uniform distribution of temperature. Fig. 13
illustrates the experimental set-up of a piece of pre-strained SMA
wire under joule heating with the length xed (so called the constrained-recovery test, which is opposite to the free-recovery test,
in which the SMA, or any SMM, is free to recover its original shape
without any constraint). Fig. 14 reveals the corresponding experimental results in terms of stress (measured by the tensile machine)
vs. strain (measured by a strain gauge as shown in Fig. 13) and
temperature (measured by a thermocouple at the point marked
in Fig. 13) vs. strain relationships. Simulation also veries the signicant non-uniformity in the wire during thermal cycling [113].
583
linear model
cosine model
350
300
200
ng
oo
l in
250
He
ati
Transformation start stress (MPa)
400
150
100
50
Mf
10
20
Af
As
Ms
30
40
50
60
Temperature (C)
Fig. 9. V-shape in the transformation start stress versus temperature relationship.
(Reproduced from Ref. [102], with permission.)
Fig. 11. Experimental results of a 0. 5 mm diameter, 112 mm long NiTi wire under a
sudden applied load of 110 MPa. (a) Time (t) against stress (r) relationship; (b) time
vs. temperature (T) relationship; (c) time against overall strain (e) curve. (Reproduced from Ref. [113].)
Fig. 10. Snapshots of phase transformation front movement in a 1 mm diameter

NiTi wire at different strain rates. (a) 1.30 103/s; (b) 2.60 104/s; (c)
1.30 104/s. (Reproduced from Ref. [113].)
From the application point of view, above phenomena remind us

that we need to pay enough attention on the possibly reduced performance due to the non-uniformity in temperature distribution.
Even we can assume a piece of SMA is uniform and homogeneous everywhere, the inuence of heat generated upon phase
transformation will cause additional strain rate effect. As revealed
by simulation in Fig. 15, a higher strain rate results in a wider
hysteresis.
Using a sharp indenter, such as a Vickers indenter, depending
on the testing temperature, sink-in or pile-up indent can be produced atop a SMA (Fig. 16), which can be partially explained by
the strain hardening theory [119]. However, after heating for shape
recovery, all indents become pile-up (Fig. 17), which is due to the
SME. In addition, upon thermal cycling, the depth of indent
changes accordingly, i.e., at low temperatures the indent is deeper,
while at high temperatures the indent becomes shallower
[120,121]. This is a phenomenon traditionally known as the twoway SME [122,123], in which both the high and low temperature
shapes can be remembered during thermal cycling.
There are a few ways to develop the two-way SME in a SMA
which originally has only the one-way SME, i.e., only the high temperature austenite shape can be recovered (that is intrinsic) [26].
The underlying mechanism behind the two-way SME is an elastic
stress eld, which is introduced into the SMA by means of thermomechanical training. As such, upon cooling, certain martensite variant(s) will be produced in a free standing SMA, which results in a
particular shape at low temperatures (martensite shape). Most of
training approaches require many thermomechanical cycles, which
are not convenient. Severe plastic distortion, such as in indention
using a sharp indenter as mentioned above and applying a large
torque to twist a SMA rod beyond its elastic limit [124], does not
have such a problem. Re-heat treatment is another training technique in which the SMA is annealed one more time at the same
584
Fig. 12. Propagation of the phase transformation front in a 1 mm diameter wire under different impact loads (W). (ac) Infrared images taken right after impact; (d)
experimental set-up (A deadweight, W, is released from the top end of the wire and hits the bottom stopper).
Fig. 13. Illustration of experimental setup in thermal cyclic test by joule heating.
(Reproduced from Ref. [113].)
temperature as in the rst time but with a shortened (most likely

half) annealing time and in another xed shape [125].
As revealed in Fig. 18, a piece of SMP wire (1 mm diameter)
closes upon heating and opens after cooling back to room temperature. This piece of wire was annealed twice at 500 C. In the rst
time, it was 1 h and xed around a larger shaft, and in the second
time, for half an hour xed around a smaller shaft [126]. The stability of this training approach has been experimentally conrmed
[127].
The advantages of this training technique have been demonstrated in a NiTi SMA thin sheet based micro gripper in Fig. 19.
To reduce the possible damage to the material caused by high heat
in laser cutting, a femtosecond laser was used to cut out the
groove, so that the gripper can be operated by passing electrical
current for joule heating [63]. Furthermore, this technique has
been used to fabricate two-way torsion spring (Fig. 20), expansion/contraction spring, etc.
We need to bear in mind that, according to the previous denitions, the two-way SME is actually a phenomenon that belongs to
the SCM, since the shape change is instant and spontaneous in the
presence of the right stimulus, which is heat in this case. Another
point which is more on the application aspect is that the performance of this two-way SME (we may call it intrinsic two-way
SME or materials two-way SME) is very much limited in terms of
the maximum recoverable strain and maximum actuation stress.
As such, utilizing the mechanical two-way SME, which will be discussed later, is preferred from the engineering application point of
view.
In addition to the well known SME in SMAs, the temperature
memory effect (TME) has been observed since about two decades
ago [129], which has attracted great attention and found in many
SMAs and different transformations [130134]. The TME refers to
a phenomenon that in an incomplete transformation in a SMA,
the previous temperature of interruption (upon heating) can be
memorized and revealed in the following heating process. As
shown in Fig. 21, which is a typical DSC result, a NiTi SMA is heated
to about 50 C, which is in the middle of the reverse martensitic
transformation, so that it is a mixture of austenite and martensite.
Subsequently, the sample is cooled down to become fully martensite. In the next step, the sample is heated gradually. Instead of one
trough as that in a complete DSC cycle, we see two troughs upon
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Fig. 14. Response of a SMA wire in thermal cyclic test by joule heating. (a) Stress vs. strain relationship; (b) zoom-in view of (a); (c) temperature vs. strain relationship; (d)
zoom-in view of (c). (Reproduced from Ref. [113].)
Fig. 15. Simulation of strain rate effect (unit for strain rate is /s). Left: stress vs. strain relationship; right: temperature vs. strain relationship. (Reproduced from Ref. [113].)
Depth (m)
Depth (m)
-1
41.9C
36.3C
-2
27C
23.2C
-2
17C
20.6C
24.5C
36.5C
54.6C
68C
-3
19.9C
-4
-4
12.8C
-5
0
10
20
30
40
50
60
70
X Axis (m)
Fig. 16. Cross-sectional view of indents produced at selected temperatures in a
cooling process (measured at about 17 C). (Reproduced from Ref. [119], with
permission.)
heating, which means that the reverse transformation is virtually

split into two steps. A close-look reveals that the peak temperature
20
40
X Axis (m)
Fig. 17. Cross-sectional view of a sink-in indent upon heating. (Reproduced from
Ref. [119], with permission.)
among these two troughs is always a few degrees above the previous heating stop temperature. Furthermore, even after many
incomplete thermal cycles, which follow a decreasing order in
586
Fig. 18. Two-way SME. (a) At room temperature; (b) upon heating.
terms of the heating stop temperature, we can still see many peaks
which actually correspond to these individual heating stop temperatures. As believed and numerically simulated, the cause of this
effect is that when the material is in the middle of heating process,
instead of the growth of old martensite variants, new martensite
variants are produced upon cooling [28,135]. Despite this is a generic phenomenon found in many SMAs, the interest is still limited
within the academic community right now. Its real application is
seemingly unclear, since there is not any shape change associated
with this effect.
We should take note that the SME is still observable in SMAs
down to nanometer scale [136], which provides the possibility to
achieve The material is the machine [137139]. As a machine,
not just a simple two-position actuator, it is ideal that the motion
of a SMA follows a prescribed sequence in a programmable manner, which requires some intermediate shape(s)/position(s) to be
reached.
It has been observed that pre-straining can signicantly increase the transition temperature for shape recovery in SMAs
(e.g., [140,141]), which is due to the additional driving energy
requirements either from higher energy dissipation [142] or from
a kind of locked-in mechanism [95]. As such, by pre-straining a
piece of SMA strip at required location(s) to different levels, a gradient transition temperature eld is introduced into the strip. Subsequently, upon heating, the less pre-strained part will recover rst
and more pre-strained part will only recover at a higher temperature as revealed in Fig. 22.
An alternative approach to produce a gradient transition temperature eld is by means of local thermomechanical treatment
[143]. However, in this case, the gradient transition temperature
eld is permanent.
Fig. 20. Two-way SMA torsion spring at low temperatures (a) and high temperatures (b).
Fig. 21. Typical DSC result reveals the TME in a polycrystal NiTi SMA. Gray lines: a
complete full thermal cycle; o symbols: heating stopped half-way within the M ? A
transformation; black line: nal heating to full austenite. (Reproduced from Ref.
[28], with permission.)
Instead of introducing a gradient transition temperature eld,

some special mechanisms can be used to achieve the multipleSME (i.e., with multiple intermediate shapes/positions). As shown
in Fig. 23, a microbeam can reach two or three positions depending
on how it is joule heated. While the microbeam switches between
two shapes, if it is gradually joule heated; buckling, which happens
when a constant high current is applied or suddenly removed, results in one additional shape between two ordinary shapes.
Fig. 19. NiTi SMA thin lm gripper based on the two-way SME. (a) Prototype; (b1) at room temperature; (b2) upon joule heating; (c) in operation to grab a piece of eraser; (d)
illustration of assembly. (Reproduced from Ref. [128], with permission.)
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Fig. 22. Triple-SME upon heating after local bending to introduce a gradient transition temperature eld.
1.5
2.0
Heating
Cooling
1.5
Tip diflection, mm
Tip deflection, mm
1.2
1.0
0.5
0.0
-0.5
0.9
0.6
0.3
-1.0
-1.5
0.0
-2.0
-5
10
15
20
25
30
35
Time, s
(a)
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
Electrical Current, mA
(b)
Fig. 23. Tip deection in a 1.6 mm long, 15 lm thick silicone beam with 5 lm thick of sputter deposited NiTi thin lm atop (electrical circuit was formed by means of laser
cutting). (a) Triple-SME in both joule heating with a constant current of 0.6 mA and cooling (power off); (b) tip deection against gradually applied electrical current.
A recent nding reveals the possibility to achieve at least tripleSME in SMA ribbons by programming in terms of bending in a uniform manner throughout the whole length [21]. As shown in
Fig. 24a, after programming, the tip of the ribbon moves toward
one direction and then toward the opposite direction upon heating.
There is no two-way SME in the ribbon, evidenced by the observation that the ribbon keeps straight during cooling. In this demonstration, the involved recovery strain is very small (less than
0.1%). Our recent investigation shows that not only much higher
recovery strain (more than 2.5%) is achievable (Fig. 24b, in which
the maximum recoverable strain is 0.8%), but also the exact recovery sequence can be programmed. Fig. 25 reveals two recovery patterns. At a low pre-strain, the tip moves downwards and then
upwards; while at a high pre-strain, the tip moves upwards and
then downwards.
2.2. Applications
As reported in [145], SMA based actuators are outstanding in
terms of high power/weight ratio over other types of actuators.
They are ideal, in particular for microsystems [146]. From actua-
tion point of view, there are three basic types of SMA actuators utilizing the one-way SME (Fig. 26) [44].
Fig. 26a shows a one-way actuator. The SMA element is elongated initially at low temperatures, and then is heated up to
pull element P to the left.
Fig. 26b shows a biased actuator, which is capable of moving the
element P forward and backward upon heating/cooling the SMA
element.
Fig. 26c shows a two-way actuator, which has two one-way
SMA elements. P may move back and forth by heating/cooling
the two SMA elements alternately.
From working mechanism point of view, a biased actuator is
similar to a SMA with the material two-way SME, but at a macroscopic (structural) level. Therefore, we may call this as the mechanical two-way SME, which strictly speaking, is also a phenomenon
under the category of SCM. Although both materials and mechanical two-way SMEs serve essentially the same type of function, the
mechanical two-way SME is more powerful (e.g., higher actuation
stress and larger actuation strain) and reliable. The mechanical
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Fig. 24. Triple-SME in a 0.2 mm thick NiTi ribbon. (a) Tip deection vs. time upon heating (Reproduced from Ref. [21], with permission); (b) snapshots upon heating in large
pre-strain case.
Fig. 25. Two different recovery patterns in a NiTi ribbon.
two-way SME has been widely adopted in many engineering

applications.
As mentioned above, due to pre-straining, the recovery temperature of a SMA may increase due to an increased energy barrier as
compared with that in a freestanding sample [95,142]. On the other
hand, in the case of thermal recovery with a xed length (so called
constrained recovery) or against an elastic constraint (as in
Fig. 26a), the hysteresis and other transformation characteristics
will be altered accordingly [147149]. Generally speaking, a higher
heating temperature is required for a complete recovery, i.e., the
four characteristic transition temperatures (As, Af, Ms, Mf) derived
from the result of DSC test are more for freestanding samples without pre-straining/stressing, while in real practice in actuators, a
higher driving energy, i.e., higher heating temperature is required.
Basically, SMAs may be heated up by three methods, i.e.,

[44]
By passing an electrical current through them (joule heating).
This method is only applicable to SMA wires or springs, etc.
with a small diameter.
By passing an electrical current through a wire or tape which is
with high electrical resistance and wrapping it around the SMA.
This method is applicable to bulky SMA pieces.
By hot air/water or exposing to thermal radiation.
We have seen a wide range of applications of SMAs in the past
years. Due to space constraint, it is impossible to cover all of them
within this section. Here, only typical and/or new ones will be
discussed briey. Interested readers may refer to, for instance

[11,26,43,57,59,60,150,151], for comprehensive reviews.
It should be pointed out that medical application of SMAs is always a hot topic due to the needs, in particular for minimally invasive surgery, which has become a standard practice at present.
Reconstruction surgery is another application eld [152]. Stent,
guide wire, lter, and clip made of SMAs have been widely used
[153156]. For an extensive review of this topic, readers may refer
to, for instance [157] for details about the history and current progress of SMAs in minimally invasive surgery. (A brief summary in
the development of SMMs for minimally invasive surgery till early
2009 can be found in Appendix A. Note that Nitinol is a short term
for NiTi based shape memory alloy, which is widely used by the
SMA industry.)
2.2.1. MEMS applications

NiTi based thin lms can be produced by various ways, for instance, laser ablation, ion beam deposition, arc plasma ion plating,
plasma spray, ash evaporation and sputter deposition, etc. Among
them, sputter deposition is the most widely adopted technique for
its high quality in terms of uniformity in lm thickness and composition, high deposition rate and good compatibility with the standard MEMS process, etc. [71,158160]. Various MEMS devices
have been developed using NiTi based thin lms for actuation.
In terms of work per unit volume, SMA is outstanding among all
currently available micro-actuators [161]. As such, SMA becomes
an ideal actuation material for micro-actuators [146,162]. For an
extensive review on the current progress in SMA thin lms and
applications, readers may refer to Miyazaki et al. [11].
P
SMA
P
F
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It should be pointed out that, as a thermo-responsive SMM, the

actuation speed of SMA based devices is very much dependent on
the heating speed (and cooling speed, if in cyclic actuation) of SMA.
While a high heating speed can be reached by applying a high electrical current for joule heating, cooling speed is always limited by
the speed of heat dissipation [163]. Given a higher surface vs. volume ratio at a smaller size, SMA thin lm based devices, in particular those activated by means of joule heating, can reach a much
higher frequency in cyclic actuation.
A critical challenge in SMA thin lm based actuators is how to
pre-strain the SMA thin lms, so that upon heating, actuation
can be triggered by the SME in the pre-strained SMA thin lms.
For freestanding SMA thin lms in, for instance, micro pumps
and micro valves [69,164], pressure from liquid/gas provides the
driving force to pre-strain SMA. Thermal mismatch due to the difference in thermal expansion coefcient is a commonly applied
working principle for pre-straining SMA thin lms atop an elastic
substrate, most likely silicon wafer [165167]. However, the maximum pre-strain that can be achieved by the latter is very much
limited.
Fig. 27a reveals a microgripper, which was made by bonding
two cantilever beams (sputter deposited 5 lm thick of NiTi thin
lm atop 15 lm thick silicon beam) together with a silicon spacer
in between [168]. The NiTi thin lms are pre-strained due to the
difference in thermal expansion coefcient between NiTi and silicon after cooling from the annealing temperature (for crystallization), which is typically around 450 C.
The recovery of the pre-strained NiTi thin lm upon heating results in the closure of the gripper as shown in Fig. 28. For 680 lm
and 1650 lm long beams, the tip deections are about 70 lm and
400 lm, respectively. As reported in [169], numerical simulation
reveals that a few thermal cycles are required before the closeopen motion of the beam becomes stable.
From engineering application point of view, in particular in
MEMS applications, joule heating is a convenient approach for
SMA
(b)
(a)
P
SMA
SMA
(c)
Fig. 26. Three basic types of SMA actuators based on the one-way SME. (a) One-way
actuator; (b) biased actuator and (c) two-way actuator. (Reproduced from Ref. [44],
with permission.)
Fig. 28. NiTi-silicon micro gripper in actuation. (a) At room temperature; (b) upon
heating.
Fig. 27. NiTi-silicon microgripper (a) (Reproduced from Ref. [169], with permission) and a beam with a groove for joule heating, (b) (Reproduced from Ref. [63], with
permission).
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heating SMAs, in particular NiTi based SMAs, which have a high

electrical resistivity [44]. By cutting out a groove using a femtosecond laser (which minimizes the high temperature effect on NiTi
during cutting), an electrical circuit is formed (Fig. 27b). Subsequently, the operation of the gripper can be controlled by electrical
current directly (Fig. 29).
The interesting phenomenon of reversible surface morphology
change atop SMAs during the martensitic transformation results
in the reversible change in surface roughness and surface reection
[78,82,84,170]. This effect is the most signicant in NiTi thin lms

with reversible wrinkles atop (Fig. 30). If we can precisely control
the areas with/without such wrinkles at micron scale, we will be
able to produce micro mirrors for optical applications [78,82,171].
In addition to the laser cutting, drilling, patterning and cleaning
[172,173], laser has been proved to be an effective approach for local annealing of NiTi thin lms [64,174176]. Laser assisted growth
of NiTi thin lms might be the most recent development in this
direction [177].
Fig. 29. NiTi-silicon microgripper activated by joule heating. (a) Open position; (b) closure position.
Fig. 30. Reversible wrinkling atop NiTi SMA thin lm. (a) At room temperature; (b) upon heating to high temperatures; (c) after cooling back. (Reproduced from Ref. [84],
with permission.)
Fig. 31. One annealed line (scale bar is 200 lm) (a) and 3-dimensional surface scanning over an area of 150 ( 150 lm using AFM (b).
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Fig. 32. AFM results at the edge of a CO2 laser annealed line at different temperatures upon heating. The scanned area is 20 20 m. The top-right part is unannealed.
SMA wire
(hot)
Elastic spring
SMA wire
(cold)
Elastic spring
(a)
(b)
Voltage (V)
2.6
2.2
1.8
0
0.01
0.02
0.03
Time (s)
(c)
Fig. 33. Circuit production mechanism. (a) On-position; (b) off-position; (c) typical
experimental result (time against voltage in the circuit).
As we know, sputter deposition of NiTi based thin lms can be

done at either room temperature (which results in amorphous NiTi
thin lms without the SME) or high temperatures (above around
400 C, which results in crystallized NiTi thin lms with the
SME). In the former case, post-annealing is required at about
400 C or above for crystallization of NiTi thin lms. In both situations, the required high temperature, either during sputtering or in
post-annealing, is not compatible with the conventional integrated
circuit (IC) processes.
Laser local annealing provides the just-right solution to this
problem. Fig. 31 shows a line about 100 lm wide produced by a
CO2 laser beam with a beam spot size of 100 lm [174]. Numerical
simulation reveals that the high temperature zone during laser
annealing is about within the spot size of the laser beam [173,178].
Fig. 32 further reveals the 3-dimensional surface morphology
upon heating at the edge of an annealed line using an AFM. As
we can see, there is no signicant change in surface morphology
within the area without laser annealing (as it is still amorphous),
while the annealed part shows dramatic change due to the martensitic transformation in the crystallized part. Although it appears
to be preliminary, this also demonstrates the possibility to produce
micro mirrors with precisely controlled pattern at micron scale.
Since the transition temperatures of NiTi SMA are very sensitive
to the exact composition, alternately depositing Ni and Ti layers
has been proposed to achieve precise composition control [179].
Fig. 34. Four-bar linkage.
592
We have theoretically proved that laser annealing is also applicable

to Ni/Ti multi-layered thin lms [180].
2.2.2. Electrical device applications
Right after the invention of NiTi SMA, numerous applications
have been explored for various electrical devices [26,57]. Fig. 33
illustrated the working principle of an electrical circuit protection
system, in which a piece of pre-stretched NiTi SMA wire is used
to automatically break the circuit once it is over heated. As we
can see, the reaction speed is at 1/100 s level. Fig. 34 is a fourbar linkage, in which two pieces of 1 mm diameter SMA wires
are alternately joule heated. In a typical full cycle, it takes about
1 min. As compared with the traditional linkages which require a
motor to drive them, this four-bar linkage is simpler and more
compact.
Fig. 35 is a linear motor. By alternately heating the right-/leftside of the SMA spring, a reversible linear motion is produced.
Based on the same concept, a bi-stable arch reaches either of the

stable positions by heating a particular side of the SMA spring.
The main advantages of this latter concept are twofold. On the
one hand, electrical power is only required to switch from one position to another by joule heating one side of the spring. No energy
is required to maintain the shape. On the other hand, both positions can be precisely reached with a high repeatability (see
Fig. 36).
Contrary to traditional pipeline joints by means of welding or
soldering, SMA couplings provide a convenient alternative [181].
Beyond couplings, SMA can be used for active assembly [182]. Over
5% recoverable strain in NiTi SMAs can be utilized to assemble
components together tightly. In Fig. 37a and b, a piece of SMA
was pre-stretched and then inserted into a hole, which is just
slightly bigger than the diameter of the pre-stretched SMA wire.
Upon heating, the wire expanded which resulted in good bonding.
In Fig. 37c, a piece of CuZnAl SMA ring was pre-expanded and then
Fig. 35. A two-SMA spring-based linear motor.
Fig. 36. Bi-stable arch (a piece of plastic rule) activated by alternately joule heating two SMA springs. (a) After the right-side spring is heated; (b) left-side spring is heated.
Fig. 37. SMA for active assembly. (a) NiTi SMA wire (0.5 mm diameter) and aluminum plate; (b) NiTi SMA wire (1 mm diameter) and read/write head of hard disk; (c) CuZnAl
ring and spindle of hard-disk [(c) only, Reproduced from Huang et al. [183], with permission].
mounted to the shaft of a hard-disks spindle. After heating for

shape recovery, the SMA ring shrank and rmly held to the shaft.
Experimental results and simulation reveal that good assembly is
achievable if dimension control can be well managed during fabrication/processing.
The multi-SME provides a possible approach to achieve active
assembly after heated once and then active disassembly if heated
again. This could be very much useful for temporary couplings.
Platforms with multi-degree-of-freedom are required in many
engineering applications for, for instance, position control. Fig. 38
presents one such platform, in which three pieces of 0.2 mm diameter NiTi SMA wire and a two-way SMA spring (made of 0.5 mm
diameter NiTi wire) were used to drive the motion. Heating SMA
wires individually or in a two-combined manner will make the
platform tilt to the required direction. Basically, this part is based
on the same concept as used in an active endoscope proposed by
Hirose et al. [184] (but SMA springs are replaced by SMA wires).
To add in one more degree-of-freedom, in this design, there is a
593
two-way SMA torsional spring at the center, which can twist the
platform up to 45 once it is joule heated. Since the torsional spring
is with the two-way SME, it twists back once it is back to room
temperature.
2.2.3. Actuators/grippers
SMAs are ideal for electromechanical and/or thermal actuators
[185,186]. SMA based micro-rotary actuators have been investigated for many years [187189]. Fig. 39 presents a few power
hinges, which can be activated electrically [113]. While the actuators in Fig. 39ac use NiTi SMA wires (1 mm in diameter in Fig. 39a
and 0.5 mm in diameter in Fig. 39bc), the rotary actuator in
Fig. 39d is based on a NiTi SMA rod (6.5 mm in diameter). A simple
setup as in Fig. 39a can provide relatively fast reaction, so that it is
suitable for low speed rotation angle control [113]. By wrapping
wires around a specially designed shaft, actuators not only become
compact (Fig. 39b) but also achieve the mechanical two-way function when one is placed against another (Fig. 39c). The rod based
Fig. 38. SMA based platform with multiple degree-of-freedom. (a) Exposure view; (b) after assembly; (c) fabricated prototype.
Fig. 39. Four types of SMA hinges. (ac) SMA wire based; (d) SMA torsion bar based. (Reproduced from Ref. [113].)
594
Fig. 40. Average power consumption of the actuator in Fig. 39a. (a) Symbols:
experimental results with different applied torques; lines: theoretical prediction
giving the upper/low boundary. (Reproduced from Ref. [113].)
actuator (Fig. 39d) is more compact. However, given the size of the
rod (which is required to achieve high actuation torques), an external heating system is necessary to drive the actuation and thus signicantly slows down the reaction speed.
Power consumption is an important factor for comparing and
selecting actuators. The measured average power consumption of
one actuator (Fig. 39a) with different applied constant torques
was plotted against the time connected to the power supply in
Fig. 40 and compared with the theoretical prediction by two methods, which are supposed to give the upper and lower boundaries in
theory.
SMA based grippers with multiple degree-of-freedom can serve
as articial arms/hands for manipulation [190]. Fig. 41 presents a
simple gripper with two-degree-of-freedom. Three pieces of SMA
wires are used in this design. Joule heating the top two wires
causes the closure motion of the gripper, while joule heating the
bottom wire induces a signicant bending in the whole bottom
part. Fig. 42 is another gripper developed from the multi-degreeof-freedom platform in Fig. 38 (with the two-way SMA spring replaced by a piece of conventional elastic spring at the center).
The closure motion is activated by joule heating the 0.2 mm diameter SMA wire at the top end of the gripper.
2.2.4. Aerospace and space applications

SMA has been used in space systems for deployment of antenna,
solar array and protection shroud, etc. since two decades ago
[26,191193]. A technical and economic appraisal of SMAs for
aerospace applications with a particular concern on SMA adaptive
serrated nozzle for noise reduction in the next generation gas turbine engines can be found in [194].
SMA wire/rod or even tube can serve as the driving mechanism
to rotate a panel as shown in Fig. 43. After pre-twisting the SMA,
upon heating the panel will return to its original position. If the
SMA is with the two-way SME, upon cooling it will recover its cold
temperature position automatically. Given the remarkable temperature difference (one side, which faces the sun, is up to 120 C,
while the other side, which is in the shadow, is up to 150 C),
SMA and two-way SMA are ideal actuation materials for outer
space missions.
As reported in [150], many years ago, SMA was once proposed to
control the shape/surface of an adjustable camber. Nowadays,
shape morphing of aircraft wings provides a wonderful stage for
Fig. 41. A simple SMA wire based gripper with two-degree-of-freedom.
SMMs, in particular SMAs as the actuation material [195]. Morphing wings, instead of xed wings, are required to effectively reduce the drag accordingly, depending on the exact ight speed
during a ight journey (i.e., take-off/landing, cruise, and in combat).
Fig. 44 is a SMA wire (1 mm in diameter) based hinge. Upon
joule heating the top half of the wire, the hinge closes, while joule
heating the bottom half of the wire, the hinge opens. This is a very
simple mechanism for winglet position control.
SMA composites, i.e., an elastic matrix embedded with SMA,
have been investigated for many years for vibration/buckling/
shape control [196203]. It also provides a simple solution for
wing morphing [204].
As shown in Fig. 45 (left), a piece of 1 mm diameter wire was
embedded inside a silicone beam. Depending on whether the
SMA is joule heated, the wing shape changes correspondingly. In
addition to signicant shape change, slight wing-tip tilt can be
achieved as well (Fig. 46). SMA wire has been used to mimic
unfolding motion of a beetle hind wing [205]. In such applications,
adhesion/bonding between matrix and embedded SMA is an
important issue in real applications [206,207].
Instead of embedding SMA inside, wing morphing can be
achieved by SMAs externally xed to an elastic beam/plate.
Fig. 45 (right) presents a prototype and details of xing SMA thin
wire to the thin elastic plate. Fig. 47 is a two-piece-wing frame,
which can fold individually or together by joule heating two
springs individually or together. Elastic steel strips were used for
unfolding automatically when power supply is turned off.
595
Fig. 42. A SMA wire based gripper atop a platform with multiple degree-of-freedom (exploded view). (a) Assembled drawing; (b) picture of prototype (with a piece of paper
rmly grabbed).
Fig. 43. Panel position control using SMA rod/wire. (a) Twisting SMA; (b) heating SMA for shape recovery; (c) picture of prototype.
Fig. 44. SMA wire based two-way hinge.
596
Fig. 45. Morphing wings. Left: silicone beam embedded with a piece of 1 mm diameter NiTi wire. (a) Top view; (b) side view; (c) before heating; (d) upon joule heating. Right:
composite beam with externally attached thin NiTi wire. Upon joule heating, from (a) to (e); and upon cooling from (e) to (a). Zoom-in view of details (f) and illustration (g).
Fig. 46. Snapshots of a silicone beam embedded with a piece of 1 mm diameter wire upon joule heating for wing-tip tilt.
Fig. 48 is an improved version, in which two 0.2 mm thick,

2 mm wide NiTi strips were embedded inside silicone membranes
that mimic the wing skin of a bat. The NiTi strips were pre-trained
into a zigzag shape but straightened before being embedded into
silicone membrane. Subsequently, upon joule heating the NiTi
strips, they turn to zigzag shape again. Consequently, the wing
closes. When the power is off, the wing opens automatically.
Fig. 49 is another version of morphing wing, which is able to shift
quickly between two positions (curve-down and curve-up) upon
joule heating the top and bottom pieces of SMA alternately. Both
SMA pieces (at spring shaped NiTi SMA with a wire diameter of
0.2 mm) were pre-stretched by 100% before being embedded into
the silicone beam, which is about 5 mm thick. The reaction speed
is less than 1 s.
2.2.5. Micro vehicles
We have seen proposals of SMAs in automotive applications
over two decades ago [208]. Instead of using traditional motors,
which are complicated and bulky, high actuation stress and large
recovery strain in NiTi SMAs enable us to realize, highly possibly,
the simplest driving mechanism for micro vehicles. SMA based micro vehicles have been well explored and toys of such are available
in the market.
The simplest micro vehicle might be the one presented in
Fig. 50, in which a thin SMA wire is used for actuation, and an elastic steel strip serves not only as the body of the vehicle, but also as
the elastic spring to stretch the SMA during its cooling when power
is off. The two ends of the steel strip need to be carefully polished,
so that it is easier to move in one direction than the other. A
slightly more complicated version but virtually more efcient in
terms of much longer distance in one stoke and much faster is presented in Fig. 51, in which two one-way wheels are used together
with a SMA coil spring.
Fig. 52 shows a rolling car which is based on the working principle of moving gravity center. SMA springs are alternately joule
heated so that the mass at the center shifts accordingly. The mov-
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Fig. 47. Wings (frame) open/closure by joule heating SMA springs (ac). Zoom-in view of the joints at closure (d) and open (e) positions. Details of one joint (f).
Fig. 48. Wings open/closure by joule heating the embedded SMA strips. Left column: side view; right column: top view.
ing of the gravity center results in the car moving forward or

backward depending on the heating program, which is controlled
in a remote wireless fashion. Such rolling car can be further developed to have the ability to roll on the horizontal plane into any
directions.
Fig. 53 shows a microboat. Two SMA wires are joule heated
alternately to drive the rotation of the tail, which generates the
propelling force for the boat to move forward.
As we can see, SMA provides a simple actuation mechanism
that can signicantly simplify the design and fabrication, which
is particularly useful in micro sized actuations. We can effectively
combine the structure and actuation functions together to realize
The material is the machine [137].
2.2.6. Energy conversion

The concept of SMA based heat engine has been proposed and
demonstrated long time ago [26,209212]. Such heat engines can
be used as an environmental friendly alternative to extract
mechanical energy from low-grade energies, for instance, warm
wastewater, geothermal energy, etc. Typical SMA heat engines include turbine engine, offset crank engine, eld engine and kick engine, etc., using SMAs in the form of spring/coil or wire.
Fig. 54 is a simple schematic diagram to explain the theory behind the rotation of a SMA spring coil (presented by straight lines
for simplicity) based heat engine upon half-immersed into hot
water. The small ring at center represents a ball bearing where
one end of the SMA coil is attached to. The other end of the SMA
598
Fig. 49. Fast reaction morphing wing.
Fig. 50. SMA wire based inch worm. (a) Working principle; (b) picture of prototype (without power and control system).
Fig. 51. SMA spring based inch worm (without power and control system).
Fig. 52. Rolling car (power and control system is detached).
coil is attached to the wheel which is represented by a bigger

circle.
The force generated by a piece of SMA coil during the shape
recovery process at high temperatures is signicantly greater than
what is required for stretching at low temperatures. The net work

generated by the heat engine can be expressed simply as the difference in the work produced by the contracting of SMA coils and the
work required to extend the SMA coils.
The efciency of such heat engines has been investigated both
experimentally and numerically [213216]. It has been concluded
that SMA spring/coil based heat engines are low in efciency, less
than 5%. SMA rod/wire can improve the efciency but only slightly.
More importantly, it has been numerically proven that low temperature hot water is more efcient for low speed rotation, while
high temperature hot water is more efcient for high speed rotation. In other words, SMA heat engines can be designed to have
high efciency even the difference between high and low temperatures is small.
The low efciency nature of SMA heat engines eventually drove
most researchers interest away for a number of years before the
recent new round of energy crisis. The desperation for new sources
of clean energy brings a few old techniques back into the eld of
our vision.
Ocean thermal energy conversion, which utilizes the water
temperature difference between at the sea surface and in deepsea, has been investigated for a number of years. It was not fully
599
Fig. 53. Microboat activated by SMA wires. (a) Picture of prototype; (b) driving mechanism; (c) top-view (without top cover); (d) zoom-in view of the driving part.
Fig. 54. Schematic diagram of wheel rotation in a SMA based heat engine driven by hot water.
developed for massive engineering practices, largely because it also

suffers the disadvantage of low efciency. However, it does have a
number of apparent advantages, such as high reliability and high
stability, which can easily beat all other types of new clean energies, for instance, wind, tide and sunlight, in particular in the area
around the equator where the water temperature at sea surface level is pretty much constant all year round. Given such massive easily available ocean thermal energy on earth, if properly explored, it
could be a potential endless new clean energy source for human
being forever.
It must be pointed out that the traditional approaches for
extracting ocean thermal energy require as large temperature difference as possible for higher efciency in order to be economically
feasible. Practically speaking, the maximum possible temperature
difference between surface and deep sea is normally less than
24 C even down to 1000 m from the sea surface, which severely
limits the applications of this type of clean energy into only within
a small number of patches on earth.
On the contrary, since it has been proven that SMA heat engines
could be efcient as well even the temperature difference is small,
efcient SMA heat engines can be produced using SMAs with small
hysteresis and narrow transition temperature range purposely for
utilizing the ocean thermal energy, which has the limit temperature difference. As reported in [44], the transition temperature of
NiTi SMA could be tailored from below 0 C to over 100 C, while

the hysteresis could be as small as 2 C. In addition, NiTi SMA
has excellent corrosion resistance. Consequently, ocean thermal
energy could be a niche source for NiTi SMA heat engines to
explore.
The missions in the outer space require energy for, for instance,
running payloads, powering on-board electrical equipments and
communicating with the ground stations. At present, on-boardbattery is still heavy and very expensive and cannot last very long.
Thus, it is not able to provide enough power for long-term space
missions.
As a solution, solar energy turns out to be the source for additional power supply. Currently, the most well adopted approach
is to use solar cells, which convert solar energy into electrical energy that can be either used directly or stored in a battery for later
on usage.
Since the surface temperature of the part of a satellite which directly faces the sun could be over 120 C, while that of the part in
the shadow could be as low as 150 C, we have proposed SMA solar engine for space missions (Fig. 55). Although it is based on the
same working principle, the SMA solar engine can directly convert
solar energy (radiation), instead of thermal energy, into mechanical motion (rotation). Numerical simulation has been carried out
to investigate its performance under different conditions [217].
600
SMA spring
Solid ring
Non-covered
area
Solid bar
Covered
area
SMA spring
shaft
(a)
(b)
Fig. 55. Illustration of SMA spring based engine driven by solar radiation. (a) Without cover; (b) with cover. (Reproduced from Ref. [217], with permission.)
Fig. 56. Sunlight directly activated SMA heat engine (without cover). (a) Overall view (including the supporting base); (b) top view of engine; (c) details.
ground surface temperature: 45 C;

relative humidity: 40%;
sunlight intensity: 122 103 lux
has been recorded. The average output power is estimated to be
0.25 W.
In addition to heating SMAs directly upon exposing to a heat
source, recently it has been proposed to convert the chemical energy of high-energydensity fuels to mechanical energy. Such approach, rather than converting electrical energy into mechanical
energy as used in our daily life, is much closer to natures choice
to power muscles. Using high-energydensity fuels and Pt catalyst-coated NiTi SMA wire, it has been demonstrated that the actuation stroke (about 5%, which is 25% of human muscle) and power
density (68 W/kg, which is about the same as the typical value of
natural skeletal muscle, 50 W/kg) are comparable to those of natural skeletal muscle while the stresses generated, over 150 MPa,
are 500 times greater than that of typical human skeletal muscle
(0.3 MPa) [218].
We should bear in mind that theoretically speaking, all types of
SMA thermal engines mentioned above are limited to a maximum
efciency of 13%.
Direct splitting of water into oxygen and hydrogen under sunlight radiation has been an exciting research eld for some years
[219]. The produced hydrogen is ideal, in particular for fuel cell,
which is another hot topic at present aiming for high energy efciency. It is well known that titania, i.e., TiO2, is able to split water
into oxygen and hydrogen (photo-catalyst effect), but only under
ultraviolet light radiation, which accounts for only about 4% of
the incoming solar energy. Efciency can be improved if we can
use visible light, which accounts for about 43% of the incoming solar energy. Some progress has been made recently to enable TiO2
60
Concentration (at%)
Although the efciency of such solar engines is also low, they

could be integrated as parts of a satellite structure (thus, without
much requirement for additional weight and space during launching and operation in space) and may be used as driving mechanism
for deployable structures (smooth deployment without shock),
thermal shield (e.g., to auto-protect infrared cameras), and dust
cleaning (for instance, in missions on Mars). There are some potential applications for exploration.
As a supplement to traditional energies, solar energy is environmental friendly and clean, and is the origin of almost all kinds of
energies. Other than radiation in outer space, SMAs can be heated
by sunlight directly on earth through a lens for concentration.
Fig. 56 shows the prototype of an offset crank type of NiTi SMA
strip based solar engine. An average speed of 2 rpm under the conditions of
Ni 2p
O 1s
50
Ti 2p
40
30
C 1s
20
10
0
0
200
400
600
800
Etching Time (s)

Fig. 57. Typical XPS depth prole of a NiTi SMA thin lm at room temperature,
which reveals a thin TiO2 layer about 1020 nm atop NiTi thin lm. (Reproduced
from Ref. [84], with permission.)
working under visible light. Apart from using nitrogen-doped TiO2

nanotube array [220], another approach is to introduce an internal
stress in patterned TiO2 thin lm atop a polymer substrate [221].
High cost in fabrication of nanotubes is apparently a problem in
the former technique, while in the latter one, the adhesion and
durability between brittle TiO2 layer and polymeric substrate is always a big concern in real applications.
It has been reported that there is always a naturally produced
thin oxidation layer of TiO2, about 1020 nm, atop sputter deposited NiTi based thin lms (Fig. 57). Furthermore, following a particular heat-treatment procedure, reversible wrinkles can be formed
atop the lm surface upon thermal cycling [79,222] (Fig. 30). It
has been proven that the wrinkles are the result of elastic buckling
of the TiO2 thin layer [79], which results in the micron and submicron sized surface uctuation. Consequently, some parts of the
TiO2 (convex) are under tension, while some others (concave) are
in compression. This is ideal for water splitting under a wider
range of light spectrum, from ultraviolet to visible light. In addition, as the layer of TiO2 is resulted by natural oxidation and very
thin, the adhesion and durability between TiO2 and NiTi substrate
is not a question anymore.
This is probably a new research direction for NiTi SMAs in energy conversion utilizing water and abundant clean solar energy
in the greenest way. Of course, there is still a long way to go. For
instance, it is important to ensure the right type of TiO2 (anatase)
to be produced atop NiTi lms for the photo-catalyst effect.
2.2.7. Other applications
SMAs have attracted interest not only from engineering community, but also from artists. SMAs have been used as the actuation material for moving sculptures. Fig. 58 is an articial
mimosa, which rises upon joule heating the thin SMA wire, and
falls when the power is cut off. With a built-in sensor, such response can become fully automatic when someone touches it. Similarly, articial wigs using very thin SMA wires can be designed
601
which are able to instantly change styles, e.g., from straight to

curly, according to ones current mood.
Tactile displays based on SMA technology have been proposed
for computer interfacing and virtual reality applications to complement the visual presentation of information [223]. Fig. 59 reveals a
nger reading system for the blind. Each Braille cell includes an array of 2 3 protrusive dots. By heating individual SMA wires, particular dots disappear. This concept sounds simple, but is
practically limited by the reliability of the underneath mechanism
and becomes more complicated due to the dimensions constraints.
A new nger reading system will be discussed later on using SMPs.
Due to high energy absorption ability, SMA has been proposed
for aseismic isolation and passive control of buildings [224230].
In recent years, we have seen more applications of SMAs in civil
engineering, particularly for reinforcement and repair of damaged
structures due to, for instance, aging and decay [231238].
Files and Olson [239] might be the pioneers in crack healing
using SMA, followed by many others (e.g., [231,240,241]). In almost all previous studies, NiTi SMAs were used (owing to their
excellent corrosion resistance) and they were all embedded inside
a matrix. Given the still-high price and high density of NiTi, it turns
out to be unrealistic to massively apply this technique in civil
structures.
Instead of embedded NiTi SMAs, Fig. 60 shows that a piece of
external NiTi wire (1 mm diameter, which is xed to the bottom
of the beam through two adaptors) is used for not only shape restoration and but also crack closure of a silicone/nanoclay composite beam while it is still in service, i.e., with external load being
applied. The actuation is triggered by joule heating a 4% prestrained NiTi wire to about 55 C. The beam becomes almost fully
straightened and the crack is hardly visible after the NiTi wire is
heated. Together with standard structural repair/strengthening approaches, for instance, ber plate reinforcement (as in [242]) or
adhesive (as in [241,243]), the NiTi wire can be removed later on
and reused elsewhere. This technique can provide a convenient
Fig. 58. Articial mimosa. From left to right: upon joule heating SMA wire; from right to left: upon cooling.
Fig. 59. SMA based nger reading system for the blind. (a) Exposure view; and (b) cross-sectional view.
602
Fig. 60. Experimental set-up (a), zoom-in view of the cracked beam upon being loaded by a 3 kg deadweight (b) and overall view of cracked beam (fully closed) after NiTi
SMA wire is joule heated (c).
and cost-effective alternative to in situ repair of damaged structures even without interruption to their current service.
The SME has been observed atop NiTi thin lms at nano scale by
means of nano-indentation [244]. Based on this, high density data
storage (up to 0.5 Tbit in2) atop NiTi SMA thin lm has been demonstrated [245].
Lab on chip can effectively shrink a full sized laboratory down
to the size of a coin and has attracted a lot of interest from many
communities [246]. Microvalves and micropumps are required to
manage the ow of liquid within micro-channels [247]. SMA is
ideal for mini-actuators and has been proposed as the actuation
material for microvalves/pumpers [248250]. As illustrated in
Fig. 61a (bottom), two SMA springs were embedded inside a piece
of silicone (PDMS), which has a micro-channel in it. Both SMA
springs were pre-stretched before silicone was cured. The left
spring was not joule heated, so that the micro-channel was kept
open, while the right spring was heated by passing an electrical
current, so that the micro-channel within that part was closed. Silicone serves as the elastic spring to drive the SMA spring back to its
original shape when electrical current is switched off. This is virtually a valve, which is normally open, and can be activated instantly
and electrically (as demonstrated by a prototype in Fig. 61a, top). A

normally close valve can be designed in a similar way. If we have
three SMA springs, which are all pre-stretched, as shown in
Fig. 61b, following the right sequence to heat them, liquid can be
driven to move toward the right-side of the channel. This is a
micropump. The advantage of using SMA springs, instead of SMA
wires (or thin lms) as in many similar applications, is the large
reversible deformation that SMA springs can provide.
While Hirose et al. [184] are pioneers in SMA based active endoscope, one of the recent focuses in medical applications of SMAs is
on stents [251]. Traditionally once a SMA stent is deployed at the
required position, it will stay there forever [252254]. As a matter
of fact, retractable stents are highly demanded in many applications [255257], for instance, in patients recovering from complications of bladder and prostate cancer operations. Since stenosis
may develop at the anastomosis site in up to 18% of these patients,
repeated dilatations to allow for a reasonable voiding is required
by means of regular mechanical dilation, endoscopic incision or laser vaporization. Removable stent does not require a highly specialized reconstructive bladder neck repair procedure and only
needs for treatment once a year.
Fig. 61. Microvalve (a) (bottom: illustration; top: prototype) and micropump (b).
One of the approaches to realize retractable stents is to embed a

piece of SMA inside an elastic polymer ring/tube as illustrated in
Fig. 62a. An originally star shaped SMA ring was expanded into a
circular shape and then embedded inside a polymer tube. We
can properly design the stent (in terms of the stiffness of polymer,
dimensions of polymer/SMA, and how SMA is embedded within
polymer matrix) so that it can be deployed at the required location
(by means of many conventional approaches, for instance, pushing
it out of a catheter if it is highly elastic, or otherwise using a balloon for expansion). Once the stent is heated to above the transition temperature of SMA, SMA will try to recover its original star
shape, which causes the diameter of the stent reduced, to be ready
for removal. Fig. 62b is a prototype, in which the biocompatible
polymer is silicone. Since a SMA strip instead of a SMA ring was
used for the star shaped SMA, eventually, the stent did not contract
uniformly in all directions. Even so, we still can clearly see that the
concept is workable.
The working principle of the above discussed retractable stent is
the mechanical two-way SME. The material two-way SME together
603
with programmed recovery (either by means of gradient transition

temperature eld or the multi-SME) are additional options [258].
3. Shape memory polymers
While many engineering polymers do have the ability for a certain level of shape recovery, their SME is limited [259262]. Till today a lot of SMP systems have been developed and we still expect
to see more [16,36,263268].
In comparison with SMAs, the major advantages of SMPs are
[262]:
(1) Density is lower. As an example, the typical bulk density of
PU SMP is 1.25 g/cm3 [46,269]; while that of NiTi SMA is
6.4 g/cm3 [44].
(2) Not only the cost of raw material but also the cost in fabrication and processing is lower. In addition, SMP products
can be easily produced with high quality into almost any
specied shapes (including thin/ultrathin lms/wires, foam
Fig. 62. Polymer stent using embedded SMA for retraction. (a) Illustration. (a1) Original star shaped SMA; (a2) circle shaped SMA (temporary shape) embedded within elastic
polymer tube; (a3) after heating SMA for retraction; (b) snapshots of prototype upon heating by hot water.
Fig. 63. Shape recovery in a 300 nm thick PU SMP lm (produced by water oat casting) upon heating. (Reproduced from Ref. [270], with permission.)
604
with different porosity, etc.) at different scales using various

traditional and advanced polymer processing technologies
(such as, injection molding, extrusion, dip coating, spin coating, water oat casting, etc.) [25,46,262,270,271]. As typical
examples, Fig. 63 shows a piece of 300 nm thick PU SMP fabricated by water oat casting, Fig. 64 shows a PU SMP micro
spring, and Fig. 65 shows a nano sized PU SMP bead produced on a carbon nanotube (CNT).
(3) Recoverable strain is normally an order higher than that in
SMAs [44]. As shown in Fig. 66, a piece of PU SMP is able
to fully recover from a few hundred percent of pre-strain
(4)
(5)
(6)
(7)
Fig. 64. PU SMP microspring. Scale bar is 50 lm.
(8)
(9)
(10)
(11)
Fig. 65. Nano sized PU SMP bead on CNT (within dashed circle).
(12)
(13)
(14)
(after uniaxial tension at well above the glass transition temperature, Tg). For PU SMP foam, over 95% pre-compression is
fully recoverable [272,273].
It is easy to tailor the thermo-mechanical properties of SMPs
by means of, for instance blending with different types of
llers or varying the compositions [25,269,274288].
Fig. 67 reveals the dispersion of attapulgite, which is a nanofabric type of clay [282], within PU SMP matrix and the inuence of amount of clay in vol.% on the micro hardness of
composites. Fig. 68 shows the dispersion of carbon black
(powder) and Ni powder within PU SMP. The inuence of
carbon black on the Youngs modulus, elongation limit and
maximum recovery stress is revealed in Fig. 69.
It is possible to be always transparent [283,292], electrically
conductive [291,293], magnetic [294], and even with builtin threshold temperature sensors [295]. Fig. 70 reveals the
inuence of carbon black (CB) and Ni powder on the resistivity of PU SMP composites, while Fig. 71 shows the formation
of Fe3O4 magnetic chains within PU SMP.
Shape recovery temperature range can be easily altered
within a wide range and even gradient [297,298]. For
instance, after immersing into water for a different period
of time, a gradient Tg is introduced into the PU SMP wire.
As such, after programming into an m shape, the wire
recovers its original shape in a segment by segment manner
upon heating (Fig. 72).
Damping ratio in particular within the transition range is
higher [269].
The potential for recycle and reuse at low cost is higher
[299].
Many SMPs have excellent chemical stability, biocompatibility and even biodegradability [283,300307]. The degradation rate can be adjusted if required [308,309].
SMPs can be used as a drug carrier as an additional function
to effectively prevent infection [310,311].
Stimuli for SMPs include heat (by means of direct heating,
Joule heating, induction heating, infrared/radiation heating,
laser heating, etc.), moisture or solvent or change in pH
value, light, etc. [36,312319]. Fig. 73 reveals the moistureresponsive feature in a 1 mm diameter PU SMP wire upon
immersing into room temperature water, while Fig. 74
shows the recovery of electrically conductive PU SMP composites by joule heating under power of 30 V (about 1.2 W).
It is possible for truly wireless/contactless operation inside a
human body [294,320], offered by remote-contactless actuation by means of, for instance, applying an alternating magnetic eld for induction heating.
It is possible for a SMP to be activated by more than one type
of stimulus [275,297,317,318] and even with temperature
sensing function by means of color change [295].
The multiple-SME can be achieved by means of synthesis or
programming [27,321327]. Multi-stimuli or functionally
gradient SMPs have more advantages and exibility for the
multi-SME following a required recovery sequence (refer to
Fig. 75).
3.1. Mechanisms and concerns in implementation
Fig. 66. The SME in a PU SMP. Left: in uniaxial tension (well above Tg); middle: after
pre-stretching; right: after heating for shape recovery.
The SME in SMPs is based on a totally different mechanism.

Regardless of the types of the stimuli, there are two basic segments/domains in a SMP, one is elastic segment, and the other is
transition segment, as illustrated in Fig. 76a. While the elastic segment always maintains high elasticity within the whole SME cycle,
the transition segment does change its stiffness signicantly at the
presence of the right stimulus. We take thermo-responsive SMP as
an example in the following discussion.
605
Fig. 67. PU SMP/attapulgite composite. (a) SEM image of dispersion of attapulgite in PU SMP (30 vol.% of heat-treated clay). The scale bar is 200 nm [289]. (b) Micro hardness
of PU SMP/attapulgite composites as a function of clay content. (Reproduced from Ref. [290], with permission).
200
160
120
80
40
1
Young's modulus
Elongation limit
0
0
10
15
20
Elongation limit (%)
Young's modulus (GPa)
Fig. 68. Dispersion of carbon black and Ni powder in PU SMP. (a) Without Ni; (b)
randomly distributed Ni; (c) chained Ni. Gray dots: carbon black; white dots: Ni.
Maximum recovery stress (MPa)
Refer to Fig. 76b. Upon heating to above the Tg or melting temperature (Tm) of the transition segment, the transition segment
becomes soft and can be deformed easily. Thus, upon stretching,
the resistance is largely from the elastic segment. After that, upon
cooling the transition segment regains its stiffness while keeps
the deformed shape. Subsequently, the elastic segment is effectively prevented from returning back to its original shape even
after the removal of constraints. This is the temporary shape
(Fig. 76c), and the above procedure is the process for programming. It should be pointed out that elastic spring energy is maintained within the elastic segment, which is the driving energy for
the SME. In the last step, heating the SMP to above the softening
temperatures of the transition segment again, so that the elastic
segment is able to recover the original shape, which completes
a SME cycle (Fig. 76d).
Carefully examining the mechanism behind the SME reveals
that opposite to that in SMAs, SMPs normally are hard at low temperatures and become soft at high temperatures (dashed line in
Fig. 77). Therefore, SMPs alone are normally not applicable in cyclic
actuation, unless there is a V-shape in the stiffness vs. temperature
curve upon heating (solid line in Fig. 77), which has been found in a
couple of SMPs [329,330].
Above mentioned programming is done at above the softening
temperatures of the transition temperature. Practically speaking,
2.0
1.6
1.2
0.8
0.4
0
0
10
15
Volume fraction of carbon powders (%)
Volume fraction of carbon powders (%)
(a)
(b)
20
Fig. 69. PU SMP/carbon black composites. (a) Relationship of the Youngs modulus and elongation limit vs. volume fraction of carbon black at room temperature in uniaxial
tension; (b) maximum recovery stress against volume fraction of carbon black. (Reproduced from Ref. [269], with permission.)
606
Fig. 70. Resistivity vs. volume fraction of carbon black with/without 0.5 vol.% of Ni.
Inset gure illustrates how the resistance was measured. (Reproduced from Ref.
[291], with permission.)
some SMPs (e.g., MM series PU SMP currently marketed by SMP

Technologies, Inc. Japan) can be deformed at low temperatures as
well. However, we should pay attention on the similar front propagation phenomenon (as in SMAs) and possible fracture at micro
scale within SMPs when deformed at low temperatures. Fig. 78 reveals the buttery and switch phenomena in a piece of PS SMP,
which demonstrates the potential damage to the material if the
temperature during programming is not high enough [331].
A SMP sample (which had been well-polished to achieve very
smooth surface) was uniaxially stretched at a temperature which
is slightly below the glass transition nish temperature
(Fig. 78a). As such, some parts of the material, which were still
hard (indicated by a gray line), broke when the strain reached a
certain level (Fig. 78b). Given the SME at this temperature, at the
broken point, two peaks were formed together with two troughs,
which were perpendicular to each other and the peaks were parallel to the direction of uniaxial tension (Fig. 78c). After cooling back
and then removal of constraint, many micro sized butteries,
which were in slightly different sizes but all aligned along one
direction, could be virtually observed at the surface using a 3dimensional surface scanner (Fig. 78d). Subsequent slight polishing
(Fig. 78e) and heating of the sample (Fig. 78f) resulted in 90
switch of all butteries (Fig. 78g).
Fig. 72. Recovery in a programmed manner in a 1 mm diameter PU SMP wire upon

heating. (Reproduced from Ref. [297], with permission.)
Unlike that in SMAs, as reported in [27], the multi-SME can be

easily achieved in all SMPs and even in SMP foam [262] (Fig. 75b).
The TME, although appears in a different manner as compared with
that in SMAs (i.e., the temperature corresponding to the maximum
actuation stress in a pre-strained SMP sample upon heating is about
the temperature at which the sample is previously programmed),
has also been found and the mechanism has been investigated
[27,325].
Some SMPs are able to respond to more than one type of stimulus. This is an additional great advantage of SMPs over SMAs,
which can be utilized to achieve The material is the machine
[137]. Take the thermo/moisture-responsive PU SMP as an example. The PU SMP invented by Hayashi was originally synthesized
for the thermo-responsive feature only [46]. The nding of its
moisture-responsive feature began in 2002 from a piece of thin
lm PU SMP (about 1 mm think) which was pre-bended and left
in the air. Several weeks later, it came to us as a surprise that the
Fig. 71. Formation of Fe3O4 magnetic chains within PU SMP at different volume fraction of Fe3O4 powder (right vertical label) and different holding times of a magnetic eld
(top label). (Reproduced from Ref. [296], with permission.)
Fig. 73. Moisture-responsive feature in a PU SMP upon immersing into room

temperature water. (Reproduced from Ref. [297], with permission.)
SMP fully recovered its original shape and even became more exible than it originally was. This reminded us about the previous
observation in a piece of PU SMP foam, in which similar phenomenon was also found [272] but without any proper explanation at
that time. Subsequent experiments revealed that the Tg of this
SMP continuously dropped with the increase in the days exposed
in the air (Fig. 79). Shortly, high humidity in the air in Singapore
607
was identied as the possible cause behind this [332]. Eventually,

bonded water was spotted as the exact driving force for the moisture induced SME [333]. This dual-stimuli feature can be utilized
not only for moisture-responsive, but also for programmed recovery [270,297,334]. Till now, the thermo/moisture-responsive feature has been extended from PU SMPs to their composites
[275,276,282,312,317] (Fig. 80).
As compared with a few transitions and phases in SMAs, SMPs
are seemingly much simpler. However, the reality is actually just
the opposite. Apart from that traditionally, the behavior of polymers is known to be much more difcult to predict precisely (due
to reasons, such as signicant relaxation, degradation, etc.) than
that of metals/alloys, it has been reported that the SME in SMPs
may be affected by the programming conditions [335,336]. On the
other hand, same as that in SMAs [337,338], in the implementation
of the SME in SMPs in real engineering applications, there is another
concern which is about the possible change in the mechanism properties after programming [339]. According to Fig. 81, the stress vs.
strain curves of the elastic portion of a piece of PU SMP with/without 15% pre-strain are about identical. Beyond the elastic range, signicant strain hardening is observed if with 15% pre-strain. What is
reported in Fig. 81 is a short-term study (tested immediately after
programming). Middle/long-term studies (also including the SME)
on SMPs are still rather rare [272,340,341] despite the importance
in real engineering applications.
As for the triggering mechanisms for thermo-responsive SMPs,
joule heating of embedded SMA wire [342] and laser heating
[343346] have been developed as alternative heating methods.
3.2. Typical applications
Although SMPs caught peoples attention from various engineering communities much later than that of SMAs, at present they
are apparently undergoing rapid growth and becoming the leading
member within the fantastic world of SMMs. We have seen a wider
Fig. 74. Joule heating for shape recovery in electrically conductive PU SMP composites. Infrared images of samples with 10 vol.% of CB and 0.5 vol.% of chained Ni powder (a);
10 vol.% of CB and 0.5 vol.% of randomly distributed Ni powder (b); and 10 vol.% of CB only. (Reproduced from Ref. [291], with permission.) (Refer to Fig. 68 for typical
dispersion of particles and Fig. 70 for their electrical resistivity.)
608
Fig. 75. The multi-SME in thermo/moisture-responsive PU SMP upon immersing into room temperature water (moisture-responsive) (a) (Reproduced from Ref. [297], with
permission) and upon heating (thermo-responsive) (b) (from a1 to a4: straightening; from b1 to b4: untwisting).
(a)
(b)
(c)
(d)
Fig. 76. Schematic illustration of the mechanism in a SMP. (a) Original conguration in which the elastic and transition segments are tangled together (transition
segment is shown as a straight line for better visualization); (b) stretching at high
temperatures (transition segment becomes soft and can be easily deformed, while
the elastic segment is elastically deformed accordingly); (c) temporary shape at low
temperatures (transition segment becomes hard at low temperatures and thus the
recovery of the elastic segment is largely prevented); (d) shape recovery upon
heating which causes the softening of transition segment (the elastic energy in the
pre-deformed elastic segment is released). (Reproduced from Ref. [328], with
permission.)
range of applications than those of SMAs, from deployable structures in the outer space to medical implant, such as stents and sutures, from textile to active disassembly of obsolete electrical
devices, due to the advantages discussed above, in particular their
low cost and high versatility (e.g., [47,264,311,347358]).
Fig. 77. Change of stiffness in thermo-responsive SMMs upon heating.
There are a few good references for a comprehensive review

about the applications of SMPs. Among them, [16,262,359] are recently published books, which report extensively the updated progress in SMPs, from fundamentals to applications. For a brief
summary of medical applications of SMPs in minimally invasive
surgery till early 2009, one may refer to Appendix A.
In this section, only a couple of typical applications, in particular some novel ones developed recently, are presented.
3.2.1. Medical applications
Suture is a commonly used device in medical operations. However, in minimally invasive surgery, in general there is only a limited space for tying knots in order to secure the suture in place.
609
Glass transition temperature (C)
Fig. 78. Buttery and switch phenomena in a PS SMP. (Modied from Ref. [331].)
36
34
32
30
28
26
24
22
20
0
10
15
20
25
30
Days exposed in the air

Fig. 79. Decrease of Tg against the days exposed in the air in a thin lm PU SMP.
Even worse, the surgeons have to tie knots remotely through small
holes. SMP provides a good solution to this problem. Self-tightening SMP suture (even with biodegradable function) has attracted
great attention since this concept was proposed [303]. Instead of
using heat or light, Fig. 82 reveals a PU SMP suture which is able

to self-tighten a knot upon immersing into room temperature
water without any other interference. SMP wires with a diameter
of 10 lm, much thinner than human hair, can be easily produced
[262] (Fig. 64).
Stent is another promising area for SMPs. SMP stents can be
made into a solid tube shape to effectively prevent tissue ingrowth. Drug eluting is easier to achieve to prevent infection
[310,311]. Fig. 83 shows that by folding a circular shaped SMP
ring into a star shape at high temperatures, it is going to be much
easier to pack the stent into a catheter for later on delivery and
deployment. Biodegradable polymer stents, based on, for instance,
PVA poly(vinyl alcohol), PLA polylactide and PEG poly(ethylene
glycol), etc., have been invented in recent years [360]. Many
degradable SMPs have also been developed (e.g., [308,309]). Even
so, the ability of instant removal (due to any unforeseen reasons)
in any type of SMP stents is apparently a great advantage. Retraction in SMP stents can be achieved utilizing the moisture-responsive feature (Fig. 84) or the multi-SME [262]. The latter, i.e., the
multi-SME, has been proven to be an intrinsic feature of all SMPs
[27].
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Fig. 80. Moisture-responsive in PU/clay composite. (a) PU; (b) PU with 5 vol.% of treated clay; (c) PU with 5 vol.% non-treated clay; (d) PU with 10 vol.% non-treated clay.
40
Tensile Stress (MPa)
With 15% pre-strain

Without pre-strain
30
20
10
0
0
10
Tensile Strain (%)

Fig. 81. Strain vs. stress curves in a piece of PU SMP with/without 15% pre-straining
(programmed at Tg + 15 C).
Targeted drug release on specied cells at molecular level is an

attractive topic in current medical research [361]. On the other
hand, toward a miniaturized mechanical surgeon [362], we need
many tiny tools/machines. SMMs, in particular SMPs, could be
the right material for them [21,270]. Fig. 85 reveals the delivery
of a PU SMP coil into a jellysh by injection, which demonstrates
the feasibility of concept to deliver a big object through a small
hole.
Of course, for real cellular surgery, this is not enough. We need
to develop tiny machines, which might be activated directly by a
laser beam from outside of the cell [363]. Micro sized (Figs. 65
and 86c) and even nano sized beads (Fig. 65) have been produced
on carbon ber or carbon nano tube using PU SMP. Fig. 86a further
reveals that upon joule heating a piece of carbon ber which was
immersed into PU/dimethylformamide(DMF) solution, SMP beads
were produced and they grew bigger and longer, and eventually
became a wire at a prolonged heating time. For a better view, we
plotted the geometrical dimensions of beads against heating time
in Fig. 86b. Refer to Fig. 86c for the denitions of the geometrical
dimensions. It is clear that the size/shape of the beads can be controlled. In addition, the SME in the beads has been veried (refer to
Fig. 87 for typical result).
Fig. 82. Self-tightening of a SMP knot upon immersing into room temperature water. (Reproduced from Ref. [334], with permission.)
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Fig. 83. SMP stent.
Fig. 84. Retractable stent utilizing the moisture-responsive feature in PU SMP. (Reproduced from Ref. [334], with permission.)
Excellent shape recovery has also been demonstrated in a

170 nm thick PU SMP thin lm [21] and nano sized PU SMP protrusion (Fig. 88). At this point, we may conclude that we have indeed
established a solid platform to explore cellular surgery using SMP
based tiny machines. We expect that tiny machines might be produced by using a similar technique of cell printing (at a smaller
scale, [364]), laser assisted polymer growth [365] or self-assembly,
etc.
3.2.2. Surface patterning
Braille is a form of printing for the blind or partially sighted people to read and write by means of nger touching. It consists of
patterns of raised dots in a conguration of a 3 2 matrix. Those
dots made either manually by stylus and slate or automatically
by a thermo-set typing machine (Fig. 89a) atop a conventional paper or plastic paper (called braille paper or braillon) are rather difcult to remove. SMP braille paper enables the removal of any
typos instantly using hot water (Fig. 89b) or a point-heater for
dot-removal [366], just like normal writing with eraser, or to recycle the whole piece of paper by heating (Fig. 89c1-c3).
A technique called IndentationPolishingHeating (IPH) has

been developed to produce various shaped and sized (down to submicron size) protrusions atop SMP [367,368]. Although indentation
test may not always be able to produce identical indents [352], it is
a good technique in IPH to produce protrusions. As shown in
Fig. 90, depending on the indentation temperature, polishing depth
and with/without pre-in-plane-stretching, circular/elliptical and
at head/crown head/trench shaped protrusions are resulted. If a
sharp indenter (e.g., Berkovich indenter) is used instead of a spherical indenter as used in the experiments of Fig. 90, we can get different types pf pyramid shaped protrusions with at or sharp tops.
It should be pointed out that same as in SMAs, whether the resulted indent is pile-up or sink-in in SMPs is also indentation temperature dependent. However, since SMPs are soft at high
temperatures and stiff at low temperatures, which is right opposite
to SMAs, the temperature condition for pile-up or sink-in in SMPs
is also opposite.
An array of protrusions can be produced at different scales by
compressing compactly packed hard balls atop SMP or laser heating
a pre-compressed SMP [366,370,371]. The latter approach is instant
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Fig. 85. Delivery of a SMP coil into a jellysh by injection. (a) Original coiled shape;
(b) after being straightened at high temperatures; (c) ready for injection; (d)
recovered shape. (Reproduced from Ref. [21], with permission.)
and more convenient for massive fabrication over a large area, in

particular when a microlens array is used so that an array of protrusions can be instantly produced in one single shot (see Fig. 91).
As well known, surface tension and many other surface related
properties (e.g., reection, bonding, adhesion and friction etc.) at
the surface of a material depend on the surface conditions (e.g.,
[372376]). A number of approaches have been proposed to produce various types of patterned surfaces based on different principles [377379]. IPH is one of them, which utilizes the SME in SMPs
to produce protrusive patterns.
Wrinkling is a natural approach to release the elastic energy.

This phenomenon has been widely used to produce surface patterns in a cost-effective manner [380]. Although most of the wrinkling study in the literature is atop soft polymer substrates, due to
the shape memory feature, wrinkling atop SMPs is more exible
and convenient [369,370,381].
If a piece of SMP is pre-stretched and then coated with a very
thin layer of elastic lm, e.g., gold, after heating for shape recovery,
the strain mismatch between the SMP substrate and the gold thin
lm will result in the elastic buckling of gold lm. Consequently,
strip shaped micro wrinkles are formed (Fig. 92a). On the other
hand, if the SMP sample is coated with an elastic layer but without
pre-stretching, after heating to much higher temperatures than the
Tg, labyrinth shaped wrinkles will be produced (Fig. 92b).
The wavelength of wrinkles can be altered through controlling
the mechanical properties and the thickness of the system [382].
So far, submicron sized wrinkles have been observed [383].
Fig. 93 reveals submicron sized wrinkles produced on the surface
of a PU SMP thin wire. It has been reported that a wrinkled surface
has remarkable inuence on the shape and contact angle of a water
droplet [384]. Xie et al. [385] demonstrated the feasibility to encode localized strain history through wrinkles based structural colors atop SMP.
A combination of wrinkle/protrusion atop SMPs enables us to
produce various types of surface patterns in a cost effective manner [262,386]. For instance, a close-look of the wrinkles atop the
surface of a micro sized spherical protrusion in Fig. 94 undoubtly
reveals the variety of wrinkles patterns, which were resulted by
a different pre-strain eld introduced onto the sample surface after
processing.
A surface pattern with double roughness, e.g., wrinkles atop micron/submicron sized protrusions, has been identied as a very
effective technique developed by nature for, for instance selfcleaning in lotus leaf [387]. Fig. 95 reveals a wrinkled surface with
some micron sized protrusions on the surface. A zoom-in-view,
Fig. 95c and d, reveals two levels of wrinkles (i.e., wrinkles within
wrinkles), which is another form of double roughness.
As compared with SMAs, SMPs are more exible in surface patterning for different patterns at different scales, and the resulted
surface patterns are more permanent.
Fig. 86. Evolution of geometrical dimensions of micro beads at different joule heating time. (a) Superimposing of typical beads (and eventually wire) produced at different
joule heating time for easy comparison; (b) geometrical dimensions against heating time relationships; (c) denitions of geometrical dimensions.
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Fig. 87. The SME in a PU SMP microbead. (a) After compression; (b) after heating for shape recovery.
Fig. 88. The SME demonstrated by indentation test (using a at-end indenter). Top: 3-dimensional view; bottom: comparison of cross-sections (inset: depth vs. force curve in
instrumented nano indentation test).
3.2.3. Other applications

3.2.3.1. Active assembly/disassembly. Screw is a commonly used
component for assembly. Conventionally, different sized screws
are required for respective different sized holes. However, a SMP
screw can be used as a one-for-all solution for a range of different
sized holes, with/without thread and even a screw driver is not
needed for tightening [262,366].
Similarly, SMP coupling provides a good solution to tightly hold
two tubes in a range of different diameters together. This concept,
so called active assembly, was demonstrated as a micro tag xed to
the leg of an ant in Fig. 96. The advantages of SMP tag are:
Due to a high recoverable strain normally in an order of 100%,
SMP tag can be pre-expanded into a very large diameter. As
such, it is easy to mount it onto the leg of an ant.
The required heating temperature to trigger the SME can be tailored. In this particular case, the Tg of this SMP is 35 C, which is
well within the safe range.
The recovery stress upon heating can be controlled to avoid

over compression to the leg.
After cooling back to room temperature, the SMP tag becomes
hard and is rmly attached to the leg.
While we are enjoying the convenience brought to us from the
development in advanced technologies, obsolete electrical devices
have become a big environmental threat. Active disassembly
using SMAs and SMPs has been proposed to massively disassemble them for recycling in a cost-effective manner [355,388,389].
Two basic concepts of active disassembly using SMPs are demonstrated here.
Fig. 97 shows automatic opening of a hole upon heating. The
cover panel is made of SMP with an original size slightly smaller
than the hole. It was compressed at high temperatures to t into
the hole and stayed there rmly after cooling back to working temperatures. Upon heating to above the Tg, the SMP shrank and consequently, the hole opened.
614
Fig. 89. Refreshable Braille paper.
Fig. 90. Protrusions produced by IPH method. Right: numerical simulation and comparison with different shaped protrusions from experiment. (Reproduced from Ref. [369],
with permission). Left: elliptical shaped protrusions (with pre-in-plane-stretching.)
A SMP screw can function as an ordinary plastic screw

(Fig. 98a). However, upon heating, the thread disappears
(Fig. 98b). If an electrical device is assembled using a few this kind
of SMP screws but with different shape recovery temperatures,
when heated gradually, the device will disassemble into parts in
a step-by-step manner. As such, it becomes convenient to sort
out different parts at different stages for recycling with high

efciency.
Given its low-cost, electrically nonconductive and large recoverable strain nature, SMPs are more ready for active assembly/disassembly than SMAs. The multiple-SME may be utilized to
integrate active assembly and active disassembly together.
615
Fig. 91. Array of protrusions. (a) By compressing a layer of compactly packed hard spherical balls atop SMP (Reproduced from Ref. [371], with permission); (b) by laser
heating (Reproduced from Ref. [366], with permission).
Fig. 92. Two types of wrinkles atop SMP. (a) Strips; (b) labyrinths. Left: 2-dimensional view; right: 3-dimensional view. (Reproduced from Ref. [369], with permission.)
Fig. 93. Submicron sized wrinkles atop a PU SMP thin wire.
3.2.3.2. Morphing wings and deployable structures. As an actuation

material, SMAs are more powerful than SMPs. The actuation stress
in SMAs is 10s MPa and above, while that in SMPs is a few MPa at
the most. However, SMPs have the advantages of low cost, lightweight and large recoverable strain. SMPs can be integrated into
mechanical/structural design as one part or parts of a structure
for load carrying under normal working situation.
Fig. 99 demonstrates the feasibility to achieve wing morphing
using SMP in an airplane model. The whole left wing is made of
a piece of electrical conductive SMP. When joule heated, the SMP
wing recovers its original shape and becomes at. Fig. 100 is a
hinge, in which a pre-stretched SMP thin lm is used to activate
the atting motion when heated. This hinge can be used to tilt
winglet.
Deployable structures, including wheels, masts, solar sails, solar
arrays and antennas, etc., are expected to be compact when packed
inside the launching rocket, and once in position, change to an expanded conguration [390]. SMP foam, which can be compressed
by up to 95%, and is stiff enough at low temperatures to carry a rea-
616
Fig. 94. Different wrinkles patterns atop PS SMP spherical protrusions. Left column: 3-dimensional view; right column: 2-dimensional view from top.
Fig. 95. Protrusions and double wrinkles. (a) SEM image; (b) zoom-in view of a protrusion and wrinkles within wrinkles in the surrounding area; (c) 2-dimensional view of
(b).
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4.1. Basic mechanism and working principle
Fig. 96. SMP micro tag. (Reproduced from Ref. [273], with permission.)
sonable amount of load after shape recovery, is ideal for such missions. As demonstrated in Fig. 101, a micro car (SMP transformer)
can signicantly shorten its length in the compact conguration.
4. Shape memory hybrids
Despite the properties of SMPs can be more easily tailored than
SMAs, the successful synthesis of a particular SMP for a special application normally requires strong chemical/polymer background,
years of experience and great efforts in trial and error. This is not
readily accessible to even every materials researcher. SMH can
provide an alternative solution that is based only on some simple
concepts and utilizes only ordinary materials, which have wellunderstood properties but do not have shape memory as an individual. Thus, the design of a SMM for a particular application turns out
to be a routine which is easily accessible by ordinary engineers and
even non-professionals in a do-it-yourself (DIY) fashion [262].
The mechanism behind the shape memory phenomenon in

SMPs is the elastic-transition segment/domain system. This concept can be explored further and wider. For example, we can select
silicone and wax, both are biocompatible, as the elastic matrix and
the transition inclusion, respectively (Fig. 102a). While silicone
normally keeps its high elasticity characteristic within a wide
range of temperatures, wax melts upon heating to its melting temperature, and becomes very soft. As such, we can easily compress
the sample as illustrated in Fig. 102b. The silicone matrix is elastically deformed, so that an elastic energy is stored in it. When the
sample is cooled back to room temperature, wax becomes solid
again, which can effectively prevent the release of the elastic energy in the silicone matrix. Consequently, after the constraint is
fully removed, the sample largely maintains its deformed shape
(Fig. 102c) until it is heated again to above the melting temperature of wax (Fig. 102d).
This looks identical to that of SMPs. However, in SMHs, both the
matrix and inclusions are not limited to polymers only, but can be
selected from any materials. Previously, [391] has mixed an elastomeric ionomer and low molar mass fatty acids and their salts in the
design of SMPs. This is very close to the concept of SMHs.
In order to work out a right SMH which meets the required
function(s) in a particular application, both matrix and inclusion
can be chosen from metal, organic and inorganic, etc. (Fig. 103).
Ideally, in a SMH, there is not any chemical interaction between
the matrix and the inclusion, so that the properties of individual
materials are largely maintained. Therefore, we can well predict
the properties of SMH from the very beginning. For instance, the
transition temperature of SMH is the softening temperature of original inclusion material. Aging, relaxation, and fatigue etc. can be
well controlled.
Fig. 97. Automatic hole-opening upon heating.
Fig. 98. SMP screw for active disassembly. (a) SMP screw in normal working condition; (b) threads disappear after heating for shape recovery.
618
Fig. 99. Wing morphing (in left wing) by joule heating. (Reproduced from Ref. [366], with permission.)
Fig. 100. SMP based hinge.
Fig. 101. SMP transformer. (a) Packed shape; (b) shape restored. (Adapted from Ref. [273], with permission.)
Some unconventional approaches can be applied to not only

fabricate and but also program SMHs. Fig. 104 reveals the hole-closure process in a sample upon immersing into room temperature
water. It demonstrates the quick water-responsive feature (within
about 6 min) of this SMH, which is made of elastic sponge (as the
matrix) and cupric sulfate pentahydrate (as inclusion). High watersolubility is the reason that cupric sulfate was selected to achieve
water-responsive feature. The fabrication/programming procedure

is integrated together [29]. The main steps are,
(1) Insert a cone into the sponge.
(2) Immerse the sponge (with the cone) into saturated cupric
sulfate solution at 100 C and squeeze the sponge for full
absorption of solution.
619
Fig. 102. Illustration of mechanism for the SME in SMH.
and high recovery stress are not easy to be satised simultaneously

in SMPs by means of polymer modication. However, in SMHs, by
selecting the right matrix material and its microscopic conguration (a right processing technique with a certain composition,
etc.), we can design a SMH which meets both of them.
4.2. Demonstration of features in SMHs
Typical experimental results are presented in this section to
demonstrate what we can achieve in SMHs. It should be pointed
out that the samples used in these tests were not optimized (in
terms of composition and fabrication technique, etc.), so that improved performance might be achieved after further investigation.
Fig. 103. Possible components of SMH.
(3) Cool down the solution for crystallization of the cupric sulfate pentahydrate.
(4) Remove the cone.
The exibility in design and fabrication of SMH provides an easy
access to ordinary people, even without much chemical/polymer
background. Furthermore, one can predict the major properties
and behaviors of the SMH even in the early design stage by means
of materials selection and simple estimation. As such, anyone can
conveniently and quickly design his/her own SMH and fabricate
it shortly. On the other hand, SMHs are convenient to be tailored
to meet the exact requirement(s). For instance, high recovery strain
4.2.1. Thermo-responsive SMH

As mentioned above, a hybrid made of silicone and wax is an
ideal example to discuss about the concept of SMHs. Its excellent
SME is demonstrated in Fig. 105, in which a piece of pre-bent silicone/wax (around 30 vol.%, with a melting temperature of 45 C)
sample fully recovers its original straight shape in 15 s upon
immersing into hot water, which is about 25 C above the melting
temperature of the wax.
The multi-SME in silicone/wax hybrid is examined in two ways.
In one sample, two types of waxes with melting temperatures of
45 C and 65 C, respectively, were used. The exact programming
procedure is revealed in Fig. 106. The straightened piece of SMH
becomes curved at 24 C and then straightened at 80 C as shown
in Fig. 107, i.e., the tip deection is in a down-up fashion.
Instead of loading two different waxes, down-up type of tip motion upon immersing into hot water has been achieved in a silicone/wax hybrid with only one type of wax (Fig. 108). This is
essentially based on the same working principle for the multiSME in SMPs [27]. A wider melting range is ideal for programming
to show the multi-SME.
One such hybrid (with one type of wax) was placed against an
elastic strip at its free-end and the whole setup was placed inside
Fig. 104. Shape recovery (hole closure) of sponge/cupric sulfate pentahydrate hybrid upon immersing into room temperature water. (Reproduced from Ref. [29], with
permission.)
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Fig. 105. Shape recovery in a silicone/wax SMH upon immersing into hot water.
Fig. 106. Programming process.
Fig. 107. Shape recovery sequence upon heating to different temperatures.
Fig. 108. Shape recovery in a silicone/wax SMH (with one wax). (Reproduced from Ref. [21], with permission.)
621
Fig. 109. SMH in cyclic actuation. (Reproduced from Ref. [21], with permission.)
a hot-water bath (Fig. 109). During heating, the hybrid pushed the
elastic strip downwards (i.e., the hybrid became stiffer), while during cooling, the elastic strip pushed the hybrid upwards (i.e., the
hybrid became softer). Such thermal cycling was repeated many
times and everytime the response was the same. As such, the ability of this SMH for cyclic actuation is proven. To have a more
understanding of the actuation stress quantitatively, a piece of
cylindrical shaped SMH (20 mm diameter, 12 mm high) was thermal cycled in a hot chamber against a constant pressure of 176 kPa.
Heating/cooling was kept at a very low speed to aim for a more
uniform temperature distribution within the sample. As revealed
in Fig. 110, more than 6% reversible strain, which is comparable
to that in SMAs, was achieved.
Instead of using wax as the inclusion material, water can be
loaded into silicone. Since the transition from ice to water is at
around 0 C, the shape recovery temperature range of this SMH is
very sharp (Fig. 111).
Additionally, we have demonstrated the possibility to trigger
the shape recovery either by heating or cooling in a silicone/metal
SMH (Fig. 112).
4.2.2. Multi-stimuli-responsive SMH

Same as cupric sulfate pentahydrate, sodium acetate trihydrate
is dissolvable in the water as well. In addition, unlike cupric sulfate
pentahydrate, which does not melt when heated to release the
water molecules, sodium acetate trihydrate melts at around
70 C (i.e., sodium acetate dissolves within its own released water).
It is an ideal inclusion material to demonstrate the thermo/waterresponsive feature [29]. As revealed in Fig. 113, while shape recovery can be nished within a couple of seconds upon heating to
above the melting temperature of sodium acetate trihydrate, it
takes much longer time for water induced shape recovery, because
sodium acetate trihydrate micro powders are embedded inside silicone so that the penetration of water into the sample to dissolve
sodium acetate trihydrate is slower.
4.2.3. Pressure-responsive SMH
Stress-responsive materials have been developed (e.g., [392]),
but stress-responsive SMMs have yet to be well explored, although
they do have great application potentials as well [393]. Two approaches have been proposed by [262] to achieve pressure-respon-
Co
g
oli
n
Co
ing
oli
n
10
Heat
Compression Strain (%)
15
10
Time (H)
Fig. 110. Compression strain against time (in hour) in a SMH during thermal
cycling against a constant stress of 176 kPa.
Fig. 111. The SME with sharp transition temperature range using water/ice as
transition inclusion.
622
Fig. 112. Thermo-responsive SMH by either heating (a) or cooling (b) for shape recovery.
Fig. 113. Thermo-responsive (a) and water-responsive (b) SME in a SMH.
Fig. 114. Pressure-responsive SMH. (a) Original shape; (b) pre-compressed shape; (c) after compression (impact load).
sive feature in SMHs. One approach is to load special llers into a

thermo-responsive SMM. Such ller should be able to generate
heat upon pressing, so that the SMM can be self-heated for shape
recovery. The other approach is based on the concept of SMH, in
which the transition segment (inclusion) softens when compressed. Preliminary result following the second approach is demonstrated in Fig. 114. After 17% pre-compression, over 60%
recovery was observed after applying a compressive load to it.
623
Fig. 115. Rubber-like SMH (at low temperatures). (a) Cyclic tensile result of original dog-bone shaped sample; (b) cyclic tensile result of deformed sample. Both strain and
stress values are nominal.
624
Fig. 116. Retractable stent using rubber-like SMH.
Fig. 117. Self-healing in a rubber-like SMH. (a) SMH with an embedded SMA spring inside (illustration); (b1b2) pulling SMH till fracture; (b3b4) joule heating SMA coil for
self-healing; (c) healed sample; (d) healed sample in bending. (Reproduced from Ref. [21], with permission.)
0.8
0.9
(1,0,0)
(0,0,-1)
(1,0,-1)
(1,1,0)
(0,-1,-1)
0.8
0.7
0.6
1-K/K max
1-K/K max
0.6
0.5
0.4
0.3
0.5
0.4
0.3
0.2
0.2
0.1
0.1
0
(1,0,0)
(0,0,-1)
(1,0,-1)
(1,1,0)
(0,-1,-1)
0.7
0.2
0.4
0.6
(a)
0.8
0.2
0.4
0.6
0.8
DM
(b)
Fig. 118. n vs. (1 K/Kmax) of NiTi under different stress-state in the phase transformation (a) and detwinning (b). (Reproduced from Ref. [441], with permission.)
4.2.4. Rubber-like SMH with repeated instant self-healing function

In fact, all silicone based SMHs show a certain level of rubberlike behavior at room temperature, which is due to high elasticity
of silicone. However, at room temperature, silicone/melting glue
hybrid has even better elasticity than silicone (Fig. 115a), even
(a)
(b)
625
after being programmed (Fig. 115b). The enhanced elasticity in silicone/melting glue hybrid was found to be the result of the plastize
effect due to the dispersed melting glue chains at submicron scale.
Melting glue also serves as the transition segment. A series of
experimental investigation reveals that the shape recovery temperature is determined by the melting temperature of the melting
glue. 100% recoverable strain was observed in a silicone/melting
glue (40 vol.%) hybrid.
A combination of good elasticity and excellent SME enables this
hybrid to be a potential candidate for retractable stents. As demonstrated in Fig. 116, a piece of star shaped SMH was expanded by
15% (in terms of the total length of SMH) at high temperatures.
After cooling back to room temperature, the stent was close to
hexagon shape and much bigger than the original star shape. The
programmed stent can be packed into a very small size (e.g., inside
catheter), delivered to the required position and then elastically
deployed. Upon heating, the stent returned its original shape,
which is much smaller, so that it is ready to be taken out.
The SME refers to the ability to recover the original shape (e.g.,
crack closure). However, strength recovery (e.g., crack healing) is
actually more important in structural materials. Tremendous efforts have been devoted into developing self-healing materials in
recent years [394,395]. Most of the techniques developed so far
use healing agent, which is either embedded inside micro-capsules
or delivered to the required location through micro-channels for
healing small cracks [396398]. This concept is only applicable to
cracks with limited size and once the healing agent is used up,
the healing process ceases. In addition, since it is a polymerization
process, healing time cannot be shortened to within a few minutes
[399]. Brownian motion induced polymer chain crawling has also
been applied for self-healing but with limited performance
[400,401]. In recent years, the DielsAlder reaction, metalligand
coordination, hydrogen bonding have been proposed as alternatives to achieve repeated self-healing in composites [402407].
Silicone/melting glue hybrid has been demonstrated to have the
ability for repeated and instant self-healing [21]. Fig. 117a reveals,
a SMA spring, which when joule heated, serves as the heating
source and pulls SMH together, was embedded inside a silicone/
melting glue hybrid. The SMH was stretched until it broke into
two parts (but linked by the stretched SMA spring). Passing an
electrical current to joule heat the SMA resulted in not only the
two SMH parts joined together, but also the whole piece of SMH
was heated (Fig. 117b). After cooling back to room temperature,
when being bent, the piece of SMH is as elastic as it previously
was and there is no apparent crack (Fig. 117cd).
5. Modeling of SMMs
(c)
Fig. 119. Yield surfaces of SMAs in some special principal stress planes (the
maximum scheme). (a) In (r1 r2, r3 = 0)-plane; (b) in (r1 + r2, r3 = 0)-plane; (c)
position of apex, where (dep ep1 ep2 ep3 [(a) and (c) are reproduced from Ref.
[450], with permission].
Simulation has become a very important part in engineering design in these days. Modeling of materials is the fundamental part in
engineering simulation. A good understanding of the behavior of a
material is the pre-requirement for modeling it with good accuracy. Systematical and extensive experimental works under various conditions are the technical foundation in order to obtain
complete knowledge for modeling.
At present, it should be reasonable to claim that the underlying
background of the SME in SMMs at microscopic level has been
more or less well captured. However, in terms of precisely modeling the thermo-mechanical response of SMMs, which is at macroscopic level, our understanding is still well lagging behind. It seems
that we have got well documented experimental results in the literature for different SMMs, in particular for SMAs. However, a close
look reveals that it is rather rare that a particular SMM has been
systematically reported for all its behaviors under all kinds of conditions. At least such information is not easily available in any pub-
626
zz
II
I
II
6
7 8
5
4
1
10
11
2
xx
yy
1
0
(a)
(b)
Fig. 120. Strains satisfy the von Mises criterion in the (exx, eyy, ezz) space. (a) Overall view; (b) details in zones I and II. (Reproduced from Ref. [451], with permission).
60
1.5
1
40
0.5
20
0
-0.5
-1
2 (MPa)
2 (MPa)
6M1
M18R
-1.5
M18R
-20
6M1
-40
-2
-2.5
-60
6M2
-3
-3.5
6M2
-80
-3
-2
-1
-80
-60
-40
-20
1 (MPa)
1 (MPa)
(a)
(b)
20
40
60
Fig. 121. Yield surfaces of CuAlBe (a) and CuZnAl (b). Black: maximum scheme; gray: average scheme; symbols: experimental data from Ref. [446].
lic domain, but (maybe) being kept deep inside the cabinet by individual manufacturers.
For conventional engineering materials, they are off the shelf and
only need a couple of standard experiments for characterization (in
most of cases, these results are already available in the catalog for
customers to compare and select). Unfortunately, the situation for
SMMs is totally different. On the one hand, so far even for SMAs,
there is not any international standard at all. Each supplier develops
its own products and has its own standard. On the other hand, in
terms of characterization, SMMs are far more complicated than conventional engineering materials. As such, in many occasions, except
a couple of parameters, e.g., the transformation temperature and
maximum strain, which we can get from the suppliers, we need to
do the rest of the characterization works by ourselves.
In this section, a brief discussion on modeling of SMMs is presented. We focus on practical approaches, which are more suitable
in engineering practice.
5.1. Modeling of SMAs
Many constitutive models have been developed to describe the
thermomechanical behavior of SMAs. In [113], the models for
SMAs are divided into the following categories:
Phenomenological models based on the uni-axial stressstraintemperature data [408411];

A theory of non-equilibrium thermostatics that describes the
thermodynamic paths of SMA [412];
Models based on the interaction of the different sets of atoms in
the alloy [413];
Models derived from a special free energy formulation
[414,415];
Models based on thermodynamic laws [105,416];
Constitutive laws based on a model for hysteresis, e.g., Preisach
model [417];
Model based on nonlinear thermo-plasticity theory, general
plasticity, or visco-plastic theory [418,419];
Mathematical models for the dynamics of phase boundary
motion [420,421];
Models derived from the deformation of crystal structure during phase transformation [422,423];
Constitutive laws that allows for micro-structural deformation
during phase transformation and the free energy concept, using
an energy dissipation or energy balance approach [424427].
Although the above categories were proposed more than
10 years ago, these categories are still largely intact, although on
the one hand the members under some categories have expanded
signicantly and on the other hand some hybrids have been developed (e.g., [428,429]). The recent book edited by Lagoudas [43] is a
good reference for a summary of various models, in particular
those theoretical ones.
Although it is necessary to start from the very basic, i.e., the micro-structural changes that occur during transitions, in order to
work out the underlying mechanisms, in practice, we have a lot
of difculties to determine many parameters in modeling
[430,431]. It becomes even more complicated in polycrystals with
multiple transitions due to non-uniformity and/or incomplete
transformations in phase transformations and reorientations (e.g.,
[93,94,166,432437]). As reported in, for instance, [338] and
[337], while the Youngs modulus of SMAs follows a V-shape curve
in cyclic uniaxial tension, the energy dissipation also varies simultaneously. As such, it is still not easy to develop a theoretical model
to precisely simulate the response of SMAs under all conditions.
627
From an engineering application point of view, the most practical and productive approach for modeling is still based on phenomenological ones. This is particularly applicable in proportional
loading cases, which are practically more common in actuators
made of polycrystal SMAs under cyclic actuation and in one dimensional loading. Historically, Prof. K. Tanaka should be the pioneer,
who proposed the rst phenomenological model for SMAs
[408,409].
Consider a one-dimensional case, in which a piece of SMA is under uniaxial tension. In a phenomenological model, the total strain
(e) includes three parts, namely elastic strain (ee), transformation
strain (et) and thermal strain (eT), i.e.,
e ee et eT
As a rst order estimation, we assume that the Youngs modulus (D)

and thermal expansion coefcient (a) of a SMA are always constant.
As such, one has
Fig. 122. Transformation start surface of NiTi (polycrystal, austenite) in 3-dimensional principle stress space. (a) The maximum scheme; (b) the average scheme. (Reproduced
from Ref. [102], with permission.)
628
ee
r
D
et etmax n
eT a DT
2
3
From modeling point of view, in the case of loading at a given

temperature, according to the classic theory of plasticity, n determines the hardening response of a material.
where r is tensile stress, etmax is the maximum transformation

strain, n is the fraction of transformation, a measure of the transformation progress, and T is the temperature difference from the
reference temperature. Within normal working temperature range
(i.e., from 50 C to 150 C), when compared with et, eT is relatively
small (about 0.2% even for a temperature variation of 200 C) and
may be ignored for simplicity.
The next step is to nd etmax and n. etmax can be experimentally
determined by conducting a few stretching/heating tests [438].
For commercially available polycrystal NiTi SMA wires, it is about
6.7% [438,439]. n, the transformation function, is a function of (r, T)
and is thermo-mechanical history dependent.
5.1.1. Transformation function

Tanaka and Iwasaki [409] assumed an exponential function of
stress and temperature for n. Later on, Liang [438] proposed a cosine function for n in his study. Brinson [411] used two n functions
for the martensitic transformation and reorientation, respectively.
Of course, linear function, which is the simplest, has also been suggested for n, in particular for a parametric study. In [113], n is
determined experimentally. It should be pointed out that in any
situations, experiments on SMAs should be carried out under both
displacement control and temperature control to ensure good
accuracy [440].
Numerical simulation based on a micromechanical model reveals that n in both the martensitic transformation (nM) and reorientation (nDM) depends on the stress state of the applied load [441].
As shown in Fig. 118, exponential function, cosine function and linear function are possible for n. Refer to Huang [441] for the physical
meaning of (1 K/Kmax).
5.1.2. Yield surface

To extend a one-dimensional model into multi-dimensional
study, same as in the classic theory of plasticity, we need to nd
the yield (transformation start) surface. Well documented experimental results reveal signicant differences in tension and compression of many SMAs (e.g., [426,442,443]). It was found that in
general, the transformation start stress in the stress induced phase
transformation cannot be described by the traditional criteria, for
instance, von Mises or Tresca (e.g., [444447]). Thamburaja and
Anand [448] suggested that texture is the reason behind, while
Huang [449] proposed a micromechanical model to explain this
phenomenon and the results were compared with the available
experimental results reported in the literature. Later on, Lexcellent
et al. ([446,447]) further developed it for more complicated transition systems.
It can be proved that under given conditions, the driving energy
for the phase transformation is a constant [449]. Subsequently, the
criterion for the start of transformation in a SMA single crystal can
be expressed as
Max R : epl K
16l6m
where K, the driving energy, is a constant. R and epI l 1; 2; . . . m

are the applied stress and the phase transformation strain (which
can be determined from the lattice structures of crystals before
and after transformation), respectively. m is the total number of
possible transformation systems in this single crystal (which also
can be determined from the lattice structures of crystals before
and after transformation). Subsequently, the transformation start
surface can be worked out for this single crystal.
To apply the above concept into non-textured polycrystal SMAs,
Huang [449] has proposed two schemes, namely the maximum
scheme and the average scheme.
Fig. 123. Schematic diagram of yield surface in the (r1 = r2, r3) plane. rTen is the yield start stress of uni-axial tension.
In the maximum scheme, the start of yielding depends only on

one grain, which produces the maximum strain (thus correspondingly the applied stress is minimal). Interactions among grains are
ignored. This is analogous to have all grains placed in series. It has
been proven that the yield surface of the maximum scheme can be
expressed in a closed-form as
r1 ep1 r2 ep2 r3 ep3 C
6
p
1;
where r1, r2 and r3(r1 P r2 P r3) are the principal stress, e ep2
and ep3 ep1 P ep2 P ep3 are the principal phase transformation strain,
and C is a constant. Subsequently, the corresponding yield surfaces
in some special stress planes and the apex can be easily plotted (as
illustrated in Fig. 119).
The average scheme is analogous to let all grains be placed in
parallel, which is another commonly applied practice in the traditional theory of plasticity. So far, it is not possible to work out a
closed-form solution for this scheme. Numerical expressions have
been obtained for some particular cases [102].
Furthermore, according to Huang and Gao [451] (refer to
Fig. 120),
If the start of yielding initiates from one grain, and the principal
plastic strain of this material is b(1, 0, 1) (where b is a constant), the yield surface of this material is the Tresca yield
surface.
629
If the start of yielding is from the contribution of all grains, not

all the plastic strains that satisfy the Tresca yield surface can
produce the von Mises yield surface. In the (exx, eyy, ezz) space
(the principal strain space), these strains that satisfy the von
Mises yield surface form a continuous curve plus a separate single point at the center.
It has been shown that above approach is applicable not only to
SMAs with single type of transformation [449,450], but also to
some SMAs which depending on the stress-state, may have different types of transformations. Fig. 121 shows the resultant yield surfaces of CuAlBe and CnZnAl against the experimental results
reported by Lexcellent et al. [446]. Note that in Fig. 121, the results
of the maximum scheme are in black, while these of the average
scheme are in gray. It reveals that the experimental results of both
SMAs in the biaxial tensile stress regime are very close to the analytical results of all three types of transformations, while in the
biaxial compression stress regime, 6M1 and M18R are seemingly
to be the dominant types.
Same as in the classic theory of plasticity, after assuming
that the ow direction is perpendicular to the yield surface,
now we have all three elements, namely yield surface, hardening rule, and ow rule, to construct a constitutive model for
SMAs.
Fig. 124. Transformation start surface upon cooling (a) and heating (b). Left: the maximum scheme; right: the average scheme. (Reproduced from Ref. [102], with
permission.)
5.2. Modeling of SMPs/SMHs
1.4
Transformation Start Stress (GPa)
5.1.3. Further remarks

This yield surface theory has been successfully applied to predict the behavior of SMAs under other stress-state based on the
experimental curve of, for instance, uniaxial tension [449,450].
This could be the most applicable approach for simple engineering
applications, in which the applied load is proportional.
In the above discussions, for simplicity, we assume the properties of a SMA are independent on the exact phase. This might be
reasonable for estimation purpose. However, the reality is that
the properties of austenite SMA could be remarkable different from
those of martensite SMA [44].
The inuence of different Youngs moduli on the yield surface
could be substantial. Fig. 122 shows that there is only one apex
in the yield surface in 3-dimensional principal stress space for a
non-textured NiTi polycrystal following either the maximum
scheme or the average scheme, in which the Youngs modulus is taken as a constant. Apparently, this apex is the result of volume
change during the phase transformation (refer to Fig. 119c). However, when different moduli are assigned to austenite and martensite, there are two poles, as illustrated in Fig. 123. Only if there is not
any volume change in the phase transformation, i.e., dep = 0, these
two poles are symmetrical about the origin [452].
The yield surface is actually a function of not only testing temperature, but also thermal history [102]. As shown in Fig. 124, the
yield surface keeps changing in both the heating process and cooling process. On the other hand, the yield surface in the heating process is also different from that in the cooling process.
Furthermore, the situation becomes even more complicated if
different Youngs moduli are considered for austenite SMA and
martensite SMA [453]. As we can see in Fig. 125, the well-known
and widely adopted ClausiusClapeyron equation, which reveals
a linear function of the transformation start stress against temperature, is only valid when a constant Youngs modulus is applied.
NiTi (Monoclinic-I)
DA = 2 DM
DA DM
0.8
0.6
0.4
0.2
10
15
20
25
30
35
40
dT (Deg C)
(a)
1.6
NiTi (Trigonal)
1.4
1.2
DA DM
D A = 2 DM
0.8
0.6
D A = 4 DM
0.4
0.2
0
From thermomechanical modeling point of view, since the

underlying mechanism for the SME in SMPs and SMHs are more
or less the same, it should be possible to consider them as one
group. In comparison with numerous models for SMAs, the progress in modeling of SMPs is considerably less fruitful.
Apparently, at present, materials scientists are in a far advanced
stage, i.e., in the very frontier of SMPs research by means of keeping
on inventing new fancy materials almost every week, if not every
day, while materials/mechanical engineers all lag well behind in
accumulating knowledge for a good understanding of individual
material before any reliable models can be developed. Based on
the scientic publications, only a couple of SMPs have been extensively investigated in terms of its thermo-mechanical and shape
memory properties. Prof. H. Tobushi and his co-workers have contributed signicantly over the past 15 years to study the properties
and behaviors of a PU SMP, which was originally invented and then
further developed by Dr. S. Hayashi. A phenomenological model has
been developed for this SMP [454,455], which is able to predict
experimental data with reasonable accuracy, but limited to only
some simple situations (e.g., uniaxial stress/strain state) [456].
On the other hand, given the highly complex nature of polymers, micro-structural models (e.g., [457,458]), derived from the
underlying mechanisms at micro-structural level, still have tremendous difculties in the quantitative prediction for real engineering applications [456].
Recently, Sun and Huang [27] proposed a framework to explain
the multi-SME and TME in SMPs. In this framework, within a representative unit element, the elastic segment is considered to be
embedded inside the transition segment. The transition segment
is assumed to be progressively softened or frozen from one side
DA = 4 DM
1.2
Transformation Start Stress (GPa)
630
dT (Deg C)
(b)
Fig. 125. Phase transformation start stress vs. dT relationship of NiTi for monoclinic-I martensite (a) and trigonal martensite (b). Gray line: phase transformation
start stress in compression; dark line: phase transformation start stress in tension.
Tension
Shearing
Compression
Fig. 126. Yield surface of foam. (Reproduced from Ref. [462], with permission.)
of the element to the other side upon heating or cooling. This

framework, which is able to qualitatively re-produce both the multi-SME and TME, could serve as the starting point to develop full
models for a quantitative analysis. For instance, in the case of programming at high temperatures, according to this framework, the
transition segment is fully softened. Consequently, we may simplify the SMP as a porous material, i.e., a piece of elastic foam (a
network of the elastic segment), if the contribution from softened
transition segment can be ignored. Subsequently, we may refer to
the previous studies on foam for the mechanical analysis of SMPs
in programming at high temperatures. The yield surface of foam
in three-dimensional stress space illustrated in Fig. 126 can be
adopted here for multi-dimensional analysis. Readers may refer
to, for instance, [459461] for detailed modeling techniques for
foam.
In some situations, it is not necessary to have a complete model
for SMPs. For instance, in above mentioned IPH approach for patterning atop SMPs (refer to Fig. 90, left), only the rst step is technically challenging, i.e., modeling the indentation process atop
SMP. The later two steps (i.e., polishing and heating for shape
recovery) are technically straightforward in nite element analysis.
Therefore, we may simulate SMP as an ordinary polymer in indentation. This is a well established research eld. The model proposed
by, for instance, [463], might be the right reference to start with.
As for SMP micro springs (refer to Fig. 64), according to [464],
for linear elastic analysis,
The materials properties of springs can be experimentally
obtained.
The mechanical response of even down to nano sized elastic
spiral spring can be well predicted by classical closed form solutions (e.g., [465]).
6. Conclusions and outlook

The development in some emerging technologies, for example,
minimally invasive surgery, lab-on-chip/microsystems, and unmanned aviation vehicles, etc., requires non-conventional materials to lead the breakthrough.
Take minimally invasive surgery as an example. The minimally
invasive surgery is regarded as one of the most important achievements in modern medicine. However, the minimally invasive surgery is more technically demanding as compared with the
conventional surgery, because the surgical intervention is executed
remotely via two-dimensional imaging of the operative eld, with
loss of tactile feedback, restricted maneuvrability, and less efcient
control of major bleeding [466468]. SMMs provide the just right
solutions to many problems in the minimally invasive surgery
[23,29,59,60,468].
In this paper, in addition to introducing some new features and
phenomena developed in SMMs in recent years, we present a number of novel applications of SMMs, in particular in these emerging
technologies. As demonstrated here, the unique SME in SMMs adds
a new dimension in terms of the materials properties and characterization, and consequently unfolds an exciting new eld for
materials selections in engineering design. At this point, we may
comfortably dene the shape memory technology (SMT) as a technology in which the SME in SMMs forms its core technique.
As we can see, SMAs/SMPs have started to reshape our traditional design methodology in many aspects in particular in those
applications, which are often problematic for traditional materials
and approaches. The emergence of SMHs, which are right on the
horizon, could further enhance the accessibility to almost everyone. As revealed above, each of them has its own advantages and
disadvantages.
631
While we are observing rapid development from new materials

to new functions in the eld of SMMs, for instance, in SMAs, Ni-free
Ti-based SMA [469], porous SMA [470,471], high temperature SMA
[472], surface modication of NiTi SMA [473], the elastocaloric effect in CuZnAl SMA [474] and the barocaloric effect in NiMnIn
magnetic SMA [475], etc., we should bear in mind the requirements in order to be relevant in our daily life and sustainable for
the future.
Among the issues which are important for future developments in SMMs, we should pay more attention on the
following.
Some specic SMMs could well nd their own niche market (as
a matter of fact, in many occasions some SMMs were indeed developed/tailored to meet such particular needs), but for SMMs as a
whole, we need a few heavy weight players to maintain the thrust
for expanding into more application areas and inertia for long term
development.
Standardization is essential for a new type of materials to become an off-the-shelf engineering material, easily accessible to a
world-wide range of potential users. A roadmap to provide a
necessary guide in SMMs selection, in particular for those newcomers, is very much useful. Unfortunately, except some preliminary works on SMAs [44], this is still largely not in place at
present. Although for some SMMs, such as NiTi SMAs, which
are very much sensitive to the exact composition and fabrication/processing conditions, it is difcult to have a complete
and stable database for them, we do seemingly have accumulated a lot of experimental results even in the literature for
some others (such as, the polyurethane SMP from SMP Technologies, Japan, and the polystyrene SMP from Cornerstone Research Group, USA).
High reliability/durability, well understood and precisely
predictable properties/behaviors are some major reasons that
engineering materials have a wide range of engineering applications. Currently, we are lacking in condence in most of SMMs
in these aspects. Although we have seen some efforts (e.g., in
[476] for SMPs), long term reliability/durability of SMMs is still
a topic yet to be well explored. On the other hand, more
attention should be focused on systematical characterization
and modeling/simulation of some important individual SMMs.
A couple of communities, particularly from mechanical
engineering and materials/polymer engineering, could play a
leading role.
Since most likely it is very much troublesome to introduce a
new material into the industry to replace the existing ones, the
advantages of advanced SMT, in which the SME is developed in
conventional materials (instead of in SMMs in SMT), are apparent.
So far, we have observed excellent SME in a number of engineering metals/alloys and polymers. Hopefully, advanced SMT will become the next hot topic very soon to push the SMT into a new
era.
Acknowledgements
W.H. Huang would like to thank Prof. Sergio Pellegrino and Dr.
Witold M. Sokolowski for bringing him into the wonderful world of
shape memory alloys and shape memory polymers, respectively,
and also all current and previous members in his research group
for their support. W.M. Huang would also like to extend his thanks
to Drs. Ming Dong Cai, Yong Qing Fu, Shunichi Hayashi, Kazuhiro
Otsuka, Jaco Pretorius, Thorsten Pretsch, Xiao Bing Ren, Tat Hung
Tong, Qiong Xie, Tao Xie and Profs. Abhijit Bhattacharyya, Franck
Chollet, Clifford M. Friend, Ming Hui Hong, Jin Song Leng, Yi Nong
Liu, Shuichi Miyazaki, Cheng Li Song, Hisaaki Tobushi, Ivan Eduardovitch Vahhi, Wei Xu et al. for their kind help in various ways
in the past years.
632
Appendix A. Historical development of SMMs for minimally

invasive surgery (till early 2009) [468]
Appendix A. (continued)
Year
Device
Reference
SMP with adjustable hydrolytic

degradation rate
Endoscopic bleeding control device
SMP for soft tissue xation
Thin lm SMA microtube and stent
SMP with built-in threshold
temperature sensor
Sirolimus-eluting SMP stent
[308]
Year
Device
Reference
2007
1963
1971
1976
1977
1981
1983
1983
1990
1990
1991
1993
1995
1995
1995
1996
1996
1998
1999
1999
2000
2000
2000
2000
Discovery of nitinol
Orthodontic braces
Harrington rod for scoliosis
Simon vena cava lter
Orthopedic staple
Prosthetic joint
Nitinol stent
Thin lm SMA
Thin lm microdevices
Variable curvature spatula
Laparoscopic hernia repair mesh
Laparoscopic clamp
Laparoscopic retractor
Thin lm microgripper
RF ablation device
Hernia repair retractor
Atrial septal occluder
Thin lm SMA microvalve
Laparoscopic suturing clip
Abdominal wall lift
Vascular ligation clip
Multipoint injector
Self-tightening biodegradable SMP
suture
Gastric loop snare
Microelectrode for neural recording
Drug-eluting stent
Thin lm microwrapper
Thin lm microstents
SMP micro actuator for treating
ischemic stroke
Laser activated SMP for treating stroke
SMP foam for endovascular
intervention
SMP stent with drug delivery system
Active SMP microudic reservoir
Laparoscopic anastomosis ring
Light-responsive SMP
SMP intravascular thrombectomy
device
Thin lm SMA heart valve
Multi-transition temperature SMP
Water-driven programmable SMP
SMP nanoparticle
SMP neuronal electrode
SMP neurovascular stent
Triple-shape SMP
Two-way SMP ber
SMP micro tag
Magnetic SMP device
Laser-activated SMP vascular stent
SMP endovascular thrombectomy
device
SMP foam stent for endovascular
embolization
SMP dialysis needle adapter
Retractable SMP stent
Water-driven self-tightening SMP
suture
[477]
[58]
[58]
[478]
[479]
[480]
[481]
[482,483]
[66]
[484]
[485]
[486]
[487]
[161]
[488,489]
[490]
[491,492]
[493]
[153,494,495]
[496]
[496]
[496]
[303,497,498]
2007
2008
2008
2008
2000
2000
2001
2001
2001
2002
2002
2003
2003
2004
2004
2005
2005
2005
2005
2005
2005
2006
2006
2006
2006
2006
2006
2007
2007
2007
2007
2007
2007
[499]
[500,501]
[502]
[503]
[504]
[505]
[343]
[347]
[506]
[349]
[507509]
[313,510,511]
[344]
[512]
[324]
[297]
[513]
[514]
[515]
[322,323]
[516]
[273]
[320]
[346]
[342]
[517]
[518]
[334]
[334]
2009
[519,520]
[283,521]
[522,523]
[295]
[310]
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Stimulus Responsive Shape Memory Materials A Review

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Materials and Design 33 (2012) 577640

Contents lists available at ScienceDirect

Materials and Design

Stimulus-responsive shape memory materials: A review

School of Civil Engineering, Shenyang Jianzhu University, Shenyang 110168, PR China

crystal) do have the ability for shape change at the presence of a

L. Sun et al. / Materials and Design 33 (2012) 577640

Stimulus-responsive material (SRM)

reversible orderdisorder transition [13,3537]. Recently the

products with a wide range of transition temperature in various

2. Shape memory alloys

L. Sun et al. / Materials and Design 33 (2012) 577640

nating magnetic eld (inductive heating) to trigger the SME

mance index and Ashbys Chart [73] for engineering applications

(a) Shape Memory Effect

L. Sun et al. / Materials and Design 33 (2012) 577640

symmetry, group theory can be applied to conveniently describe

(3) Detwinned martensite (variant k) transforms into another

L. Sun et al. / Materials and Design 33 (2012) 577640

ther plastic deformation occurs at the boundary between the initial

L. Sun et al. / Materials and Design 33 (2012) 577640

Instead of stretching at a constant strain rate, a quasi-constant

L. Sun et al. / Materials and Design 33 (2012) 577640

Transformation start stress (MPa)

Fig. 10. Snapshots of phase transformation front movement in a 1 mm diameter

From the application point of view, above phenomena remind us

L. Sun et al. / Materials and Design 33 (2012) 577640

temperature as in the rst time but with a shortened (most likely

L. Sun et al. / Materials and Design 33 (2012) 577640

heating, which means that the reverse transformation is virtually

L. Sun et al. / Materials and Design 33 (2012) 577640

Instead of introducing a gradient transition temperature eld,

L. Sun et al. / Materials and Design 33 (2012) 577640

L. Sun et al. / Materials and Design 33 (2012) 577640

Fig. 25. Two different recovery patterns in a NiTi ribbon.

two-way SME has been widely adopted in many engineering

Basically, SMAs may be heated up by three methods, i.e.,

L. Sun et al. / Materials and Design 33 (2012) 577640

discussed briey. Interested readers may refer to, for instance

2.2.1. MEMS applications

It should be pointed out that, as a thermo-responsive SMM, the

L. Sun et al. / Materials and Design 33 (2012) 577640

heating SMAs, in particular NiTi based SMAs, which have a high

[78,82,84,170]. This effect is the most signicant in NiTi thin lms

L. Sun et al. / Materials and Design 33 (2012) 577640

As we know, sputter deposition of NiTi based thin lms can be

Fig. 34. Four-bar linkage.

L. Sun et al. / Materials and Design 33 (2012) 577640

We have theoretically proved that laser annealing is also applicable

Based on the same concept, a bi-stable arch reaches either of the

Fig. 35. A two-SMA spring-based linear motor.

L. Sun et al. / Materials and Design 33 (2012) 577640

mounted to the shaft of a hard-disks spindle. After heating for

L. Sun et al. / Materials and Design 33 (2012) 577640

2.2.4. Aerospace and space applications

Fig. 41. A simple SMA wire based gripper with two-degree-of-freedom.

L. Sun et al. / Materials and Design 33 (2012) 577640

Fig. 44. SMA wire based two-way hinge.

L. Sun et al. / Materials and Design 33 (2012) 577640

Fig. 48 is an improved version, in which two 0.2 mm thick,

L. Sun et al. / Materials and Design 33 (2012) 577640

ing of the gravity center results in the car moving forward or

2.2.6. Energy conversion