NATIONAL INSTITUTE OF FASHION

TECHNOLOGY

INTERDISCIPINARY MINOR

TOPIC – SHAPE MEMORY POLYMERS

SUBMITTED BY-
NeelakshiSrivastava
InzamamulHaq
ShreyaRastogi
CERTIFICATE

This is to certify that Neelakshi Srivastava, who is a student of Bachelor of Fashion

Technology (Apparel Production) of NIFT Patna has worked on the project “Shape Memory
Polymers” under the guidance of our faculty Mr. Kunal Singha & has successfully
completed it.

______________

Mr.KunalSingha
ACKNOWLEDGEMENT

We would like to thank all the people who supported and guided us in collecting information
for our project on “Shape Memory Polymers”; without whom this report wouldn’t have been
in its present form. We are highly grateful to our faculty Mr.KunalSingha for active direction
for my project. We would like to express our deep gratitude to him who mentored to
complete the given project successfully; which was full of learning and enhanced our
experience. Gratitude are also extended to all the faculty of NIFT Patna for their valuable
suggestions
TABLE OF CONTENTS
Certificate...................................................................................................................................2
Acknowledgement......................................................................................................................3
1.0 Shape Memory Polymers.....................................................................................................6
2.0 Classification Of Shape Memory Polymers.........................................................................7
2.1 Mode Of Activation.................................................................................................................8
2.1.1 Thermo Responsive Smp...........................................................................................8
2.1.2 Photoresponsive Smps...............................................................................................9
2.1.3 Electrically Responsive Smps..................................................................................10
2.1.4 Magnetically Responsive Smps...............................................................................10
2.1.5 Solution-Responsive Smps......................................................................................11
2.1.6 ph-Responsive Smps................................................................................................11
2.2 Shape Memory Function........................................................................................................12
2.2.1 Thermoplastic Shape-Memory Polymers................................................................12
2.2.2 Thermosetting Shape-Memory Polymers................................................................12
3.0 Shape Memory Alloy.........................................................................................................13
3.1 Mechanism Of Shape Memory Alloy..................................................................................13
4.0 Shape Memory Effect........................................................................................................14
5.0 Comparison Between Smp And Sma.................................................................................15
6.0 Application Of Shape Memory Polymers..........................................................................16
6.1 Smart Textiles.........................................................................................................................16
6.1.1 Shape Memory Fibers..............................................................................................16
6.1.2 Smf Yarns, Fabrics And Garment Design...............................................................17
6.1.3 Shape Memory Fabric..............................................................................................18
6.1.4 Shape Memory Polymer Solutions For Finish Applications...................................21
6.1.5 Shape Memory Polymer Film, Foam And Laminated Textile................................22
6.1.6 Implementation Of Aesthetic Attributes In Fabric Design......................................23
6.2 Shape Memory Polymer In Wearable Technology.............................................................26
6.2.1 Steng........................................................................................................................26
6.2.2 Organic Light-Emitting Diodes On SMP Substrates For Wearable Electronics.....28
6.2.3 Elastic SM Hybrids Programmable At Body-Temperature For Comfort Fitting....28
6.3 Biomedical..............................................................................................................................29
6.3.1 Suture Less Anastomosis Based On Smp................................................................29
6.3.2 Clot Removal Devices Based On Smp....................................................................31
 6.3.3 Tissue Reconstruction..............................................................................................31
6.3.4 Orthodontics Based On Smp....................................................................................32
6.4 Kinetic Building Envelopes For Building Energy Efficiency..........................................33
7.0 Smp Composites Reinforcementapplication......................................................................35
7.1 Aerospace................................................................................................................................35
Hinge.................................................................................................................................35
Ground-Based Deployable Mirror....................................................................................36
Morphing Structures.........................................................................................................37
7.2 Self-Healing 3d Woven Fabric Reinforced Smp........................................................38
8.0 Key Challenges And Possible Future Directions...............................................................39
9.0 Conclusion..........................................................................................................................41
10.0 References........................................................................................................................42
LIST OF FIGURES
Figure 1 Thermally Induced One-Way Shape-Memory Effect..................................................7
Figure 2 Thermomechanical Cycle Of Thermally Responsive Shape Memory Polymers........9
Figure 3 Molecular Mechanism Of Photoresponsive Smps.......................................................9
Figure 4 Magnetically Responsive Smps.................................................................................10
Figure 5 Mechanism Of Shape Memory Alloy........................................................................13
Figure 6 Microscopic And Macroscopic Views Of The Two Phases Of SMA.......................14
Figure 7 Shape Memory Effect................................................................................................14
Figure 8 Wet Spinning Process For Preparing SMPU Fibers..................................................16
Figure 9 :Oricalco Shirt............................................................................................................18
Figure 10 Diaplex®..................................................................................................................19
Figure 11 Dermizax®...............................................................................................................19
Figure 12 Shape-Memory Foam Applications.........................................................................19
Figure 13 Back Of A Nike ‘Sphere React Shirt’ With A Smart Vent Structure......................20
Figure 14 Finishing Fabrics.....................................................................................................21
Figure 15 Working Principle Of Diaplex Membrane (Diaplex)..............................................22
Figure 16 Woven Samples Structures......................................................................................23
Figure 17 Woven Sample Structure 3D...................................................................................24
Figure 18 Woven Sample Simulating The Effect Of SMP......................................................24
Figure 19 3-Dimensional Textile Concept...............................................................................25
Figure 20 Stretchability And Shape-Memorized Transformation Ability Of The STENG.....26
Figure 21 STENG As A Sensor In The Form Of A Shape Adaptive Wrist Splint..................27
Figure 22 Curved SMP Substrate.............................................................................................28
Figure 23 The Prototype Of Vascular Stents Based On SMP..................................................29
Figure 24Recovery Of Shape Memory Polymer Stent............................................................30
Figure 25 Process Of SMP Stent Deployment In The Mock Artery........................................30
Figure 26 Star-Shaped Stent Based On Film Polyurethane SMP............................................31
Figure 27 Arch Wire Based On Shape Memory Polymer Installed In A Dental Model.........32
Figure 28 Thermally Responsive Smps In Heat Controls Of Window Blinds........................33
Figure 29 Schematic Diagram Of Composite Smps In Shading Controls...............................34
Figure 30 Hinge........................................................................................................................35
Figure 31Shows The Deployment Process For The SMP-Composite Hinge..........................36
Figure 32 Deployable Ground-Based Mirror Produced Using EMC Resin............................36
Figure 33 An Illustration Of Reflective Mirror Fabricated By SMP.......................................36
Figure 34 Z-Shaped Morphing Wing Produced By Lockheed Martin....................................37
Figure 35 3D Woven Fabric Reinforced SMP Syntactic Foam Test Specimens.....................38
Figure 36 Before And After Healing.......................................................................................39
1.0 SHAPE MEMORY POLYMERS
Since the discovery of the shape-memory polymers (SMPs) in the 1980s, international
research interest into the shape-memory effect in polymers has been rapidly growing. Shape-
memory materials are stimuli-responsive materials. They have the capability of changing
their shape upon application of an external stimulus. A change in shape caused by a change in
temperature is called a thermally induced shape-memory effect. The shape- memory effect is
not related to a specific material property of single polymers; it rather results from a
combination of the polymer structure and the polymer morphology together with the applied
processing and programming technology.

Shape memory behaviour can be observed for several polymers that may differ significantly
in their chemical composition. The process of programming and recovery of a shape is shown
schematically in Figure 1. First, the polymer is conventionally processed to receive its
permanent shape. Afterwards, the polymer is deformed and the intended temporary shape is
fixed. This process is called programming. The programming process either consists of
heating up the sample, deforming, and cooling the sample, or drawing the sample at a low
temperature (so called cold drawing).

Typical examples of polymers which can exhibit this shape memory effect include
(meth)acrylates, polyurethanes, and blends of polyurethane and polyvinylchloride.

Figure 1 Schematic representation of the thermally induced one-way shape-memory effect.

The permanent shape is transferred to the temporary shape by the programming process.
Heating the sample to a temperature above the switching transition T(trans) results in the
recovery of the permanent shape.The permanent shape is now stored while the sample shows
the temporary shape. Heating up the shape-memory polymer above a transition temperature
T(trans) induces the shape- memory effect. As a consequence, the recovery of the stored,
permanent shape can be observed. Cooling down the polymer below the transition
temperature leads to solidification of the material, however, no recovery of the temporary
shape can be observed. The effect described is named as a one-way shape- memory effect. By
further programming, including mechanical deformation, the work piece can be brought into
a temporary shape again. This new temporary shape does not necessarily match the first
temporary shape.. The permanent shape is recovered with a precision of more than 99% with
appropriately optimized programming conditions. This precision makes these materials
suitable for highly demanding applications.
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2.0 CLASSIFICATION OF SHAPE MEMORY POLYMERS
Shape memory Polymers can be classified on the basis of these three criteria:

1. Mode of activation
2. Shape Memory Function

2.1 MODE OF ACTIVATION

Shape-memory polymers (SMPs) are able to respond to a specific external stimulus by means
of certain significantly macroscopic properties such as shape. The actuation methods of
SMPs can be generally divided into:

2.1.1 THERMO RESPONSIVE SMP

The shape memory polymers which change in shape with the change of temperature are
called thermo responsive shape memory polymers. By far these are the most common shape
memory polymers.  These thermally responsive SMPs can be regarded as thermoplastic
elastomers, in which there is a hard phase with a high glass transition temperature (Tg) and a
second, switching phase, with an intermediate or melting temperature (Tm) that enables the
thermally responsive behavior.The temperature surpassing Tg (orTm ) is syhmbolized
as T(high) and the temperature being lower thanTg (or Tm ) is symbolized as T(low) . First,
the SMPs can be processed into any shape desired as the permanent shape. Then, when the
temperature is higher than Tg (or Tm )and reaching , a temporary shape can be induced that
can be then “frozen” by cooling the deformed state at the low temperature
condition, . Consequently, when heated aboveTg (or Tm )the SMPs transform back to their
permanent shape. The schematic drawing in Figure 2 shows this thermally responsive
process.Molecular switches and net points are two major molecular-level components of
thermally responsive SMPs. Molecular switches are segments with a thermal transition
at Tm that fixes the temporary shape by forming physical crosslinks. Net points that link
these switching segments and determine the permanent shape of the polymer network can
either be physical crosslinks through physical intermolecular interactions or chemical
crosslinks through covalent bonds.
 Figure 2Thermomechanical Cycle Of Thermally Responsive Shape Memory Polymers

2.1.2 PHOTORESPONSIVE SMPS

Photoresponsive SMPs can respond to light stimuli by undergoing reversible changes in their
properties. There are two main mechanisms that operate in light-induced SMPs:
photochemical reactions leading to deformation and the employment of particles that convert
light to heat . In photochemical reactions, intrinsically photoresponsive SMPs are produced
by incorporating reversible photoreactive molecular switches when a special wavelength of
light strikes them; this alters the structure of their crosslinked polymer networks. For
example, Lendlein et al. showed that SMPs containing cinnamic groups can be deformed and
fixed into predetermined shapes when exposed to alternating wavelengths ( λ>260nm or
λ<260nm ) (Figure 5). The accumulation of structural alterations leads to an evolution of the
polymer network and even subsequent macroscopic deformation. Consequently,
photochemical SMEs are produced. This stimulation is considered unrelated to any
temperature changes. Therefore, it should be differentiated from the indirect actuation of
thermally responsive SMPs. Another photosensitive function is that molecular switches
convert light to heat and then actuate thermally responsive SMPs.Therefore, illumination
with the radiant thermal energy of infrared light possessing a wide range of spectra
(500∼4000 cm−1) can serve as a heat source for photoresponsive SMPs; these can then be
applied with noncontact nonmediums.

Figure 3 Molecular Mechanism Of PhotoresponsiveSmps

2.1.3 ELECTRICALLY RESPONSIVE SMPS

Electrically responsive SMPs are also intrinsically of the thermally responsive type.
Thermally active SMPs are usually filled with electrically conductive ingredients that reach a
certain level of electrical conductivity; this means that electricity, as a stimulus, enables their
resistive actuation. Most SMPs have high levels of electrical and thermal resistance when the
actuation is remotely controlled. They are heated via an electric current that passes through
the conductive ingredient network within.If the internal temperature is above the transition
temperature,Tg , resulting in the permanent shape, then the SMP can be deformed into any
shape. If the temperature is between Tg andTm , a temporary shape can be induced and fixed
by cooling the SMP to below Tm . Consequently, heating above the melting temperature, Tm
, may trigger deformation recovery (Figure 4) . Compared to the direct external heating
method, the internal resistive joule heating method by electricity presents certain advantages,
such as convenience, uniform heating, and remote controllability.
2.1.4 MAGNETICALLY RESPONSIVE SMPS

Similar to electrically responsive SMPs, thermally active SMPs embedded with magnetic
particles are magnetically responsive. An alternating magnetic field (AMF) produces
inductive heating, which triggers the recovery process. The temperature can be increased
rapidly since the heat is normally generated inside the polymer itself .Relaxation (eddy
current losses), Brownian motion relaxation (rotational losses), and hysteresis losses are the
three main heating mechanisms that operate AMFs. In the relaxation mechanism, in response
to an externally applied AMF, a particle’s magnetic dipole changes its orientation within the
particle. The particle’s magnetic moment of resisting this orientation produces heat, which is
also counted in the particle’s magnetism. In Brownian motion relaxation, in response to an
externally applied AMF, a particle physically rotates to align with the magnetic field; the
friction between the rotating particles (responding to the externally applied AMF) and the
carrier fluid (due to the viscosity effect of resisting the particle rotation) results in heat. In
addition to relaxation losses in larger particles with a particle size > 20 nm, thermal energy
can be stemmed from magnetic hysteresis losses .Hysteresis describes a path that depends on
the magnetic response of magnetic materials to an applied magnetic field. Hysteresis losses
mainly occur in domain wall motion, such as when multidomainferro- or ferrimagnetic
particles are exposed to an AMF. The generated heat is proportional to the area of the
hysteresis loop and frequency of the AMF. Basically, the heating power associated with
relaxation loss lower than that of the hysteresis losses .

Figure 4 Magnetically Responsive Smps

2.1.5 SOLUTION-RESPONSIVE SMPS

Solution-responsive SMPs present a significant decrease in the modulus during phase

transition .In general, water or solvent molecules are able to infiltrate SMPs. Due to the
plasticizing effect of water and solvent on SMPs and the increase in flexibility of
macromolecules, the glass transition temperature,Tg , can be decreased after the addition of a
small amount of water. When the glass transition temperature,Tg , approaches the ambient
temperature, the recovery process of the water-induced SMP is triggered .

The interaction between macro- and micropolymeric molecule of the solution is the main
mechanism behind this phenomenon. Three major reasons causing it are as follows:
 The flexibility of the polymeric chains is magnified by the hydrogen bonding;

 Based on the continuum theories of rubber elasticity, the Mooney–Rivlin equation,

and volume change refinement theory, the polymer modulus is destroyed due to the
volume change in the polymer caused by the interaction;
 The solution makes the polymer tender until  decreases to the Tgtemperature of the
solution while Tg of the polymer is higher than the temperature of the solution or the
ambient temperature.

Consequently, the solution continues affecting the polymer’s other aspects. Tg can decrease
significantly and reach to the temperature of the solution because the micromolecular of the
solution can weaken the elasticity modulus of the SMP. Therefore, the solution can trigger off
the actuation of SMPs by means of reducing  Tgof the material itself through immersing the
SMPs into solution .Solution-driven SMPs provide an alternative approach, making
stimulation by heating unnecessary. The actuation can be triggered upon immersion of the
material into solution. Instead of heating the material to above its Tg, shape recovery can be
achieved by means of reducing the Tg of the material itself upon immersion of the SMP into
a solution that is, in principle, similar to the process used for water-driven PU SMPs.
2.1.6 pH-RESPONSIVE SMPS

The pH-responsive SMPs have great potentials in medical applications. The physiological pH
values vary in different sites of the body, which generally appears as a sharp gradient across
biological systems on both the cellular and systemic levels in pathological states .A pH-
responsive SMP can be processed into a temporary shape at pH 11.5 and recover to its initial
shape at pH 7.A pH-responsive SMP based on polyurethane and the pH-stimulated DNA
hydrogels have been also proposed. The mechanism of pH-responsive SMP is mainly based
on the polymer swelling at different pH values of the environment. The pH value of the
environment can act as a switch to control the shape memory without temperature variations.
If the pH-responsive SMP prepared with some chemical materials, the key for realizing the
SME is the hydrogen bond interaction.
2.2SHAPE MEMORY FUNCTION
Like normal polymers, SMPs also possess three-dimensional molecular network-like
architectures. The network architectures are thought to be constructed through cross-linking
net points, with polymer segments connecting adjacent net points. These strongly cross-
linked architectures ensure that the polymer can maintain a stable shape on the macroscopic
level for enabling both the original and recovered shapes.The domain of the cross-linking
netpoints can be either physically or chemically cross-linked structures.

2.2.1 THERMOPLASTIC SHAPE-MEMORY POLYMERS

Physically cross-linked polymers (thermoplastics) exhibit a reversible nature ,meaning that
they can be melted or dissolved in certain solutions. The interconnection of the individual
polymer chains in a physically cross-linked network is achieved by the formation of
crystalline or glassy phases.Damental mechanism behind the thermally induced shape-
memory effect of these materials. One phase provides the physical cross-links while another
phase acts as a molecular switch.

They can be further classified into linear polymers, branched polymers or a polymer
complex. The linear SMPs consist of block copolymers and high molecular weight polymers.
Among thermoplastic SMPs, the polyurethane SMP performs many advantages when
compared with other available SMPs, including higher shape recoverability (maximum
recoverable strain >400%), a wider range of shape recovery temperature (from 30 to 70 C),
better biocompatibility and better processing ability.

2.2.2 THERMOSETTING SHAPE-MEMORY POLYMERS

For the chemically cross-linked polymers (thermosets),the individual polymer chains are
connected by covalent bonds, which are more stable than the physical cross-linking network
and show an irreversible nature.For the chemically cross-linked SMPs, there are two methods
to synthesize covalently cross-linked networks. First of all, the polymer network can be
synthesised by adding a multi-functional cross-linker during the polymerization. The
chemical, thermal and mechanical properties of the network can be adjusted by the choice of
monomers, their functionality, and the cross-linker content. The second method to obtain
polymer networks is the subsequent cross-linking of a linear or branched polymer.The
networks are formed based on many different polymer backbones, such as polystyrene,
polyurethanes, and polyolfines. Covalently cross-linked SMPs possess chemically
interconnected structures that determine the original macroscopic shape of SMPs. The
switching segments of the chemically cross-linked SMPs are generally the network chains
between netpoints, and a thermal transition of the polymer segments is used as the shape-
memory switch. The chemical, thermal, mechanical and shape-memory properties are
determined by the reaction conditions, curing times, the type and length of network chains,
and the cross-linking density. Additionally, according to the thermal transition of the
switching segment, SMPs can be divided into two categories. Either the transition
temperature Ttrans is a melting temperature Tm or a glass transition temperature Tg. If the
thermal transition belongs to a glass transition, the micro Brownian motion of the network
chains is frozen and the temporary shape is fixed at low-temperatures; correspondingly, the
network chain segments are in the glassy state. The SMPs will remember the temporary
shape and store the strain energy. When heating at or above Tg, the micro Brownian motion
will be triggered and the ‘switch’ will be opened. In the case of glass transition, glass
transitions always extend over a broad temperature range. When the thermal transition is a
melting point, the switching segments crystallized at low-temperature as a fixed segment to
store the strain energy, and then recover the original shape at elevated temperatures at or
above Tm. In the case of melting temperature, the transition presents a relatively sharp
transition in most cases.

3.0 SHAPE MEMORY ALLOY

A shape-memory alloy is an alloy that can be deformed when cold but returns to its pre-
deformed ("remembered") shape when heated. It may also be called memory metal, memory
alloy, smart metal, smart alloy, or muscle wire. Parts made of shape-memory alloys can be
lightweight, solid-state alternatives to conventional actuators such as hydraulic, pneumatic,
and motor-based systems. They can also be used to make hermetic joints in metal tubing.The
two most prevalent shape-memory alloys are copper-aluminium-nickel and nickel-
titanium (NiTi), but SMAs can also be created by alloying zinc, copper, gold and iron.
Although iron-based and copper-based SMAs, such as Fe-Mn-Si, Cu-Zn-Al and Cu-Al-Ni,
are commercially available and cheaper than NiTi, NiTi-based SMAs are preferable for most
applications due to their stability and practicability. and superior thermo-mechanic
performance. SMAs can exist in two different phases, with three different crystal structures
(i.e. twinned martensite, detwinned martensite and austenite) and six possible
transformations.

3.1 MECHANISM OF SHAPE MEMORY ALLOY

The two unique properties described above are made possible through a solid state phase
change, that is a molecular rearrangement, which occurs in the shape memory alloy. A solid
state phase change is similar in that a molecular rearrangement is occurring, but the
molecules remain closely packed so that the substance remains a solid. In most shape
memory alloys, a temperature change of only about 10°C is necessary to initiate this phase
change. The two phases, which occur in shape memory alloys, are Martensite, and Austenite.
In shape memory polymer there are two state ,Ground state-Martensite and Excited state-
Austensite, H is Enthalpy and S is entropy.It works on entropy & enthalpy.

Figure 5 Mechanism Of Shape Memory Alloy

Martensite, is the relatively soft and easily deformed phase of shape memory alloys, which
exists at lower temperatures. The molecular structure in this phase is twinned which the
configuration is shown in the middle of Figure 6. Upon deformation this phase takes on the
second form shown in Figure 6, on the right. Austenite, the stronger phase of shape memory
alloys, occurs at higher temperatures. The shape of the Austenite structure is cubic, the
structure shown on the left side of Figure 6. The un-deformed Martensite phase is the same
size and shape as the cubic Austenite phase on a macroscopic scale, so that no change in size
or shape is visible in shape memory alloys until the Martensite is deformed.

Figure 6 Microscopic and Macroscopic Views of the Two Phases of Shape Memory Alloys

4.0 SHAPE MEMORY EFFECT

Shape Memory describes the effect of restoring the original shape of a plastically deformed
sample by heating it. This phenomenon results from a crystalline phase change known as
“thermoelastic martensitic transformation”. At temperatures below the transformation
temperature, shape memory alloys are martensitic. In this condition, their microstructure is
characterized by “self-accommodating twins”. The martensitic is soft and can be deformed
quite by de-twinning. Heating above the transformation temperature recovers the original
shape and converts the material to its high strength, austenitic, condition.

Figure 7 Shape Memory Effect

5.0 COMPARISON BETWEEN SMP AND SMA
Shape-memory alloys (SMAs) can deform at a low-temperature and then recover to their
prior shape upon heating above a particular temperature-related to the properties of alloy.
SMAs mainly include three types: nickel-titanium (NiTi) alloys, copper–zinc–aluminum–
nickel and copper–aluminum– nickel. SMA changes from austenite to martensite upon
cooling. The martensite phase exists at lower temperatures and is the relatively soft and easily
deformed phase of SMAs. Austenite is a stronger phase of SMAs that occurs at higher
temperatures. When the temperature of the SMA is cooled to below the transition temperature
(Ts), the shape-memory effect can be observed and the alloy is entirely composed of
martensite. Upon re-heating above the transition temperature, the deformed shape will
recover to its initial shape. The deformed martensite transformes into the cubic austenite
phase. SMAs show both one-way and two-way shape-memory effect. For one-way shape-
memory effect, upon heating a SMA at deformed martensite phase, the shape changes to its
original. However, when the metal cools again it will remain in the hot shape. With the one-
way effect, cooling from high temperatures does not cause a macroscopic shape change.

An external deformation is necessary to createthe low-temperature shape. For two-way

shape-memory effect, when a SMA is cooled at hot austenite phase it will automatically
deform without any external deformation. That is to say, the cool deformed shape and hot
original shape can automatically transfer in the heating–cooling cycle.

On the other hand, the shape-memory effect of SMPs depends on the existence of separated
phases related to the coiled polymer structure and cross-links, etc. In the deformed shape
below Tg, molecular chains of the SMPs are constrained by chemical or physical cross-
link.When reheated again, these molecular chains will go back to the random coiled
configuration.

The shape-memory transformation depends on the mechanism by which polymer molecules

transpose between the constrained and random entangled conformations ]. SMPs only show
one-way shape-memory effect. That is, the SMP at ‘‘soft’’ stage can only deform with the
help of external force rather than automatically deform by cooling. The advantage of SMPs
over SMAs relies mostly on their intrinsic properties such as lower cost, lower density, easier
processing and larger attainable strains. SMPs exhibiting up to 200% strain have been
reported compared to less than 10%, 1%, and 0.1% for SMA, shape-memory ceramics, and
glasses, respectively .
6.0 APPLICATION OF SHAPE MEMORY POLYMERS
As a novel kind of smart materials, SMPs currently cover a broad range of application areas
ranging from outer space to automobiles. Recently, they are being developed and qualified
especially for deployable components and structures in aerospace. The applications include
hinges, trusses, booms, antennas, optical reflectors and morphing skins. In addition, SMPs
also present additional potential in the areas of biomedicine, smart textiles, self-healing
composite systems and automobile actuators. Additionally, there are many patents in relation
to SMPs applications, such as gripper, intravascular delivery system, hood/seat assembly and
tunable automotive brackets in vehicles.

6.1 SMART TEXTILES

SMP is a more appropriate raw material for the clothing industry because of its features such
as high elongation, wellprocessability, lightness and touching. SMPs can be produced in a
fiber form, i.e. macro, micro and nanofibers, as solution, film or foam. They are used in such
textile and clothing applications as nonwoven, coating, finish, lamination, weaving and
knitting.

6.1.1 SHAPE MEMORY FIBERS

Macro-scaled shape memory fibers can be produced with wet, dry and melt spinning methods
Shape memory polyurethane (SMPU) fibers were prepared for the first time in 2006 with
wet-spinning. In Figure 5, the wet-spinning process of fiber is shown. Under compressed
nitrogen gas, shape memory polyurethane solution is pulled into the coagulation bath of
6m/min through 30 spinneret holes of 0,08 mm diameter pinholes. The coagulated fibers are
wrapped after being dried and rinsed through the cylinder with 10 m/min speed . However, as
it includes harmful dimethyl formamid and coagulation bath, melt spinning method is more
environmental. In addition, it has the advantage of being more economical. In order to gain a
commercial importance, the shape memory fibers need to have anti-oxidant, anti-thermal,
chlorine-resistant and anti-aging features.Melt spinning process was applied in order to get
rid of the problems observed in wet-spinning. The shape memory fibres (SMF’s) that are
melt-spinned provide a higher resistance, a controllable elongation, a linear density, shape
permanence, elasticity and key temperature. Shape recovery is better in melt spinning as a
higher micro-phase distribution is obtained during its process. At the same time, this soft
spinning method enables to prevent some problems such as environmental pollution and low
production efficiency.[ CITATION Placeholder1 \l 16393 ]

Figure 8 : Wet spinning process for preparing SMPU fibers

These fibers’ key transition temperature was calculated as 41 °C, durability as 1,14cN/dtex,
elongation at break as 682 %, and the recovery rate as 89 %. However, when they increased
the ambient temperature above the transition temperature, the fiber turned back to its original
diameter again. These fibers can be used for thermal adjustments in smart textiles and as
fibers in pillow and cushions, or can be used in smart filtration, for controlled oscillation of
the medicine and fluid transfer.

Cross-section of the fiber change section according to the ambient temperature. While the
cross-section of the fiber takes a hollow shape (like the shape of a crescent) in hot weather, it
will take a closed shape in cold weather. As a result, the clothes produced with this fiber will
be worn in both hot and cold weathers.

6.1.2 SMF YARNS, FABRICS AND GARMENT DESIGN

The appeal of the application of SMFs to textiles is their shape fixity and lengthwise recovery
along the fibre, accompanied by changes in their stress. SMFs have been made into yarns by
ring and friction spinning techniques, and the yarns have been applied to the knitting and
weaving of fabrics.Shape memory fibers can be turned into yarns together with other fibers
by using friction or ring technology.

With these yarns, knitted or woven fabrics can be produced .With the fabrics including shape
memory fiber, textile and clothing products that react to (adapt to) the temperature changes
can be produced. The features of the fabrics with shape memory effect include shrinkage,
bending and thickness increase. The clothes made out of shape memory fibers can enlarge in
accordance with the body shape of the person wearing them. In contrast to the clothes made
out of conventional spandex fibers, these clothes take the shape of its user in a better way and
decrease the user’s negative energy. The fabric produced with the shape memory fibers with
developed perception comfort can be used in women lingerie and low-pressure socks.

Some biological evaluations were made in order to prove the compatibility of fabrics
containing shape memory fiber with human body. These initiated the applications of shape
memory effect fabrics in biological and medical areas. For the effective application of shape
memory fabrics in medical textiles, corselets were foreseen. For instance, therapeutic clothes
for burned skins, sport clothes skin and some casual dresses including female lingerie (Hu et
al., 2012; Meng et al., 2009). With the usage of shape memory polymers in medical area as
controlled drug release, biodegradable sewing yarn, stent, implants, the relevant studies have
been increasing (Lendlein and Langer, 2002; Wache et al., 2003; Lendlein et al., 2010;
Goraltchouk et al., 2011). In this area, sewing yarns with biodegradable shape memory
feature was studied. With the increase in temperature, filament presses the scar and enables it
to be closed (Figure 6). In addition, SMP’s having minimal temporary shape can be
implanted into the body from the small scars and take their original shape with body
temperature. The shape memory products of the medical area need to be supported with such
controlled features as biodegradability and drug release (Lendlein et al., 2010).

Jing et al. (2010) studied the fabrics woven with core-spun shape memory yarns. The shape
memory yarns whose core was formed with shape memory fiber were produced in two ways:
One of them was ring technology while the other was friction technology. Two different
fabrics were woven with these yarns. While the core-spun yarn in one of them was added to
the fabric, shape memory fibers were incorporated into the yarns through ring or friction
spinning method and these yarns are produced as knitted or woven fabric. They concluded
that shape memory core-spun yarns have as much good shape effect as the shape memory
fibres. The shape memory effect was observed more on weft side. It was also found out that
the yarn produced with a ring machine and having shape memory core had better shape
memory effect when compared to that produced with friction. Liu et al. (2007) tested three
types of fabric prepared with different contents.

The contents of these fabrics are as follows: 1. 100%SMPU, 2. 50/50% SMPU/Cotton and 3.
16/84% SMPU/Cotton. In the study, shape memory behaviours were examined by comparing
shape memory behaviours and contents of fabrics in different temperatures. In addition, shape
memory of shape memory fibres were verified by comparing them with Lycra knitted fabrics.
At the end of the study, when the fabric shape memory polymer was heated above transition
temperature, the shape memory effect increased in an obvious way. In fabrics with higher
amount of shape memory fiber, more shape memory effect was observed. When compared to
the fibres, the fabrics produced with shape memory fibers displayed shape difference in an
obvious way.

6.1.3 SHAPE MEMORY FABRIC

The sleeves shorten as room temperature rises up,Shape memory fabrics/garments so
produced are novel fabrics which respond to the temperature stimulation. The concept of
shape memory fabric is new and these fabrics were prepared by applying waterborne shape
memory polymers in Polyurethane series (SMP) onto fabrics through specific finishing
processes.The shirt with long sleeve could be programmed temperature becomes hotter. The
fabric can be rolled up, pleated, creased and returned to its former shape by applying heat.
Ex: blowing air through hair dryer.
CorpoNove developed Oricalco shirt. In the shirt, the sleeves are programmed in such a way
that the sleeves shorten when temperatures increases with a few degrees. Morever, the fabric
can be pleated, plied, crushed and crease (Figure 9).

Figure 9 :Oricalco Shirt

Mitsubishi have discovered Diaplex® membrane as Shape-Memory Polymer. Diaplex® is
affected by heat or moisture, so this provides users thermal comfort ability(Figure 10).

Figure 10Diaplex®

The other example of Shape-Memory polymer is Dermizax®. This textile polymer is affected
by microclimates. As the microclimate rises, the openings between the polymer molecules in
the membrane expand, thereby increasing the fabric moisture permeability. As the
temperature drops the pores close, thereby trapping heat (Figure 10).

Figure 11Dermizax®

Figure 18 shows shape memory foams. Bayer developed a pillow, this pillow can adjust its
shape to the contour of the neck and shoulder according to body temperature. SMP foams can
be used as memory mattresses to provide body comfort. SMP foams can be used to prepare
insoles, which can effectively improve shoe fitting (Gefen A, Megido-Ravid M, Itzchak Y.
&Arcan M., 2002).

Figure 12 Shape-Memory Foam Applications

Sphere React Shirt has been made to be affected by user’s heat. This shirt has vents on it
when user start to make performance because of high temperature of body. This vents open
and air starts to enter the body so sweat can be evaporate fast (Figure 19).

Figure 13 Back of a Nike ‘Sphere React Shirt’ with a smart vent structure

Some more common examples of Shape Memory Polymer are as follows:-

 DAMPING FABRICS

SMPs can absorb impact energy due to their good damping properties at around Tg. Allied
Signal Inc. manufactured an automotive seatbelt fabric using SMP fibers (Securus fibers)
which can absorb the kinetic energy and so effectively increase a passenger’s safety by
utilizing the damping effect of the SMPs. The Securus fibers are made of shape memory
poly(ethylene terephthalate)-poly(caprolactone) block copolymers. It is reported that the fiber
can absorb energy from the body’s forward motion and thus improves the safety of
passengers during an accident. At first, the seatbelt holds the passenger securely in place;
then, it elongates slightly and cushions the body as the belt absorbs the force from the body.

 DEODORANT FABRICS
Such special fabrics have an ability of releasing deodorant agents at certain temperatures. The
smart fabric is fabricated by coating a stimuli-responsive polymeric hydrogel on the textile
surface. The hydrogel is attached to the textiles surface through chemically cross-linking by
using a functional monomer, such as acrylamide, and a cross-linking agent such as 2-
(diethylamino)ethyl acrylate. Deodorant is generally incorporated into the hydrogel during or
after the cross-linking reaction. Usually, β-cyclodextrin is loaded with polymeric gel for
further enhancing the controlled release properties of hydrogel-modified textiles. β-
cyclodextrin has a hydrophobic interior cavity and a hydrophilic external surface in its
structure . Therefore, different types of hydrophobic guest deodorant moieties can be
included in its cavity. Recently, a few body-responsive deodorant hydrogel products are also
available on the market. Even though such advantages of deodorant fabrics, it is not fully
explored. Few issues such as soft handle and high stability of the products need to be taken
into consideration for development of such fabric. Another important factor is controlling of
the hydration degree of the product in the open environment.
6.1.4 SHAPE MEMORY POLYMER SOLUTIONS FOR FINISH APPLICATIONS
Another method of obtaining shape memory fabrics is the finish applications with shape
memory chemicals. This process is based on the principle of transferring shape memory
features from the polymers to the fabrics. When compared to the fabrics knitted or woven
with shape memory fibres, finish process is quite an effective method. With the finish
applications of shape memory polymers, various features such as anti-piling, elasticity/force
protection, dimensional stability, non-shrink resistance, a good flat apperance, three-
dimension pattern easiness and bulginess can be transferred into the fabric. Hu et al. (2013)
developed a finish chemical for wool from shape memory polymer. The thermal and
hygrothermal effects of wool fabrics were examined. They concluded that synthetic shape
memory polymers affected the thermal and hygrothermal behaviours of the wool fabrics.
Surface outlook of shape memory treated and untreated fabrics. Wool fabric treated with
SMP did not get harmed after having been washed and dryed 25 times in accordance with
AATCC wool washing standard while untreated fabric felted after having been washed (Hu,
2010). In another study carried out by Liu et al. (2005), modification with finish having
polyurethane was tested on a cotton fabric. At the end of the study, cotton fabrics modified
with shape memory polyurethane as well as fabrics resistant to washing and corrugations
were obtained.

FINISHING FABRICS
Thermo-responsive SMPs can be applied in the textile via garment finishing. Wrinkle-free,
crease retention, anti-shrinkage and dynamic aesthetic textiles are fabricated by treating
SMPs on fabrics. The cotton fabrics treated with SMP show good wrinkle-free effect. Cotton
fabric treated with SMPU can recover to its original flat shape (wrinkle-free) within a minute
upon blowing steam over it (Figure 1a). SMP-treated fabrics possess good crease and pattern
retention ability (Figure 14 b). As a result, good aesthetic appeal is achieved in such treated
fabric.(a) Wrinkle-free effect and (b) crease and pattern retention ability of SMPU-treated
cotton

Figure 14 Finishing Fabrics

6.1.5 SHAPE MEMORY POLYMER FILM, FOAM AND LAMINATED TEXTILE
The functions of shape memory polymer films applied to textile products include waterproof,
water vapour permeability, seam sewing, prevention and stabilization of crease (Hu et al.,
2012). Water vapour permeability in textile is a feature that is applied in broad areas. Because
of their water vapour permeability, shape memory polyurethanes are ideal for the water
vapour permeable non-porous laminations. In addition to the thermomechanical features of
SMPs, they displayed other outstanding features such as moisture permeability above and
below transition temperature

PU has a large number of micro-pores to allow the distribution of perspiration molecules.

However, it also has enough smallness to prevent water droplets from going through the
fiber. While water droplet penetration is prevented, the vapour can easily be expelled because
while the diameter of water vapour molecule is about 0,4 nm, the diameter of water droplet
molecules is between 1000-200000 nm. As far as the comfort of garment is considered, high
water vapor penetration is necessary for physiological comfort (Hu, 2007; Mondal and Hu,
2007). In a study carried out by Cho et al. (2004), water vapor penetration and mechanical
properties of a material coated with shape memory polyurethane on a polyester fabric was
examined according to polyurethane concentration and hard segment.

It was observed that with the increase in the coating solution concentration, water vapor
penetration decreased to a great extent. Mechanical properties of the coated fabric were
significantly affected by the hard segment content of the shape memory polyurethane.
Another example is the laminated fabrics that are breathable and produced by the Mitsubishi
Heavy Industries (Hu, 2007); these fabrics were sold under the commercial brand name,
Diaplex. They enable the wearer to feel comfortable under some conditions such as rain and
snow. They are waterproof and expel the sweat. This product was produced with the SMP
lamination between two layers and a new membrane was formed (Figure 15).

Figure 15 Working principle of Diaplex membrane (Diaplex)

6.1.6 IMPLEMENTATION OF AESTHETIC ATTRIBUTES IN FABRIC DESIGN

The unique characteristic of movement from Shape Memory Material is integrated into the
knit and woven structure to give textiles the ability to react to environmental changes
moreover, visually transform to a prescribed design.
THE WOVEN STRUCTURE FOR INTERIORS
All samples were produced on a Harris eight-harness table loom. It is essential that when
producing a warp with a wire composite that the tension be applied evenly. When the warp is
transferred on to the loom it is important that the tension is not exceedingly tight or slack, as
this will result in yarn ends breaking during the weaving process. To achieve a three-
dimensional form in relation to the movement of the SME, a range of conventional wire and
diameters were woven solely. The samples were manipulated to achieve a three-dimensional
structure. Each sample simulates a different movement such as a wave effect, structures
shrinking and expanding and structures opening and closing. The aspiration of these samples
is to visualise the possibilities of motion within a three-dimensional structure.

Figure 16 Woven Samples Structures

Exploring open weave structures in consideration of the SME developed the woven structure.
This was achieved by adjusting the set of the warp, i.e. the number of ends per inch, as this
would influence the design and performance of the SME. In addition, to achieve spaces in the
woven structure gaps were intentionally assembled in a uniform manner in the reed. This
effect was successful as when the weave structure opens it reveals the textured yarn
composites.

Double-weave cloths were also explored to achieve versatile three-dimensional forms. The
two layers can be joined or separated and pockets or tubes can be formed. The interchanging
threads from the layers create the innovative designs. The SME would be effective as these
layers could transform a flat textile to a three-dimensional textile. (Figure 17) shows a
doubleweave sample constructed of three-dimensional tubes in a form of pleats. When the
SMM is stimulated and the martensitic phase is activated, these pleated tubes close, hence
shrinking the textiles. When the temperature returns back to the ambient temperature the
textile returns to its parent shape. The sample shown in (Figure17) exhibits how an over-fed
SMP yarn could be applied on the surface of a woven textile woven textile. This
characteristic has been applied in combination with a double-cloth structure, allowing two
effects to perform when stimulated. (Figure 17) is using double-cloth principles, sections of
the top cloth are interchanging on both sides, and this is where the SMM would be applied.

Figure 17 Woven Sample Structure 3D

The interchanging sections become a raised rounded form when stimulated. The double-cloth
technique allows the design to be visually creative on both sides of the textiles. This
characteristic would be particularly beneficial for interior applications. In consideration for
SMP the woven structure was tackled a different approach (Figure 18). SMP is a softer
material in comparison to SMA; therefore the handle of the fabric is lighter and will have
adequate drape qualities. Spandex has similar properties to SMP. Within the yarn composite
it was used created the dynamic movement of the yarn and was taken into consideration when
incorporated into the woven structure. This influenced the other yarns used in the woven
structure, as bulkier yarns were used to enhance the surface effect from the spandex
composite. It is believed that this principle will enrich the SME in the woven structure when
SMP is applied.
 Figure 18 Woven sample simulating the effect of SMP

THE KNIT STRUCTURE FOR FASHION APPAREL

Figures 19 illustrate how the SME would be placed within the selected areas of a garment.
The inclusion of SMM’s into the knitted structure introduces a new garment form. This
evolution in form, changing the garment from static to active and presents dimensional
changes that add value to the garment.

Figure 19 3-dimensional textile concept

Through the decorative process, it is possible to produce a textile with particular functional
attributes. The textile would not only evolve into another aesthetic, the SME would
simultaneously produce structures that open and close, depending upon the environmental
conditions and/or the body temperature of the wearer. A single fabric could alter from
compact and warm to open and cool. This combination gives a high-performance textile with
decorative characteristics.

6.2 SHAPE MEMORY POLYMER IN WEARABLE TECHNOLOGY

6.2.1 STENG
Being stretchable, deformable, and durable are important device requirements in the
application of wearable electronics. The STENG could maintain its performance after being
stretched by 60% while keeping the area of silicone constant (Figure 20C), which meant that
the whole output performance of the stretched device was improved if the enlarged area was
counted. It is worth noting that by varying the amount of conductive liquid in the STENG, the
stretchability of the device could be well tuned as the fracture strain of the materials was
much higher than this value. All of the reported deformable devices should keep the external
load to hold their deformed shape, which was equivalent to make the device stretchable.

In this case, the STENG was able to fix its deformed shape without any external force after
the thermal process as mentioned above, making it a transformable TENG. Figures 20 E,F
show images of the STENG in its original shape and after being stretched by over 50% with
thermal treatment, respectively. As is clearly shown, the elongated device was well
maintained after the thermal process.

The device was able to recover its original shape after another thermal stimulation (Figure
20G) and change to a curve shape while adapted to a tube (Figures 20H,I). This unique
property makes the STENG a smart design that could be applied to various areas, such as
complicated soft robotics and implanted medical devices.
 Figure 20Stretchability and shape-memorized transformation ability of the STENG

A) Images of 150 green LEDs lit by the STENG when being tapped. B) Images of an
electronic watch powered by tapping on the STENG. C) σr of the STENG under different
strains. D) Image of the setup for strain test. Images of a STENG E) before and F) after being
stretched by 50% and thermally processed. Images of a STENG G) before, H) during, and I)
after being deformed on the surface of a tube.To examine the durability of the STENG, a
long-termed motion test was carried out. The STENG was able to remain 97% of its initial
performance after ≈21 000 cycles, proving the excellent durability of the dielectric material.
The output signal of the TENG induced from mechanical motion is touch sensitive and thus it
could be used as a self-powered mechanical sensor.Smart materials place the as fabricated
STENG beyond the conventional applications such as touch panel and flexible sensor. Carpal
tunnel syndrome (CTS) is a medical condition arising from the compression of the median
nerve, which is a possible result from the repetitive wrist work including computer work or
work requires a strong grip. As nowadays people are spending more time than ever on
computer or cellphone, this syndrome is likely to occur among a larger group of people. It has
been reported that ≈5% of people in the United States have CTS.[38,40] Wearing a wrist
splint is an effective method to alleviate the symptoms. Here, we developed a STENG-based
smart wrist splint with an alarm system that could be used to modify the wrist motion. A 1.5
cm × 1.5 cm sized TENG was fabricated on a large SMP film as shown in (Figure 28A). To
improve the sensitivity of the mechanosensation, a pyramid structured silicone rubber was
encapsulated, which could induce larger contacting area change at a certain degree of
pressure (Figure 28B). The film was then heated to over 55 °C and fitted on a wrist during the
cooling process to achieve a desired shape (Figure 28C). It is worth noting that this process is
repeatable to fit the splint on different wrist.A) A film-like STENG before thermal shaping.
B) An image of the pyramid structured silicone rubber. C) An image of the splint STENG
after being transformed on a wrist. D) Relationship of the applied pressure and the induced
Voc of the STENG. E) Setup of the smart splint alert system. F) Working mode of the smart
splint system in states I and/or II with a green logo. G) Working mode of the smart splint
system in state III with a red alarm. H) The voltage signal from the splint induced by
movements between hand and the STENG. There are three different corresponding motion
states of hand: I, still; II, moving but not touching on the splint; III, touching on the splint.

Figure 21 STENG as a mechanosensation sensor in the form of a shape adaptive wrist splint

6.2.2 ORGANIC LIGHT-EMITTING DIODES ON SHAPE MEMORY POLYMER

SUBSTRATES FOR WEARABLE ELECTRONICS
The green phosphorescent inverted top-emitting OLEDs were demonstrated on SMP
substrates. These devices employed a novel ambipolar host/HTL material with a high Tg
value >110 C to yield films thermally and morphologically stable enough to withstand the
thermal stimulation needed to trigger the change in elastic modulus for the SMP substrates.
When compared to devices fabricated on glass reference substrates, these OLEDs showed
remarkably identical diode characteristics, but yielded higher current and power efficacy
values of 33 cd/A and 21 lm/W, respectively, compared to 26 cd/A and 16 lm/W,
respectively, at luminance values of 1000 cd/m2 and produced a maximum luminance over
30,000 cd/m2 .(Figure 22)These results demonstrate an alternative method to fabricate
flexible electronics using conformable substrates, and can be extended to a wide-range of
potential applications ranging from bioengineering to flexible displays and lighting.

These tests successfully demonstrate the ability to thermally evaporate these inverted top-
emitting OLEDs on SMP substrates for flexible and conformable devices.
 Figure 22 Curved SMP substrate

6.2.3 ELASTIC SHAPE MEMORY HYBRIDS PROGRAMMABLE AT AROUND

BODY-TEMPERATURE FOR COMFORT FITTING
A SMH normally includes at least two components, one is elastic component and the other is
the transition component. The elastic component is always highly elastic and stores the elastic
energy after programming, while the transition component is able to soften upon heating to
above the transition temperature and then largely maintains the deformed shape after cooling
for hardening. Upon heating to soften the transition component again, the elastic energy
stored in the elastic component is released, which provides the drive force for shape recovery
of the hybrid. The particular feature of SMHs is that these two components are carefully
selected to avoid any interaction between them. Based on the concept of SMH, a new type of
SMH, namely SPPM, is developed and characterized in terms of the heating-responsive SME
in particular. The SYLGARD® 184 silicone elastomer kit comes with two parts, namely the
base material (resin monomer)and curing agent. A series of elastic SMHs were fabricated.
Their shape memory performance and elasticity at room temperature with/without
programming were systematically investigated. In addition, the stresses vs. strain
relationships of these materials during fitting at 37 °C were characterized. It was found that
(a) these materials are always highly elastic, not only during fitting but also after
programming/fitting; (b) the elasticity of such silicone based hybrids can be adjusted if
different PPMs are used; (c) the hardening time during programming at 37 °C is always more
than 10 min. With relatively higher shape fixity ratios in SPPM2 and SPPM4, these two
models are more capable of maintaining the deformed shape while others can provide more
elastic recovery. Thus, in terms of comfort fitting, SPPM2 and SPPM4 are two most suitable
and their difference in hardness is just right for different applications. Hence, we may
conclude that this type of SMH has great potential as an elastic SMM for comfort fitting.

6.3 BIOMEDICAL
Shape-memory polymers (SMPs) are a class of mechanically functional “smart” materials
that have generated substantial interest for biomedical applications. SMPs offer the ability to
promote minimally invasive surgery, provide structural support, exert stabilizing forces, elute
therapeutic agents, and biodegrade. This review focuses on several areas of biomedicine
including vascular, orthopedic, and neuronal applications with respect to the progress and
potential for SMPs to improve the standard of treatment in these areas. Fundamental studies
on proposed biomedical SMP systems are discussed with regards to biodegradability,
tailorability, sterilization, and biocompatibility.
6.3.1 SUTURE LESS ANASTOMOSIS BASED ON SMP

Traditional surgical suture needs a doctor to possess adept knot tying technique. If the force
of tying is relatively high, it will cause the surrounding tissue necrosis. On the other smaller
forces will also leave scars. Therefore traditional sutures can potentially cause wound
infection. In recent researches have shown that the surgical sutures based on biodegradable
SMP can provide a steady, uniform restoring force .In 2002, Lendlein et al. reported a kind of
surgical suture made by biodegradable shape memory polyurethanes (SMPU). This suture
had shape memory function and was biodegradable (Fig. 23).

Figure 23The prototype of vascular stents based on SMP

They used SMPU monofilament which is in slack state to suture wound. When the
temperature rose to body temperature, the suture returned to its original shape and
automatically triggered by restoring force and the wound gap is closed .Besides, in terms of
wound closure, shape memory alloy (NiTi) has certain advantages. However, some
drawbacks of limited deformation, non-biodegradable greatly limit its development in
biomedical application .Recently, biodegradable stapler has attracted more and more attention
in minimally invasive surgery. Various staples can be emitted continuously and relatively
easy to reach the depths of human body by minimally invasive surgery. However, it does not
mean that this method is used for wound closure without any problems. To meet the
requirement of different tissues, varisized staples are needed. Staples that made up with SMP
can shrink to achieve the most suitable locked state by applying certain stimuli on it, which
can meet different needs of sizes with just only one dimension. The SMP staples are able to
exert gentle force for wound closure .
 Figure 24Recovery of shape memory polymer stent

A compression method has been developed for a long time for wound sutured anastomosis.
Spring of shape memory polylactic acid has been fabricated for suture less anastomosis. As
shown in Fig. 25, the spring was pre-expanded to a certain extent, and then placed it into
intersection of the two tubes. When it was heated to body temperature, the spring tightened
up gradually and frapped the two tubes together. Furthermore, the possibilities for application
in bleeding control are greatly extended due to its degradable function

Figure 25 Process of SMP stent deployment in the mock artery

6.3.2 CLOT REMOVAL DEVICES BASED ON SMP

Stroke is a common disease. Blood clots occurs with the blood vessels become narrow, and
when blood clots start to block the flow of blood, stroke will happen.. Such circumstance is
life-threatening if left untreated. However, medication treatment for stroke will waste too
much time, and those drugs are strictly controlled. Therefore, many researchers have
proposed a non-drug treatment method for stroke patients. Compared with drug treatment,
non-drug treatment method can quickly restore blood flow. Using shape memory thermoset
polyurethanes, Maitland research group developed a thrombectomy device for stroke patients.
Firstly, the thrombectomy device is guided into the thrombus accumulation area via tube.
After puncturing the clot, the device recovers to its coil shape. And then it collects thrombus
and pulls it out.
 Figure 26 Star-shaped stent based on film polyurethane SMP

6.3.3 TISSUE RECONSTRUCTION

Porous polymer scaffolds are heavily used in tissue engineering applications where the
polymer matrix can serve as a scaffold for tissue ingrowth and provide a temporary structural
support for the cells during regeneration of the target tissues. While traditional porous
polymers have provided utility as tissue engineering scaffolds, they lack the shape changing
properties of SMPs. There is a growing interest in SMPs for tissue reconstruction due to their
tunable biocompatibility, shape recovery, Tg, and mechanical properties. Additionally, SMPs
can be implanted in the body via minimally invasive surgery that requires miniaturized
devices to pass through small incisions. A porous SMP can be miniaturized into a small cross
section and inserted in the body through a catheter. Using body heat, the foam can be
deployed to a larger predetermined shape when in the desired anatomy. Pore size and
porosity of the foams can also be optimized for tissue specific applications.The fibers within
an electrospun thermoplastic polyurethane scaffold were shape set into axial alignment via
uniaxial strain. Stem cells showed preferential alignment along the fibers, but subsequent
scaffold actuation into random fiber orientations showed a loss in cellular orientation without
a loss in adhesion or cell viability. This study shows promise that the shape memory effect
could be leveraged to help mimic the dynamic microenvironment of biological processes.
Similarly, a SMP scaffold that would self‐fit into a critical‐sized defect in the
craniomaxillofacial (CMP) bone. 

The highlighted advantages of this material were its ability to be implanted through
minimally invasive procedures and its shape changing capacity to fill the defect. The PCL‐
based scaffold maintained comparable modulus to other systems that support bone growth,
highly interconnected pores, and allowed osteoblast adhesion and proliferation.
6.3.4 ORTHODONTICS BASED ON SMP
Because of aesthetic appeal and shape memory effect, SMP also has a great potential in
application of orthodontics.Compared with traditional orthopedic fixation materials, SMP
possesses more advantages, such as easy to install and easy to adjust shape, light weight and
comfortable. The essential requirements for orthopedic fixation material are excellent shape
fixed rate and shape recovery ratio.

Nakasima, a dentist, first proposed the concept of using thermal SMP as orthodontic arch
wire for teeth, which not only can provide sufficient restoring force, and looks more
aesthetically appealing than conventional arch wires. In 2010, reported a kind of shape
memory polyurethanes which can provide more stable recovery force for teeth and can be last
for three months at 50 °C. The fixed effect of shape memory polyurethanes was demonstrated
in vitro dental model. As shown in Fig. 27, orthodontics based on shape memory
polyurethanes looked more aesthetically appealing. It is common that the anterior cruciate
ligament is torn partially or completely in athletes, which will lead to destabilization of knee.

Figure 27 Arch wire based on shape memory polymer installed in a dental model

6.4 KINETIC BUILDING ENVELOPES FOR BUILDING ENERGY EFFICIENCY

Highly conditioned buildings via mechanical devices may make such buildings insensitive to
the environment and uncouple the building envelope from its role as an environmental
moderator. However, this ignores the nature of sustainable buildings and their ability to
acclimate (or climatically respond) to the environment, taking full advantage of the positive
influences found in nature. In the field of building “acclimation,” we found many studies
from around the world that addressed building envelopes and their impacts on building
energy usage and indoor environment issues. Building envelopes are one of the most
important design parameters determining the indoor physical environment, thermal and visual
comfort, and even occupant work efficiency; thus, the effect on energy usage is substantial.
In particular, the thermophysical and optical properties of building envelopes are factors that
should be defined by the materials and geometry of building envelope components. Interest is
increasing in net-zero energy buildings, but even current high-performance envelopes can
rarely achieve that goal.

Most available envelope designs function either as heating or cooling in the dominant
climate, but not both. In short, such envelope designs provide less-than-optimal building
performance during certain times of year. One way to improve building energy efficiency is
to develop kinetic building envelope systems that can alter their thermal and optical
properties according to seasonal/daily climatic variations. As more research works related to
kinetic buildings have emerged, kinetic building envelope systems have become increasingly
likely as a means of defining the optimal climatic responses and heightening indoor comfort.
For instance, the developed envelopes with kinetic thermal insulation properties may achieve
∼42.6–47.2% cooling and heating energy use savings, relative to the conventional envelopes
with static insulation properties in compliance with ASHRAE 90.1-2013 Energy Standard .

Figure 28 Schematic diagram of thermally responsive SMPs in heat controls of window blinds

Importantly, incorporating the shape memory effect into a building envelope component may
substantially change its optical and thermal behaviour from the point of view of building
energy savings. According to the building energy savings mechanism, the behaviours of
envelope assemblies including windows, window attachments (i.e., blinds, overhangs,
coatings, etc.), wall surfaces, wall insulations, and roof structures are considered an important
strategy for responding to external stimuli such as different sun positions, solar radiation
levels, wind speeds, temperatures, humidity levels, etc. In order to ensure the significance of
such behaviours in a specific envelope component, the stimulus (e.g., temperature, magnetic
field, etc.) and application of the SMP must both be considered.

For instance, when it comes to movable window blinds that respond to a variety of solar
angles in different seasons (i.e., winter and summer) to potentially utilize or mitigate solar
heat gain, a type of thermally responsive SMP can potentially be used in the hinges of the
blind structures. The different external air temperatures in winter and summer would then
actuate the shape change in the SMP and adjust the angles of the blind slats, as seen in the
schematic in Figure 28. Similarly, different SMP layers in a single unit with different values
could form various shapes in response to external air temperature changes, which in turn
might act as a daylighting control system for potential lighting energy savings, as seen in the
schematic in Figure 29. Ideally, these envelope components’ changes would be reversible as
external stimuli (i.e., temperature, humidity, wind, etc.) are normally periodical. To that end,
two-way SMPs show great promise for applications in the fields of dynamic building facades
and energy savings. Next, we discuss the mechanisms, properties, and associated
possibilities/challenges with two-way SMPs.

Figure 29 Schematic diagram of composite SMPs in shading controls

7.0 SMP COMPOSITES REINFORCEMENTAPPLICATION

7.1 AEROSPACE
Due to the traditional structures having some intrinsic disadvantages, such as high weight,
high cost and high deployable shock effect, which will take up much room in spacecraft and
decrease the effectiveness of aerospace missions, some new kinds of materials and structures
have been developed to improve the effective space usage in the device. On the other hand,
SMP/SMPC, which can be packaged and deployed with simple mechanical properties under a
variety of external environments, is attracting more and more attention.
HINGE
Leng et al. investigated a carbon-fiber-reinforced SMP composite that can be used in actively
deformable structures. In these structures , the flexural deformation is the main mode of the
deformation in the structures with thin shells where the bending angle is almost larger than 90
but the strain is often smaller than 10%. In this way, the shape recovery process of the
structure concerns structural deployment dynamics.

Figure 30 Hinge

As shown in Fig. 29, an SMP-composite hinge was designed, which consists of two curved
circular SMP-composite shells in the opposite directions, Illustration of the hinge (1: curved
SMP-composite shell; 2, 3: fixture of the hinge). A voltage of 20 V is applied on the resistor
heater embedded in each circular laminate. The temperature of the hinge remains at about 80
C after heating for 30 s. The whole deployment process takes about 100 s. During the
launching of a spacecraft, the room inside the spacecraft is quite limited. Hence, the
spacecraft needs lightweight, reliable and cost effective mechanisms for the deployment of
radiators, solar arrays or other devices. Composite Technology Development (CTD), Inc. has
developed epoxy SMP composites reinforced by carbon-fiber (Elastic Memory Composite,
EMC) material. The EMC materials show very high recoverable strains and high deployed
stiffness- and strength-to-weight ratios. CTD has developed a deployable hinge fabricated
with EMC materials. Recently, CTD performed an extensive ground testing on an EMC
deployable hinge that may be used for deployable spacecraft components .

Figure 31Fig. 30 shows the deployment process for the SMP-composite hinge.
GROUND-BASED DEPLOYABLE MIRROR
With their unique properties, SMPs are suitable for the fabrication of thin, lightweight
deployable ground-based mirrors . The mirror consists of a SMP composite substrate and the
coated reflective side of the composite-reflector (see Fig. 32).

Figure 32 Deployable ground-based mirror produced using EMC resin

The reflective surfaces are mainly composed of electroplated nickel to provide high quality
reflectance. The electroplated nickel metal surface, which is less than 30 lm thick, is adhered
on the surface of the SMP-composite mirror. The substrate has the ability to be deformed for
packaging and then achieve shape recovery upon Joule hearing from an external power
supply. Similarly, Cornerstone Research Group (CRG), Inc. has proposed a deployable
mirror fabricated by SMP composites, as show in. The support structure of the mirror consists
of a honeycomb support structure fabricated by SMPs and a mirror surface, including carbon
nanofibers, a reflective coating, fabrics, and microspheres.

Figure 33An illustration of reflective mirror fabricated by SMP

MORPHING STRUCTURES
Flight vehicles are envisioned to be multi-functional so that they can perform more missions
during a single flight, such as an efficient cruising and a high manoeuvrability mode . When
the airplane moves towards other portions of the flight envelope, its performance and
efficiency may deteriorate rapidly. To solve this problem, researchers have proposed to
radically change the shape of the aircraft during flight. By applying this kind of technology,
both the efficiency and flight envelope can be improved. This is because different shapes
correspond to different trade-offs between beneficial characteristics, such as speed, low
energy consumption and manoeuvrability. For instance, the Defense Advanced Research
Projects Agency (DARPA) is also developing morphing technology to demonstrate such
radical shape changes.
 Figure 34 z-shaped morphing wing produced by Lockheed Martin

As illustrated in Fig.34, Lockheed Martin is addressing technologies to achieve a z-shaped

morphing change under the DARPA’s program fund. During the development of morphing
aircraft, finding a proper skin under certain criteria is crucial. Generally, a wing skin is
necessary, especially for the wing of a morphing aircraft. Researchers focus their works on
investigating proper types of materials that are currently available to be used as a skin
material for a morphing wing. In this case, the SMPs show more advantages for this
application. It becomes flexible when heated to a certain degree, and then returns to a solid
state when the stimulus is terminated. Since SMPs holds the ability to change its elastic
modulus, they could potentially be used in the mentioned concept designs.

 FOLDING WING Cornerstone Research Group (CRG) developed an improved

SMP, which appears to be a prime candidate for seamless skin at the wing folds
 VARIABLE CAMBER WING A morphing concept of a variable camber wing was
developed .It comprises a flexible SMP skin, a metal sheet and a honeycomb
structure. Metal sheet is used to replace the traditional hinges to keep the surface
smooth during the camber changing. Honeycomb, which is high-strain capable in one
direction without dimensional change in the perpendicular in-plane axis, provides
distributed support to the flexible skin. The flexible SMP skin is covered to create the
smooth aerodynamic surface. The baseline airfoil is assumed to have an NACA 0020
profile and a chord of 150 mm.

7.2 SELF-HEALING 3D WOVEN FABRIC REINFORCED SMP

The problem is that many times cracks form without notice and through continued use of the
component (cyclic loading) finally cause the component to fail. Damage due to impact is
particularly problematic for fiber reinforced polymer composites because after the material
has been impacted it may show no apparent damage on impact point and yet significantly
damaged within. Self-healing materials offer a method of combatting this problem.Intrinsic
healing systems include polymers with thermally reversible covalent bond (TRCB) ,ionomer,
supramolecule chemistry (hydrogen bonds, metal-ligand coordination’s, stacking
interactions) . The reason is that in load bearing structures, the polymer matrix must have
sufficient strength and stiffness, even using fibers as reinforcement.In 2008, Li and John
used shape memory effect to repeatedly close impact induced cracks in a sandwich
composite. This idea was also extended to close impact induced cracks in grid stiffened
composite and 3-D woven fabric reinforced composite.
THREE-DIMENSIONAL FIBER
Three-dimensional fiber (3-D) reinforced polymeric materials have been shown to have good
impact tolerance , making them attractive candidates in weight sensitive industries such as the
aerospace, auto, and maritime. The composite was fabricated using a gravity assisted method
by impregnating 3-D woven fabric with the shape memory polymer (SMP) based syntactic
foam, which was formed by dispersing 40% by volume of micro balloons into the SMP
matrix

Figure 35 3D woven fabric reinforced SMP syntactic foam test specimens.

DAMAGE EVALUATION BY VISUAL INSPECTION

Figure 37 shows photographs of a typical group 1 specimen after impact (a) and after healing
(b). After healing, it is seen that the indentation was recovered. This indicates that damage in
the form of dents can be recovered. From the above theory we can see that, the methodology
to fabricate 3-D fiber reinforced shape memory polymer syntactic foam for structural
applications was developed. The effect of impact energy on the ability of SMP foam panels to
seal damage and mitigate impact was investigated in terms of the number of impacts to
complete perforation. It was found that by healing surface dents and closing internal damage,
perforation was delayed (from 9 impacts to 16 impacts at 32 J impact energy and from 5
impacts to 7 impacts at 42 joules impact energy).

Figure 36Before and after Healing

8.0 KEY CHALLENGES AND POSSIBLE FUTURE DIRECTIONS
The advantages of SMPs include lower density, lower cost, easier processing, larger
recoverable strains, etc. However, some of the major drawbacks of SMPs are their relatively
low modulus that results in their lower recovery stress/forces, their long response time, their
lower cycle life, and their weak material stability. SMPs show only one-way shape-memory
effect, which is different from that of SMAs. This is because most SMPs become much softer
upon applying the corresponding stimuli. In order to obtain cyclic operation for SMPs, an
automatic resetting system may be developed . Reliable thermomechanical properties of a
SMP are required in the early design stage for engineers. Due to different processing
techniques and procedures, the variation in properties (e.g., the shape fixity, shape recovery,
switching and response temperature), recovery speed, and fill factor) provides us a
convenient way for tailoring a material for better performance, but in the meantime, brings
the challenge and/or uncertainty in design . As such, first-hand experiments are most likely
required to get reliable data for applications. Considering the comparison between chemically
cross-linked thermosets and physically crosslinked thermoplastics, it shows that the former
SMPs are better candidate for realistic applications. The advantages of chemically cross-
linked thermoset SMPs include excellent shape fixity and recovery ratio, higher transition
temperature, better chemical and thermal stability. Recently SMPs shows interest in making
medical devices. One of the key challenges in realizing SMP medical devices is the
implementation of a safe and effective method of thermally actuating various SMP devices in
vivo. One of the possible way is to load ferromagnetic particles into SMP to realize remote
stimuli, namely by applying an alternating magnetic field to induce heating . The drawback is
that the required power is quite high but the efficiency is quite low. Based on the previous
results, the potential directions and applications of SMPs are proposed to be developed in
future research:

(I) Novel SMPs. Prospective SMPs may include: energy harvesting from solar energy
(light-responsive SMP), chemical energy (chemical-responsive SMP) or waste heat,
SMPs with functionally graded Tg at different locations, two-way SMPs, and SMPs
controlled in multi-step manners. For instance, the deformation of an SMP may be
better controlled in a step-by-step manner than current ones, which is achieved by
having either two Tgs for different transitions (two-step) or functionally graded Tgs
at different locations. Additionally, two-way SMPs may be developed to achieve
cyclical deformation as is the case for shape-memory alloys.
(II) Stimulus of SMPs. Wireless and remote-controllable SMPs are proposed (magnetic-
field actuated SMP composites filled with ferroelectrics, electric-field actuated SMP
composites filled with pizeoelectrics, intrinsically light-induced SMPs). High
actuation force and fast actuation speed in the new SMPs are necessary. In thermo-
responsive SMPs, a narrow transition temperature range, down to only a few degrees,
could dramatically increase the actuation speed. Alternative stimuli, e.g., light (in
particular, visible light), sound, chemicals or molecular stimuli, for actuation may be
developed. Chemical-responsive SMPs can be designed to detect the change in
environmental conditions and even make reactions automatically.
(III) Multi-functional SMPs. The following directions are proposed: self-healing or self-
repairing composite systems, automatic chemical sensing and water cleaning after
harmful chemicals based SMPs. In addition to the shape-memory effect, built-in
temperature sensors have been integrated into SMPs for temperature monitoring.
SMPs with other types of sensing capabilities should be very useful.
(IV) Applications of SMPs in biomedicine. Potential research interests may include:
polymer vascular stents with shape-memory polymers as the drug delivery system,
smart surgical suture, synthesis of protein-polymer conjugates for therapeutic, laser-
activated SMP microactuators to remove clots in a blood vessel, implants for
minimally invasive surgery, SMPs with excellent biocompatibility and/or bio-
degradability with adjustable degradation rates for intelligent medical devices.
(V) Other applications of SMPs. The following applications are prospective: space
deployable structures, such as for hinges, trusses, mirrors and reflectors, SMP skins
used for morphing aircraft wings, automobile actuators such as hood/seat assemblies
and tunable automotive brackets, smart textiles and fabrics, self-disassembling
mobile phones, and shape-memory toys. As a relatively new type of shape-memory
material, the current development and application of SMPs seemingly lag behind
other smart materials. However, given their advantages and multi-functional nature,
SMPs and their composites are expected to become one of the leading roles in the
field of smart materials in near future.

9.0 CONCLUSION
Shape memory polymers (SMPs) and their composite (SMPCs) have exhibited exceptional
features that led to proposed them to be implemented as advanced materials for the current
and potential applications. However, the traditional shape memory characteristics and
features are quite limited to due to their abilities of recovering the original shape using the
heating source only. Therefore, the reinforcements with micro/nano-fillers and particles or
fibers are essentially important to be considered to meet the needed functions and
performances. Furthermore, the reinforced SMPs and SMPCs are not only demonstrated a
significant mechanical and shape memory properties, but also obtained noble features after
being exposure to any electro-or-thermal heating source. Based on the previous researchers,
the foreseeable future concepts of SMPs and SMPCs may well-rely on how to adopt the
benefits of this kind of properties, in addition to, exceptional attributes as advanced
alternatives. On the positive front, the practical applications probability of SMPs and SMPCs
are found extensively when displayed in the remarkably distinct application principles which
may have seemed in the recent peer-reviewed publications and also patents. Moreover, we
believe that the investigation of the advanced features of these types of materials is still in
development of new design and/or incorporations. The actual vital, hence, can be found in the
finding of substantial beneficial functions wherefore SMPs and SMPCs are enablers or even
no less than tremendously excellent substitutes.

10.0 REFERENCES