Shape Memory Polymers

Material Science and Metallurgy Course Assignment

Gaurav Gupta
Student ID: SC21B026
Aerospace Engineering, Indian Institute of Space Science and Technology,
Thiruvanthapuram

May 2022
IIST, Thiruvanthapuram Shape Memory Polymers

Contents
1 Introduction 2

2 Types of Shape Memory Polymers (SMP) 2

2.1 Linear Block Copolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2.2 Chemically Crosslinked SMPs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2.3 Light-Induced SMPs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2

3 Parameters of comparsion for SMPs 3

4 Working of Shape Memory Polymers 3

5 Applications of SMPs 4

6 Shape Memory Polymers v/s Shape Memory Alloys 5

7 Case Study of PLA (Poly-Lactic Acid) 5

7.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
7.2 Production of PLA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
7.3 Physical and Mechanical Properties of PLA . . . . . . . . . . . . . . . . . . . . . . . . . . 6
7.4 Shape Memory Propery of PLA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6

8 Conclusion 7

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IIST, Thiruvanthapuram Shape Memory Polymers

1 Introduction Anionic Polymerisation is a form of chain-

growth polymerization where vinyl monomers
Shape Memory Polymer are special polymer with strong electronegative groups are polymer-
which can return to its permanent shape ized [2]. Here, different monomers are combined
(Fig.1.b) from a deformed or temporary shape as block copolymers and produces a single poly-
(Fig.1.a) [1]. mer with multiple advantages.

Some popular examples of shape memory

block polymers are Polyethylene terephthalate
(PET) (Fig.2) and Polyethyleneoxide (PEO)
(Fig.3), block copolymers containing polystyrene
and poly(1,4-butadiene), and ABA triblock
copolymer made from poly(2-methyl-2-oxazoline)
and polytetrahydrofuran [1].

(a) Deformed Object

Figure 2: Polyethylene terephthalate (PET)

Figure 3: Polyethyleneoxide (PEO)

(b) Recovered Object

Figure 1: 3D printed Shape Memory Polymer 2.2 Chemically Crosslinked SMPs

object (Photo Credits: SciNews YouTube)
The main limitation of physically crosslinked
polymers for the shape-memory application is ir-
The change in the shape of the polymer is
reversible deformation during memory program-
induced by some external stimuli like tempera-
ming due to the creep. The network polymer can
ture change, light, electric or magnetic field. The
be synthesized by either polymerization with mul-
polymer is available in wide range of properties
tifunctional crosslinker [1].
like stable to biodegradable, soft to hard, elastic
to rigid, thermoplastic and thermoset. SMPs are
known to able to store three different shapes in 2.3 Light-Induced SMPs
memory [1].
Light activated shape-memory polymers use the
process of photo-crosslinking and photo-cleaving
2 Types of Shape Memory to change the glass temperature of the material.
One wavelength of light establishes the crosslink-
Polymers (SMP) ing between the copolymers while another wave-
length is used to cleave the cross-linked bonds
2.1 Linear Block Copolymers
(Fig.4). The polymers can be switched between
These polymers are physically cross-linked and elastomer and a rigid polymer using this prop-
manufactured using the anionic polymerisation. erty. Polymers containing cinnamic groups can

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IIST, Thiruvanthapuram Shape Memory Polymers

be fixed into predetermined shapes by UV light il-

lumination and recover their original shape when
exposed to UV light of different wavelength [1].

Figure 5: Ideal Thermodynamic Cycle of tensile

test on SMP (Image Source:[3])

Figure 4: Representation of working of Light ac-

tivated shape-memory polymers (Image Source:
Wikipedia)

3 Parameters of comparsion
for SMPs
Quantities that are used to describe shape-
memory effects are the strain recovery rate (Rr )
and strain fixity rate (Rf ).
If a polymer is elongated to a constant strain
ϵm at a constant rate and a constant high temper-
ature Tl (Fig.6). Then the polymer is cooled to
the temperature Tu and unloaded. Upon remov-
ing the load, a recovery strain due to the stress
ϵu occurs. When the polymer is heated again to Figure 6: Experimental Thermodynamic Cycle of
the temperature Tl , the polymer starts return- tensile test on SMP (Image Source:[4])
ing to the permanent shape where some residual
strain ϵp remains. Ideally, on heating the poly-
mer it should completely return to the permanent
shape (Fig.5) [3] but, some residue strain always
4 Working of Shape Memory
remains [4]. Polymers
Strain Recovery Rate: The Strain Recov- The polymers have semi-crystalline structure
ery rate describes the ability of the material to which means they are both amorphous and crys-
memorize its permanent shape. talline at the same time [5]. They have a visi-
ϵm − ϵp ble (temporary) form and a stored (permanent)
Rr % = ∗ 100 (1) form. First the permanent form is manufactured
ϵm
using conventional methods, then the material is
Strain Fixity Rate: It describes the abil- changed into another temporary form by process-
ity of switching segments to fix the mechanical ing though heating, deformation and cooling [1].
deformation. In simple words, it means how ef-
ficiently the polymer can fix the new temporary Now, the polymer maintains the temporary
shape after unloading. shape until the shape is changed into the perma-
ϵu nent form, activated by a predetermined external
Rf % = ∗ 100 (2) stimulus.
ϵm

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IIST, Thiruvanthapuram Shape Memory Polymers

be manufactured using the SMPs. A surgi-

cal suture was produced using SMP which
tightens on elevation of temperature [7].

Figure 7: Working of the Shape-Memory Effect

(Image Source: Wikipedia)

The molecular network structure which con-

tains at least two separate phases. The perma-
nent shape phase shows the highest thermal tran-
sition temperature that must be exceeded to es-
tablish the physical crosslinks [1]. Generally, this
is used to program the polymer and set its perma-
nent shape. Here, the movement of the polymer
segments are frozen. Figure 8: Self-Tightening Suture based on SMPs
(Image Source: [7])
In the temporary shape phases have a certain
transition temperature after which some of the
crosslinks break and the material softens (Fig.7). ˆ Robotics: Various kinds of soft robotics
Due to the external stress applied on the material can take advantage of the SMPs to change
to deform it, the crosslinks form to retain the tem- shapes based on the external stimuli. The
porary shape while cooling. When the material SMPs can also be used to provide a soft
is heated again, the crosslinks between polymer grip when gripping objects. It can also
segments breaks. In the absence of applied exter- be used as muscle actuators in humanoid
nal force, the material returns to its permanent robots (Fig.9) [8].
shape. This can be based on entropy. As, we ap-
ply external force and try to deform the material,
it becomes more ordered whereas the segments
would naturally prefer to go for randomness [5,
6]. Hence, they will return to the state of max-
imum randomness i.e. permanent shape in the
absence of external stress.

5 Applications of SMPs
The unique feature of changing the shape in re-
sponse to external stimuli allows a wide range of
dynamic applications in the real world. Some of
the popular and exciting applications are as fol- Figure 9: Application of SMPs as a muscle actu-
lows [5], ator in an arm (Image Source: [8])

ˆ Smart Wearable/Fabrics: Fabrics with ˆ Buildings: Shape Memory Foams can be

the capability to nourish and moisture skin, used to seal window frames as sealant. They
breathable garments that can regulate heat expand and contract to keep the window
and moisture of the wearer’s body are frames sealed during different seasons.
features of smart wearables that can be
achieved using the SMPs. Automotive seat ˆ Self-Repairing Structures: Proposals
belts using SMPs can absorb kinetic energy and ideas have been presented to de-
increasing safety. Wearable electronic de- sign structures with SMPs to achieve self-
vices can heavily benefit from the SMPs. repairing properties. For example, a dent
on car body is repaired automatically on
ˆ Biomedical Applications: Smart medi- some external stimuli or aircrafts with
cal implants, tissue scaffolds and medical wings whose shape can be morphed. Satel-
devices can be produced using the SMPs. lites and Space Shuttles often face minor
Customised orthopaedic devices and self- collisions with space junks and rocks, caus-
fitting vascular and coronary grafts can also ing damage to them. Thus, SMPs can

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IIST, Thiruvanthapuram Shape Memory Polymers

be extermely helpful in satelites and space polymers over the alloys. The shape memory al-
shuttles. loys display two distinct crystal structures. Tem-
perature and stresses determine the phase that
ˆ Packaging: In addition to biomedical, the SMA will be at. The shape changes when-
SMPs are used in more common areas, for ever the crystal structure or phase is changed. At
example in packaging. PE or crosslinked lower temperatures, the metal can be deformed to
self-tightening PET, under thermal stim- any shape but as the metal is heated, the crystal
ulation, adhere perfectly to the size and structure changes, and the material returns to its
shape of the product. original structure [10]. This is different from the
working of the Shape Memory Polymers.

6 Shape Memory Polymers

v/s Shape Memory Alloys
A shape-memory alloy (SMA) 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 [9].

The shape memory alloys like Nitinol

(Fig.10) were studied prior to shape memory Figure 10: Shape Memory effect in Nitinol

Table 1: A general comparison between the properties shape memory polymers and shape memory alloys.

Property Shape Memory Polymer Shape Memory Alloy

Young’s Modulus of Elasticity SMPs have lower Young’s mod- SMAs have higher Young’s
ulus and elongate more. modulus and elongate lower.
Complex Geometries Complex Geometries can be de- The design is not so easy.
signed easily.
Softness SMPs are soft in general. SMAs are hard.
Cost SMPs are comparatively SMAs are expensive.
cheaper.
Processing SMPs are easy to process. SMAs are difficult to process.
Density SMPs have low density. SMAs have high density.

7 Case Study of PLA (Poly- up to 130k g/mol. The reaction is reversible, and
water is continuously removed to push the reac-
Lactic Acid) tion forward. This crude polymer can be crys-
tallised from melting to produce PLA of even
7.1 Introduction higher molecular weights [11] (Fig.12).
Poly-Lactic Acid or PLA is a widely used mate-
rial for 3D printing. PLA being biodegradable
is a great choice for making rapid prototyping.
The material can be economically and easily pro-
duced. The monomers lactic acid and lactide are
typically made from fermented plant starch [11].

7.2 Production of PLA

The direct condensation of the lactic acid
monomers (Fig.11) can be used to produce PLA.
The method produces PLA of molecular weights Figure 11: Lactic Acid Molecule

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IIST, Thiruvanthapuram Shape Memory Polymers

Another method is by contacting lactic acid use it as implants. Since custom implants can be
with a zeolite. This condensation reaction is a easily and quickly designed and fabricated using
one-step process and runs at lower temperature a 3D printer.
[11].

Figure 12: Production of PLA through two meth- Figure 13: PLA filaments used for 3D printing
ods
In research, the shape memory properties of
7.3 Physical and Mechanical Prop- PLA based scaffold was studied [12]. It was
meant to be used for regeneration of damaged
erties of PLA or missing bone. The scaffold was 3D printed
PLA is a non-toxic, biocompatible polymer. They from a custom prepared blend of PLA and Hy-
come with various kinds of structures from amor- droxyapatite (HA) (Fig.14) [12]. HA acts as a
phous glassy to semi-crystalline and highly crys- composite for synthetic bone replacements as it
talline. The polymer has a glass transition tem- composes 65% of the natural bone [13]. Later,
perature of about 60-65 deg C and melts at tem- the scaffolds were stress-tested (Fig.15), and the
perature of 130-180 deg C. It has a Young’s PLA/15%HA porous scaffolds obtained by 3D-
Modulus of 2.7-16 GPa [11]. The basic me- printing with shape recovery of 98% were found
chanical properties of PLA are between those of to have the potential to be used as self-fitting
polystyrene and PET. implants for bone replacements [12]. Such re-
placements will cost substantially lower than the
7.4 Shape Memory Propery of SMA ones, making bone replacement accessible
to greater fraction of the community.
PLA
PLA is one of the famous and very easily acces-
sible shape-memory polymers in the market. Be-
ing used for 3D printing (Fig.13), items built
with PLA can be accommodate the shape mem-
ory property. While 3D printing, we basically
program the permanent shape of the item. Then,
we can deform it into desired shape while heating
it below the glass transition temperature. The
item can recover its original shape as we heat it a
little above the glass transition temperature. %
Shape Recovery of PLA is also very high around
98%.

This property of PLA is extensively re- Figure 14: 3D-printed PLA/HA scaffold in the
searched and exploited in the biomedical field to research (Source:[12])

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IIST, Thiruvanthapuram Shape Memory Polymers

Figure 15: Shape Memory Effect of the PLA/HA scaffold (Source:[12])

PLA based actuators are also manufactured [3] Patrick T Mather, Xiaofan Luo, and Ingrid
and being used to replace the pneumatic actua- A Rousseau. “Shape memory polymer re-
tors earlier used to actuate soft robots [14]. The search”. In: Annual Review of Materials Re-
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such robots as a single piece with almost no me- Xu. “Polyurethanes having shape mem-
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the production and prototyping of the robots pp. 5781–5793.
quick and easy.
[5] British Plastics Foundation. Shape Mem-
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[7] Changdeng Liu, Haihu Qin, and PT
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mers, a new class of materials with a unique prop- memory polymers”. In: Journal of materi-
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in the real-world. It is cheap, easy to produce,
biodegradable, non-toxic and less dense as com- [8] Christopher B Cooper et al. “High En-
pared to shape memory alloys. This makes it a ergy Density Shape Memory Polymers Us-
better choice than shape memory alloys in various ing Strain-Induced Supramolecular Nanos-
present and future applications. tructures”. In: ACS central science 7.10
(2021), pp. 1657–1667.
[9] Wikipedia. Shape Memory Alloy. https://
[Link]/wiki/Shape-memory_
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IIST, Thiruvanthapuram Shape Memory Polymers

[12] Fedor S Senatov et al. “Mechanical proper- sciencedirect . com / topics / chemical -
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