Assignment: 1st

Group: 3

Name: M.Ahsan Aftab, Haseeb Ahmad

Ali Shehbaz, Muzammal hussain
Hasan Kashif

Reg. No: 20-NTU-TE-0043,152, 92,86,101

Semester: Fifth

Department: Textile Processing

Date of submission: 30/06/2022

Submit to: Dr. Usman Zubair

National Textile University

 Shape Memory Polymers

Introduction:
 Shape-memory polymers (SMPs) are a class of smart materials capable of
undergoing a programmed shape change upon application of an external
stimulus and remembering the original shape.
 Upon exposure to an external stimulus, shape-memory polymers can
change their shape.

 This ability opens up numerous fields of application, such as intelligent,

bulky implants, which can be inserted in a compressed, temporary shape
into the body through a small incision, or auto bodies, which could be
brought back to their original shape after a collision by a simple heat
treatment.
Classification of Shape Memory Polymers (SMPs):

Classification of SMP based on their mode of activation:

 Thermo responsive shape memory polymers
The shape memory polymers which change in shape with the change of
temperature are called thermo responsive shape memory polymers. By far these
are the most common shape memory polymers.
• Electrical heating induced shape memory effect
The shape memory polymers are generally non-conductive. So they are made
conductive by blending with carbon nano powders. The electric current is
converted into heat. They recover the original shape when an electric current is
passed through the shape memory polymers.
• Light induced shape memory polymers
The shape memory polymers which are to be activated by light should have
some photo sensitive groups which act as molecular switches. The shape
memory polymers are stretched and illuminated by a light of wavelength greater
than a fixed wavelength and the photosensitive groups form cross links.
 • Magnetically induced shape memory effect
Non-contact triggering of shape changes in polymers has been realized by
incorporating magnetic nanoparticles in shape memory polymers and inductive
heating of these compounds in alternating magnetic fields.
• Water activated shape memory effect
The actuation of the polymer can be achieved by immersion in water. A shape
memory polymer which has the permanent shape of a straight rod is
programmed into a Z shape. The left part of the polymer is dipped into water
and the right part is not dipped. There is a reduction of the glass transition
temperature for the left part and it gets actuated i.e. gets back to its original
form with the help of the room temperature water itself.

Features and properties of SPMS:

Shape Memory Polymer are rubbery in nature, composed of long , entangled-
polymer chains and these chains gets stretched under tension to accommodate
the deformation.

 High elastic deformation ( strain up to 200% in most of the materials)

 Low cost, low density and biocompatibility and biodegradability
 SMPs are capable of recovering fully under low deformation level. If
these are cooled below their glass transition temperature and deformed by
external forces. Once the external forces are removed it will return to its
previous unreformed state.
 When the temperature is greater than "Glass transition temperature" (Tg),
the material enters the soft rubber phase and becomes easily definable.

Principle of Shape Memory Polymer (SMPs):

In shape memory polymers, typical shape recovery process begins at a
temperature above Tg. At this temperature, the polymer is in a rubbery elastic
state. The polymer is then deformed with an applied stress which creates a strain
in the polymer. When cooled below Tg, the material autonomously returns to
the original shape (shape recovery characteristic). This property of the material
which repeatedly returns to its original shape is called "shape memory".
Structure and Mechanism of SMPs:
The figure demonstrates the progress of representative models developed for
thermal-sensitive SMPs. The figure consists of molecular bonds such as
covalent bonds and physical interactions. If the working temperature is higher
than Ttrans, then the switching domains are flexible, resulting in an entropic
elastic behaviour of the polymer network above Ttrans. If the sample has been
previously deformed by application of an external stress, it snaps back into its
initial shape once the external stress is released.

Mechanism of Shape Memory Effect

Examples of Shape-Memory Polymers (SMPs):

Typical examples of polymers which can exhibit this shape memory effect
include
 (Meth)acrylates,
 Polyurethanes
 Blends of polyurethane and polyvinylchloride
 Manufacturing of Shape Memory Polymers
Manufacturing of Polyurethanes:
As polyurethanes are made from the reaction between an isocyanate and a
polyol, the section is divided into three parts:
 Production of Isocyanates
 Production of Polyols
 Production of Polyurethanes
Production of isocyanates:
Although many aromatic and aliphatic polyisocyanates exist, two are of
particular industrial importance. Each of them has variants and together they
form the basis of about 95% of all the polyurethanes. They are:
 TDI (toluene diisocyanate or methylbenzene diisocyanate)
 MDI (methylene diphenyl diisocyanate or diphenylmethane diisocyanate)
TDI was developed first but is now used mainly in the production of low
density flexible foams for cushions.

The mixture of diisocyanates known as TDI consists of two isomers:

The starting material is methylbenzene (toluene). When it reacts with mixed

acid (nitric and sulfuric), two isomers of nitromethylbenzene (NMB) are the
main products.
If this mixture is nitrated further, a mixture of dinitromethylbenzenes is
produced. In industry they are known by their trivial names, 2,4-dinitrotoluene
and 2,6-dinitrotoluene (DNT). 80% is 2,4-DNT and 20% is 2,6-DNT:

The mixture of dinitrobenzenes is then reduced to the corresponding amines:

In turn, the amines, known commercially as Toluene Diamines or TDA, are

heated with carbonyl chloride (phosgene) to produce the diisocyanates and this
process can be carried out in the liquid phase with chlorobenzene as a solvent at
about 350K:

MDI is more complex and permits the polyurethane manufacturer more process
and product versatility. The mixture of diisocyanates is generally used to make
rigid foams.
The starting materials are phenylamine (aniline) and methanal (formaldehyde)
which react together to form a mixture of amines, known as MDA
(methylenedianiline). This mixture reacts with carbonyl chloride (phosgene) to
produce MDI in a similar way to the manufacture of TDI. MDI contains the
following diisocyanates:

Production of Polyols:
The polyols used are either hydroxyl-terminated polyethers (in about 90% of
total polyurethane manufacture) or hydroxyl-terminated polyesters. They have
been developed to have the necessary reactivity with the isocyanate that will be
used and to produce polyurethanes with specific properties.
Production of polyurethanes:
If the polyol has two hydroxyl groups and is mixed with either TDI or MDI, a
linear polymer is produced. For example, a linear polyurethane is produced by
reaction with a diisocyanate and the simplest diol, ethane-1,2-diol,
a condensation polymerization occurs:

A much used polyurethane is made from TDI and a polyol derived from
epoxypropane:

If the polyol has more than two reactive hydroxyl groups, adjacent long-chain
molecules become linked at intermediate points. These crosslinks create a
stiffer polymer structure with improved mechanical characteristics which is
exploited in the development of 'rigid' polyurethanes. Thus a diisocyanate, such
as MDI or TDI which reacts with a polyol with three hydroxyl groups, such as
one derived from propane-1,2,3-triol and epoxyethane, undergoes crosslinking
and forms a rigid thermosetting polymer.
 Processing of Shape Memory Polymers
Processing of Polyurethane:
 Process 1
At the start of polyurethane foam production, the reacting raw materials
are held as liquids in large, stainless steel tanks. These tanks are equipped
with agitators to keep the materials fluid. A metering device is attached to
the tanks so that the appropriate amount of reactive material can be
pumped out. A typical ratio of polyol to diisocyanate is 1:2. Since the
ratio of the component materials produces polymers with varying
characteristics, it is strictly controlled.
 Process 2
The reacting materials are passed through a heat exchanger as they are
pumped into pipes. The exchanger adjusts the temperature to the reactive
level. Inside the pipes, the polymerization reaction occurs. By the time
the polymerizing liquid gets to the end of the pipe, the polyurethane is
already formed. On one end of the pipe is a dispensing head for the
polymer.
 Process 3
The dispensing head is hooked up to the processing line. For the
production of rigid polyurethane foam insulation, a roll of baking paper is
spooled at the start of the processing line. This paper is moved along a
conveyor and brought under the dispensing head.
 Process 4
As the paper passes under, polyurethane is blown onto it. As the polymer
is dispensed, it is mixed with carbon dioxide which causes it to expand. It
continues to rise as it moves along the conveyor. (The sheet of
polyurethane is known as a bun because it "rises" like dough.)
 Process 5
After the expansion reaction begins, a second top layer of paper is rolled
on. Additionally, side papers may also be rolled into the process. Each
layer of paper contains the polyurethane foam giving it shape. The rigid
foam is passed through a series of panels that control the width and height
of the foam bun. As they travel through this section of the production
line, they are typically dried.
  Process 6
At the end of the production line, the foam insulation is cut with an
automatic saw to the desired length. The foam bun is then conveyored to
the final processing steps that include packaging, stacking, and shipping.

Applications of Shape Memory Polymers

The fields of application for SMPs are manifold, although, the high cost and the
high specificity of the material make them today particularly appreciated in the
biomedical field.

1. Shape Memory Polymers in Orthodontics

There are numerous examples in which they replace metal wires in
orthodontics: although the polymeric thread has mechanical properties of
resistance to stress and fatigue lower than that of metal, it has a much lower
aesthetic impact, increasing patient satisfaction.

2. Shape Memory Polymers in Bandages

Shape memory materials have also been used for the production of rigid
bandages able to adapt perfectly to the patient's skin, also presenting the
advantage of being completely recyclable and transparent to X-rays.

3. Shape Memory Polymers in Suture Threads

Self-shrinking suture threads have also been developed, able to bring the edges
of a wound closer in a few seconds: the wire undergoes an extension of over
200 percent of its length when hot, while once applied, it is able to withdraw in
just 20 seconds. Furthermore, the thread is made of bioresorbable material and
therefore, once healing is complete, the patient's body automatically eliminates
the stitches.

4. Shape Memory Polymers in the Treatment of Cerebral Aneurysms

Systems built with shape memory materials are also used for the treatment of
cerebral aneurysms, generally treated with platinum spirals: the metal has no
affinity with the organism and leads to a fairly high failure of the implants,
whereas if the spiral is constituted from a biomaterial, the treatment is more
effective.

5. Shape Memory Polymers in Window Blinds

Researchers from the Institute of Biomaterial Science (Department of
Helmholtz-Zentrum Geesthacht in Germany) have developed a polymer that can
change its shape based on temperature changes. The image represents a blind
window, whose slats are closed or opened in relation to the environmental
conditions; users can program the temperature range in which the slats move.

6. Shape Memory Polymers in Packaging

In addition to biomedical, SMPs are used in more common areas, for example
in packaging. PE or crosslinked self-tightening PET, under thermal stimulation,
adhere perfectly to the size and shape of the product.

7. Shape Memory Polymers in Self-Tightening Tubes

In the same way, self-tightening tubes are produced that can adapt to the ducts
and prevents leakage.

8. Shape Memory Polymers in Textile Industry

In the textile field, mixed cotton or wool yarns and shape memory
polyurethanes are obtained, capable of being reshaped at a temperature higher
than the transition temperature of the material, so as to customize the product
for the customer to the extreme.

Shape memory polymers have also been used for the production of underwear:
the possibility of modeling the head on the forms of the human body greatly
improves the comfort given by the product.