IIT Delhi

APL 102

Non crystalline solids: Polymers

Concepts: long chains, molecular weight, crystallinity, thermoplastic, thermosets

Lecture 12
 Recap
IIT Delhi
Ionic Solids (Next lab)
Local coordination-------- Long range arrangement------- Ionic crystal

Ligancy - function of Radius Ratio  RRCa  Overall electrical neutrality-net charge be zero
Mixed nature of bonding (ZnS)

RNa  RCs  RZn 2

 0.54  0.91  0.48
RCl  RCl  RS 2
 Ligancy 6  Ligancy 8  Ligancy 4
Octahedral Coordination Cubic Coordination Tetrahedral Coordination
 Recap
2─
IIT Delhi
Structure of Silica (SiO2) – Bond is 50% ionic and 50% covalent
RSi 4 Silicate tetrahedron
 0.29
RO 2 electrically unbalanced
4+
 Ligancy 4 (share corners) 2─ 2─
Tetrahedral Coordination
2─

Crystalline Silica Non-Crystalline Silica Network modifiers

Quartz Glass Network Soda glass
Modifiers

Leads to breaking of primary bonds between silicate

tetrahedral and hence lowers the softening temperature
Impurity Bond breakage Viscocity
IIT Delhi
Question for thought?

Can metals be made into a glassy structure??

Yes, in the form of Bulk Metallic Glasses

IIT Delhi

Non crystalline solids:

Polymer
 Polymer
IIT Delhi

Poly mer = many units

Polymers have a carbon-carbon backbone with varying side-groups

Materials: engineering, science, processing and design, 2nd edition Copyright (c)2010 Michael Ashby, Hugh Shercliff, David Cebon
 Polymer Bonding
IIT Delhi

Polymer chains bond to each

other through weak hydrogen
bonds

Red lines indicate strong cross-

linked carbon-carbon bonds

Materials: engineering, science, processing and design, 2nd edition Copyright (c)2010 Michael Ashby, Hugh Shercliff, David Cebon
 Polymer microstructure
IIT Delhi

mer mer mer

H H H H H H H H H H H H H H H H H H
C C C C C C C C C C C C C C C C C C
H H H H H H H Cl H Cl H Cl H CH3 H CH3 H CH3
Polyethylene (PE) Polyvinyl chloride (PVC) Polypropylene (PP)
IIT Delhi

Schematic Representation of a Polymer

(spheres represent repeating units of the chain not the atoms)
Ref: Wulff Series
 Characteristics: Molecular weight & Crystallinity
IIT Delhi

 Molecular weight, Mw: Mass of a mole of chains

smaller Mw larger Mw

Mw of the Polymer = Degree of polymerization X Mw of mer unit

Mw of chains typically range from 10,000 to 1,000,000

 Crystallinity: % of material that is crystalline crystalline

region
- long chains alignment promotes crystallinity amorphous
region
- Annealing cause crystalline regions to grow
- formation of hydrogen bonds between
chains in place of weak van der waals bond % crystallinity density
Ref.: H.W. Hayden, W.G. Moffatt,and J. Wulff, The Structure and Properties of Materials, Vol. III, Mechanical Behavior, John Wiley and Sons, Inc., 1965.)
IIT Delhi
Question for thought?

How do the Mw and crystallinity influence the properties of polymer??

Tensile strength (TS) and E often increases with Mw and % crystallinity ---- Why?

Longer chains are entangled (anchored) better

 Polymer Structure
IIT Delhi
(a): No regular repeating pattern of
polymer chains – results in a
glassy or amorphous structure

(b): Regions in which polymer chains

line up and register – forms
crystalline patches

(c): Occasional cross-linking allowing

the polymer to stretch – typical
of elastomers

(d): Heavily cross-linked polymers

– typical of epoxy
Materials: engineering, science, processing and design, 2nd edition Copyright (c)2010 Michael Ashby, Hugh Shercliff, David Cebon
IIT Delhi
Covalent chain configurations and strength

secondary
bonding

Linear Branched Cross-Linked Network

Direction of increasing strength

 Classification of Polymers
IIT Delhi

Arrangements of monomers in space

Linear polymer/chain polymer

Arrangement of monomers in curvilinear fashion

Network polymers

Arrangement of monomers in cross network i.e. in 3 dimensions

 Long chain polymers
IIT Delhi

Plastics: chains are placed in zig-zag manner, the bond along the chain is
strong covalent bond while the bond between the chain is weak Vander Random orientation of
Wall type long chain molecules

Fibres: chains of different lengths are aligned parallel to one and other,
the bond along the chain is strong covalent while the bond between the Alignment of chains
chain is weak hydrogen type.
Very strong and stiff along the axis of fibers.

Elastomers: Long chain polymers with few cross links across the chains. Long chain molecules
Importantly the cross links are of primary bond between chains. Chains with rubbery
have translation mobility at RT. behaviour
 Examples of Long Chain Polymers
IIT Delhi

Plastics bag Nylon Tyre

Plastics Fibre Elastomer

IIT Delhi

Plastics
 Structure of Long Chain Polymers
IIT Delhi

Degree of Polymerization:
No. of repeating monomers in a chain
IIT Delhi
On the basis of monomer unit other plastics
can be described

R1 R2

R3 R4

Monomer Unit

Side groups can be labelled as R1, R2, R3 and R4

 Ethylene Based Long Chain Polymers
IIT Delhi

Name Monomer Structure Uses

R1 R2 R3 R4

Polyethylene (Polythene) H H H H Sheets, tubes and containers

Polyvinyl chloride (PVC) H H H Cl Electrical insulation, gramophone recorders

Polypropylene H H H CH3 Ropes and filaments, vacuum flask, flash

light casing

Polymethylemethacrylate H H CH3 COOCH3 Transparent windows and fixture

(Plexiglass)

Polystyrene H H H C6H5 As Styrofoam, sound proofing in

refrigerators and buildings
 Continued…………
IIT Delhi

Polytetrafluoroethylene F F F F Coating for frying pans,

razors and bearings,
chemical ware,
humanbody implants

Polyacrylonile H H H CN Acrylic fiber used as wool

substitute in clothings
IIT Delhi
Common Plastics
Name R1 R2 R3 R4 Uses
PE H H H H Containers, bags
PVC* H H H Cl Piping's, tubing
PP H H H CH3 Dash boards, bumpers of
cars, buckets
PMMA H H CH3 COOCH3 Plexiglass, window pane

Polystyrene H H H C6H5 Styrofoam, packaging

material
PTFE F F F F Sliding and rotating
bearings

* Plasticisers are often added to make it soft

 Common Plastics
IIT Delhi

Varying side groups

IIT Delhi
Question for thought?

Can two or more monomers polymerized or mixed together ?

Yes, they get bonded in random sequence along the chain length producing copolymers

Copolymers are the polymeric analog of solid solutions

IIT Delhi
Question for thought?

What other classification of polymer is possible?

 Classification of Polymers
IIT Delhi

Based on the behaviour with temperature

Thermoplastics

Thermosets
 Thermoplastics
IIT Delhi

Thermoplastics:

 Long chain molecules held together by secondary bonds

 Secondary bonds can be easily broken with temperature and pressure

 This allows the polymer to be moulded and shaped readily

 They retain shape on cooling

 Thermosets
IIT Delhi

Thermosets:

 3 dimensional network of primary bonds

 They have many cross-links, making them stiffer and stronger than
thermoplastics

 The cross-links become hard and cannot be broken by heat

 They cannot be thermally moulded

 Thermoplastics vs Thermosets
IIT Delhi

T
 Thermoplastics: Callister,
viscous rubber
-- little cross linking Fig. 16.9
mobile liquid Tm
-- ductile liquid tough
-- soften w/heating and harden on cooling plastic
Tg
-- polyethylene (PE), polypropylene (PP)
polycarbonate, PVC, PMMA, polystyrene partially
crystalline
crystalline
 Thermosets: solid
solid
-- large cross linking (10 to 50 % of mers)
-- hard and brittle Molecular weight
-- do NOT soften w/heating
-- vulcanized rubber, epoxies, bakelite (switches)
polyester resin, phenolic resin

(F.W. Billmeyer, Jr., Textbook of Polymer Science, 3rd ed., John Wiley and Sons, Inc., 1984.)
IIT Delhi
Question for thought?
Which one of these two behave more like a thermoplastic??