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Lec17 Polymeric Structure

This document provides an overview of a course on the nature and properties of materials. The course covers topics such as molecular weight, polymer chemistry, crystallinity, tacticity, and glass transition temperature. It discusses concepts like number average molecular weight, weighted average molecular weight, polydispersity index, homopolymers and copolymers, crystalline and amorphous regions in polymers, isotactic and syndiotactic configurations, and methods for determining the glass transition temperature and factors that affect it. The course aims to explain fundamental properties of materials at the molecular level.

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53 views18 pages

Lec17 Polymeric Structure

This document provides an overview of a course on the nature and properties of materials. The course covers topics such as molecular weight, polymer chemistry, crystallinity, tacticity, and glass transition temperature. It discusses concepts like number average molecular weight, weighted average molecular weight, polydispersity index, homopolymers and copolymers, crystalline and amorphous regions in polymers, isotactic and syndiotactic configurations, and methods for determining the glass transition temperature and factors that affect it. The course aims to explain fundamental properties of materials at the molecular level.

Uploaded by

Mahesh
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
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Course

on
Nature
and
Properties of Materials

A Project funded by MHRD, Govt. of India

Instructor : Prof. Bishakh Bhattacharya


Department of Mechanical Engineering
IIT Kanpur, India
E-mail: bishakh@iitk.ac.in
Polymeric Structure
Contents

Concept of molecular weight

Chemistry of polymers

% Crystallinity

Tacticity in polymers
Molecular Weight

The molecular weight distribution is important in thermoplastics.


In thermosets, a gelled network of essentially infinite molecular weight is formed, so
the idea of a "molecular weight distribution" is non-sensical.

Two ways:-
a) Number average molecular weight (Mn): Total weight of all the polymer molecules in a
sample, divided by the total number of polymer molecules in a sample.

Number average molecular weight, =

Where, Mi = molecular weight of ith polymer chain;
Ni = number of chains of that molecular weight.

b) Weighted average molecular weight (Mw): It's based on the fact that a bigger molecule
contains more of the total mass of the polymer sample than the smaller molecules do.
2
Weighted average molecular weight, = More appropriate

Degree of Polymerization


=

where, = Number average molecular weight
m = repeat unit molecular weight (no. of atoms x atomic wt.)

= 21,150 g/mol
Example: Suppose for Polyvinyl chloride,
Then, repeat unit molecular weight, m = 2 x 12 + 3 x 1 + 1 x 35
= 62 g/mol
21,150
DP = 62
= 341
Reference: Kalpakjian, Schmid - Manufacturing Processes for Engineering Materials, 5th ed.

Melting Temperature
Repeat unit contains 2 carbon, 3
hydrogen and 1 chlorine atom

PVC
Degree of Polymerization
Polydispersity Index

Polydispersity index,PI =

The larger the polydispersity index, the broader


the molecular weight.
Monodisperse polymer, where all the chain
lengths are equal (such as a protein) has an PI = 1.
Step polymerization reactions typically yield
values of PI 2.0
Chain polymerization reactions yield values
between PI = 1.5 - 20.

Distribution of molecular weights for a typical polymer

Reference: W.D Callister, 7 Ed.


Example

No. of Mass of each Total mass of each


molecules molecule (Mi) type of molecule, Number average molecular weight, =
(Ni) (g/mol) (NiMi) in g/mol
50,000,000
1 800,000 800,000 6.4 x 1011 = 100
= 500,000 g/mol

3 750,000 2250,000 16.8 x 1011


5 700,000 3500,000 24.5 x 1011
8 650,000 5200,000 33.8 x 1011 2
Weighted average molecular weight, =
10 600,000 6000,000 36 x 1011
13 550,000 7150,000 39.3 x 1011 370.75 x 1011
= 50,000,000 = 741,500 g/mol
20 500,000 10,000,000 50 x 1011
13 450,000 5850,000 26.3 x 1011
10 400,000 4000,000 16 x 1011
98 x 1011
Polydispersity index, PI = = 1.48
8 350,000 2800,000
5 300,000 1500,000 4.5 x 1011
3 250,000 750,000 18.75 x 1011
1 200,000 200,000 0.4x 1011
= = 370.75 x 1011
=
50,000,000
(Total mass)
Chemistry of Polymer molecules

When all the mers are the same, the When there is more than one type of mer
molecule is called a Homo-polymer. present, the molecule is a Co-polymer.

Mer units that have 2 active bonds to Mer units that have 3 active bonds to
connect with other mers are called connect with other mers are called tri-
bi-functional. functional. They form 3-D molecular
network structures.

Polyethylene
Phenol-formaldehyde (Bakelite)
Possible Physical States for Polymer Materials
Traditional classification of physical states (gases, liquids, crystals) is not informative
for polymer materials.

Classification of polymer materials:-


Partially crystalline state
Viscoelastic State (polymer melt)
Highly elastic state (e.g. Rubbers)
Glassy state (e.g. Organic glasses from poly(styrene),
poly(methylmethacrylate), poly(vinyl chloride))
Lamella grow like the spokes of a
bicycle wheel from a central
nucleus.
The whole assembly is called a
Spherulite. In a sample of a
crystalline polymer weighing only
a few grams, there are many
billions of Spherulites.
Crystallinity
Crystalline region: Orderly arrangement of molecular chains.
High crystallinity means - higher density, more strength, higher resistance to both dissolution and
softening by heating.

Degree of crystallinity in Polymers


Ranges from completely amorphous to about 95%
crystalline.
Metal specimens are almost always entirely crystalline.
Ceramics are either totally crystalline or totally
non-crystalline.

For same material & molecular weight


>
(due to close packing) Remember: No polymer is 100% crystalline

Reference: Kalpakjian, Schmid - Manufacturing Processes for Engineering Materials, 5th ed.
Crystallinity dependence
Degree of crystallinity is affected by:-
Rate of cooling during solidification
More the rapid cooling lesser the time for alignment poorer the crystallinity.

Chain configuration
More the side branching & cross linking - more the restriction to prevent the chain alignment
lesser the crystallinity .
Thus, linear polymer have high degree of crystallinity.
Most network and crosslinked polymers are almost totally amorphous.

Reference: Kalpakjian, Schmid - Manufacturing Processes for Engineering Materials, 5th ed.
Tacticity in Polymers
Different atomic configurations
for the same composition.
Tacticity is the way pendant
groups are arranged along the
backbone chain of a polymer.
Isotactic & Syndiotactic regular
geometry facilitates fitting of
adjacent chain, thus more
crystalline.
Atactic Poorly Crystalline due to
irregularity of side group. Stereoisomers
Also, larger the side-bonded
groups of atoms - the less is the
tendency for crystallization.
Some Highly Crystalline Polymers:
Polypropylene
Syndiotactic polystyrene
Nylon
Kevlar and Nomex

Some Highly Amorphous Polymers


Poly(methyl-methacrylate), PMMA
Atactic polystyrene
Polycarbonate
Polyisoprene
% Crystallinity

( )
% = x 100
( )

where, : Density of specimen


: Density of the totally amorphous polymer,
: Density of the perfectly crystalline polymer
The values of , and are measured by experimental means.
In the next lecture, we will learn about:

Glass Transition temperature (Tg)


Experimental methods to determine Tg
Factors affecting Tg

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