Shape-memory polymers

(SMPs)

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 Introduction

 Shape memory materials:

• Are materials that remember their permanent shape.
• The shape change is triggered by an external stimulus.

 The materials showing shape memory effect can be

classified as:
• (a) Shape memory alloys
• (b) Shape memory ceramics
• (c) Shape memory polymers
• (d) Shape memory gels
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 Shape memory polymers (SMPs)

 Definition: Shape memory polymers (SMPs) are smart

materials that can be deformed and fixed into a temporary
shape and can recover their permanent shape after the
release of the external stimulus.

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 Properties of SMPs

• SMPs cover a wide range of properties 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.

• SMPs have demonstrated recoverable strains of above 800%.

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 Advantages and Limitations of SMPs

 Advantages of SMPs  Limitations of SMPs

• Excellent structural
• Low thermal and
versatility
electrical conductivity,
• Light weight
weak mechanical
• Low cost
properties, and inertness
• Easy processing to electromagnetic
• High elastic strain (more stimuli in comparison to
than 200%) well-researched shape
• Biocompatibility memory ceramics and
• Biodegradability. metallic alloys.
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• Two important quantities are used to describe shape-memory
effects, they 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.

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 Parameters for characterization of SMPs

• Shape or strain fixity

• Recovery stress
• Strain or shape recovery
• Recovery time

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 Working mechanism of SMPs

• SMPs are compound plastics

polymers that have a special
chemical structure. Most
stimuli generate heat in
polymers.
• Glass transition temperature
(Tg) plays an important role
in SMPs.
• SMP become rubbery, elastic
and flexible above Tg.
• Deformed shape become
fixed and will remain stable
before recovery.
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  Shape memory effect in SMP
relay on:
• Crystallization and cross-
linking
• Entanglement of polymer
chains
• Microstructure of polymer
• Position 1- The polymer will be in
active stage.
• Position 2- In elastic or frozen.
• Position 3- Polymer will be hard and
rigid.
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 Classification of SMPs

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 Classification by composition and structure

 Segmented block copolymers

• Segmented block copolymers are comprised of many
alternating small blocks of two or more different types of
repeating unit (monomers).
• The shape-memory effect depend on glass transition
temperature of co-monomers.
• Examples: polyurethanes and polyesters.

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  Cross-linked homopolymers
• Cross-linked homopolymers are polymers in which long
polymer chains are crosslinked together to form a 3D matrix
of interconnected polymer chains
• Example: semicrystalline PLA.
• Unfortunately, shape-memory effect of PLA homopolymer is
limited.

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  Polymer Blends
• There are two types of polymer blends with shape-memory
effect: miscible and immiscible.
• Miscible blends can be made from semicrystalline polymers
or from semicrystalline and amorphous polymers. Example
blends of PCL, polydioxanone, polyurethanes, poly(vinyl
chloride), and phenolic resin.
• Immiscible blends like PCL matrix with poly(styrene-b-
butadiene-b-styrene) (SBS) or PLCA with PLGA.
• They have shape-memory effect that depend on polymers.

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  Supramolecular polymer networks/hydrogels
• Supramolecular polymer networks/hydrogels are materials
crosslinked by reversible supramolecular interactions, such as
hydrogen bonding or electrostatic interactions.
• They show very interesting and useful properties resulting
from their dynamic nature, such as self-healing, stimuli-
responsiveness and adaptability.

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  Composites/Nanocomposites
• A small amount of micro/nano-sized fillers can significantly
improve the properties of SMPs.
• SMPCs not only exhibit improved mechanical and shape-
memory properties but also possess novel properties like
multishape-memory effect, indirect SME, gradient SME, two-
way SME, and complicated movement SME.
• SMPCs can also enable or enhance thermal stimuli-active
effects including; electroactive effect, magnetic-active effect,
water-active effect, and photoactive effect.

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 Classification by type of stimulus

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  pH
• pH-activated SMPs change shape in response to change in
surrounding pH.
• They have weak acidic or basic groups that release protons
whenever there is a change in pH.
• The increase in pH leads to the conversion of acids from
neutral to anionic state, whereas bases are converted from
cationic to the neutral state.

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  Temperature
• The SMPs which change in shape with the change of
temperature are called thermo responsive SMPs.
• These are the most common SMPs. The thermal activation
mechanism can be divided into direct and indirect depending
on the heating methods.

 Electric field
• The SMPs are generally not conducting. They are made
conductive by blending with carbon nanofillers. The electric
current is converted into heat. They recover the original shape
when electric current is passed through the SMP.
  Light
• The light activated SMPs, have some photo sensitive groups
which act as molecular switches. Under exposure to certain
UV light wavelengths, photo sensitive groups can efficiently
carry out photo-reversible cyclo-addition reactions (stretching
and restoring original shape).
 Magnetic field
• Magnetic field-sensitive SMPs can be achieved by
incorporating magnetic nanoparticles (iron (III)oxide) in the
structure. The magnetic nanofillers produce heat when they
are subjected to magnetic field and as a result the shape of
polymer change.
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  Water
• Water has a plasticizing effect on the SMP. The water
molecules can penetrate the amorphous phase of the
polymer, leading to improvement of polymer chain mobility,
which will lead also to a decrease in its Tg. That free water
can be fully removed by heating the SMP to temperatures
above 120⁰C to achieve recovery.
 Solvents
• By using a solvent, its molecules will be absorbed into the
polymer matrix, leading to an interruption of the secondary
bonding between the polymer macromolecules, which in
turn will lead to polymer swelling, i.e., the activation
mechanism will be related to the swelling/shrinkage process.20
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  Oxidation- reduction
• SM effect in hydrogels is mostly stimulated with use of a redox
reaction. The reversible gel–sol transitions were achieved by
adding an oxidant (NaOCl) and then a reductant (glutathione).
What is more interesting is that the self-healing property of
the hydrogel can be controlled by redox reactions.

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 Classification by shape memory function

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  One-way SMPs
• In one-way SMPs, the recovery of shape is irretrievable, which
means that shape-transformation through the process of
recovery can only progress via an intermediate to a stable
shape and not the contrary.

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  Two-way SMPs
• In two-way SMPs, the change in shape is retrievable; which
means that the early and transient shapes can be overturned
with the arrival and closure of the stimulus.

 SMPs can be categorized as dual-, triple-, or multi-SMPs based

on the number of shapes involved in each shape-memory
cycle.

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  Dual SMPs
• A typical SMP has dual shapes (a temporary from converted
and a permanent shape).

 Triple-way SMPs
• The triple-SMP could recover two shapes induced by more
than one stimulus in shape-memory cycle (triple-SMPs have
two interim shapes, in addition to its permanent one).
 Multiple-SMPs
• Multiple-SMPs have the ability to remember more than two
interim shapes and then recover in an extremely controllable
way.
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 Net point classification

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 Applications of SMPs

 Biomedical applications
• Artificial muscles
• Fiber sutures
• Drug carriers
• Sensors and acturaors
• Intravascular stents
• Orthopedic braces and splints
 Textiles
 Damping elements
 Structural materials

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 References

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• 3. Arun DI, Chakravarthy P, Arockiakumar RSB (2018) Shape memory materials, 1st edn.
CRC Press, Florida
• 4. Buehler WJ, Gilfrich JV, Wiley RC (1963) Effect of low-temperature phase changes on the
mechanical properties of alloys near composition TiNi. J Appl Phys 34:1475–1477.
https://doi.org/ 10.1063/1.1729603
• 5. Dhanasekaran R, Sreenatha Reddy S, Girish Kumar B, Anirudh AS (2018) Shape memory
materi als for bio-medical and aerospace applications. Mater Today Proc 5:21427–21435.
https://doi.org/ 10.1016/j.matpr.2018.6.551
• 6. Hornbogen E (2006) Comparison of shape memory metals and polymers. Adv Eng Mater
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• 7. Uo M, Watari F, Yokoyama A et al (2001) Tissue reaction around metal implants observed
by X-ray scanning analytical microscopy. Biomaterials 22:677–685.
https://doi.org/10.1016/S0142 9612(00)00230-1
• 8. Uchino K (2016) Antiferroelectric shape memory ceramics. Actuators.
https://doi.org/10.3390/ act5020011
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 Thanks

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