Shape-memory polymer

From Wikipedia, the free encyclopedia

Shape-memory polymers (SMPs) are polymeric smart materials that have the ability to return
from a deformed state (temporary shape) to their original (permanent) shape induced by an
external stimulus (trigger), such as temperature change.[1]

Contents
[hide]

 1 Properties of shape-memory polymers

o 1.1 Triple-shape memory
 2 Description of the thermally induced shape-memory effect
o 2.1 Thermodynamics of the shape-memory effect
o 2.2 Physically crosslinked SMPs
 2.2.1 Linear block copolymers
 2.2.2 Other thermoplastic polymers
o 2.3 Chemically crosslinked SMPs
 2.3.1 Crosslinked polyurethane
 2.3.2 PEO based crosslinked SMPs
 2.3.3 Thermoplastic shape-memory
 3 Light-induced SMPs
 4 Electro-active SMPs
 5 Shape-memory polymers vs. shape-memory alloys
 6 Applications
o 6.1 Industrial applications
o 6.2 Medical applications
o 6.3 Potential medical applications
o 6.4 Potential industrial applications
o 6.5 Brand protection and anti-counterfeiting
 7 See also
 8 References

Properties of shape-memory polymers[edit]

SMPs can retain two or sometimes three shapes, and the transition between those is induced by
temperature. In addition to temperature change, the shape change of SMPs can also be triggered
by an electric or magnetic field,[2] light[3] or solution.[4] As well as polymers in general, SMPs also
cover a wide property-range from stable to biodegradable, from soft to hard, and from elastic to
rigid, depending on the structural units that constitute the SMP. SMPs
include thermoplastic and thermoset (covalently cross-linked) polymeric materials. SMPs are
known to be able to store up to three different shapes in memory.[5] SMPs have demonstrated
recoverable strains of above 800%.[6]
Two important quantities that are used to describe shape-memory effects are the strain recovery
rate (Rr) and strain fixity rate (Rf). The strain recovery rate describes the ability of the material to
memorize its permanent shape, while the strain fixity rate describes the ability of switching
segments to fix the mechanical deformation.

Result of the cyclic thermomechanical test

where N is the cycle number, εm is the maximum strain

imposed on the material, and εp(N) and εp(N-1) are the
strains of the sample in two successive cycles in the stress-
free state before yield stress is applied.
Shape-memory effect can be described briefly as the
following mathematical model:[7]

where Eg is the glassy modulus, Er is the rubbery

modulus, fIR is viscous flow strain and fα is strain for t
>> tr.
Triple-shape memory[edit]
While most traditional shape-memory polymers can
only hold a permanent and temporary shape, recent
technological advances have allowed the
introduction of triple-shape-memory materials. Much
as a traditional double-shape-memory polymer will
change from a temporary shape back to a
permanent shape at a particular temperature, triple-
shape-memory polymers will switch from one
temporary shape to another at the first transition
temperature, and then back to the permanent shape
at another, higher activation temperature. This is
usually achieved by combining two double-shape-
memory polymers with different glass transition
temperatures[8] or when heating a programmed
shape-memory polymer first above the glass
transition temperature and then above the melting
transition temperature of the switching segment.[9][10]

Description of the thermally

induced shape-memory effect[edit]

A schematic representation of the shape-memory

effect

Polymers exhibiting a shape-memory effect have

both a visible, current (temporary) form and a stored
(permanent) form. Once the latter has been
manufactured by conventional methods, the material
is changed into another, temporary form by
processing through heating, deformation, and finally,
cooling. The polymer maintains this temporary
shape until the shape change into the permanent
form is activated by a predetermined external
stimulus. The secret behind these materials lies in
their molecular network structure, which contains at
least two separate phases. The phase showing the
highest thermal transition, Tperm, is the temperature
that must be exceeded to establish the physical
crosslinks responsible for the permanent shape. The
switching segments, on the other hand, are the
segments with the ability to soften past a certain
transition temperature (Ttrans) and are responsible for
the temporary shape. In some cases this is the glass
transition temperature (Tg) and others the melting
temperature (Tm). Exceeding Ttrans (while remaining
below Tperm) activates the switching by softening
these switching segments and thereby allowing the
material to resume its original (permanent) form.
BelowTtrans, flexibility of the segments is at least
partly limited. If Tm is chosen for programming the
SMP, strain-induced crystallization of the switching
segment can be initiated when it is stretched
above Tm and subsequently cooled below Tm. These
crystallites form covalent netpoints which prevent
the polymer from reforming its usual coiled structure.
The hard to soft segment ratio is often between 5/95
and 95/5, but ideally this ratio is between 20/80 and
80/20.[11] The shape-memory polymers are
effectively viscoelastic and many models and
analysis methods exist.
Thermodynamics of the shape-memory
effect[edit]
In the amorphous state, polymer chains assume a
completely random distribution within the matrix. W
represents the probability of a strongly coiled
conformation, which is the conformation with
maximum entropy, and is the most likely state for an
amorphous linear polymer chain. This relationship is
represented mathematically by Boltzmann's entropy
formula S = k ln W, where S is the entropyand k is
Boltzmann's constant.
In the transition from the glassy state to a rubber-
elastic state by thermal activation, the rotations
around segment bonds become increasingly
unimpeded. This allows chains to assume other
possibly, energetically equivalent conformations with
a small amount of disentangling. As a result, the
majority of SMPs will form compact, random coils
because this conformation is entropically favored
over a stretched conformation.[1]
Polymers in this elastic state with number average
molecular weight greater than 20,000 stretch in the
direction of an applied external force. If the force is
applied for a short time, the entanglement of
polymer chains with their neighbors will prevent
large movement of the chain and the sample
recovers its original conformation upon removal of
the force. If the force is applied for a longer period of
time, however, a relaxation process takes place
whereby a plastic, irreversible deformation of the
sample takes place due to the slipping and
disentangling of the polymer chains.[1]
To prevent the slipping and flow of polymer chains,
cross-linking can be used, both chemical and
physical.
Physically crosslinked SMPs[edit]
Linear block copolymers[edit]
Representative shape-memory polymers in this
category are polyurethanes, polyurethanes with
ionic or mesogenic components made
by prepolymer method. Other block copolymers also
show the shape-memory effect, such as, block
copolymer of polyethylene terephthalate (PET)
and polyethyleneoxide (PEO), block copolymers
containing polystyrene and poly(1,4-butadiene), and
an ABA triblock copolymer made from poly(2-
methyl-2-oxazoline) and polytetrahydrofuran.
Other thermoplastic polymers[edit]
A linear, amorphous polynorbornene (Norsorex,
developed by CdF Chemie/Nippon Zeon) or organic-
 inorganic hybrid polymers consisting of
polynorbornene units that are partially substituted by
polyhedral oligosilsesquioxane (POSS) also have
shape-memory effect.

Chemically crosslinked SMPs[edit]

The main limitation of physically crosslinked
polymers for the shape-memory application is
irreversible deformation during memory
programming due to the creep. The network
polymer can be synthesized by either polymerization
with multifunctional (3 or more)crosslinker or by
subsequent crosslinking of a linear or branched
polymer. They form insoluble materials which swell
in certain solvents.[1]
Crosslinked polyurethane[edit]
This material can be made by using excess
diisocyanate or by using a crosslinker such
as glycerin, trimethylol propane. Introduction of
covalent crosslinking improves in creep, increase in
recovery temperature and recovery window.[12]
PEO based crosslinked SMPs[edit]
The PEO-PET block copolymers can be crosslinked
by using maleic anhydride, glycerin or dimethyl 5-
isopthalates as a crosslinking agent. The addition of
1.5 wt% maleic anhydride increased in shape
recovery from 35% to 65% and tensile strength from
3 to 5 MPa.[13]

Hard phase Crosslinker Tr (°C) Rf(5)(%) Rf(5)(%)

Glycerol/dimethyl 5-
PET 11–30 90–95 60–70
sulfoisopthalate

PET Maleic anhydride 8–13 91–93 60

AA/MAA copolymer 90 99
N,N'-methylene-bis-
 acrylamide

MAA/N-vinyl-2- Ethyleneglycol
90 99
pyrrolidone dimethacrylate

PMMA/N-vinyl-2- Ethyleneglycol 45,

99
pyrrolidone dimethacrylate 100

Thermoplastic shape-memory[edit]
While shape-memory effects are traditionally limited
to thermosetting plastics,
some thermoplastic polymers, most notably PEEK,
can be used as well.[14]

Light-induced SMPs[edit]

A schematic representation of reversible LASMP

crosslinking

Light-activated shape-memory polymers (LASMP)

use processes of photo-crosslinking and photo-
cleaving to change Tg. Photo-crosslinking is
achieved by using one wavelength of light, while a
second wavelength of light reversibly cleaves the
photo-crosslinked bonds. The effect achieved is that
the material may be reversibly switched between
anelastomer and a rigid polymer. Light does not
change the temperature, only the cross-linking
density within the material.[15] For example, it has
been reported that polymers containing cinnamic
groups can be fixed into predetermined shapes
by UV light illumination (> 260 nm) and then recover
 their original shape when exposed to UV light of a
different wavelength (< 260 nm).[15] Examples of
photoresponsive switches include cinnamic
acid and cinnamylidene acetic acid.

Electro-active SMPs[edit]
The use of electricity to activate the shape-memory
effect of polymers is desirable for applications where
it would not be possible to use heat and is another
active area of research. Some current efforts use
conducting SMP composites with carbon
nanotubes.[16] short carbon fibers (SCFs).[17][18] carbon
black, metallic Ni powder. These conducting SMPs
are produced by chemically surface-modifying multi-
walled carbon nanotubes (MWNTs) in a mixed
solvent of nitric acid and sulfuric acid, with the
purpose of improving the interfacial bonding
between the polymers and the conductive fillers.
The shape-memory effect in these types of SMPs
have been shown to be dependent on the filler
content and the degree of surface modification of
the MWNTs, with the surface modified versions
exhibiting good energy conversion efficiency and
improved mechanical properties.
Another technique being investigated involves the
use of surface-modified super-paramagnetic
nanoparticles. When introduced into the polymer
matrix, remote actuation of shape transitions is
possible. An example of this involves the use of
oligo (e-capolactone)dimethacrylate/butyl acrylate
composite with between 2 and
12% magnetite nanoparticles. Nickel and hybrid
fibers have also been used with some degree of
success.[17]

Shape-memory polymers vs.

shape-memory alloys[edit]
A summary of the major differences between SMPs and SMAs[19]

SMPs SMAs

Density (g/cm3) 0.9–1.2 6–8

Extent of
up to 800% <8%
deformation

Required stress
1–3 50–200
for deformation (MPa)

Stress generated
1–3 150–300
upon recovery (MPa)

Transition −10..100 −10..100

temperatures (°C)

1s –
Recovery speed <1s
minutes

<200 °C >1000 °C
Processing
low high
conditions
pressure pressure

Costs <$10/lb ~$250/lb

Shape-memory polymers differ from shape memory

alloys (SMAs) [20] by their glass transition or melting
transition from a hard to a soft phase which is
responsible for the shape-memory effect. In shape-
memory alloysmartensitic/austenitic transitions are
responsible for the shape-memory effect. There are
numerous advantages that make SMPs more
attractive than shape memory alloys. They have a
high capacity for elastic deformation (up to 200% in
most cases), much lower cost, lower density, a
broad range of application temperatures which can
be tailored, easy processing, potential
biocompatibility and biodegradability,[19] and probably
exhibit superior mechanical properties than SMAs.[21]

Applications[edit]
Industrial applications[edit]
One of the first conceived industrial applications was
in robotics where shape-memory (SM) foams were
used to provide initial soft pretension in
gripping.[22]These SM foams could be subsequently
hardened by cooling making a shape adaptive grip.
Since this time the materials have seen widespread
usage in e.g. the building industry (foam which
expands with warmth to seal window frames), sports
wear (helmets, judo and karate suits) and in some
cases with thermochromic additives for ease of
thermal profile observation.[23] Polyurethane SMPs
are also applied as an autochoke element for
engines.[24]
Medical applications[edit]
Most medical applications of SMP have yet to be
developed, but devices with SMP are now beginning
to hit the market. Recently, this technology has
expanded to applications in orthopedic surgery.[14]
Additionally, SMPs are now being used in various
ophthalmic devices including punctal plugs,
glaucoma shunts and introacular lenses.
Potential medical applications[edit]
SMPs are smart materials with potential applications
as, e.g., intravenous cannula,[24] self-adjusting
orthodontic wires and selectively pliable tools for
small scale surgical procedures where currently
metal-based shape-memory alloys such as Nitinol
are widely used. Another application of SMP in the
medical field could be its use in implants: for
example minimally invasive, through small incisions
or natural orifices, implantation of a device in its
small temporary shape. Shape-memory
technologies have shown great promise for
cardiovascular stents, since they allow a small stent
to be inserted along a vein or artery and then
expanded to prop it open.[25] After activating the
shape memory by temperature increase or
mechanical stress, it would assume its permanent
shape. Certain classes of shape-memory polymers
possess an additional property: biodegradability.
This offers the option to develop temporary implants.
In the case of biodegradable polymers, after the
implant has fulfilled its intended use, e.g.
healing/tissue regeneration has occurred, the
material degrades into substances which can be
eliminated by the body. Thus full functionality would
be restored without the necessity for a second
surgery to remove the implant. Examples of this
development are vascular stents and surgical
sutures. When used in surgical sutures, the shape-
memory property of SMPs enables wound closure
with self-adjusting optimal tension, which avoids
tissue damage due to overtightened sutures and
does support healing and regeneration.[26]
Potential industrial applications[edit]
Further potential applications include self-repairing
structural components, such as e.g. automobile
fenders in which dents are repaired by application of
temperature.[27] After an undesired deformation, such
as a dent in the fender, these materials "remember"
their original shape. Heating them activates their
"memory." In the example of the dent, the fender
could be repaired with a heat source, such as a hair-
dryer. The impact results in a temporary form, which
changes back to the original form upon heating—in
effect, the plastic repairs itself. SMPs may also be
useful in the production of aircraft which would
morph during flight. Currently, the Defense
Advanced Research Projects Agency DARPA is
testing wings which would change shape by 150%.[5]
The realization of a better control over the switching
behavior of polymers is seen as key factor to
implement new technical concepts. For instance, an
accurate setting of the onset temperature of shape
recovering can be exploited to tune the release
temperature of information stored in a shape
memory polymer. This may pave the way for the
monitoring of temperature abuses of food or
pharmaceuticals.[28]
Recently, a new manufacturing process,
Mnemosynation, was developed at Georgia Tech to
enable mass production of crosslinked SMP
devices, which would otherwise be cost-prohibitive
using traditional thermoset polymerization
techniques.[29] Mnemosynation was named for the
Greek goddess of memory, Mnemosyne and is the
controlled imparting of memory on an amorphous
thermoplastic materials utilizing radiation-induced
covalent crosslinking, much
like Vulcanization imparts recoverable elastomeric
behavior on rubbers using sulfur crosslinks.
Mnemosynation combines advances in ionizing
radiation and tuning the mechanical properties of
SMPs to enable traditional plastics processing
(extrusion, blow molding, injection molding, resin
transfer molding, etc.) and allows thermoset SMPs
in complex geometries. The customizable
mechanical properties of traditional SMPs are
achievable with high throughput plastics processing
techniques to enable mass producible plastic
products with thermosetting shape-memory
properties: low residual strains, tunable recoverable
force and adjustable glass transition temperatures.
Brand protection and anti-
counterfeiting[edit]
Shape memory polymers may serve as technology
platform for a safe way of information storage and
release.[30] Multifunctional labels may even make
counterfeiting increasingly difficult.[31][32] Shape
memory polymers have already been made into
shape memory film by extruder machine, with covert
and overt 3D embossed pattern internally, and 3D
pattern will be released to be embossed or
disappeared in just seconds irreversibly as soon as
it is heated; Shape memory film can be used as
label substrates or face stock for anti-counterfeiting,
brand protection, tamper-evident seals, anti-
pilferage seals, etc.

See also[edit]

 Smart material
 Shape-memory alloy

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Categories:
 Polymers
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