Smart polymer

Smart polymers, stimuli-responsive polymers or functional polymers are high-performance polymers that change according
to the environment they are in.
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Temperature sensitive polymers: Polymers that respond to temperature and undergo a phase transition in aqueous solution

The first established low critical solution temp. (LCST) is 32C for Poly(N-
isopropylacrylamide) (PNIPAM) in water solution (reported by Prof. Heskins in
1960).
Poly(N-isopropylacrylamide) (PNIPAM)

PNIPAM undergoes a sharp coil to

globule (compact coil) transition
(changes hydrophilic to
hydrophobic state with increase in
temp).

poly(2-isopropyl-2- oxazoline) (PIOZ)

Poly(N,N- diethylacrylamide) (PDEAAM) Poly(N-vinylcaprolactam) (PVCL)

poly(vinyl methyl ether) (PVME)

PH sensitive polymers: Responds to the change in PH of surrounding medium

Expand or collapse depending on the PH of surrounding environment

Due to presence of certain functional groups in polymeric chain, these polymers either release protons or accept protons
Polybases:
Polyacids:

poly(acrylic acid) (PAA)

poly(4 –vinylpyridine) (PVP) poly(vinyl imidazole)

poly(methacrylic acid) (PMAA)

polyallyamine (PAM)

poly(N,N 0 -dimethyl aminoethyl

poly(4-styrenesulfonic acid) (PSSA)

Photo sensitive polymers: undergo a reversible/ irreversible change in conformation in respect to light
Biodegradable Polymers

PHBH: Poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)
 The majority of the polymers in use today have been developed within the last 60 years.

 A large proportion of these are synthetic products, which basically means that they are prepared from simple
technical monomers.

 Their principal advantages are light weight, high impact and tensile strengths, resistance to corrosion, salt-water
and most chemicals, as well as suitability for use over a wide range of temperatures. The various possibilities to
fine-tune their properties for plentiful applications have resulted in continuously growing polymer production
over the years.
 The excess use of polymers cause a disposal problem due to the longevity and undefined environmental fate of the
materials. For this reason, waste management of polymers is of high interest. Waste disposal sites only shift the
problem and cause new environmental concerns. Recycling of polymeric products can solve problem, but, is
extremely cost-intensive and is hindered by the use of non-mono-material products.

 Therefore, one smart way to deal with this problem is the use of biodegradable representatives especially in short-
term applications such as packaging, foils, and utilities in agriculture.
Biodegradable polymers are macromolecules
mainly derived from renewable sources, which
can be enzymatically or hydrolytically degraded
into low molecular parts. These parts can be
reabsorbed by microorganisms, which ideally
convert them to CO2 and water heading to an
environmentally closed circular flow economy
between growing of nutrients, production,
utilization, and material recycling.
In the recent years, new markets have arisen for biodegradable polymers such as poly(butylene adipate-
terephthalate), poly(lactide), poly(butylenesuccinate), or poly(3-hydroxybutyrate) and poly(carbonates).
They constitute a new class of “green polymers” with wide application potential for packaging, clothing, carpets,
applications in automotive engineering, foils, and utilities in agriculture.

The chemistry of the key degradation process, is represented by following Equations;

where CPOLYMER represents either a polymer or a fragment from any of the degradation processes.

The polymer is considered to be composed only of C, H and N; other elements may, of course, be incorporated in the
polymer, and these would appear in an oxidized or reduced form after biodegradation depending on whether the
conditions are aerobic or anaerobic, respectively.
Mechanism of the Biodegradation of Polymers
 Microbiological degradation can take place through the action of enzymes or by products (such as acids and peroxides) secreted by
microorganisms (bacteria, yeasts, fungi, etc).

To use organic molecules as a food source, microorganisms have to be able to take up the substance and metabolize it within their cells. A
prerequisite is that the molecules are water-soluble and that they are small enough to pass through the cell walls and membranes of the
microorganism. Polymers are typically not water-soluble and, by definition, are not small molecules. Therefore, the biodegradation of
polymers typically needs to follow four distinct steps.

 In a first step, the secondary structures of the polymer (side chains) have to be dissolved during the degradation process and temporarily
flexible chains formed.
 Second, the polymer needs to be broken down into small fragments. Microorganisms excrete extracellular enzymes that cleave the
polymeric chains. This converts the polymer chain into smaller oligomers and monomers.
 As a third step, the oligomers and monomers formed need to be small enough and water-soluble to pass through the cell walls and
membranes of the microorganism.
 Finally, within the microorganisms the fragments are ultimately converted into water, gaseous products (CO2 or methane) and, most
importantly for the microorganism, to biomass and energy.
 Examples of Biodegradable Polymers
Polyglycolic Acid (PGA)
Polyglycolide or poly(glycolic acid) (PGA), is a biodegradable, thermoplastic polymer and the simplest
linear, aliphatic polyester

It can be prepared starting from glycolic

acid by means of polycondensation or
ring-opening polymerization. PGA has
been known since 1954 as a tough fiber-
forming polymer.
Initially, PGA had found little use because of its sensitivity to hydrolysis
when compared with other synthetic polymers. However, in 1962 this
polymer was used to develop the first synthetic absorbable suture which was
marketed under the tradename of Dexon.
PGA suture is classified as a synthetic, absorbable, braided multifilament. It is
naturally degraded in the body by hydrolysis and is absorbed as water-soluble
monomers, completed between 60 and 90 days.

Sutures made from polyglycolic acid. These

sutures are adsorbable and are degraded by the
body over time.
Polylactic Acid (PLA)

 Polylactic acid also known as polylactide is a thermoplastic polyester obtained by

condensation of lactic acid with loss of water (hence its name). It can also be
prepared by ring-opening polymerization of lactide.

 PLA is the most widely used plastic filament material in 3D printing. Its low melting
point, high strength, low thermal expansion, good layer adhesion, and high heat
resistance when annealed make it an ideal material for this purpose.

 PLA is used in a large variety of consumer products such as disposable tableware,

cutlery, housings for kitchen appliances and electronics such as laptops and
handheld devices, and microwavable trays. (However, PLA is not suitable for
microwavable containers because of its low glass transition temperature).

 It is used for compost bags, food packaging and loose-fill packaging material.

 PLA can degrade into innocuous (non-harmful) lactic acid, making it suitable for use
as medical implants in the form of anchors, screws, plates, pins, rods, and mesh.
Depending on the type used, it breaks down inside the body within 6 months to 2
years.

Biodegradable PLA cups

Poly β-hydroxybutyrate – co-β-hydroxy valerate (PHBV):
It is derived by combining 3-hydroxy butanoic acid and 3-
hydroxy pentanoic acid, in which monomers are cross-linked
by an ester linkage. It decomposes to form carbon dioxide and
water. It is brittle in nature, and it can be used in the
production of drugs and the manufacturing of bottles.
 It is biodegradable, nontoxic, biocompatible
plastic produced naturally by bacteria and a
good alternative for many non-biodegradable
synthetic polymers.
 It is a thermoplastic linear aliphatic polyester. It
is obtained by the copolymerization of 3-
hydroxybutanoic acid and 3-hydroxypentanoic
acid.
 PHBV is used in specialty packaging, orthopedic
devices and in controlled release of drugs.
 PHBV undergoes bacterial degradation in the
environment.
Polyhydroxybutyrate (PHB):

It is formed by the condensation of hydroxybutyric acid (3-hydroxy butanoic acid) molecules.

CH3 O
Condensation CH3 O
Polymerization H3C

HO OH O
- H2O
3-hydroxybutanoic acid Polyhydroxybutyrate (PH B)

PHB hold the potential to replace plastics linear use and dispose practices with a fully circular life-cycle for plastics.
Many PHB plastics have properties that are similar to the petroleum polymers polypropylene (PP) and polyethylene (PE).

Biopol (trademark of PHB) is currently used in the medical industry for internal suture. It is nontoxic and biodegradable, so
it does not have to be removed after recovery.
Nylon 2–Nylon 6:
It is a polyamide copolymerization of glycine (H 2N−CH2−COOH) and aminocaproic acid (H2N−(CH2)5−COOH).

Uses of Nylon-2-nylon-6
• Used for making ropes and parachutes.
• Used as thread in bristles for tooth brushes.
• Used for making strings of musical instruments.
• Used in hosiery and knitted garments.
 Biodegradable Polymers: Benefits

• It is Easy to recycle biodegradable polymers: These polymers not only decompose faster when discarded but can also
be easily recycled using an organic method. Recycling helps to reduce landfill waste, and the recycled bio-waste can also
be used as compost or as a renewable energy source for biogas production.

• The amount of waste generated is reduced: Biodegradable plastic degrades in a matter of months, depending on the
material used to make it and the method of disposal.

• Reduction in carbon Emission: One of the most important benefits of using biodegradable polymers to produce plastic
bags is the significant reduction of carbon emissions during the production process instead of conventional plastic.

• Greenhouse gas emissions are reduced: As the biodegradable polymer is used instead of conventional plastics,
greenhouse gas emissions are reduced.

• Reduced use of petroleum: Oil is an essential component in the production of traditional polymer. When you consider
the amount of waste generated during refining and even during the extraction of oil from the earth, it is no surprise that
petroleum harms the environment.

• They consume less energy during their manufacture: Although the initial investment may be marginally higher,
biodegradable plastics need less energy in the long run and require the reprocessing of fossil fuels to produce polymers.
Biodegradable Polymers: Disadvantage

• Landfills are designed to be moisture-free and airtight to store potentially dangerous materials. These
anaerobic conditions help to prevent toxic chemicals from being released from landfills.

• The cost of biodegradable polymers is prohibitively expensive.

• They are not readily available.

• Biodegradable polymers are not good candidates for mixed plastic recycling.
 Polymer composites
Composite materials
A composite material can be defined as a combination of two or more materials that
results in better properties than those of the individual components used alone.
OR
A Composite material is a material system composed of two or more macro constituents
that differ in shape and chemical composition and which are insoluble in each other.

In contrast to metallic alloys, each material retains its separate chemical, physical, and
mechanical properties.

The main advantages of composite materials are their high strength and stiffness,
combined with low density, when compared with bulk materials, allowing for a weight
reduction in the finished part.
Traditional composites:
Composite materials that occur in nature or have been produced by civilizations for many
years.
wood, is a composite – it is made from long cellulose fibres (a polymer) held together by a
much weaker substance called lignin.

Cellulose is also found in cotton, but without

the lignin to bind it together it is much weaker.
The two weak substances – lignin and cellulose
– together form a much stronger one.
The bone in our body, is also a composite. It is made from a hard but brittle material called
hydroxyapatite (which is mainly calcium phosphate) and a soft and flexible material called
collagen (which is a protein).

Collagen is a structural protein, containing

Hydroxyapatite (HA), Ca5(PO4)3(OH), 3 amino acids repeatedly

Collagen is also found in hair, but it not strong like bone.

On its own it would not be much use in the skeleton but it can combine with
hydroxyapatite to give bone the properties that are needed to support the body.
 Polymer composites
Most composites are made of just two materials.
One is the matrix and second is binder (reinforcement).
It surrounds and binds together fibres or fragments of the other material, which is
called the reinforcement (distribution, size, shape, and orientation).

Matrix: sets up the part geometrically, gives cohesion to the material, it is usually flexible
and not very resistant and transmits efforts from one fibre to another.

Reinforcement: provides rigidity and resistance.

 Types of composite materials

Matrices

Polymer Metal Ceramic Carbon and

Graphite

Thermosets Glass
(Epoxy, Polyester)
Alloys Ceramics
(Steel) (Cerements)
Thermoplasts
(Polystyrene,
Nylons) Cements
Types of composite materials

Reinforcements
 Classification of composites:
Based on Matrices:
Organic Matrix Composites (OMCs)
Polymer Matrix Composites (PMCs)
Metal Matrix Composites (MMCs)
Ceramic Matrix Composites (CMCs)
Carbon‐carbon composites

Based on Reinforcements:
Fibres reinforced composites
Laminar composites
Particulate composites
 Types of composite materials

Matrices

Polymer Metal Ceramic Carbon and

Graphite

Thermosets Glass
(Epoxy, Polyester)
Alloys Ceramics
(Steel) (Cerements)
Thermoplasts
(Polystyrene,
Nylons) Cements
Types of composite materials

Reinforcements
 Classification of composites:
Based on Matrices:
Organic Matrix Composites (OMCs)
Polymer Matrix Composites (PMCs)
Metal Matrix Composites (MMCs)
Ceramic Matrix Composites (CMCs)
Carbon‐carbon composites

Based on Reinforcements:
Fibres reinforced composites
Laminar composites
Particulate composites
Many materials are composites made up of at least two constituents
Classification of polymer composites
Fillers/Reinforcement
Boron trinitride (BN) is a low atomic numbered nonmetallic compound; its melting temperature (~3000 °C) is very high so
as to be used as thermal insulation. BN/polymer composites can decrease thermal expansion and increase thermal
conductivity while enhancing the electrical insulation properties.

Carbon black is a very important filler, especially in the rubber industry. Its fine particle size, high particle porosity, and
compatibility with organic materials make it an obvious candidate for use as fillers. The strong interaction between polymer
and carbon black particles improves the mechanical properties of the composites

Minerals are added to polymers to modify selected physical properties and reduce cost. The mineral increases the modulus
but elongation and impact strength are drastically reduced.
Calcium carbonate (CaCO3) is one of the strongest inorganic fillers in the polymer industry. Calcium carbonate (GCC) is used
as a cost-reducing filler in polymer systems.
Carbon fiber (CF) offers the maximum extent of strength and wear resistance enhancement and also boosts the thermal
conductivity. In general, carbon fibers help in imparting additional lubricity because of the layer-lattice structure of
graphite. A notable advance in the polymer industries has been the use of fiber and particulate fillers as reinforcement in
polymer matrix. Carbon fibers have been successfully used as reinforcement in polymer matrix composites for their
excellent properties. Since carbon fibers possess high strength, high modulus, and low density, the addition of carbon fibers
to polymer is one possible way to enhance the mechanical properties.

Fiberglass is the first modern composite material with wide use in boat hulls, sports equipment, building panels, and many
car bodies. The matrix is a polymer and the reinforcement that has been made into fine threads and often woven into a sort
of cloth. Glass fibers are not electrically conductive and therefore not suitable for applications that require the ability to
discharge electrostatic potentials. The most widely used glass fiber is “E-glass fiber,” which contains SiO2 as the main
component with the remainder being oxides of other metals such as Al, Mg, Ca, etc.
 Composites are used in a variety of applications ranging from household appliances to
aeronautics. Polymer composites can be used in a large variety of applications including
wall
boards, furniture, insulation boards, ceiling boards, and roof tiles.

 Polymers are commonly mixed with a variety of natural and synthetic compounds to
improve their performance.

 Polymer composites come in all shapes and sizes. They come with an enormous variety of
useful materials. Continuous and distributed phases can be metallic, polymeric, ceramic or
organic.

Polymeric phase is usually called matrix phase.

Polymeric phase typically:
 Provides environmental protection
 Supports and binds reinforcing agents together
 Is more compliant (meeting or in accordance with rules or standards)
 Carries shear stresses of the composite
Reinforcing Phase
Polymer composites are controlled by the reinforcing material content present in them.
Reinforcing phase is distributed within the matrix. It is often fibrous or particulate and
provides the composite with its high stiffness and strength properties.

Reinforcement phase typically:

• Is stiffer and stronger than polymer
• Provides the composite with its high stiffness and strength properties
• Can reduce environmental pollution by addition of filler or fibers due to the relative
amount of polymeric materials being reduced.

Many of the characteristic properties of polymer composites are achieved by the

incorporation of filler either in particulate or fiber form. These materials are often used to
enhance mechanical properties such as tensile strength, rigidity, etc. They also improve
thermal properties such as deflection temperature.