RUBINSTEIN BOOK - POLYMER PHYSICS
INTRODUCTION
Staudinger Founder of polymer chemistry , proposed macromolecular hypothesis ,
polymers made up of covalently bonded elementary units callled monomers.
Long chainlike structure (polymers) by chemical interaction not by physical
aggregation.
Before this hypothesis every scientists think that polymers are made by small molecules
with non covalent bonds but he said, long chain molecules with covalent bonding and their
properties will be studied or known by the lenght and the structure of the chain .
That polymer posses high molecular weight (It explains mechanical and physical
properties. Like elasticity in rubber and strength of plastics)
Colloidal properties macromoleules Colloidal particles
Size range 1 nm to 1000 nm 1 nm to 1000 nm
Flexibility & Conformation Flexible & capable of diff Rigid structure
conformation .
Conformational flexiblity affects No change in shape
the properties like viscosity
Solvation (interaction with Interact with the entire polymer Interaction depends on surface
solvents) . chain. It affects the conformation chemistry
and the size. (good solvents – Form a solvation shell, but it does not
swelling , bad solvents - affect the overall structure remains
shrinking) unchanged.
Molecular weight (Thousands to millions of Uniform molecular weight, not critical
Daltons). Plays significant role as to their properties
in physical and mechanical
properties
examples polymers nanoparticles, micelles, emulsions, and
clay particles
During 1930 – 60 the polymer era is began.
1.2 polymer structure : pg no:02
poly - many
mer – partscd
monomers – 2 types - chemical monomers and khun monomers.
Polymerization – entire structure of polymer is generated. (The process which by the elementary
particles are bonded together)
Degree of polymerization N – no of monomers in a polymer molecule .
Molar mass M of a polymer = N Mmonomer
categories of isomerism:
Sequence / positional structural/constitutional Stereo/ spatial isomerism
isomerism isomerism
Head to head isomers C4H10 Types: skeletal, Types: optical and geometrical
positional,functional isomerism
Head to tail isomers
(common microstructure)
Order or sequence of Different connectivity b/w Different in spatial arrangement
copolymer is different. atoms or branching of substituent groups
Ex: random , alternating and Ex:Linear, branched polymers Isotactic, syndiotactic , atactic
block copolymers polypropylenes
These structure bariations of isomers measured using NMR spectroscopy
HOMOPOLYMERS and HETEROPOLYMERS:
pg no : 5,6,
HOMOPOLYMERS :
Homopolymers
small no. of. Monomers – obligomer
Monomers of one type
.....A – A – A – A – A -A ...
in linear polymers 20 – 10 billion monomers.
Ex: tacticity, structural and sequence isomers
Types of polymer architectures:
linear , ring , star branched, H branched, comb , ladder , dendrimer, randomly based
HETEROPOLYMERS:
High degree of crosslinking – polymer network
Heteropolymers
Different types of monomers
.....A – A – B– A – A -B - ...
2 monomers – copolymers
2 block of polymers – diblock
3 blocks of polymers – triblock
Many blocks of polymers – alternative
....A – B - C -
3 monomers – terpolymers
Ex: random terpolymers(polyampholytes)
ABC triblocks
1.4 Fractal nature of polymer conformations :
During polymerization , structure , architecture, deg of polymerization , chemical composition are
changed only while breaking the covalent bond.
After polymerization, even a single molecule can also exhibit in different conformations.
Conformation of polymers depends on 3 characteristics:
1) Flexibility of the chain
2) Interaction b/w monomers
3) Interaction with surroundings ( monomers / other chains / solvent )
4 types of interactions with the monomers:
polymer chain size :
n = 1010 bonds ( DNA molecule ) , bond length = 10-10 , the entire DNA molecule length – order of
mts
Scalling of bond length:
all bond lengths by a factor 108 , then only we can get the single bond length is 1 cm
Strong Attraction Dense object – collapsed 10 10 cm3 linear about
(classroom) globule 20cm
No interaction spread more R = 1 km (n 1/2) Random walk
(campus size)
Short range repulsion Repel each other R = 10 km (n 3/5) Self avoiding
(city size)
Long range repulsion Stretches even more R = 105 km (n) Extended conformation
(quarter of moon )
V = ( 4π / 3 ) R 3
V = R3 (mass)
Radius of the ball increases by Factor 2, then its mass increases by a factor
2 3 = 8 , the exponent is the dimension of the ball .
m ~ r3 ( exponent – dimension )
For example :
1)self similar object with a regular fractal structure called
koch curve
m ~ r D (D – fractal dimension)
( 3r2 ) D = 4r2D
PP
D = log 4 / log 3 = 1.26
3 - fig a - scaling factor , divide the line segment as 3 equal parts
4 - fig b – 4 segments
2) Sierpinski gaskel - equilateral triangle
D = log 3 / log 2 = 1.58
2 - fig a - scaling factor – 2 triangles
3 - fig b – removing the centre part , we will get 3
segment
D = log Cm (self similar pieces) / Cr (scallling factor)
For single polymer ideal chain,
The mean square end to end distance is proportional to the
Degree of polymerization.
N ~ ˂ R2 >
g monomers and size r : g ~ ˂ r2 >
For ideal chain the fractal dimenion is 2. chain structure is self similar. It shows the whole
chain.
For polymeric chain – within the finite range of length scales only it shows the self similar
properties. { From bond leength (dis b/w one monomer to another monomer) to polymer overall
size R (End to end distance or Rg) } bond length (l) < r < R
g ~ (√ ˂ r2 >) D
1.5 Type of polymeric substance:
Polymeric substance
liquids Solids Liquid Crystal polymers
Semicrystaline Polymeric glass
Polymer melts Polymer Solutions
Macromolecules Dissolving in a polymer
can form bulk solvent
liquid state.
Ex: Wood protectants
Ex: Silly Putty (Varnish) & Floor shines
Overlap
Dilute Semidilute ⱷ=ⱷ*
ⱷ<ⱷ* ⱷ>ⱷ* P=1
Polymer melts Polymer Solution
In this state, the polymers are heated above their Mixture of polymers dissolved in a solvent,
Tg & melting point, it flows without any solvent. solvent surrounds the polymer and affects the
No added solvent only the pure polymer chain arrangement and interactions
Densely packed, strong interchain interaction Reduce the strength of the interaction b/w chains.
bcoz the absence of solvent
Pure polymer, so no chance of concentration At dilute – less interaction,
Semidilute/Concentrated - overlapping
High viscosity , resistance to flow In dilute – low viscosity
Semi/con. - increase in viscosity
CHAPTER – 2
IDEAL CHAINS :
chains – no interaction b/w monomers
Not real chains but some chains are nearly ideal
At high temp – chains swell ( repulsion )
At θ temperature - chains are nearly ideal ( coz the attraction and repulsion cancel each other)
θ temperature - Boyle’s temperature
2.1 -
Trans state
__________ reduce crowding , more stable
180 deg
In polymer , trans state make a straight chain ( stronger and stiffer material )
torsional angle – 0 deg
Gauche state : angle - 120
U
ΔE ΔE
- 120 deg 0 deg + 120 deg
Gauche - trans Gauche +
Conformations Torsional Angle Energy
Trans 0 degree Low
Gauche + or – 120 degree Medium
Eclipse 180 degree High
All torsional angles are trans , then that chain has largest end to end distance
End to end distance Rmax = nl cos θ / 2
n – [Link]. Skeleton bonds
l – contour length ( full length of the fully stretched polymer chain )
2.2 Conformations of an ideal chain
Ideal state of polymer - when no interaction between the atoms.
The avg end to end dis of an isotropic collection of chain is zero.
Ensemble average
Average all possible states of system
To connect macroscopic properties lilke pressure, Temperature, RDF, MSD
For the freely jointed chain: universal joint
Flory characteristics:
2.3 Ideal chain models:
Every model ignores interaction b/w monomers seperated by large distance along chain
1) freely rotating chain:
This model ignores all probabilities of different torsion angles and assumes all torsion angles
in equal probability
Ignores variation of potential
< ri . Rj > = l^2 ( cos θ ) ^ |j – i |
3 . excluded volume
ⱷ* = bd N / Rd (: R = bN1/2)
ⱷ* = N 1- d / 2
