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Introduction to Polymers
M.Vasanth,
Research scholar,
VIT University,
Vellore, Tamilnadu.
Introduction to Polymers
– Polymers are extremely important materials. we have been
using polymeric materials in our daily life.
– Have known since ancient times – cellulose, wood, rubber,
etc…
– Biopolymers – proteins, enzymes, DNA , etc…
– Last ~50 years – tremendous advances in synthetic polymers.
Polymers
e.g. polyethylene is built from ethylene units.
Polymers are compounds which consist of very large molecules
formed by repeated joining of many small molecules.
n Ethylene units
polymerization
Polyethylene
It is the process of joining together many small molecules
repeatedly to form very large molecules.
These are compounds that join together repeatedly to
form polymer in polymerization.
Polymerization
Monomers
n monomer units
polymerization
polymer
Homopolymer and Copolymer
Homopolymer
If formed from one type of monomers (all the repeat units
are the same type) – this is called homopolymer.
Copolymer
If formed from multiple types of monomers (all the repeat
units are not the same type) – this is called copolymer.
e.g. -A-A-A-A-A-A-A-A-A-A-A-
e.g. -A-B-A-B-A-B-A-B-A-B-
Copolymer types
Two different monomers polymerized together to give
different types of copolymers.
Random Copolymers:
A and B randomly positioned along chain.
-A-B-B-A-A-B-A-B-B-
Alternating Copolymers:
A and B alternate in polymer chain.
-A-B-A-B-A-B-A-B-
Block Copolymers:
Large blocks of A units alternate with large blocks of B
units.
-A-A-A-A-B-B-B-B-
Graft Copolymers:
Chains of B units grafted onto A backbone.
-A-A-A-A-A-A-A-A-
B-B-B-B-B-
Types of polymerization
There are two types of polymerization
• Addition polymerization
• Condensation polymerization
Addition polymerization:
When molecules just add on to form the polymer, the
process is called addition polymerization.
e.g. polyethylene
Condensation polymerization
When molecules do not just add on but also undergo
some reaction in forming the polymer, the process is called
Condensation polymerization.
Degree of Polymerization:
The size of the polymer molecule is decided by the
number of repeat units present in it. this number denotes the
degree of polymerization.
Classification of polymers
Polymers can be classified in different ways.
Natural polymers:
those isolated from natural materials are called natural
polymers.
e.g. cotton , silk, wool and rubber.
Synthetic polymers:
polymers synthesized from low molecular weight
compounds are called synthetic polymers.
e.g. Polyethylene, Nylon , PVC and Terylene.
Organic polymers:
A polymer whose backbone chain is essentially
made up of carbon atoms is termed an organic polymer.
The majority of synthetic polymers is organic
polymers.
Inorganic polymers:
The molecules of inorganic polymers generally
contain no carbon atom in their backbone chain.
e.g. Glass , Silicone and Rubber.
Thermoplastics
• Those which soften on heating and then harden again on cooling.
these are called thermoplastics.
• These polymer molecules consist of long chains which have only
weak bonds between the chains.
• The bonds between the chains are so weak that they can be
broken when the plastic is heated.
• The chains can then move around to form a different shape.
• The weak bonds reform when it is cooled.
• Thermoplastic material keeps its new shape.
Thermosetting
• Those which never soften once they have been moulded.
These are called thermosetting polymers because once set into
a shape, that shape cannot be altered .
• These polymer molecules consist of long chains which have
many strong chemical bonds between the chains.
• The bonds between the chains are so strong that they cannot be
broken when the plastic is heated.
• This means that the thermosetting material always keeps its
shape.
MOLECULAR WEIGHT
High MW
• Polymers can have various lengths depending on the number of
repeat units.
• During the polymerization process, not all chains in a polymer
grow to the same length, so there is a distribution of molecular
weights. There are several ways of defining an average molecular
weight.
Average molecular weight
• Each molecule has the same molecular weight for all the low
molecular weight compounds.
• In polymer, it comprises molecules of different molecular
weights and, hence, its molecular weight is expressed in terms
of an ‘average’ value.
Molecular weight: a few definitions



i
i
i
ii
n
N
NM
M
__
Mn -Number average molecular weight



i
ii
i
ii
w
MN
MN
M
2
__
Mw -Weight average molecular weight
Mi –Molecular weight of the ith polymer chain
Ni -Number of polymer chains with molecular weight Mi
17
Molecular weight
Molecular weight is expressed as follows,
m- Molecular weight of the monomer or the
repeating unit.
Dp- The degree of polymerisation.
M=Dp.m
The ratio of the weight to number average molecular
weights is called Polydispersity Index.
Polydispersity Index(PDI)
PDI ˭
Weight average molecular weight
Number average molecular weight
Glass transition temperature
• The transition from glassy solid state to molten liquid
state occurs at a temperature. This is known as the
glass transition temperature (Tg).
• The temperature at which the change of state occurs
( from solid state to liquid state ) is called the melting
temperature (Tm).
With the low molecular weight substances in the condensed state,
we can have two states of affairs.
• The first without Brownian movement, but with long range
order when stress transfer phenomenon is possible. This state
is called solid.
• The second with Brownian movement, but without long range
order and with energy dissipation. This state is called liquid.
The two types of motions exhibited within a polymeric material,
namely,
• The localised mobility of the segments, this is called
segmental motion. its another name is called as the internal or
micro Brownian movement.
• The total mobility of the molecule as a whole, this is called
molecular motion. its another name is called as the external or
macro Brownian movement.
There are three major observations in states of phase.
• Both crystalline and amorphous solids are in the solid state of
aggregation, whereas only crystalline solid exist in the
crystalline state phase.
• Although amorphous solids are in a solid physical state, they
really exist in a liquid phase state.
• Both amorphous and crystalline substances can exist in a
molten liquid state.
Glass transition temperature
Low molecular weight substance
Crystalline Amorphous
BM : -
LRO : +
ST : +
Crystalline solid
BM : -
LRO : -
ST : +
Glassy solid
BM : +
LRO : -
ST : -
Liquid
T
e
m
pe
ra
tu
re
Tm
Tg
Polymeric materials
Crystalline Amorphous
IBM : -
EBM : -
LRO : +
ST : +
Crystalline solid
IBM : +
EBM : -
LRO : -
ST : +/-
Rubber
IBM : -
EBM : -
LRO : -
ST : +/-
Glassy solid
IBM : +
EBM : +
LRO : -
ST : - polymer melt
Tm
Tg
Tf
T
e
m
pe
ra
tu
re
Here,
BM-Brownian Movement
IBM-Internal Brownian Movement
EBM-External Brownian Movement
LRO- Long Range Order
ST- Stress Transfer property
- Frozen
+ Activated
- does not exist
+ exists
- Lost
+/- partially retained
+ Fully retained
Mechanical properties
• Tensile strength
• Compressive strength
• Shear strength
• Elongation
• Toughness
Thank you

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Introduction to Polymers

  • 1. Introduction to Polymers M.Vasanth, Research scholar, VIT University, Vellore, Tamilnadu.
  • 2. Introduction to Polymers – Polymers are extremely important materials. we have been using polymeric materials in our daily life. – Have known since ancient times – cellulose, wood, rubber, etc… – Biopolymers – proteins, enzymes, DNA , etc… – Last ~50 years – tremendous advances in synthetic polymers.
  • 3. Polymers e.g. polyethylene is built from ethylene units. Polymers are compounds which consist of very large molecules formed by repeated joining of many small molecules. n Ethylene units polymerization Polyethylene
  • 4. It is the process of joining together many small molecules repeatedly to form very large molecules. These are compounds that join together repeatedly to form polymer in polymerization. Polymerization Monomers n monomer units polymerization polymer
  • 5. Homopolymer and Copolymer Homopolymer If formed from one type of monomers (all the repeat units are the same type) – this is called homopolymer. Copolymer If formed from multiple types of monomers (all the repeat units are not the same type) – this is called copolymer. e.g. -A-A-A-A-A-A-A-A-A-A-A- e.g. -A-B-A-B-A-B-A-B-A-B-
  • 6. Copolymer types Two different monomers polymerized together to give different types of copolymers. Random Copolymers: A and B randomly positioned along chain. -A-B-B-A-A-B-A-B-B- Alternating Copolymers: A and B alternate in polymer chain. -A-B-A-B-A-B-A-B-
  • 7. Block Copolymers: Large blocks of A units alternate with large blocks of B units. -A-A-A-A-B-B-B-B- Graft Copolymers: Chains of B units grafted onto A backbone. -A-A-A-A-A-A-A-A- B-B-B-B-B-
  • 8. Types of polymerization There are two types of polymerization • Addition polymerization • Condensation polymerization Addition polymerization: When molecules just add on to form the polymer, the process is called addition polymerization. e.g. polyethylene
  • 9. Condensation polymerization When molecules do not just add on but also undergo some reaction in forming the polymer, the process is called Condensation polymerization. Degree of Polymerization: The size of the polymer molecule is decided by the number of repeat units present in it. this number denotes the degree of polymerization.
  • 10. Classification of polymers Polymers can be classified in different ways. Natural polymers: those isolated from natural materials are called natural polymers. e.g. cotton , silk, wool and rubber. Synthetic polymers: polymers synthesized from low molecular weight compounds are called synthetic polymers. e.g. Polyethylene, Nylon , PVC and Terylene.
  • 11. Organic polymers: A polymer whose backbone chain is essentially made up of carbon atoms is termed an organic polymer. The majority of synthetic polymers is organic polymers. Inorganic polymers: The molecules of inorganic polymers generally contain no carbon atom in their backbone chain. e.g. Glass , Silicone and Rubber.
  • 12. Thermoplastics • Those which soften on heating and then harden again on cooling. these are called thermoplastics. • These polymer molecules consist of long chains which have only weak bonds between the chains. • The bonds between the chains are so weak that they can be broken when the plastic is heated. • The chains can then move around to form a different shape. • The weak bonds reform when it is cooled. • Thermoplastic material keeps its new shape.
  • 13. Thermosetting • Those which never soften once they have been moulded. These are called thermosetting polymers because once set into a shape, that shape cannot be altered . • These polymer molecules consist of long chains which have many strong chemical bonds between the chains. • The bonds between the chains are so strong that they cannot be broken when the plastic is heated. • This means that the thermosetting material always keeps its shape.
  • 14. MOLECULAR WEIGHT High MW • Polymers can have various lengths depending on the number of repeat units. • During the polymerization process, not all chains in a polymer grow to the same length, so there is a distribution of molecular weights. There are several ways of defining an average molecular weight.
  • 15. Average molecular weight • Each molecule has the same molecular weight for all the low molecular weight compounds. • In polymer, it comprises molecules of different molecular weights and, hence, its molecular weight is expressed in terms of an ‘average’ value.
  • 16. Molecular weight: a few definitions    i i i ii n N NM M __ Mn -Number average molecular weight    i ii i ii w MN MN M 2 __ Mw -Weight average molecular weight Mi –Molecular weight of the ith polymer chain Ni -Number of polymer chains with molecular weight Mi
  • 17. 17 Molecular weight Molecular weight is expressed as follows, m- Molecular weight of the monomer or the repeating unit. Dp- The degree of polymerisation. M=Dp.m
  • 18. The ratio of the weight to number average molecular weights is called Polydispersity Index. Polydispersity Index(PDI) PDI ˭ Weight average molecular weight Number average molecular weight
  • 19. Glass transition temperature • The transition from glassy solid state to molten liquid state occurs at a temperature. This is known as the glass transition temperature (Tg). • The temperature at which the change of state occurs ( from solid state to liquid state ) is called the melting temperature (Tm).
  • 20. With the low molecular weight substances in the condensed state, we can have two states of affairs. • The first without Brownian movement, but with long range order when stress transfer phenomenon is possible. This state is called solid. • The second with Brownian movement, but without long range order and with energy dissipation. This state is called liquid.
  • 21. The two types of motions exhibited within a polymeric material, namely, • The localised mobility of the segments, this is called segmental motion. its another name is called as the internal or micro Brownian movement. • The total mobility of the molecule as a whole, this is called molecular motion. its another name is called as the external or macro Brownian movement.
  • 22. There are three major observations in states of phase. • Both crystalline and amorphous solids are in the solid state of aggregation, whereas only crystalline solid exist in the crystalline state phase. • Although amorphous solids are in a solid physical state, they really exist in a liquid phase state. • Both amorphous and crystalline substances can exist in a molten liquid state.
  • 23. Glass transition temperature Low molecular weight substance Crystalline Amorphous BM : - LRO : + ST : + Crystalline solid BM : - LRO : - ST : + Glassy solid BM : + LRO : - ST : - Liquid T e m pe ra tu re Tm Tg
  • 24. Polymeric materials Crystalline Amorphous IBM : - EBM : - LRO : + ST : + Crystalline solid IBM : + EBM : - LRO : - ST : +/- Rubber IBM : - EBM : - LRO : - ST : +/- Glassy solid IBM : + EBM : + LRO : - ST : - polymer melt Tm Tg Tf T e m pe ra tu re
  • 25. Here, BM-Brownian Movement IBM-Internal Brownian Movement EBM-External Brownian Movement LRO- Long Range Order ST- Stress Transfer property - Frozen + Activated - does not exist + exists - Lost +/- partially retained + Fully retained
  • 26. Mechanical properties • Tensile strength • Compressive strength • Shear strength • Elongation • Toughness