Adama Science and Technology University

CHAPTER 4
Morphology and Molecular weight of polymer
By

Yilkal.M (M.Sc)

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 Learning Objectives
 At the end of this chapter students be able to:
Understand the morphology( crystallinity) of polymers
Determine degree of crystallinity using different methods.
Understand factors affecting degree of crystallinity
Recognize thermal transition of polymer
Recognize the influence of molar mass( molecular weight) on
polymer properties.
Understand the relationship between molecular weight and
degree of polymerization .
Understand the significant of number-average (Mn) and
weight-average (Mw) molecular weight.
Understand nature of polydispersity.

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 Introduction
 Polymer morphology is the study of order within solid
macromolecular.
 The size and shape of polymers are intimately connected
to their properties.
 The shape of polymers is also intimately connected to the
size of the various units that comprise the macromolecule.
 Solid polymers differ from ordinary, low molecular-weight
compounds in the nature of their physical state or
morphology .

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 Conti…
 Polymers in the solid state tend to be composed of
 Crystalline
 Amorphous
 The terms crystalline and amorphous are used to indicate
the ordered and unordered polymer regions, respectively.
 Crystalline- the molecular structure forms regular order
with molecules.
 Amorphous- the polymer chains are not arranged in
ordered lines.
 Not forming regular order with molecules

Most polymers show simultaneously

the characteristics of both crystalline
and amorphous solid.

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 Crystallinity
 One of the most significant characteristics of polymer is
crystallinity or degree of structural order in polymer.
 When the macromolecular chains of a polymer samples
arranged in an orderly fashion is known as crystalline polymer.
 Crystalline impart the strength of the polymeric material.
 When the chain not arranged in ordered crystal and are
disordered, even through they are solid state, the polymers are
identified as amorphous polymer
 Amorphous region of the polymer contribute on the flexibility of
polymer
 In most case there is no fully crystalline polymers, therefore we
have semi-crystalline polymers, which are composed of both
amorphous and crystalline regions.
 The combination of crystalline and amorphous regions
providing a material that has a combination of flexibility and
strength.
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6
 Degree of Crystallinity
 Degree of crystallinity is the amount (% ) of material that
is structurally crystalline.
 Degree of crystallinity determine using a number of
methods such as.
 Density method
 X-ray diffraction method
 Infrared spectroscopy
 In using all these techniques for determination of degree
of crystallinity a certain assumption are made:
A. The polymer consists two separable phases-crystalline and
amorphous.
B. The properties of the phase are additive- the property of the
material is the sum of the properties of the phase

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 Density method
 The crystalline regions in the polymer have a higher
density than the non-crystalline amorphous regions.
 Problem 1.
 Derive an equation relating the degree of crystallinity of a
semi-crystalline polymer to the sample density and
densities of the crystalline and amorphous components.

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 Let vc= total volume of the crystalline components;
 Va = total volume of the amorphous components;
 v = total volume of the specimen;
 mc, ma and m are the corresponding masses and
 ρc, ρ a and ρ are the corresponding densities. Then

 V= vc + va equation 1
 m = mc + ma equation 2
 Or ρv= ρcvc + ρava equation 3
 Substituting va in Eq. 3 from Eq.1 and rearranging leads to

equation 4
 Where ɛC is the volume fraction of crystalline components.
 The mass fraction μC of the crystalline components is similarly
defined as:
equation 5
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  Finally combine Eq.4 and 5 then give us

 % of crystallinity = mass fraction (μC) *100

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 Example
 Estimate the fraction of crystalline material in a sample
of polyethylene of density 0.983g/cm3. Density of
amorphous polyethylene 0.866 g/cm3 and Density of
crystalline material 0.996 g/cm3 .

 More crystallinity: higher density, more strength, higher

resistance to dissolution and softening by heating.

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 X-ray diffraction method
 X-ray diffraction/scattering is used for polymers to
characterize them in terms of their crystalline and
amorphous states.
 X-ray diffraction is a powerful method of determining the
degree of crystallinity because it produces different
pattern by amorphous and crystalline region of polymers:
 Scattering from the crystalline regions gives relatively sharp peaks
compared to a broad ‘hump’ produced by scattering from
noncrystalline region.

Crystalline region

Amorphous region

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 In principle, degree of crystallinity can be
determined from relative areas under the
crystallline peaks and amorphous.

 Where Aa is the area under the amorphous peak and Ac

is the remaining area under the crystalline peaks.

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 Infra--red method
Infra
 Infrared(IR) spectroscopy is also employed to determine
crystallinity.
 The vibration of atoms detected by IR spectrometer are
affected by crystalline structure.
 The spectrum of crystallline regions appear at slightly
higher energy levels than do moving freely moving atoms
in the amorphous regions.
 For example IR spectrum of polypropylene

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 % of crystallinity is equals to wave length of
crystalline divided by wavelength of semi-
crystalline times 100.

 Calculate %crystallinity for PP the crystalline sensitive

band is 10.03μm and semi-crystalline sensitive band is
10.29 μm.

 % crystallinity= 10.03 μm/10.29*100=97.5%

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 High degrees of crystallinity are found in polymers within:
 Regular, compact structures
 Strong intermolecular forces, such as hydrogen bonds
and dipolar interactions.
 As the degree of crystallinity increases, the polymer
becomes more solid.
 Highly amorphous polymers are sometimes referred to as
glassy polymers.
 Lacking crystalline domains.
 They are weaker polymers, both in terms of their
greater flexibility and smaller mechanical strength.
 On heating, amorphous polymers are transformed from a
hard glassy state to a soft, flexible, rubbery state

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 Morphology
 Example: poly(ethylene terephthalate), PET can be
made with crystalline domains of 0% to 55%.
O O
O
O
n
Poly(ethylene terephthalate)
 Completely amorphous PET is formed by quickly cooling
the melt.
 PET with a low degree of crystallinity is used for plastic
beverage bottles.
 More crystallline PET formed by slow cooling
 PET with a high degree of crystallinity can be drawn into textile
fibers and tire cords.

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  Many polymers are a mixture of amorphous and
crystalline regions, but some are highly crystalline and
some are highly amorphous.

Some highly crystalline Some highly amorphous

polymers: polymers:
Polypropylene Poly(methyl methacrylate)
Syandiotactic polystyrene Atactic polystyrene
nylon Polycarbonate
Kevlar and Nomex Polyisoprene

Polyketones Polybutadiene

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 Why some polymers are highly crystalline and
some are highly amorphous?
 There are two important factors, polymer
structure and intermolecular forces.
Crystallinity and Polymer structure
 The structure of polymers affects their crystallinity,
if it is regular and orderly, it will pack into crystals
easily.
 Polyethylene is good example, It can be crystalline or
amorphous.
 Linear polyethylene is nearly 100% crystalline. But
the branched is highly amorphous.
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 Polyethylene


100% crystalline Highly amorphous

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 Polystyrene
 There are two kinds of polystyrene.
 There is atactic polystyrene, and there is syndiotactic
polystyrene.
 One is very crystalline and one is very amorphous.

Syndiotactic polystyrene Atactic polystyrene

Has a regular structure, Has irregular structure,
so it can pack in to crystal structures so it can't pack in to crystal structure
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 Order and disorder molecular chains
 Syndiotactic polystyrene is very orderly, with the
phenyl groups falling on alternating sides of the chain.
 means it can pack very easily into crystals.
 Syndiotactic polystyrene is very crystalline.
 Atactic polystyrene has no such order. The phenyl
groups come on any side of the chain without order.
 The chains can't pack very well.
 So atactic polystyrene is very amorphous.
 Other atactic polymers like poly(methyl methacrylate)
and poly(vinyl chloride) are also amorphous.
 Stereoregular polymers like isotactic polypropylene
and polytetrafluoroethylene are highly crystalline.
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Poly(ethylene terephthalate)
 The polar ester groups make for strong crystals.
 In addition, the aromatic rings like to stack together in an
orderly fashion, making the crystal even stronger.

The polar ester groups in poly(ethylene terephthalate)

hold the polyester into strong crystals

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Thermal Transitions in Polymers
 The term “transition” refers to a change of state induced by
changing the temperatures or pressure.
 Polymeric materials are characterized by two major types
of transition temperatures.
 Crystalline melting temperature Tm
 Glass transition temperature Tg

 Melt transition temperature (Tm):

 The temperature at which crystalline regions melt.
 As the degree of crystallinity increases, Tm increases.
 Glass transition temperature(Tg)
 The temperature at which a polymer undergoes a
transition from a hard glass to a rubbery solid.

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  At low temperatures:
 Most polymers are brittle and glassy since there is not
sufficient energy to encourage segmental chain
movement.
 As the temperature is increased, at some temperature there
is sufficient energy available to allow some chain mobility.

 For a polymer containing both amorphous and crystalline

portions or is only amorphous, the segmental chain
mobility for the amorphous segments is called glass
transition temperature (Tg).

 Because there is unoccupied volume in the amorphous

polymer structure, some segmental chain movement
occurs.
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  As the temperature is increased, there is sufficient
temperature to overcome the forces present in the
crystalline portion of the polymer allowing a breaking up
of the crystalline portion.
 This temperature is referred to Crystalline melting
transition temperature (Tm).

 Finally, as the temperature continues to rise,

 There is sufficient energy available to overcome the
primary bonds holding the polymer together and the
polymer decomposes at the “decomposition
temperature,” Td .

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 Amorphous polymers exhibit only a Tg while
Semi-crystalline polymers exhibit both, a Tg
and Tm
.

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 Factors Affecting Tg
 A number of factors that affect Tg of a polymer, including:
A. Chain flexibility
B. Molecular structure (steric effects)
C. Branching and crosslinking.

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 Chain Flexibility
 The flexibility of the chain is the most important factor
that influences the Tg of a polymer.
 If the chain is highly flexible, Tg will generally be low and
 if the chain is rigid, the Tg value will be high.
 The chain flexibility depends on the rotation or torsion of
skeletal bonds.
 Chains made up of bond sequences which are able to
rotate easily are flexible.
 polymers containing –(–CH2 –CH2 –)–, –(–CH2 –O–CH2–)–,
or –(–Si–O–Si–)– links will have low values of Tg.
 For example, poly(dimethyl siloxane), which has Si–O
bonds in the backbone chain, Tg values known (-1230C).

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 The value of Tg increases by insertion of groups that
stiffen the chain by impeding rotation, since more thermal
energy is required to set the chain motion.
 Particularly effective in this respect is the p-phenylene
ring.

 Example

Polyethylene
Tg = -930C Poly(xylylene)
Tg =2800C

poly(ethylene oxide)
Tg = -67 0C Poly(phenylene oxide)
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Tg =830C
 Problem
 Account for the differences in glass transition temperatures for the
following pairs of isomeric polymers.
A. Poly(but-1-ene) (-240C) and poly(but-2-ene) ( -730C).

Tg= -240C Tg= -730C

The long and bulky side group makes The side groups are shorter, this makes
rotation difficult and higher Tg value rotation easier and lower Tg value
B. Poly(ethylene oxide) ( -67 0C) and poly(vinyl alcohol) (=850C).

Tg= -670C Tg= 850C

The backbone chain is flexible, so Steric effect of OH group restrict rotation
rotation easy and lower Tg value and polarity also increase lateral force and
31 leads higher Tg value
C. Poly(methyl acrylate) (60C) and poly(vinyl acetate) (280C)

Tg= 60C Tg= 280C

The bulky group hindered rotation The bulky part of the side group is
causing to increase Tg value farther form the chain, making the
rotation more difficult
D. Poly(ethyl acrylate) ( -240C) and poly(methyl methacrylate) (1050C)

Tg= 1050C
Tg= -240C
The presence of two side groups
The side group is longer but makes the rotation more
32 flexible so rotation is easier difficult, leading to higher Tg
 Reading assignment:
But not include in your final exam

Molecular Weight

Molecular weight (Mw)

Mass of a mole of chains

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 Introduction
 The size of macromolecules that gives them their unique
and useful properties.
 Generally, the larger the polymer, the higher the molecular
weight.
 Determination of molecular weights is very important
because as the chain length is the controlling factor in
determining solubility, elasticity, processability and
mechanical properties.

• Low molar mass substances (oligomers) : m. p. ↑

with MW ↑.
・High molar mass substances (polymers) : m.
p. constant with MW↑ but, rheological
properties : (ex.) melt viscosity ↑ with MW ↑

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 Molecular weight of polymer
A. Some natural polymer (monodisperse):
 Monodisperse polymers are molecules that have the same
molecular weights.
 polymers containing only one chain length, such as nucleic
acids, and as proteins.
 Nearly all natural polymers are monodisperse
B. Synthetic polymers(polydisperse):
 polydisperse is Polymers consisting of different chains of
lengths.
 Polymerization reactions, both synthetic and natural (but
not for all natural) lead to polymers with heterogeneous
molecular weights.
 The molecular weights of polymers are distributed

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 Many physical properties are related to molecular weight.
 Some example of physical properties of polymers are :
Tensile strength, Melt viscosity and Impact strength

Melt viscosity increases rapidly as the

chain length increases, and more
energy is required for the processing
and fabrication of large molecules.

commercial polymer range is a range where

acceptable physical properties are present
but the energy required to cause the
polymers to flow for processing is acceptable.

Relationship between molecular weight and polymer physical properties.

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 Molecular Weight
 The average molecular weight (M) of a polymer is the
product of the average number of repeat units or mers
expressed as DP times the molecular weight for the
repeating unit.
 For Example: Polyethylene (PE) with an average
repeating unit 100, calculate the average molecular
weight.
 Simply the number of repeating units(DP) are 100 and
the molecular weight of repeating unit is 28 amu
 So average molecular weight (M) = 100*28= 2800amu

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 Molecular Weight
 The molecular weight of a polymer is of prime importance
in the polymer synthesis and application
 Chemists usually use the term molecular weight to describe
the size of a molecule.
 End Groups-end groups constitute an insignificant fraction
of the mass of high molecular weight polymer and so
usually have negligible effect on polymer properties of
major interest.
 Example Calculate the end group content (weight fraction)
of polystyrene of molecular weight 150,000, assuming that
phenyl (C6H5-) groups constitute both the end groups of an
average polymer molecule.
 Answer:
Molar mass of phenyl group= 6*12 +5*1= 77 g /mol

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Wt. fraction of end groups=
 Degree of Polymerization(DP)
 The number of repeating units that constitute of a polymer
molecule.
 The relation between degree of polymerization and
molecular weight(M )of the same macromolecule is given by:
 for homoplymer M= (DP)MO
where Mo is the formula weight of the repeating unit
 for copolymer
 based on weighted average of mass of all repeating unites (Mio,
Mjo, Mko… etc) in the polymer chain:
 ……………………………………………………………….
 Exercise
 If a polymer chain has a molecular weight 280, 000, how
many units does it contains?
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 Example
 Styrene monomer containing 0.02% (by wt.) benzoyl
peroxide initiator was reacted until all the initiator was
consumed. If at this stage 22% of the monomer
remained unreacted, calculate the average degree of
polymerization of the polymer formed. Assume 100%
efficiency of the initiator (i.e., all initiator molecules are
actually consumed in polymer formation) and
termination of chain radicals by coupling alone. 1000g
amount of styrene used.

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41
 Average Molecular Weight
 Small molecules, such as benzene and glucose, have
exact structures.
 Each molecule of benzene has six carbon atoms and six
hydrogen atoms.
 By comparison, each molecule of poly-1,4-phenylene may
have a differing number of benzene-derived units.
 Single molecules (single chains) of PE may vary in the
number of ethylene units, the extent and frequency of
branching, the distribution of branching, and the length of
branching.
 A few polymers, such as nucleic acids and many
proteins, consist of molecules, individual polymer
chains that must not vary, so they have a precise
molecular weight.
 The molecular weights of polymeric materials is
dependent on the various chain lengths present in the
mixture.
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 There are several statistically described averages dependent
on how we calculate the final average molecular weight
from the chain lengths of the individual molecules within
the polymer sample.
1. Number average-molecular weight(Mn)
2. Weight average molecular weight(Mw)
3. Z-average molecular weight(Mz)
4. Viscosity average molecular weight(Mv)

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 1. Number-Average Molecular Weight(Mn)
 Count the number of chains of a particular MW (Ni
moles),multiply each number by the MW (Mi), sum these
values and divided by the total number of polymer
chains.
 The Number Average Molecular Weight ( Mn ) is the
total weight of the polymer Molecules divided by the
total number of polymer molecules.

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 Important terms and symbol
 ni : mole fraction of species i (that is, molecules of same
size with molecular weight Mi) in a sample
Ni : moles of species i
N : total of all Ni’s
wi : weight fraction of species i
Wi : weight of species i
W : sum of all Wi

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 Mn determines the polymer colligative properties and
tensile strength.
 Mn determined directly by:
 End-group analysis
 Osmometry
 ebullioscopy,(boiling point elevation)
 cryoscopy( freezing point depression)

 Example.1: Assume that we have one molecule with

molecular weight 100 and one molecule with molecular
weight 1000.

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 Example 2
 The polymer Sample has different chains, Calculate number
average MW.
Chain Moles Chain
Present, Ni Mass, MiNi
MW, Mi
120 0.10 12g
140 0.20 28
140 0.10 14
160 0.30 48
Solution
160 0.40 64
180 0.20 36
200 0.10 20
47 Sum 1.4 222
 The number-average degree of polymerization, DPn ,is defined
as

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 2. Weight average Molecular weight:
 Weight average-molecular weight(molar mass) is the sum of
the product of molar mass of each fraction(Mi) multiplied
by its weight fraction(wi).

 Mw determined by directly light scattering.

 weight-average degree of polymerization, DPw ,is defined as

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 Example
Calculate weight averaged Molecular Weight of the given data
Chain Moles Chain Mi2 NiMi2
MW, Mi Present Mass,
, Ni MiNi
120 0.10 12g 14400 1440
140 0.20 28 19600 3920
140 0.10 14 19600 1960
140
160 0.30 48 25600 7680
160 0.40 64 25600 10240
180 0.20 36 32400 6480
200 0.10 20 40000 4000
222 35720

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 Polydispersity index(PDI)
 Polydispersity index(heterogeneity index) is the ration of
weight average molecular weight to number-average
molecular weight.
PDI= Mw/ Mn
 Polydispersity index of monodisperse polymer is 1
because Mn=Mw
 In monodisperse polymer all species in a polymer sample
have the same molecular weight.
 However, monodisperse polymer not found in synthetic
polymers and it is always true that Mz > Mw > Mn

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 Exercise
 A sample of poly(vinyl chloride) is composed on according
to the following fractional distribution :

A. Calculate Mn , Mw and Mz
B. Find PDI
Solution

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  PDI= Mw/Mn= 19110/16100= 1.19

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 Example:
Here are:
10 chains of 100 molecular weight
20 chains of 500 molecular weight
40 chains of 1000 molecular weight
5 chains of 10000 molecular weight

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 3. Z-average molecular weight
 Z-average molecular weight (molar mass) is

Z = zentrifuge /centrifuge

 Melt elasticity is more closely related to the third moment

known as the z-average molecular weight.
 Mz is determined by using either light-scattering
photometry or ultracentrifugation.
 Example.1: Assume that we have one molecule with
molecular weight 1 and one molecule with molecular
weight 1000.

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 4. Viscosity-average molecular weight(Mv)

 where a is the exponent in Staudinger-Mark-Houwinks

equation : [η] = k*Ma ([η] = intrinsic viscosity).
 For a flexible polymer in a good solvent, a ≈ 0.7
 Mv is determined by viscosity measurements.
 Example: With the same two molecules as before:

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 Schematic illustration of molecular weight distributions.

•Monodisperse distribution:
•Mn= Mw= Mz= Mv
•Polydisperse distribution:
•Mn< mv<Mw<Mz

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