Biophysics [Biot 3109]

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Structure
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2.1.6 Molecular shape (conformation)
The angle between the singly bonded carbon atoms is ∼ 109o carbon atoms form a zigzag
pattern in a polymer molecule.

Moreover, while maintaining the 109o angle between bonds polymer chains can rotate around
single C-C bonds (double and triple bonds are very rigid)
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Random kinks and coils lead to entanglement, like in the spaghetti structure:

• Molecular chains may thus bend, coil and kink

• Mechanical / thermal characteristics depend on the ability of chain segments to rotate
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2.1.7 Molecular structure
The physical characteristics of polymer material depend not only on molecular weight and
shape, but also on molecular structure:
1) Linear polymers:
a long chain of connected monomers, that is, Van der Waals bonding between chains.
Examples: Polyethylene, PVC, nylon, polymethyl methacrylate

2) Branched polymers:
polymers made up of main chain(linear chain) with smaller chains as branches of main chain.
Chain packing efficiency is reduced compared to linear polymers - lower density

They have lower melting points, densities and tensile strength as compared to linear
polymers. Example: Polypropylene
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Branched polymers can be star polymer, comb polymer, etc:
[1] Star polymer:
Star polymer is the simplest type of branched polymer network which allocates a structural
composition at least two linear arm chains connected to the central core unit.
Star polymer can be named as homogeneous if the number of arms in the chain are identical
otherwise hetrogenoeus
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Star’s functionality f represents the number of arms of star polymer with f ≥ 3 where as its
values f = 1, 2 resembles linear chain polymer.
The increment in number of functionality results in the most compact and sphericity
structure.
Its compact structure which results in to have smaller radius of gyration, lower viscosity and
melting point.
Thus, star polymer’s unique shape allows in promising tools for the use of viscosity index
modifiers in oil industry, coating materials, adhesives and flocculating systems, additives in
motor oils, dispersants in cosmetic industry, potential drug delivery agents, thermoplastic
elastomers, as surfactants and Lubricants, for drug formulation, modification of proteins and
pharmaceutical molecules, biomedical coatings, and other surface modifications.
[2] Comb polymers:
are a class of branched polymers consisting of a linear backbone with a low grafting density of
side chains
- the structure of such a polymer is very similar to hair comb.
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Polystyrene (thermoplastic polymer) is a hard, brittle, and clear polymer which is mostly used
in packaging materials, bowls, toys, combs, etc.
Polystyrene is a polymer of monomer styrene (C8H8), also known as ethenylbenzene

[3] Cross-linked polymers: Chains are connected by covalent bonds.

Often achieved by adding atoms or molecules that form covalent links between chains.
Many rubbers have this structure.
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[4] Network polymers: 3D networks made from trifunctional mers.

Examples: epoxies, phenol-formaldehyde
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2.1.8 Isomerism
Isomerism:
Hydrocarbon compounds with same composition may have different atomic compositions.
Physical properties may depend on isomeric state (e.g. boiling temperature of normal butane
is −0.5 oC, of isobutane −12.3 oC.
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Two types of isomerism are possible:
Stereoisomerism and geometrical isomerism
• Stereoisomerism:
atoms are linked together in the same order, but can have different spatial arrangement
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Geometrical isomerism:
consider two carbon atoms bonded by a double bond in a chain.
• H-atom or radical R bonded to these two atoms can be on the same side of
the chain (cis structure) or on opposite sides of the chain (trans structure).
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2.1.9 Copolymers (composed of different mers)
Copolymers, polymers with at least two different types of mers, can differ in the way the
mers are arranged as shown in the Fig. shown below.
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2.1.10 Thermoplastic and Thermosetting polymers
Depending on the response to temperature increase, two types of polymers can be
distinguished:
(1) Thermoplastic polymers:
soften and liquefy when heated, harden when cooled (reversible).
Molecular structure:
linear or branched polymers
Easy to fabricate/reshape by application of heat and pressure
Examples:
polyethylene, polystyrene, poly(vinyl chlodide).
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(2) Thermosetting polymers:
become permanently hard during their
formation, do not soften upon heating.
Molecular structure:
network polymers with a large density of
covalent crosslinks between molecular chains.
Harder and stronger than thermoplastics,
have better dimensional and thermal stability.
Examples:
vulcanized rubber, epoxies, phenolics,
polyester resins.
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2.1.11 Polymer Crystallinity
Atomic arrangement in polymer crystals is more complex than in metals or ceramics (unit cells
are typically large and complex).
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Polymer molecules are often partially crystalline(semi-crystalline), with crystalline regions
dispersed within amorphous material.
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Degree of crystallinity is determined by:
# Rate of cooling during solidification:
time is necessary for chains to move and align into a crystal structure
# Mer complexity:
crystallization less likely in complex structures, simple polymers, such as polyethylene,
crystallize relatively easily
# Chain configuration:
linear polymers crystallize relatively easily, branches inhibit crystallization, network
polymers almost completely amorphous, cross-linked polymers can be both crystalline and
amorphous
# Isomerism:
isotactic, syndiotactic polymers crystallize relatively easily – geometrical regularity allows
chains to fit together, atactic polymers is difficult to crystallize
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# Copolymerism:
easier to crystallize if mer arrangements are more regular
alternating and block can crystallize more easily as compared to random and graft
Note:-
• More crystallinity:
higher density,
more strength,
higher resistance to dissolution and softening by heating
• Crystalline polymers are denser than amorphous polymers, so the degree of crystallinity can
be obtained from the measurement of density:
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Example:
Find percentage crystallinity of a specimen having a density of 2 g/cm3 when density of totally
crystalline is two times that of totally amorphous and density of totally amorphous is three-
fourth times that of a specimen.

𝝆𝒔 = 2 g/cm3
𝝆𝒂 = ¾ (𝝆𝒔 ) = 3/2 g/cm3
𝝆𝒄 = 𝟐 𝝆𝒂 = 𝟐 𝟑/𝟐 g/cm3 = 3 g/cm3
𝟑
𝟑(𝟐 −𝟐)
%𝑪= 𝟑 x100%
𝟐(𝟑 −𝟐)

𝟏
𝟑(𝟐)
%C = 𝟑 x100% = 50%
𝟐( )
𝟐
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2.1.12 Polymer Classes

• The most common carbon polymers can be divided into four classes based on the structures

of their carbon backbones, and the resulting physical properties.

(1) Fibers
• Fibers are thread formers, often used to make cloth.
• Silk, nylon, polyester, and cotton are all fibers;
• They are usually flexible;
• At the molecular level they are composed of
long carbon chains with few or no branches.
• In a fiber strand, multiple polymer molecules
line up in parallel.
• Their intermolecular forces encourage an ordered,
rather crystalline, arrangement.
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• If you pull on both ends of a strand, it will not stretch very much since the chains are already
aligned.
• Wool is an exception to this; sulfur atoms in adjacent chains find each other and form sulfur
bonds, crosslinking the chains.
This gives wool its crinkly texture (lacks moisture).
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(2) Thermoplastics
• The name thermoplastic is given to polymeric materials that are flexible at high
temperatures.
• Usually they are simply referred to as plastics.
• For example, a polyethylene milk jug can be dented without much force.
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• Polymers such as polyethylene can form either fibers or thermoplastics, depending on how
they are processed.
• A thermoplastic sample has chains going in random directions, held together by weak
secondary bonds.
• A small amount of force can make the chains slide around, thus changing the shape of the
sample.
• If a plastic is cooled it will become stiffer, and eventually brittle.
• The temperature at which a plastic becomes brittle is its glass transition temperature.
• Small molecules called plasticizers (a material to make it softer and more flexible, to
increase its plasticity) are often mixed into thermoplastics.
• The glass transition temperature for a sample with plasticizer is lower.
• Plasticizers may evaporate over time (a process that is faster at high temperatures),
increasing a sample’s brittleness.
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3) Elastomers
• Stretchy polymers like rubber and spandex are elastomers.
• They demonstrate the property of elastic deformation: when force is applied the fiber
stretches, but when the force is removed the fiber returns to its original shape and size.
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• If they are stretched and straightened, a restoring force pulls them back into the shorter,
tangled position.
• Some chains in elastomers may be crosslinked.
• Rubber can be vulcanized (the process of treating crude or synthetic rubber or similar plastic
material chemically to give it useful properties such as elasticity, strength, and stability) by
heating with sulfur, to create new sulfur crosslinks.

• This changes flowing latex into a stiffer material, suitable for automobile tires.
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4) Thermosets
• a material, esp a synthetic plastic or resin, that hardens permanently after one application
of heat and pressure
• With certain polymers, heat can cause crosslinks to form irreversibly.
• The sample hardens so its shape is ”set.”
• Thermoset polymer such as epoxy, polyester, polyurethane, and vinyl ester resins are
typically utilized as a coating or as a matrix material for reinforcement materials/fillers,
forming a reinforced polymer composite
(principally added to polymers to improve the material performance).

Polycarbonate lenses
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• Unlike thermoplastics, thermoset samples will not soften upon heating.

• Some common uses for thermoset plastics across various industries and sectors include gas
and water pipelines, automotive parts, medical equipment, construction machinery parts,
signage, storage boxes, electrical plugs and casings, kitchen appliances and toys.