CN 6162

ADVANCED POLYMERIC MATERIALS

ASSIGNMENT 1

SHAPE MEMORY POLYMERS: A BRIEF

OVERVIEW AND BIOMEDICAL
APPLICATIONS

SUBMITTED BY
DEBIRUPA MITRA
(A0123258)

CONTENTS

INTRODUCTION ............................................................................................................. 1
1.1 Shape memory effect (SME) ....................................................................................... 1
1.2 Shape memory polymers (SMP) ................................................................................. 2
1.3 Characterisation of SME in polymers ......................................................................... 4

Classification of SMPs ....................................................................................................... 5

2.1 Classification based on polymer structure................................................................... 5
2.1.1

Chemically cross-linked SMPs ..................................................................... 5

2.1.2

Physically cross-linked SMPs....................................................................... 6

2.2 Classification based on external stimulus ................................................................... 8

3

General mechanisms of SME in polymers ....................................................................... 12

3.1 Dual state mechanism (DSM) ................................................................................... 13
3.2 Dual component mechanism (DCM) ........................................................................ 14
3.3 Partial Transition Mechanism (PTM)........................................................................ 16

SMPs from a biomedical perspective............................................................................... 17

4.1 Design considerations in SMPs for biomedical applications .................................... 17
4.2 Biomedical applications of SMPs ............................................................................. 18
4.2.1

Drug delivery systems ................................................................................ 18

4.2.2

Devices for minimally invasive surgery ..................................................... 21

Conclusion ....................................................................................................................... 28

References ........................................................................................................................ 29

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LIST OF FIGURES
Figure 1 One-way shape memory effect ..............................................................................................2
Figure 2 Thermally induced SME in PTFE (I), PLA (II) and EVA (III). ............................................3
Figure 3 A typical thermo-mechanical shape response and the corresponding strain response ..........4
Figure 4 Various molecular structures of SMPs ..................................................................................5
Figure 5 The quintuple SME of poly(methyl methacrylate)/poly(ethylene glycol) ............................7
Figure 6 Light induced heating shape recovery of polyurethane SMP wire ........................................8
Figure 7 Synthesis of biodegradable multi-block polyester urethane ..................................................9
Figure 8 Swellingshrinkage behaviour in ionic based hydrogel by changes in pH. ........................10
Figure 9 Retraction of polyurethane shape memory polymer stent in water. ....................................10
Figure 10 Schematic illustration of the electro-triggered CNTs filled SMP .....................................11
Figure 11 Thermally induced shape recovery due to surface tension ................................................12
Figure 12 Basic working mechanisms for the heating-responsive SME ...........................................13
Figure 13 The SME in silicone ..........................................................................................................14
Figure 14 Thermo-responsive SME in EVA......................................................................................15
Figure 15 Concept of programming, shape recovery, and drug release ............................................19
Figure 16 Chemical Structure of Branched Oligo(-caprolactone) ...................................................19
Figure 17 Molecular scheme of the polymer network of HD-polydiolcitrate elastomers .................20
Figure 18 Representative images illustrating the programming and recovery process. ....................21
Figure 19 Temperature-controlled release kinetics of DCF from HD and EF polymers ...................21
Figure 20 Schematic representation of SMP microactuator ..............................................................22
Figure 21 Stent deployment ...............................................................................................................23
Figure 22 Photographs exhibiting the self-expansion of the stent .....................................................24
Figure 23 CHEM processing cycle ....................................................................................................25
Figure 24 Deployment of two SMP coils under simulated flow conditions ......................................25
Figure 25 In vivo application of a degradable shape-memory suture for wound healing. ................26
Figure 26 Schematic figures of the shape memory mechanism of polymer blends ..........................27
Figure 27 An example for the recovery process of shape memory effect .........................................27

LIST OF ABBREVIATIONS
EVA: Ethylene Vinyl Acetate
IPN: Inter Penetrating Network
PLA: Poly (Lactic Acid)
PLGA: Poly (Lactic-co-Glycolic Acid)
PTFE: Poly (tetrafluoroethylene)
PCL: Poly (-caprolactone)
PMMA: Poly (methyl methacrylate)
PEG: Poly (ethylene glycol)
PBS: Phosphate Buffered Saline
SBS: Styrene-Butadiene-Styrene

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INTRODUCTION

Materials science and technology has been one of the most rapidly growing areas in the last
century. During this time, the world has seen numerous advanced materials or advanced
applications of various materials for use in almost every kind of industry; microelectronic and
biomedical industries being two new industries which are heavily materials dependent as well
as fast growing. In fact, advances in materials have always characterized stages of mankind
development right from the stone age to the present age of polymers and composites. One of
the most interesting discoveries was perhaps the discovery of Shape memory materials.
Shape memory materials (SMM) are those materials which can switch their shapes between
a temporary shape and a permanent shape by the application and removal of some externally
applied stimulus. Possibly, the first shape memory effect was observed in Gold-Cadmium
alloy in the 1930s and since then these materials have been extensively investigated. Initially
shape memory effects were being explored only in allows and ceramics and then in 1960s the
first polymer reported to have a shape memory effect was a matrix of ethylene irradiated with
gamma radiation which could memorize its shape. Since then, Shape memory polymers or
SMPs as they are called have been investigated widely for their applications in aerospace,
electronics, textiles, biomedical and other fields.

1.1

Shape memory effect (SME)

Traditionally, SME refers to what is known as "one way shape memory effect" i.e., on
application of a stimulus, the permanent shape of a material (also called the fixity phase)
changes into a temporary phase which is retained as long as the stimulus is active. Once the
stimulus is removed, the fixity phase is recovered from the temporary phase. So, there are
essentially two steps in one-way SME: the "programming" step and the "recovery" step as
shown in Figure 1. For example, if the external stimulus is temperature, the material changes
from its fixity to temporary shape when heated above the transition temperature of the
material. So, the material is subjected to some kind of strain during the programming phase
and the strain is recovered during the recovery phase. This is true for any SMM but the actual
mechanisms by which the materials program and recover is different in alloys, ceramics and
polymers. There are materials which also show "multi-shape memory effect" i.e., these
materials can remember more than one shape.
1

Figure 1 One-way shape memory effect

1.2

Shape memory polymers (SMP)

Though the term SME was coined in the 1930s, polymers that can shrink in presence of heat
or water have been known for ages. Polymers as materials are advantageous over alloys and
ceramics owing to their ease of processing, variety of functionalities possessed by a whole
range of polymers and copolymers, ease of design and low cost. A comparison between
alloys, ceramics and polymers showing SME is shown in Table 1. The large strain recovery
observed in polymers is also a reason for choice of SMPs. The only drawback of polymers is
its weak mechanical properties; however, their mechanical strength can be increased by the
addition of fibers, fillers and nanoparticles.
Table 1 Comparison between alloys, ceramics and polymer properties for use in SME

A majority of the SMPs are actually thermally-induced (external stimulus is temperature),

though some can be activated by other stimuli also as will be described later. This is because
of the existence of the glass transition temperature Tg or the melt temperature Tm depending
on whether the polymer is mostly amorphous or crystalline. Polymers can undergo relaxation
of their chains due to changes in temperature which is mainly the reason for its thermally
induced SME. The mechanisms will be described in more detail in. Figure 2 shows thermally
induced SME in three very common engineering polymers.

Figure 2 Thermally induced SME in PTFE (I), PLA (II) and EVA (III). (I) PTFE: (a) original shape; (b) after
stretching at room temperature; and (cd) after gradually heating to 340 C in two steps (above the
glass transition temperature and at the melting temperature). (II) PLA: (a) original shape; (b) after
expansion at high temperatures; and (c) after heating for shape recovery. (III) EVA: (a) original star
shape; (b) after expansion into circular shape at high temperatures; and (c) after heating for shape
recovery.

1.3

Characterisation of SME in polymers

As mentioned before most polymers showing SME are thermally induced ones, so this report
will mainly focus on that category; however others will be mentioned as and where needed.
In general, there are no standard ways of characterizing all types of SMPs. Thermoresponsive SMPs can be characterised by temperature-programmed mechanical tests like the
stress-strain and the bending tests just like their alloy counterparts. Microscopy analysis can
also reveal mechanisms in SMP.
Stress-strain test: This is a general four-step procedure which is often used to characterize
SME in polymers. First the polymer is heated to above its transition temperature and then
strain applied to deform it (the strain produced in this step is denoted by m). Then it is cooled
down and when the temporary shape is fixed the stress is removed (the residual strain after
this step is u). Finally, if the polymer is heated again to above the transition temperature, it
recovers its original shape (the strain after this is denoted p). The cycle is usually repeated to
study the SME. A typical 3-axis diagram of stress-strain-temperature is shown below.

Figure 3 A typical thermo-mechanical shape response and the corresponding strain response

The parameters calculated are:

Strain recovery % = {

} 100 (the ability of the polymer to return to its original shape)

Strain fixity = ( the ability to hold the shape during switching)

Bending test: This is similar to the above but here, the polymer is subjected to bending and
the initial (i) and final angles (f) of deformation are measured. This also recognizes the
polymer's ability to recover its shape.

Bending recovery =
4

Classification of SMPs

SMPs can be broadly classified according to two different categories; one, on the basis of the
polymer structure and the other based on type of external stimulus which induces the SME.

2.1

Classification based on polymer structure

The structure of a polymer depends on the type of cross-linking in the polymer. Based on the
type of cross-linking, there may be the following types of SMPs described in the sub-sections
below. Figure 4 shows the molecular structures of a SMP.

Figure 4 Various molecular structures of SMPs. A stable network and a reversible switching
transition are the prerequisites for the SMPs to show SME. The stable network can be molecule
entanglement, chemical cross-linking, crystallization, and IPN; the reversible switching transition can
be crystallization-melting transition, vitrification-glass transition, anisotropic-isotropic transition,
reversible chemical cross-linking, and association-disassociation of supramolecular structures

2.1.1 Chemically cross-linked SMPs

These SMPs contain covalently cross-linked polymer chains and these cross-links act as the
fixity phase. This means a permanent shape can be fixed by the activation of these cross-links

because a covalently cross-linked polymer chain cannot change its shape any further by chain
relaxation. These cross-links can be introduced by a cross-linking agent or through some
electromagnetic radiation. For example, the polymer can be heated in presence of a peroxide
molecule which can cross-link certain polymer chains above a specific temperature or the
polymer can be exposed to gamma or UV radiations in presence of a photo-initiator to cause
cross-linking. In the latter case, there must be functionalities present in the same monomer
which can be cross-linked or there can be two or more functional monomers or a functional
monomer with an appropriate cross-linking agent.
Another type of chemically cross-linked SMPs are liquid crystalline networks in which
mesogens (molecule that forms liquid crystals) are grafted on to the polymer chains. The
SME is obtained when the mesogens in the polymer backbone undergo phase
transformations.
Temperature-sensitive polymeric hydrogel networks can also exhibit SME by virtue of their
solution critical temperature. Those exhibiting Lower Critical Solution Temperature (LCST)
are swollen below LCST and shrink above it. Those exhibiting Higher Critical Solution
Temperature (HCST) exhibit the exactly opposite phenomena.
2.1.2 Physically cross-linked SMPs
In this type of SMPs, the fixity phase is governed by physical interactions between polymer
chains like formation of crystalline phases, hydrogen bonds or ionic interactions. Due to the
physical forces involved, the fixity phase in these SMPs can be remoulded again unlike that
of chemically cross-linked SMPs. Semi-crystalline polymers containing both amorphous and
crystalline phases like PLA are examples of this type where the crystalline phase acts as the
fixity phase.
Polymers with separated phases can also be obtained by co-polymerisation where the
monomer having the highest transition temperature acts as the fixity phase. Block copolymers
show better SME than the homopolymer of the same kind due to blending of properties of
two different monomers (like increased toughness or biodegradability, etc). For example,
PLA-PLGA co-polymer shows much better SME than PLA homopolymer.
Polyurethanes synthesized from thermoplastic diols have been found to show good shape
memory properties. In this method, a polymeric diol reacts with diisocyanate to form a pre-

polymer which then reacts further with low molecular weight diols to form oligoesters. Thus,
the urethane groups form the fixity phase (by stabilization with the help of hydrogen bonding
and dipole-dipole interaction) whereas the oligoesters act as the switching phase. Shapememory polyurethanes can also be obtained by block co-polymerization resulting in the
urethane linkages.
Polymer blending is an easy and effective technique to improve the properties of polymers
and may lead to shape-memory properties. Depending on the type of polymer blends, there
may be miscible or immiscible SMP blends. Miscible SMP blends may be formed by
blending of a semi-crystalline and an amorphous polymer like PCL and polydioxianone, PCL
polyurethane with phenolic resin, etc and examples of immiscible blends may be SBS
dispersed in a PCL matrix. Two miscible polymers whose networks can be inter mingled with
one another can form fully Inter-penetrating Network (IPN) or semi-IPN. This may occur
when cross-linking of two polymers occurs in stages after initial blending. In these kind of
IPNs the chains act as the fixity phase and the cross-linked net-points of both the polymers
act as the switching phase. Figure 5 shows SME in a PMMA-PEG semi-IPN network.

Figure 5 The quintuple SME of poly(methyl methacrylate)/poly(ethylene glycol) semi-IPN with a

broadened glass transition and a crystalline segment

In many applications SMP composites have been shown to exhibit enhanced shape memory
properties along with additional properties when compared with SMPs. The addition of fillers
like nanoparticles, nanotubes, etc can significantly improve the mechanical properties of a
polymer. In this case, the fixity phase is often the interaction between the particles and
polymers.

2.2

Classification based on external stimulus

Classification of SMPs can also be done based on the stimulus which induces the SME in the
material. External stimuli may be direct or non-direct: Direct stimuli facilitates the shape
memory in both the programming and recovery step, whereas indirect stimuli is the one
which only acts on the recovery step. For indirect stimuli, usually temperature is used to fix
the temporary shape.
Temperature:
Heat-induced or thermo-responsive SMPs are the most common and widely investigated
SMPs out of all due to the presence of suitable Tg or Tm in many of the polymers. Thus, this
is also the most well understood category. The thermo-mechanical response has already been
shown before and the structural mechanisms are presented later for this class of SMPs. The
temperature rise can be caused by Joule heating, inductive heating, light-heating and radioheating.

Figure 6 shows a polyurethane SMP wire which after programming is stretched and
transparent but regains its length and transparency upon recovery.

Figure 6 Light induced heating shape recovery of polyurethane SMP wire: Left: After programming;
Right: After recovery

Light:
Light-induced or photo-responsive SMPs are those that can exhibit shape memory behaviour
in the presence of light, so they must contain some photo-responsive molecules in them.
There can be 3 types of photo-responsive molecules: photoisomerizables (change from cis to
trans in presence of light), molecules obtained by cationic induced polymerization and photoresponsive molecules like cinnamic acid. here, the covalent bonds in the polymer chains act
as the fixity phase while the photo-responsive molecule acts as the switch phase. This
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category has an advantage of its application in biomedical engineering as it does not cause
tissue damage by heating. However, successful photo-responsive SMPs for such use is still
limited due to the potential toxicity of the photo-responsive molecules themselves (like
azobenzene). Figure 7 shows a photo-responsive polyurethane containing cinnamamide as the
switch phase.

Figure 7 Synthesis of biodegradable multi-block polyester urethane containing pendant photoactive

cinnamamide groups from biodegradable soft diol (poly caprolactone diol), biodegradable hard diol
(poly-(L-lactic acid) diol), and N,N-bis(2-hydroxyethyl) cinnamamide

pH:
pH-responsive SMPs are mostly polymeric hydrogels that can cause a change in their volume
depending on the pH due to the presence of charged groups/molecules in them which show
ph-induced ionization. Depending on the type of ionizing molecule there can be polyacid or
polybase based ph-responsive hydrogel. Polyacids can accept protons at low pH whereas
polybases donate protons at high pH. Many pH responsive hydrogels are commonly used for
drug delivery and delivery applications. However, often this mechanism is coupled with
temperature effects for more effective programming and recovery. Figure 8 shows the
shrinkage of gels due to change in pH.

Figure 8 Swellingshrinkage behaviour in ionic based hydrogel by changes in pH.

Water and moisture:

Some SMPs are stimulated by the presence or absence of water or moisture. This is governed
by the presence of hydrophilic/hydrophobic moieties within the polymer. For some
hydrophilic chemo-responsive SMPs, it may stretch when immersed in water and shrink
when immersed in ethanol. Plasticizing effects in water may cause shrinkage or expansion of
a polymer in water. Figure 9 shows the retraction of a stent which can be delivered to a
specific location by a catheter after which it can expand to its permanent shape. Moistureinduced shape recovery also acts in a similar ware the moisture is slowly absorbed into the
polymer and this water acts as a plasticizer leading to a decrease in the transition temperature.

Figure 9 Retraction of polyurethane shape memory polymer stent in water.

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Electric/magnetic field:
SMPs by themselves are rarely electro-sensitive due to the non-conductive nature of
polymers. However composite SMPs obtained by the addition of conducting fillers like
Carbon nanotubes can render the polymer electro-responsive. In many cases the electroresponsive recovery is only indirect i.e., by virtue of electrical conductance if the temperature
rises to the transition temperature, shape recovery occurs. In others, the electric field induces
stresses due to the presence of conducting fillers, causing shape change as shown in Figure 10.
Magnetic-field induced SME is also similar to the electric -field induced one; here, the active
components are magnetic fillers like magnetite nanoparticles. In this case also, usually the
magnetic field causes heating of the particles leading to shape recovery.

Figure 10 Schematic illustration of the electro-triggered spatially and temporally controlled shape
recovery and the realization of multi-shapes on demand of CNTs filled SMP

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General mechanisms of SME in polymers

Every different polymer exhibiting SME is governed by a specific mechanism and that too in
response to a particular stimulus. It is understandable that not all SMPs will respond in the
same way to a particular stimulus. Also, not every SMPs will show SME in response to more
than one stimulus. Thus, it so happens that the exact mechanism for individual SMPs in
response to their corresponding external stimulus is different. For instance, shape memory
is observed in thermo-responsive EVA-based melting glue droplet. In this case, the polymer
droplet recovers its shape when heated due to a surface tension driving force which forces the
polymer to revert back to its original surface (shown in Figure 11). However, there are some
basic underlying principles by virtue of which many polymers exhibit SME. In this section,
some basic theories of understanding SME are discussed which were originally derived for
thermo-responsive SMPs but the idea can also be extended to others.

Figure 11 Thermally induced shape recovery due to surface tension in an EVA-based melting glue
droplet. (a) Original shape; (b) after indented for a line; and (c) after heating for shape recovery.

In the following sub-sections, three theories derived from understanding of thermallyinduced SME are discussed. A majority of the SMPs are heat -induced and the mechanisms
have been more clearly understood for this class of polymers by virtue of molecular
mechanisms arising from transition temperatures in polymers. Although, these principles are
applicable to heat-induced SME in polymers, they can be applied to understand SME in
most other (if not all) polymers/ composites.
Generally, the understanding is that SME is observed in polymers which have a dualcomponent system (like hard and soft segments, amorphous and crystalline segments, etc).
One of the components is elastic in the temperature domain of our interest and the other
component can deform plastically in the low stiffness regions. So the plastic domain brings
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about a change in the shape and the elastic domain stores the energy and provides the driving
force for shape recovery. Thus, the second component is active during the "programming"
step and the first component is active during "recovery" step. The deformation occurs in the
presence of the right stimulus. For heat-induced SMP, the glass transition and the melting
temperatures are utilized for causing these deformations. In the following mechanisms, timedependent strain effects and viscosity dependent effects like creeping are not taken into
account. The working mechanisms are pictorially represented in Figure 12. Most importantly,
often a combination of the following mechanisms are said to work in most of the SMPs.

Figure 12 Basic working mechanisms for the heating-responsive SME in polymeric materials. (I) Dualstate mechanism (DSM); (II) dual-component mechanism (DCM); (III) partial-transition mechanism
(PTM). (a) Original sample at low temperatures; (b) upon heating and compressing; (c) after cooling
and constraint removal; and (d) after heating for shape recovery

3.1

Dual state mechanism (DSM)

This theory is based on the existence of two states (hence the name) in polymers: the glassy
state and the rubbery state. In this theory, it is assumed the SMPs are in the glassy state
initially and then heated to above its Tg following which it is deformed. After the

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deformation in the rubbery state, if the polymer is cooled to below its Tg while maintaining
the deformed shape, the molecular motion is frozen and the polymer maintains the deformed
shape. The original shape is recovered only when the molecular motion becomes active again
by heating the polymer to above Tg. So, according to this theory, all elastomers having
achievable glass transition temperatures (corresponding to the application; like 30-40 C for
applications within the body) can exhibit SME to some extent naturally. Two main SMPs
whose behaviour can be explained by this theory are PMMA and Silicone.
In these kind of SMPs, the shape recovery phenomena is enhanced if there are net-points of
cross-linking present in the polymer matrix. These cross-linking junctions could be
chemically cross-linked or physically cross-linked or tangled polymer chains. These junctions
or points can efficiently store the energy during deformation and serve as the driving force
during the recovery step.

Figure 13 The SME in silicone. a Original shape; b cooled in liquid nitrogen (able to maintain this
shape in liquid nitrogen as stand-alone); c recovered at room temperature

3.2

Dual component mechanism (DCM)

This theory explains shape memory behaviour of polymers having two components: an
elastic component and another transition component. One of the domains/segment in these
SMPs is highly elastic and the other domain/segment is responsible for reversible phase
transitions. This phase transition is glass transition or melting for heat-induced SMPs.
Referring to, the matrix is the elastic segment and the inclusions constitute the transition
segment. When the material is heated above Tg, the inclusions soften and the matrix is
strained and deformed. If this state is maintained while the material is cooled below its Tg,
the inclusions freeze/harden and prevents further deformation/recovery. The energy is stored
in the elastic matrix and there is a residual strain observed. Upon heating again, the inclusions
soften and pushes the matrix to come back to its original shape.

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One example of such a SMP is Ethylene-vinyl acetate or EVA copolymer containing dual
segments. One component is highly elastic and the other component shows very low stiffness
at high temperatures and very high stiffness at low temperatures. So, upon heating and
deformation a ring of EVA expands (shown in Figure 14) and the expanded ring retains its
diameter once cooled due to the high stiffness of the transition component.

Figure 14 Thermo-responsive SME in EVA. a After expansion; b after heating for (full) shape recovery

Another widely explored SMP of this category is Polyurethane (PU) and different
modifications/blends/ composites of PU. In one work, two miscible grades of PU having
different melting temperatures led to the formation of a blend SMP. When the operating
temperature is between these two melting temperatures, one component (the one with the
lower melting temperature) can soften on heating while the other (the one with the higher
melting temperature) maintains the elasticity. Thus this principle can be invariably applied to
polymer blends or polymer composites with fillers containing similar dual-component
system. Some examples of such SMPs which have been investigated are PolyurethanePolyvinyl chloride, acrylonitrile-butadiene-styrene (ABS) / Polycarbonate, etc.
This DCM theory has also been extended to polymer-other component hybrid systems where
the other component could be a fatty acid, inorganic molecules, metals, alloys etc. An
example of a shape-memory hybrid is that of Silicone-paraffin wax hybrid containing 30%
by volume of paraffin wax. The circular wax droplets embedded in the Silicone matrix act as
the transition component and become elliptical after programming.

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3.3

Partial Transition Mechanism (PTM)

This theory is quite less mentioned in the literature, though so have actually utilised this
principle to some extent. According to this mechanism, the polymer does not contain
inclusions initially. During the programming step, a part of the polymer melts and behave as
the transition component and the remaining part behaves as the elastic component. So, after
programming, the hardened part prevents the rest of the polymer from regaining its shape.
This mechanism is almost similar to DCM except for the fact that the two components do not
separately co-exist in the original material and phase transition occurs for "partial" material.
This mechanism can either act alone or in combination with the other two, which is the more
frequent case. If it works alone, then the temperature control during the programming and the
recovery steps become very important.

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SMPs from a biomedical perspective

The biomedical sector is one of the fastest growing research areas at present with a lot of
emphasis on trying to translate the research for commercial applications. Since the midtwentieth century the use of polymers for biomedical applications have become not only
popular but almost indispensable. With the introduction of SMPs, research has now moved to
the next generation biomaterials. However, application for biomedical purposes require
certain characteristics to be present within the material. The SMP must be biocompatible,
may be biodegradable depending on the specific application, possess transition
temperatures around the body temperature, show minimal cytotoxicity and have small
recovery times. For specific applications, recent trend has been to use polymer blends,
composites as well as Shape memory hybrids(SMH). The following table provides a
comparison between key properties of SMAs, SMPs and SMHs.

4.1

Design considerations in SMPs for biomedical applications

SMPs seem to be a very attractive option for the design of biomaterial systems for a wide
range of applications. However, due to the restrictions imposed for their use in biomedical
applications, one has to very carefully select and design the SMPs suitable for different
purposes.
The most important property is perhaps achieving the transition temperature/ other property
to be in a safe range for the body. For example, the transition temperature for thermoresponsive SMPs must b around 37C. For light-induced SMP, the transition could be
achieved by applying UV irradiation for a small time; however, thermally-induced SMPs are
most efficient when it comes to use in physiological conditions.

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Biocompatibility of the SMPs is also another important constraint as any material for
biomedical applications should not show even the slightest of toxicity. Extensive in vitro cellculture experiments followed by in vivo testing in animals must be performed for this
purpose. It is often not enough for the SMP to be just non-cytotoxic, it should also maintain
proper functionality of the cells attached to it thus ensuring normal cell proliferation. A lot of
work has been done in this area and SMPs like poly(-caprolactone) dimethacrylate,
poly(glycerol dodecanoates) among many others have been shown to be biocompatible. Some
specific applications like use in cardio-vascular tissues may require good hemocompatibility.
Some applications require the material to be biodegradable an sometimes the rate of
degradation may be important such as in controlled release applications. So, while designing
a SMP, the biodegradation rates can be tailored by adjusting ratios of copolymers or polymer
blends or by the addition of a third component.
So, by a proper choice of polymeric composition and tailoring of its characteristics,
functional SMPs can be achieved which can find it use in biomedical applications. In addition
to the basic characteristics of a biomaterial, special properties like magnetic behaviour,
electrical nature (conducting behaviour), transparency, etc can be introduced into the SMPs
depending on their specific use, Lastly but importantly, sterilization considerations must be
kept in mind if we are designing something for commercial biomedical uses.

4.2

Biomedical applications of SMPs

Use of polymers for biomedical applications was an important landmark in advanced

applications of polymeric materials and now, the advanced design of materials have opened
new applications to be explored and investigated further. Investigation of SMP s for
biomedical purposes became only after 1990s and since the early 2000 there have been a lot
of advancements in this field. In this sub-section, the major application areas and a few
examples to illustrate the application are discussed.
4.2.1 Drug delivery systems
One of the major applications of SMPs is in fabrication on drug delivery systems. These are
so designed that on application of the external stimulus, there are changes in the polymer
network leading to release of the drug. This stimulus could be pH of the target area,
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externally applied magnetic field, body temperature, externally applied heat, etc. The concept
of drug delivery using SMPs has been illustrated in the figure below and two recent examples
are mentioned thereafter.

Figure 15 Concept of programming, shape recovery, and drug release of drug loaded SMP devices for
biomedical applications

Nagahama et al., 2009 fabricated a biodegradable SMP network by the cross-linking of

branched oligo(-caprolactone) with hexamethylene diisocyanate (Figure 16). The shapememory properties were quantified using thermo-mechanical tensile experiments and strain
fixity rates higher than 97% and strain recovery rates of 100% were observed. The shape
recovery to the permanent shape within 10 s at 42 C. A 10% theophylline-loaded SMPs was
sufficiently soft and flexible for complex shape transformation and also showed high fixity
(98%) and recovery rates (99%). Sustained release of loaded theophylline was achieved over
1 month without initial burst-release in a phosphate buffer solution (PBS; pH 7.4) at 37 C.

Figure 16 Chemical Structure of Branched Oligo(-caprolactone) and the Polymer Network Structure
Formed by Cross-Linking Reactions

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Recently, citric acid is being used to synthesize biodegradable polyester elastomers by virtue
of its polymerization with some diols. At certain compositions with specific diols, this
polymer is found to show thermally-induced SME. In a work by Serrano et al., 2011,
Hydroxyl-dominant (HD) polydiolcitrates were synthesized by using 1,12-dodecanediol
(DD). By increasing the mole ratio of hydroxyl to carboxyl groups in the reaction mixture
(4:3 in HD polymers vs 1:1 in equifunctional (EF) polymers) the esterification of carboxyl
groups from citric acid with hydroxyl groups present in the aliphatic diols allows for the
formation of hydrophobic micro-domains in the cross-linked polymer network that are
stabilized by intermolecular hydrophobic interactions (Figure 17). By using long-chain
aliphatic diols, the intermolecular packing is thermodynamically favoured resulting in a
copolymer with thermosensitive mechanical and shape-memory properties that can be
induced between room temperature (22 C) and body temperature (36.6 C). The polyester
network includes covalent net points responsible for the permanent shape and hydrophobic
micro-domains physically cross-linked by intermolecular hydrophobic interactions, which
behave as switch structures to fix the temporary shape. The SME is illustrated in Figure 18
and the drug release profiles are shown in Figure 19.

Figure 17 Molecular scheme of the polymer network of HD-polydiolcitrate elastomers

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Figure 18 Representative images illustrating the programming and recovery process in polymer films
and porous 3D scaffolds, respectively. Polymer samples resemble capital letters A, B, and C as
the permanent shape at room temperature (B13). 3D sponges behave as tough matrices at room
temperature (C2), but become soft above T trans or with further post-polymerization (C3).

Figure 19 Temperature-controlled release kinetics of DCF from HD and EF polymers

4.2.2 Devices for minimally invasive surgery

Minimally invasive surgery may be the key to more efficient surgeries in the coming years
due to its advantages over traditional surgeries. Shape-memory materials can be utilized for
this kind of application where the material is inserted when it is in the temporary shape and
then in physiological conditions undergo shape recovery to obtain the actual shape of the
implant. Shape-memory alloy of Ni-Ti is already in use as orthodontic wires and cardiovascular stents. However, the alloys have limitations in processability and in achieving high
strain recovery rates which can be overcome by using SMPs. Following are some of the
examples illustrating this specific application of SMPs.

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Microactuators for clot removal:

With rising cases of ischemic stroke worldwide, people are looking for new alternatives to
conventional clot-dissolving drugs. The key concept is to use SMPs to facilitate clot removal
under physiological pressures and flow conditions.
A promising approach proposed by Maitland et al., 2002 for treating ischemic stroke can be
the mechanical removal of thrombi using a novel microactuator device (shown in Figure 20).
The device consists of an injection-molded laser-activated SMP microactuator that is
delivered through a catheter distal to the thrombolic occlusion. The microactuator is mounted
on a diffusing optical fibre and delivered in its straight form through a catheter distal to the
occlusion, where it is deployed via optical heating into its coil shape. Once the device is
deployed, both the microactuator and the thrombus are removed from the vessel.

Figure 20 Left: Schematic representation of SMP microactuator used in treating ischemic stroke. a:
The guide catheter is pushed through or around the blockage. b: The SMP device is pushed out of
the guide catheter and actuated. The SMP device must have a small enough diameter to pass
through an appropriate neurovascular guide catheter. Current design goals have set this diameter to
be 0.01200 (300 mm) or less. c: The catheter, expanded device (coil depicted in this schematic), and
clot are pulled in unison proximally to relieve the ischemia; Right: Schematic representation of an
embolic coil release microgripper. a: The delivery device with the coil loaded and ready for
deployment. b: The delivery device after the SMP has been heated above its transition temperature.
The SMP around the coil has mechanically relaxed (expanded) to its extruded diameter. The SMP
remains in its expanded state after the laser-coupled thermal energy is turned off and the SMP cools
below its transition temperature

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Stents:
Using SPMs to fabricate different types of expandable stents has been one of the most widely
explored application. In a work by Baer et al., 2007, laser-activated photothermal SMP was
used to demonstrate deployment of a vascular stent in a mock artery (Figure 21). The SMP
stent was fabricated from a commercially available thermoplastic polyurethane having a
segmented phase micro-structure (a hard phase and a soft phase).

Figure 21 Stent deployment. Timeline of SMP stent deployment in the mock artery (zero flow) as the
laser power was gradually increased. Laser duration was approximately 6.3 min

In another work by Xue et al., 2010, block co-polymers (named as PCTBVs) containing
hyperbranched three-arm poly(3-caprolactone) (PCL) as switching segment and microbial
polyester PHBV as crystallisable hard segment were designed as biodegradable SMP for fast
self-expandable stent. PCTBVs showed desired thermal properties, mechanical properties,
and ductile nature. PCTBV containing 25 wt% PHBV (PCTBV-25) demonstrated excellent
shape-memory property at 40C (Figure 22) and shape recovery within 25s. PCTBV-25 was
also shown as a safe material with good biocompatibility by cytotoxicity tests and cell growth
experiments. The stent made from PCTBV-25 film showed nearly complete self-expansion at
37 C within only 25sec making it a probable stent for future use.

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Figure 22 Photographs exhibiting the self-expansion of the stent made from PCTBV-25 with original
outer diameter of 3.45 mm. (1) The stent was mechanically deformed, fixed on a metallic rod with
diameter of 1 mm to give outer diameter of 1.43 mm, and removed the mechanical force; (2)e(4) the
stent was put in water bath at 37C after 3s, 10s and 20s, respectively; (5) the stent was taken out
from water bath after 25s, with diameter of 3.35 mm. Viability of L929 cells after 3 days incubation
in different concentrations of aqueous extracts of PCLBV and PCDBV films

Aneurysm occlusion:
An aneurysm is a localized, blood-filled balloon-like bulge in the wall of a blood vessel
(Wikipedia) which may increase in size and lead to a rupture. In general, more than half of
these cases result in death and even those who survive may develop a permanent nerve
damage. Nowadays, novel endovascular treatments like aneurysm embolization with balloonassisted coils, flow diversion devices, open- and closed-cell stents, and embolic materials are
viewed as promising options when compared to traditional invasive surgical techniques.
However, there are certain limitations too which can possibly be overcome by the use of
SMPs.
Metcalfe et al., 2002 utilized a SMP called "Cold Hibernated Elastic Memory (CHEM)"
polyurethane (which is a polyurethane based network having a foamy structure) for
endovascular interventions in vitro as well as in trial studies on dogs. Internal maxillary
articles embolized with CHEM foam were healed in 3 weeks. The use of SME is described
by the figure below.

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Figure 23 CHEM processing cycle. Structures of any shape, made of CHEM foam, are compacted to
small volumes in a flexible state above the Tg and later cooled below Tg to a glassy state, to be
stowed for unlimited periods below Tg: The stowed structure can be heated above Tg to a flexible
state and the original shape will be precisely restored. A fully deployed structure can be rigidized by
cooling below Tg to a glassy state.

Commercially available SMP Calomer (block co-polymer of polyurethane) was used to

fabricate coils to occlude blood flow for intracranial aneurysm in a work by Hampikian et al.,
2006. Calomer coils were filled with Tantalum to increase the radio-opacity of the coil (for
detection using X-rays) and thermo-mechanical SME was evaluated. 2 SMP coils deployed
inside a simulated aneurysm model demonstrate (Figure 24) that typical hemodynamic forces
do not hinder the shape recovery process and the coils remained stable.

Figure 24 Deployment of two SMP coils under simulated flow conditions

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Degradable sutures:
Smart, degradable sutures may be the solution to minimally invasive and less painful wound
repair where the sutures may tighten across the wound themselves and may degrade after the
wound has repaired. In one work, degradable sutures were fabricated from SMPs of phasesegregated multiblock copolymers like that generated from a reaction between oligo(caprolactone)diol and 2,2(4),4-trimethylhexanediisocyanate. This specific SMP was found to
have deformations upto 400% between their temporary and permanent shapes. The use of this
SMP for wound closure was illustrated by using extruded fibers to act as sutures for closing
abdominal incision on a rat model. The sutures were stretched to 200% of their original
length and then heated to 41C to thermally-induce shape memory for the suture to return to
its original length and close the wound as depicted in Figure 25.

Figure 25 In vivo application of a degradable shape-memory suture for wound healing. An

appropriate closure of the wound was achieved by the temperature-induced shrinkage of the fiber
suture (left to right).

In a different approach, Zhang et al. developed a novel blend of styrene-butadiene- styrene

tri-block copolymer (SBS) and poly(-caprolactone) (PCL) that was able to automatically
knot within 10 s in a water bath at 70C. Here the shape memory is due to the phase
segregation of an elastomer SBS and a crystalline polymer PCL. It was found that PCL forms
the continuous phase above 30% of the polymer. The mechanism is illustrated in Figure 26
and the shape-memory behaviour for a 50% PCL sample (PCL50) is shown in Figure 27.
Although transition temperature adjustment for biomedical requirements is needed, these
shape-memory blends show promise for their use as thermo-sensitive sutures.

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Figure 26 Schematic figures of the shape memory mechanism of elastomer/switch polymer blends
concluded from SBS/PCL blend

Figure 27 An example for the recovery process of shape memory effect when the PCL50 sample was
placed in water of 70C

Other applications:
Examples from the major application areas of SMP in biomedical research have been
mentioned in this section. Apart from these well-established applications, there are various
others which utilize SMPs and some of these applications are rather new and just emerging.
Some of the other examples not mentioned in this report but equally important are the use of
SMPs as bone defect fillers, cell differentiation manipulating scaffolds, kidney dialysis
needles, micro-tweezers for surgical applications, micro-valves in miniaturized medical
devices, ophthalmic applications, orthodontic wires, pharyngeal mucosa reconstruction,
physiological monitoring, shape-changing nanofibrous scaffolds, self-healing biomaterials,
shape-memory neuronal probes, wound dressings, self-expanding device for curbing appetite
and many more. Thus, one can imagine the broad horizon of applications of SMPs in
biomedical science and research.

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Conclusion

From the overview presented in this report, it can be concluded that SMPs may turn out to be
a promising approach to many of the current research problems. Since there a large number
of polymers available and one can perform a lot of modifications in their properties, a number
of different SMPs can be designed according to specific needs. Thus, there exists an immense
adaptability and versatility in this field.
Though most of the present SMPs are thermo-responsive, heating may not always be a
desirable step for some applications like in some biomedical applications it can lead to tissue
damage. Hence, there is a wide scope of research of other stimuli-responsive SMP which at
present are not so efficient as the heat-induced ones.

Also, much more detailed

understanding of the molecular mechanisms of SMPs other than heat-induced ones are yet to
be established in great detail. The general mechanisms presented in this report are the best
understood ones but they may not apply for some SMPs like the pH-responsive ones. Once
the mechanisms are well grasped, it will provide a great help to design more SMPs.
The use of SMPs is definitely not limited to biomedical applications, although this sector still
accounts for the largest area of application till date. SMPs find applications in other areas like
aerospace engineering, defence organisations, textile and paper industry and many more.
Thus there exists a wide variety of applications and an even wider range of polymer
combinations and techniques for people to delve into this interesting phenomena of shapememory in polymeric materials for many more years to come.

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