Polymer Physics

Dr. Jinu Jacob George

Dept. of PS&RT, CUSAT
 Chemical Bonding and Polymer Structure

i. The chemical structure of the monomer (primary structure)

ii. The single polymer chain (secondary structure)

iii. Aggregation of polymer chains (tertiary structure)

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 Chemical bonding
I. Primary bonds
a. Ionic (NaCl)
b. Covalent (CH4)
c. Metallic

II. Secondary bonds

a. Dipole (HCl)
b. Hydrogen (H2O) (F, N,O vs Cl)
c. Induction
d. van der Waals

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 Primary Structure

Structure and property of polymers is the understanding of the following:

• Nature of bonds in monomers (chemical bonding)

• Type of monomers that are capable of forming polymers

(functionality)

• Mode of linking of monomers (polymerization mechanism)

• Chemical composition of monomers

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 Primary Structure
Polar and non-polar polymers

Dipole moment, µ = ql

• Presence of polar groups (C-OH, C-NH2, C-Cl ...)

• Symmetric molecules (H2, CH4, C2H6..)
• Vector sum of all the dipole moments of groups within
the molecule
Examples of CO2vs H2O, CCl4 vs CHCl3

Examples of PE, PP, PVC etc.

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• The characteristic inter-unit linkages –CO.O–,
–CO.NH–, –HN–CO–NH–, and –O.CO–NH– are polar

Polarity of a polymer depend on:

• Polarity of constituent groups

• Symmetry of spatial arrangement

• Frequency of their occurrence along the chain

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 Secondary Structure
• The size and shape of an isolated single molecule

Configuration — Arrangement fixed by primary valence

bonds; can be altered only through the breaking or reforming
of chemical bond

Conformation — Arrangement established by rotation about

primary valence bonds

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 Structural regularity
I. Recurrence regularity
II. Stereoregularity
i. Diene Polymerization
1,2, and 1,4 additions
ii. Tacticity
Polymers of monosubstituted olefins (CH2-CHX)

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 Conformation
• Steric factors
• Amorphous or crystalline
• Solution state, molten state, or solid state

Planar zigzag – PE, PVC

Helix – PP, PS

Random coil---
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Molecular weight

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Molecular weight distribution

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 Tertiary structure - Secondary bonding forces
• Intermolecular forces in polymer aggregates

Cohesive energy density

(Total energy per unit volume needed to
separate all intermolecular contacts)

𝛥𝐸𝑣 𝑉𝐿 Molar energy of vaporization and molar volume of the liquid

(Clasius- Clapeyron equation)

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For liquids of low molecular weight, the energy necessary to separate
molecules is evaluated from heat of vaporization.

Polymers cannot be evaporated, hence CED of polymers is estimated by

dissolving in liquids of known CED

In the absence of strong interactions such as hydrogen bonding, a

polymer δ2 will dissolve in a solvent δ1, if

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 Crystalline and amorphous structure
Polymers when cooled from melt : Randomly coiled and entangled
chains- hard and glassy

When concentrated from dilute solution: Individual chains are folded and
packed to form 3D long range order

• Do not have the regular shapes of normal crystals

• Only certain clusters of chain segments are aligned to

form crystalline domains

• Much smaller in size

• Contain many imperfections

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 Crystallization tendency
Intermolecular bonding
Polar groups (Cl, CN, OH etc) : dipole-dipole interaction
eg of Nylon 6,6 and Nylon 7,7

Nylon 6,6

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 Structural regularity and proximity of chains
PE(135°C), PTFE
LLDPE and LDPE
Polymer chains containing –O-, -COO-, and –CONH- assumes
extended zig-zag conformation (highly crystallizable)

Polymer chains containing irregular groups are amorphous

cis-double bonds o- and m- phenylene groups

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 Tacticity- Stereoregularity displayed by monosubstituted vinyl polymers of
olefins

Isotactic and syndiotactic are rigid, crystallizable, high melting, and relatively
insoluble

Atactic are soft, low melting, easily soluble, and amorphous

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  Chain flexibility

• During crystallization, this alignment and uniform packing of chains are

opposed by thermal agitation, which tends to induce segmental, rotational
and vibrational motions

• Rapid conformational change due to ease of rotation around single bonds

occurs if (––CO–O–), (–O–CO–O–), and (–C–N–) etc are present

• If such groups are regular, the materials are crystallizable, and if they are
irregular they are amorphous, soft, and rubbery

• Cyclic structures in the backbone and polar group such as –SO2–, and –
CONH– drastically reduce flexibility and enhance crystallizability

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  Polarity
• Molecules whose backbone contains –O– units or with polar side groups (–CN, –Cl,
–F, or –NO2) exhibit polar bonding

• The dipole character of the C–O–C group produces polar forces between adjacent
chains and are stronger than van der Waals forces

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 Bulky substituents
• PP and PS has small
substituents – tacticity

• Polymethyl acrylate and PVAc

cannot crystallize even if they
are isotactic or syndio tactic

C O CH3 O C CH3

Chain branching decreases the percent

crystallinity, broaden the melting range,
and reduces average Tm

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 Morphology of crystalline polymers
• Fringed micelle model
Crystalline regions embedded randomly in a continuous amorphous matrix

• Morphology of crystalline polymers — that is, the size, shape, and

relative magnitude of crystallites — is rather complex and depends on
growth conditions such as solvent media, temperature, and growth rate

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1. Crystal structure of polymers
 Fully extended planar zigzag (trans conformation- lower
energy than gauche form)
Eg. PE; PVA; synd. PVC; 1,2 BR, polyamides etc
Polyethylene

• Unit cell is parallelopiped with rectangular

cross-section (orthorhombic)
• a≠b≠c

 Distorted planar zigzag conformation (due to steric

hindrance)- polyesters, polyisoprene, polychloroprene etc

Polyethylene terephthalate

• The conformation is a slight distortion of the planar

zigzag

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 Main chain rotation, assumes helical conformation- most isotactic
polymers and 1,1 disubstituted ethylenes

• Benzene ring nearly in plane of zigzag, main chain make slight

angle with planar zigzag.

Polypropylene

• Isotactic form has its backbone rotated regularly by 120° (in order to reach
lowest energy state) after each repeat unit (3 per turn)-monoclinic unit cell

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 Degree of crystallinity
Polymer is considered as a two phase system

Pm   Pc  (1)Pa

Pa  Pm
Degree of crystallinity, 
Pa  Pc
𝑃𝑚 Actual or measured intensive property of the polymer

(Material properties: Specific volume, specific heat, enthalpy, electrical

conductivity)

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 Morphology of polymers single crystal grown from solution

 Growth of single crystals requires crystallization from dilute

polymer solutions at high temperatures by cooling from above Tm

 Polymer in dilute solutions is regarded as isolated chains

 In aggregated state behaviour of the chains is largely influenced

by the proximity of neighbouring chains and secondary forces

 Therefore, orientation of chains is an interplay between entropy

and internal energy

 Morphology formed depends on type of polymer and growth

conditions
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• Lamellae: thin, flat platelets, 100-120 Å thick and several microns in
lateral dimensions

• Chain folding: molecules (1000- 10000 Å) are also oriented normal to

lamellar surface. Chains fold repeatedly on themselves

• Hollow pyramidal
The hollow pyramidal structure is due to the packing of the folded chains
in which successive planes of folded molecules are displaced from their
neighbors by an integral of repeat distances
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 Morphology of polymers crystallized from melt

• Polymer melts behaves like a highly viscous liquid- chains are tangled
up with neighboring chains

• i. Creation of stable nucleus brought about by ordering of chains in a

parallel array

• ii. Growth of crystallization region

• Chain entanglements hinder the diffusion of chains into suitable

orientation and thermal motions above melting disrupt growth of
nuclei (hence Tg<Tc<Tm)

• (Tm-10K) and (Tg+30K)

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 • Mostly they have spherulite structure.

• It’s an extremely complex spherical aggregate of lamellae ranging in

size from about 0.1μm to few mm in diameter

• Spherulites expand radially at a constant linear rate until the growth

fronts from neighboring spherulites impinge

Regular folded array and Switchboard model

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 Crystallinity and polymer properties
• Overall effect of semicrystalline nature of crystalline polymer depends
on the state of the amorphous phase or the temperature of use

NR vs PS

• Density • Optical clarity

• Hardness • Permeability
• Modulus
• Tensile strength
• Stiffness
• Melting point

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 Thermal transitions in polymers

• Polymers decompose rather than boiling

• Diffuse transition from solid to liquid state – depends on

polydispersity

• Molecular motion in polymers: thermal energy vs cohesive

forces

• Tg and Tm: drastic changes in physical properties

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Relative thermal responses of (a) simple molecules and
(b) polymers

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• Amorphous and semicrystalline polymers

• Tg- Lower limit of the use of rubber and the upper limit of
the use of an amorphous thermoplastic

• Tm, for polymers corresponds to the temperature at which

the last crystallite starts melting

• Unlike simple materials, the value of Tm depends on the

degree of crystallinity and size distribution of crystallites

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Changes in physical state due to changes in temperature and MW

(a) For amorphous polymer

(b) for semi-crystalline polymer

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 Specific volume–temperature curves

ABCD : For an amorphous polymer

ABEF : For a crystalline polymer 36
 Molecular motion and glass transition
• Intramolecular forces- primary valence bonds

• Intermolecular forces- secondary forces: thermal agitation

opposes it

• Thermal degradation occurs when the energy of vibration

exceeds the primary bonding between atoms

• Transition associated with Tm and Tg are related with

rotation and vibration of molecular chains

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 Theories of Glass transition
1. Kinetic Theory (Adam-Gibbs)

• Tg depends on rate of heating/cooling, hence a dynamic phenomenon

• It predicts that the value of Tg measured depends on the time scale of

the experiment in relation to that of the molecular motions arising from
the perturbation of the polymer system by temperature changes

• The kinetic theory defines Tg as the temperature at which the

relaxation time for the segmental motions in the main polymer chain is
of the same order of magnitude as the time scale of the experiment

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• Glassification- reaction involving the movement of chain segments
(kinetic units) between energy states

• For the movement of a chain segment from one energy state to another
to occur, a critical ―hole‖ or empty space must be available

• To create this hole, need to overcome cohesive forces of the

surrounding molecules and the potential energy barrier associated with
the rearrangement

• The temperature at which the number of holes of sufficient size is great

enough to permit flow is regarded as the Tg

• The kinetic theory provides quantitative information about the heat

capacities below and above the glass transition temperature

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2. Equilibrium theory (Gibbs and DiMarzio)

• Tg is considered as a second-order thermodynamic transition, which

has equilibrium properties

• Glass transition process is a consequence of the changes in

conformational entropy with temperature

• Reduced level in molecular reorganization observed near transition

temperature is attributed to the reduction in number of available
conformations

• The equilibrium conformational entropy becomes zero when a

thermodynamic second-order transition is reached ultimately

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• At Tg, time required for conformational changes becomes infinite

• Thereupon, the conformations are essentially ―frozen in‖ since the

time required for conformational changes becomes virtually infinite

• It successfully predicts the variation of Tg with molecular weight and

cross-link density, diluent content, and other variables

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3. Free Volume Theory (Williams, Landell, and Ferry)

• The free volume 𝑉𝑓 , is defined as the unoccupied space in a sample,

arising from the inefficient packing of disordered chains in the
amorphous regions of a polymer sample

• Free volume of a substance is the difference between its specific

volume, 𝑉, and the space actually occupied by the molecules, 𝑉0

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• The free-volume theory introduces free volume in the form of segment
size voids as a requirement for the onset of molecular motion

𝑽 = 𝑽𝟎 + 𝑽𝒇

𝑽𝟎 = 𝑽/ + 𝜶𝑮 𝑻
𝑉/ the volume of glass at absolute zero
𝛼𝐺 thermal expansion coefficient of the glass

• The free volume is a measure of the space available for the polymer to
undergo rotation and translation, and when the polymer is in the liquid
or rubber-like states the amount of free volume will increase with
temperature as the molecular motion increases

• Below Tg, free volume will remain constant since the chains have now
been immobilized and frozen in position, whereas the occupied volume
will alter because of the changing amplitude of thermal vibrations
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 Free volume fraction, f, at temperature T: (WLF)

𝑉𝑓
𝑓= = 𝑓𝐺 +𝛼𝑓 𝑇 − 𝑇𝑔
𝑉

Thermal coefficient of 𝑑𝑓 1 𝑑𝑉𝑓

expansion of free volume, 𝛼𝑓 = 𝛼l − 𝛼𝐺 = =
𝑑𝑇 𝑉𝑓 𝑑𝑇

𝛼l and 𝛼𝐺 thermal expansion coefficient above and below 𝑇𝑔 (melt and glass)

• For most amorphous polymers, the free volume fraction at Tg is found

to be a constant (0.025), further there is no reduction when cooled

• Amorphous polymers are supposed to become glassy when the free

volume becomes 2.5 % of the total volume

• Above Tg, there is increase in specific volume due solely to an

increase in free volume
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Comparison of theories of Tg

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 Factors affecting Tg
i. Chain flexibility:
Presence of links such as –CH2-CH2-, -Si-O-Si-, -CH2-O-CH2-

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Enhancement of Tg by Steric hindrance

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Effect of chain flexibility on Methacrylate series

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ii. Geometric factors:
PP vs PIB, PVC vs PVdCl

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iii. Interchain attractive forces (polarity)
Effect of CED

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 iv. Copolymerization

1. Isomorphous Systems
(Homogeneous Copolymers
or Compatible Polyblends) (line 1)

𝑇𝑔 = 𝑉1 𝑇𝑔1 + 𝑉2 𝑇𝑔2

2. Nonisomorphous Systems

a. Random or alternating
• Increased disorder resulting from the random or
alternating distribution of monomers enhances
free volume and consequently reduces Tg (line 2)
1 𝑊1 𝑊2 MMA/ACN
= +
𝑇𝑔 𝑇𝑔1 𝑇𝑔2 MMA/Styrene

Monomers involved in the copolymerization process can

introduce significant interaction between chains (line 3)
(eg. Methyl acrylate/Vinyldiene chloride) 51
 b. Block and graft copolymers (incompatible copolymers)

• Phase separation occurs

• One phase will be dispersed in a

continuous matrix of the other

• Two separate Tg values will be

observed, each corresponding to
the Tg of the homopolymer

Fig.: Polyblends of polystyrene (100) and 30/70 butadiene–styrene copolymer (0).

(Numbers on the curves are the weight percent of polystyrene in the blend)

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 v. Molecular Weight
• As the number of chain ends increases (which means a decrease in Mn), the
available free volume increases, and consequently there is a depression of Tg

𝑲 𝑻∞ Tg of polymer with
𝑻 𝒈 = 𝑻∞
𝒈 −
𝒈
𝑴𝒏 infinite molecular
weight

vi. Cross-Linking and Branching

𝟑. 𝟗 × 𝟏𝟎 𝟒
𝑻𝒈 − 𝑻𝟎 =
𝑴𝒄

𝑻𝟎 : Tg of uncross-linked polymer having same chemical composition as cross-linked polymer

𝑀𝑐 :𝑀𝑛 between cross-linked points

• For highly cross-linked systems like phenolics and epoxy resins, the glass
transition is virtually infinite
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vii. Crystallinity

viii. Plasticization
• Plasticizers function through a solvating action by increasing
intermolecular distance, thereby decreasing intermolecular forces

• Plasticizer molecule produces a small region in which the rotation of

adjacent chain segments becomes facilitated; thus increasing the
relaxation rate and reducing the Tg

w1, w2 weight percentages of polymer & plasticizer respectively

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 The crystalline melting point (Tm)
• For low-molecular-weight materials, melting represents a true first-order
thermodynamic transition characterized by discontinuities in the primary
thermodynamic variables of the system

• Melting occurs when the change in free energy of the process is zero

𝜟𝑮𝒎 = 𝜟𝑯𝒎 − 𝑻𝒎 𝜟𝑺𝒎 = 𝟎

𝜟𝑯𝒎
𝑻𝒎 =
𝜟𝑺𝒎

𝛥𝐻𝑚 Change in enthalpy during melting- Difference between cohesive

energy of molecules in the crystalline and liquid state
𝛥𝑆𝑚 Entropy change during melting - Change in order between two states

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• Large size of polymers and the existence of molecular weight
distribution lead to broadening of Tm

• The process of crystallization in polymers involves chain folding which

creates inherent defects in the resulting crystal. Consequently, the actual
Tm is lower than the ideal thermodynamic Tm

• Because of the macromolecular nature of polymers and the

conformational changes associated with melting, the process of melting
in polymer is more rate sensitive

• Any property whose values are different for the crystalline and
amorphous states provides a convenient method for measuring the
crystalline melting point

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 Factors affecting crystalline melting point
i. Intermolecular bonding

• The melting points approach that of

polyethylene as the spacing between
polar groups increases

• Enhanced flexibility resulting from the

presence of oxygen atoms in the
polyester chains considerably offsets the
weak polar bonding from ester linkages

• For the same number of chain atoms in

the repeat unit, polyureas, polyamides,
and polyurethanes have higher Tm than
PE, while polyesters have lower

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Group contribution to melting temperature

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Effect of Intermolecular Bonding on Tm

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ii. Effect of Structure

• The structural dependence of the crystalline melting temperature is essentially

the same as that for the glass transition temperature

• The only difference is the effect of structural regularity, which has a profound
influence on crystallizability of a polymer. Tg is virtually unaffected by
structural regularity

Tg/Tm (K) Eg.

~ 0.5 Symmetrical polymers PE, BR
~ 0.75 Unsymmetrical polymers PS, CR

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 iii. Chain flexibility
On melting, polymers with stiff backbones have lower conformational entropy changes

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iv. Copolymerization
• For an isomorphous system, the melting point will vary smoothly over the entire
composition range

• For a nonisomorphous system, 𝑇𝑚 of the copolymer (i.e., the reduction in the melting
point (𝑇𝑚0 ) of the homopolymer due to the addition of the second constituent) is given
by
1 1 𝑅
= − ln𝑥
𝑇𝑚 𝑇𝑚0 𝛥𝐻𝑚

𝛥𝐻𝑚 and 𝑥 are the heat of fusion and mole fraction of the homopolymer or
crystallizing (i.e., major) component

𝑇𝑚0 Reduction in the melting point of the homopolymer due to the addition of
the second constituent

• Block and graft copolymers with sufficiently long homopolymer chain sequences
crystallize and exhibit properties of both homopolymers and hence have two 𝑇𝑚 s

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