PSE

Introduction to Polymer
Science & Engineering
04/11/16
Polymers in Daily Life
We start the day with toothbrush

We wear natural and synthetic polymer clothing
Get milk in plastic pouches
Drink tea and coffee in plastic cups
Have coke and pepsi in plastic bottles
Drive to work in cars, buses, and scooters with rubber tires
Bring groceries in plastic bags
Throw waste in plastic baskets and trash bags
Go to bed on foamed urethane mattresses
Cozy up with acrylic blankets
Use nylon ropes for tying
Cook with teflon coated frying pans
Use plastic boards for ski and water surfing
Paints for the house
04/11/16
High-Tech Polymers
Carbon-epoxy polymer composites used in
space shuttles and aeroplanes
UHMWPE used for knee and hip replacement
joints
Polyanilines and polysilanes used in optical
storage data and for optical transmission
Artificial heart
Insulation for electronics and electrical needs
Liquid crystal Kevlar fibers for bullet-proof vests
04/11/16
Biological Polymers
Biological Polymers collagen, proteins,
muscles, sinews, DNA, genes, chromosomes
that constitute our bodies and intellect
Polysaccharides starch, cellulose, gums
Proteins gelatin, albumin, enzymes, insulin
Nucleic Acids RNA, DNA
Form the very foundation of life and intelligence
Provide much of the food on which man exists
04/11/16
Raw Material Source for Polymers

Monomers required for polymerization are
derived from cracking of petroleum stocks
Latest raw material source from
agricultural sources poly (lactic acid)
Biodegradable plastics
Cellophane, a clear packaging film, is
based on wood cellulose
04/11/16
Polymers
A water molecule has only three atoms, one
oxygen and two hydrogen, whereas a typical
polymer molecule contains hundreds, or more
typically, thousands of atoms
A polymer is created when a large number of
identical repeating monomer units are joined
together to make a single large polymer
molecule
From the Greek polys meaning many, and
meros meaning parts. The mer is the
smallest repetitive unit in a polymer
04/11/16
Polymers
A polymer is a large molecule built up by
the repetition of small simple chemical
units
In some cases, the repetition is linear,
much as a chain is built up from its links
In other cases, the chains are branched or
interconnected to form three dimensional
networks
04/11/16
Carbon Atom
Most polymers are based on the carbon
atom. This is because carbon has these
unique abilities:
Form four bonds with other atoms
Joins to itself to form long chains and other
shapes
04/11/16
Polymerization
Polymerization describes the chemical
reaction that joins monomer units together
to form complex polymeric structures
Ethylene polymerizes to polyethylene
Propylene polymerizes to polypropylene
Styrene polymerizes to polystryrene
Vinyl chloride polymerizes to poly(vinyl
chloride)
04/11/16
The Rise of Polymer Science

Acceptance of the existence of macromolecules
came in the 1920s due to the efforts of
Staudinger (Nobel Prize in 1953).
Staudinger proposed long chain formulas for
polystyrene, rubber and polyoxymethylene
Flory elucidates the mechanism for chain
reaction polymerization (Nobel Prize 1974) and
clarified that ends of long chain molecules
consist of normal, satisfied valence structures.
04/11/16
10
Early Industrial Developments

Charles Goodyear crosslinked natural rubber with
elemental sulphur (vulcanization) in 1840 to make a
hard, tough, elastic material used primarily for tires
Hyatt commercialized cellulose nitrate plasticized with
camphor, Celluloid, which could be formed into a wide
variety of useful products by the application of heat and
pressure. Cellophane was the first clear plastic
wrapping material used.
Baekelands Bakelite (phenol-formaldehyde resin) in
1907 was the first synthetic plastic commercialized
04/11/16
11
History of Polymers
In 1940, Plunkett at DuPont accidentally discovered
polytetrafluroethylene (Teflon), used in non-stick frying
pans as coating material
In 1953, Karl Ziegler, was able to produce linear high
molecular weight (HDPE) polyethylene under ordinary
conditions of temperature and pressure
Using Zieglers coordination catalysts, Natta polymerized
highly crystalline stereospecific polypropylene in 1953
(Ziegler-Natta got Nobel Prize in 1963)
Pierre de Gennes for his work in physics of liquid
crystals, scaling concepts in polymer physics, and
dynamics of ordered to disorder transitions got the Nobel
Prize in 2000
04/11/16
12
Degree of Polymerization and

Molecular Weight
The length of the polymer chain is specified by
the number of repeat units in the chain. This is
called the degree of polymerization (DP)
The molecular weight of the polymer is the
product of the molecular weight of the repeat
unit (monomer) and the DP
Most high polymers useful for plastics,
rubbers,and fibers have molecular weights
between 10,000 and 1,000,000.
04/11/16
13
Molecular Weight
Monomer: Vinyl Chloride CH2=CHCl

Molecular Weight of Monomer = 62.5
Degree of Polymerization = 1000
Molecular weight of Polymer = 62.5 x
1000 = 62,500
04/11/16
14
Molecular Weight
For any polymer, as molecular weight
goes up:
Melting point increases
Tensile strength, stiffness, and hardness,
increases
Barrier properties will be higher (packaging)
Solubility in solvents decreases
04/11/16
15
Measurement of Molecular Weight

and Size
light scattering
solution viscosity
gel permeation chromatography
colligative properties vapor pressure
lowering; boiling point elevation, freezing
point depression, osmotic pressure
04/11/16
16
Plastics
In the molten state, polymer chains move
freely, though with enormous viscosity,
past one another if a force is applied
This is the principle used in the fabrication
of most polymeric articles
Chief example of the plasticity from which
the name plastics is derived
04/11/16
17
04/11/16
18
04/11/16
19
04/11/16
20
04/11/16
21
04/11/16
22
Thermoplastic and Thermoset

Polymers
The monomer units can simply join with each other to
form long chains as in a thermoplastic, or they can crosslink between the chains in a three dimensional pattern
resulting in a thermoset plastic.
Thermoplastics become fluid with the application of heat,
and can be softened, solidified, and resoftened a number
of times, allowing process waste and recycling of spent
material
In a thermoset (crosslinked) polymer, the chains are
interconnected and can never actually become free of
one another and flow. Accordingly, thermosets will
normally have a much higher potential use temperature
and will finally degrade rather than melt.
04/11/16
23
Molecule structures
Controlled by
chemistry
and
processing.
04/11/16
24
04/11/16
25
04/11/16
26
Comparison
04/11/16
27
Amorphous and Crystalline

Polymers
Polymer chains fit together in various ways.
Highly ordered molecular arrangements are said
to be crystalline, while completely random
arrangements are amorphous
Spaghetti (noodles) dumped on a plate would be
amorphous, but if it was combed out into
reasonably conforming bands, it would be
crystalline
The greater the ordering, the greater the degree
of crystallinity
04/11/16
28
04/11/16
29
Amorphous
Example:
Polycarbonate
04/11/16
30
Crystalline
Example: Polyethylene
04/11/16
31
Crystals
04/11/16
32
Chains assume folded

chain conformation
These collect into

lamellar crystallite
04/11/16
33
04/11/16
34
Two crystalline morphologies

(collections of lamellar crystalites)
Spherulite (no shear)
Row Nucleated (shear )

Shish-kebab
04/11/16
35
Preparation of Polyethylene
Polymerizing ethylene gas under high pressure
(1000-3000 atms) and high temperatures (250C)
in the presence of metal catalysts
Ethylene molecules link up in long chains of 5050,000 units, transforming ethylene gas to a
while crystalline solid
The product of this reaction is extruded as a hot
ribbon, cooled, and chopped into pellets
04/11/16
36
Low-Density (Branched)
Polyethylene
First produced in the Imperial Chemical Industries Ltd.
lab in England
Ethylene was subjected to 1400 atm pressure at 170C
Traces of oxygen caused polymerization to take place
High polymers of ethylene are made commercially at
pressures between 1000-3000 atm at temperature upto
250C.
Besides oxygen, peroxides, hydroperoxides, and azo
compounds used as initiators
Ethylene (b.p. -104C) made from thermal (steam) and
catalytic cracking of hydrocarbons
04/11/16
37
High Density (Linear) Polyethylene

Coordination polymerization of ethylene
utilizes a catalyst prepared as colloidal
dispersion by reacting an aluminium alkyl
and TiCl4 in heptane.
Ethylene is added to the reaction vessel
under slight pressure, at 50-75C.
Polymer forms as a powder or granules,
insoluble in the reaction mixture, filtered
and centrifuged off, washed and dried.
04/11/16
38
Polyethylene Chain Branching

High-Density Polyethylene (HDPE)- linear
chains; density 0.941-0.965; chains can be
closely packed; bottles, pails, tubs, containers,
drums
Low-Density Polyethylene (LDPE)- highly
branched chains; density 0.910-0.925; chains
cannot pack closely together; food packaging
film; non-food packaging film
Linear Low-Density Polyethylene (LLDPE)
branched, but the branches are short; stretchwrap and shrink-wrap films
04/11/16
39
04/11/16
40
04/11/16
41
04/11/16
42
HDPE Versus LDPE

Highly linear polyethylene chains with very little
side branching can be packed closely together
in a dense structure and result in HDPE
Highly branched polyethylene molecular chains
cannot pack closely together and hence produce
LDPE
A third variant linear-low-density polyethylene
(LLDPE) has short side branches
04/11/16
43
HDPE Versus LDPE

HDPEs are polyethylenes with densities
between 0.941 and 0.959.
LDPEs are polyethylenes with densities
between 0.910 and 0.925.
LLDPE is actually a polyethylene copolymer.
Including 10-20%of hexane, butene, octene or
similar monomers along with the ethylene
monomer introduces deliberate branching during
polymerization.
04/11/16
44
HDPE Versus LDPE

HDPE with its long linear chains is predisposed
to high levels of crystallinity (>90%).
LDPE with its many randomly arranged
branches has an irregular geometry and tends to
be amorphous (crystallinity <50%).
Crystalline polymers like HDPE are as a rule
translucent or opaque, while amorphous
polymers such as LDPE have higher clarity.
04/11/16
45
HDPE Versus LDPE

HDPE with its stiffness and high tensile strength
is used for piping, tubing, and a whole range of
containers, articles and vessels.
LDPE due to its flexibility, resistance for moisture
and chemicals, is generally used as a film or foil
for packaging containers, and electrical
insulation material as sheathing for wires and
cables.
LLDPE yields exceptionally tough films providing
excellent hot tack and heat seal strength for
packaging and wrapping applications.
04/11/16
46
Nonpolar nature of polyethylene

Difficult to print to bond on PE surface
Treat surface with an oxidizing flame in
order to create surface polarity
Treat surface with corona discharge (a
high voltage electrical discharge that in
turn generates high levels of ozone, a
powerful oxidizing agent)
04/11/16
47
Property
LDPE
HDPE
LLDPE
UHMWPE
Preparation
Gas phase polymerization;

benzoyl peroxide initiator;
250C; 100 atms; powder is
formed
TiCl4 and aluminium alkyl

dispersion in heptane;
ethylene gas introduced;
PE centrifuged; filtered,
dried
Heptane or octane added

as 10% conc.with ethylene
introduces small
branches
TiCl4 and aluminium alkyl

dispersion in heptane;
ethylene gas introduced;
PE centrifuged; filtered,
dried
Density
0.91
0.95
0.92
0.96
Crystallinity (%)
<50
90
75
95
Molecular Weight
100,000-500,000
250,000-600,000
200,000 450,000
1-5 million
Branching
Highly branched
linear
Small branches
linear
Packing
Not dense
Very dense
Good packing
Very dense and tight

packing
Applications
Electrical insulation, films,

foils, thin bags
Containers, pails, vessels,

buckets, thick bags,
piping, tubing
Wrapping; shrink wrap;

heat wrap
Knee-joint and hip joint

replacement; strong
fibers, dental floss
Clarity
Higher
Lower
High
Low
Softening Point
80-100C
120C
108C
130C
Tensile Strength
5-10 mPa
20-40 mPa
10 mPa
200 mPa
Elongation (%)
500
20
200
10
Gas Barrier
Lower
Higher
Low
Higher
Grease Resistance
Lower
Higher
Low
Higher
04/11/16
48
Polymer Classification:
Chemical Microstructure
Homopolymers: polymers derived from a single monomer (can be
linear, branched or crosslinked).
poly(ethylene), poly(butadiene).
Random copolymers: two monomers randomly distributed in chain.
AABAAABBABAABBA
poly(acrylonitrile-ran-butadiene)
Alternating copolymers: two monomers incorporated sequentially
ABABABABABABABAB
poly(styrene-alt-maleic anhydride)
Block copolymers: linear arrangement of blocks of high mol weight
AAAAAAAAAAABBBBBBBBBBBBBBBAAAAAAAA
polystyrene-block-polybutadiene-block-polystyrene or poly(styrene-b-butadiene-b-styrene)
Graft copolymers: differing backbone and side-chain monomers
poly(isobutylene-graft-butadiene)
04/11/16
49
04/11/16
50
Chemical Class
A popular classification scheme amongst chemists is based on polymer functionality.
O
Polyesters:
poly(ethylene terephthalate) - Dacron
C O
H O
Polyamides:
poly(caprolactam) - nylon 6
Urethanes:
carbamate linkages through reaction
of diisocyanates and diols.
N C
H O
N C O
Another (!) classification scheme, again favoured by chemists is based on differences between the
polymer and constituent monomer(s).
Condensation polymers: synthesis involves elimination of some small molecule (H 2O in the
preparation of nylon)
Addition polymer: formed without loss of a small molecule i.e. ethylene polymerization to
generate poly(ethylene)
04/11/16
Additive Classification:
Terminology
It is relatively rare for an article to be made from polymer alone. Most are polymer compounds,
consisting of a mixture of polymer and various additives. These include:
Fillers: solid additives used to modify physical properties.
Dilution - talc
Reinforcing - carbon black in tires
Toughening - rubber in ABS plastic
Plasticizers: non-volatile solvents added to improve flexibility
Dialkyl phthalates in poly(vinylchloride)
Colourants: additives used to change product aesthetics
Pigments - soluble colourants

Dyestuffs - insoluble additives
Antioxidants: compounds that reduce polymer degradation through
intervention in free radical reactions
04/11/16
Classification of Polymer
Applications
1. Elastomers
static uses: gaskets, hoses
dynamic uses: tires, sports equipment
2. Adhesives
structural: epoxy resins
non-structural: pressure-sensitive tapes, hot-melt adhesives
3. Coatings
lacquers, paints
4. Plastics
semi-crystalline: automobile exterior
amorphous: packaging films, plexi-glass
5. Fibres
natural/modified: cotton, rayon
synthetic: carpeting, apparel
04/11/16
53
04/11/16
54
04/11/16
55
Isomerism/Polymer Tacticity
Isotactic
Syndiotactic
Random
04/11/16
56
Polymer Categories: Price

Commodity
<Rs. 100/kg
Engineering
Rs. 150-500/kg
Specialty
> Rs 500/kg
04/11/16
57
Natural Product Polymers
04/11/16
58
04/11/16
59
04/11/16
60
04/11/16
61
Thermal Behavior of Polymers

In a substance where all molecules are small
and have similar molecular weight, properties
such as melting point are sharply defined.
Water, for example goes from a solid state to a
liquid state at exactly 0oC (32oF) at I atm.
Polymer molecules are large, entangled, having
different molecular weights, and restricted in
their movements, so do not have a sharp
transition point and there is no clearly visible
phase change.
04/11/16
62

Glass transition temperature (Tg) is the
temperature at which a polymeric material
changes from a rigid solid state to a soft, rubbery,
or elastic state.
Tg is related to the point where there is sufficient
energy (i.e. temperature) for segments of the
polymer molecules to move with respect to one
another.
As the temperature increases, the plastic will
enter a melt phase at the melt transition point Tm.
04/11/16
63
04/11/16
64
04/11/16
65
Stress-strain behavior of Polymers
04/11/16
66
Stress-Strain Behavior of Polymers

A reinforced or crystallizable rubber exhibits a
relative low value of breaking stress, but high
elongation
A ductile plastic like polyethylene exhibits
yielding, drawing, and at high elongations some
strengthening due to orientation
A brittle plastic such as polystyrene does not
yield much and breaks at low elongation
A fiber exhibits the highest strength, high
stiffness, and low elongation
04/11/16
67
Orientation
When a polymer melt cools without any external forces
acting on it, the orientation of molecules tends to be
random.
To orient polymer molecules permanently, the material is
physically stretched at a temperature below its glass
transition.
The general effect of aligning polymer chains is increase
in tensile strength, barrier qualities, and melting
temperature
Orientation can be monoaxial or biaxial. Unoriented
polypropylene film is soft, has high elongation and low
tensile strength. Biaxially oriented film is stiff, has low
elongation, and its tensile strength increases three or
four fold
04/11/16
68
04/11/16
69
Polymer Properties
The elements that make up the polymer molecule carbon,

hydrogen, chlorine, benzene ring
The polymer molecules polarity (unequal sharing of electrons;
molecule has positive and negative pole) influences melting
point, coefficient of friction, solubility, barrier properties,
adhesiveness
The size or molecular weight of the molecule melting point,
stiffness, solubility, viscosity
The molecules shape how large numbers of them will fit
together degree of crystallinity, clarity, melting point
The polymers thermal history every thermoplastic needs to be
melted in order to get it into a form that can be shaped thermal
history changes the plastics performance characteristics
Mechanical history how it flowed in the molten state and how it
was stressed when cold
04/11/16
70
Polymer Synthesis
Preparation of Polymers from monomers
can be by:
1. Addition Polymerization
Free radical polymerization
Cationic polymerization
Anionic polymerization
Coordination polymerization
Ring Opening polymerization
2. Condensation Polymerization
04/11/16
71
Addition (chain reaction)

Polymerization
Under correct conditions of temperature and pressure,
and with the aid of catalysts and promotors, the
monomers simply add onto themselves like links in a
chain
It involves chain reactions in which the chain carrier may
be an ion or a reactive substance with one unpaired
electron called a free radical, or a cation, anion, or
coordination complex
The free radical is capable of reacting to open the double
bond and add to it, with an electron remaining unpaired.
In a very short time, many more monomers add to the
growing chain (polyethylene, polypropylene)
04/11/16
72
Addition Polymerization
Three Steps:
1. Initiation
2. Propagation
3. Termination
04/11/16
73
04/11/16
74
04/11/16
75
Propagation
The newly generated active species
adds to another monomer, in the same
manner as the initiation step.
Monomers simply add onto themselves
like links in a chain
04/11/16
76
04/11/16
77
Termination
The termination step is one where the
growing chain with active species reacts
with other growing chain or by
spontaneous decomposition of the active
site.
In free radical polymerization, termination
follows either coupling or
disproportionation mechanism.
04/11/16
78
Termination
In cationic polymerization, termination occurs by
anion attachment or by proton abstraction.
In anionic polymerization, termination does not
take place by itself and the living chains are
made to terminate, e.g. by adding ammonia.
In coordination polymerization, termination is by
an active hydrogen compound; by transfer with
monomers; and by spontaneous internal
transfer.
04/11/16
79
04/11/16
80
Ring Opening Polymerization

Some polymers can be prepared by reactions involving
ring opening. Few typical examples of monomers for
ring-scission polymerization are cyclic ethers, cyclic
anhydrides.
The polymerization of ethylene oxide leading to a high
molecular weight polyethylene oxide (PEO) can be
accomplished by ring opening polymerization.
The monomer is added to form a chain (chain
polymerization), the polymer growth is through step wise
addition, and thus molecular weight of the polymer
increases during the course of reaction.
04/11/16
81
04/11/16
82
04/11/16
83
Autoacceleration
Trommsdorff effect
In radical polymerization we speak about:

1)
low conversion, i.e. polymer chains are in dilute solution (no contact among
chains)
2)
intermediate conversion, i.e. the area in between low and high conversion
3)
high conversion, i.e. chains are getting highly entangled; kp decreases.
Somewhere in the intermediate conversion regime:

*
polymer chains loose mobility.
*
Termination rate decreases
*
Radical concentration increases
*
Rate of polymerization increases
*
Molar mass increases
This effect is called: gel effect, Trommsdorff effect,or auto-acceleration
In the polymerization of MMA this occurs at relatively low conversion.
04/11/16
84
Condensation Polymerization
Step-growth polymerization refers to a type
of polymerization mechanism in which bi-functional or
multifunctional monomers react to form first dimers,
then trimers, longer oligomers and eventually long
chain polymers. Many naturally occurring and some synthetic
polymers are produced by step-growth polymerization,
e.g. polyesters, polyamides, polyurethanes, etc. Due to the
nature of the polymerization mechanism, a high extent of
reaction is required to achieve high molecular weight. The
easiest way to visualize the mechanism of a step-growth
polymerization is a group of people reaching out to hold their
hands to form a human chain each person has two hands
(= reactive sites). There also is the possibility to have more
than two reactive sites on a monomer: In this case branched
polymers are produced.
04/11/16
85
Step-Growth Polymerization
04/11/16
86
In condensation, or step-reaction
polymerization, two reactive monomers
join together with the release (i.e.
condensation) of a molecule of water.
Examples:
Polyester PET (polyethylene terephthalate)
Terephthalic acid + ethylene glycol PET
Polyamide Nylon
Adipic acid + hexamethylene diamine PA
04/11/16
87
04/11/16
88
Condensation Reaction
04/11/16
89
04/11/16
90
Classes of step-growth polymers - Polyester
Polyester has high glass transition temperature

Tg and high melting point Tm, good mechanical
properties to about 175 C, good resistance to
solvent and chemicals. It can exist as fibers and
films. The former is used in garments, felts, tire
cords, etc. The latter appears in magnetic
recording tape and high grade films.
04/11/16
91
Polyamide
Polyamide (nylon) has good balance of
properties: high strength, good elasticity
and abrasion resistance, good toughness,
favorable solvent resistance. The
applications of polyamide include: rope,
belting, fiber cloths, thread, substitute for
metal in bearings, jackets on electrical
wire.
.
04/11/16
92
Polyurethane
Polyurethane can exist as elastomers with
good abrasion resistance, hardness, good
resistance to grease and good elasticity,
as fibers with excellent rebound, as
coatings with good resistance to solvent
attack and abrasion and as foams with
good strength, good rebound and high
impact strength
04/11/16
93
Polyurea
Polyurea shows high Tg, fair resistance to
greases, oils, and solvents. It can be used
in truck bed liners, bridge coating, caulk
and decorative designs.
04/11/16
94
Polysiloxane
Polysiloxane are available in a wide range
of physical statesfrom liquids to
greases, waxes, resins, and rubbers. Uses
of this material are as antifoam and
release agents, gaskets, seals, cable and
wire insulation, hot liquids and gas
conduits, etc.
04/11/16
95
Polycarbonate
Polycarbonates are transparent, selfextinguishing materials. They possess
properties like crystalline thermoplasticity,
high impact strength, good thermal and
oxidative stability. They can be used in
machinery, auto-industry, and medical
applications. For example, the cockpit
canopy of F-22 Raptor is made of high
optical quality polycarbonate.
04/11/16
96
Polysulfides
Polysulfides have outstanding oil and
solvent resistance, good gas
impermeability, good resistance to aging
and ozone. However, it smells bad, and it
shows low tensile strength as well as poor
heat resistance. It can be used in gasoline
hoses, gaskets and places that require
solvent resistance and gas resistance.
04/11/16
97
Polyether
Polyether shows good thermoplastic
behavior, water solubility, generally good
mechanical properties, moderate strength
and stiffness. It is applied in sizing for
cotton and synthetic fibers, stabilizers for
adhesives, binders, and film formers in
pharmaceuticals.
04/11/16
98
Phenol-Formaldehyde
Phenol formaldehyde resin (Bakelite) have good heat
resistance, dimensional stability as well as good
resistance to most solvents. It also shows
good dielectric properties. This material is typically used
in molding applications, electrical, radio, televisions and
automotive parts where their good dielectric properties
are of use. Some other uses include: impregnating
paper, varnishes, decorative laminates for wall
coverings.
04/11/16
99
04/11/16
100
04/11/16
101
Microwaveable Plastics
Safety aspects:
They must not further react
They must not decompose into the food
They must not leach out components into the food.
Safe Microwaveable plastics are:
Type I polyethylene terephthalate (PET)
Type 2 High density Polyethylene (HDPE)
Type 5 Polypropylene (PP)
Unsafe plastics are:
Type 3 polyvinyl alcohol (PVC)
Type 4 low density polyethylene (LDPE)
Type 6 polystyrene (PS)
Type 7 polycarbonate , plasticizers leach out, like bisphenol-A.
04/11/16
102
Microwaveable Rubbers
Two important criteria polarity, conductivity of the rubber

Polar rubbers which can be used in the microwave are :
Nitrile
Chloroprene
Hypolen
Fluorinated Elastomers
Acrylic Rubber
Polyurethanes
Ethylene-Propylene Rubber
Ethylene Propylene Diene (EPDM)
The other option is to add some fillers and promoters and additives like carbon black,
silica, zinc oxide, diethylene glycol to nonpolar rubber compounds to absorb
microwave energy.
04/11/16
103
Phase Techniques in
Polycondensation
The polycondensation involves the
reactions of the functional groups and
therefore the reactants need to be in the
fluid phase.
This can be achieved either by melting the
reacting monomers (melt
polycondensation) or by dissolving them in
a suitable inert common solvent (solution
polymerization).
04/11/16
104
Phase Techniques in
Polycondensation
A third technique is called interfacial
polycondensation.
This technique uses the solutions of the
two monomers prepared separately in two
solvents immiscible with each other.
When these two solutions are brought in
contact, the polycondensation reaction
begins at the interface separating the
liquids.
04/11/16
105
Kinetics of Polycondensation
A simple relation, called the Carouthers
equation, exists between the average
degree of polymerization DP of the
polycondensation polymer at time t, and
the extent of reaction p.
DP = 1/ (1-p)
04/11/16
106
Question: What is the molecular weight of
a polymer prepared by the self
polycondensation of OH--COOH if 99.50
of the functional groups react?
04/11/16
107
Answer: Repeat unit (O--CO)n

p=0.995; DP = 1/(1-p) = 200
Molecular weight of repeat unit is
O--CO = O + C6H4 + CO
=16 + 72+ 4+ 12+ 16 = 120
Molecular weight of polymer = 120 x DP
=120 x 200 = 24,000 gmol-1
04/11/16
108
Free Radical PolymerizationInitiation

The initiator generates free radicals as the
active species through its homolytic
thermal decomposition.
A typical redox system is that of ferrous
ion and hydrogen peroxide.
Another widely used redox system is of
persulfate with thiosulfate or biosulfite as
reducing agents.
04/11/16
109
04/11/16
110
The Chain Transfer

Often the growing chain terminates before
it fully grows by interaction with a small
molecule, say RH, in such a way that a
portion of the small molecule terminates
the active chain and at the same time
produces a new radical R.
The chain transfer reaction can be shown
as follows:
----M* + RH ----MH + R*
04/11/16
111
The Chain Transfer

The chain transfer can be done by the monomer
itself, through solvent, from initiation, from
initiator, or from polymer.
It can also be intentionally done by adding
substances called chain transfer agents or chain
modifiers.
The chain transfer during the polymerization
leads to low molecular weight polymers
(sometimes desirable, at other times
undesirable)
04/11/16
112
Termination terminology
Chain growth stops by bimolecular reaction of two
growing radicals: termination
A terminator: another free radical
Forms a stable molecule with n mer units
Recombination: the termination step
Combination:
*Mi + *Mj Mi+j
Disproportionation:
*Mi + *Mj Mi + Mj
Obtaining a monomer like double bond
Hydrogen Abstraction: obtaining a hydrogen atom with
unpaired electron
04/11/16
113
Termination
Termination Growth of chain stops.
Combination Two growing chains collide.
Disproportionation A hydrogen atom is
added to the end of a growing chain.
04/11/16
114
Cationic Polymerization - Initiation

Cationic polymerization involves initiators
which produce a cationic species that
interacts with the monomer.
Initiators used include Lewis acids such as
BF3, AlCl3, etc.
Protonic acids like sulfuric acid, perchloric
acid, phosphoric acid also act as initiators.
04/11/16
115
04/11/16
116
Anionic Polymerization - Initiation

Anionic polymerization uses initiators
which produce anionic species.
Organoalkali compounds like butyl lithium,
electron transfer reagents like
disodiumnaphthalene complex, and
NaNH2 are common initiators for anionic
polymerization.
04/11/16
117
04/11/16
118
Coordination Polymerization
The reactive species in a coordination
polymerization is a coordination complex.
Ziegler-Natta polymerization is a particular
case.
These catalysts involve a variety of
transition metal complexes. These
complexes are usually based on Ti, V, or
Cr type metals and organometallic
compounds like triethyl aluminium.
04/11/16
119
Unsaturated Polyester Resins Formulation
43 lbs of phthalic anhydride

19 lbs of maleic anhydride
38 lbs of propylene glycol
Total 100 lbs
To this 100 lbs, formulator will add about 70
lbs of styrene for crosslinking
Typically, around 100-300 lbs of glass-fiber
filler will be added, depending upon end
use
04/11/16
120
Polymerization
The acid and glycol components of the polyester
resin are mixed in a resin kettle
Polymerized by step reaction to molecular
weight of 1000-5000 (highly viscous liquid)
After cooling, mixture is thinned down to
pourable liquid by addition of the monomer
Inhibitor such as hydroquinone is then added to
prevent premature polymerization
When kept cool, the mixture is stable for months
to years
04/11/16
121
Curing
Cure is begun by adding an initiator, usually an organic
peroxide, such as benzoyl peroxide, or a hydroperoxide
Promotors and acclerators like cobalt naphthalene or
alkyl mercaptans are used to promote the decomposition
of the initiator at room temperature, and thus rapid lowtemperature curing
Cure takes place in two stages. The initial formation of a
soft gel is followed by rapid polymerization
The heat evolved can lead to quite high temperatures in
large masses of resins
04/11/16
122
Polyester Resins Fabrication

Laminating
Molding
04/11/16
123
Laminating
Separate piles of reinforcing material are
coated or impregnated with resin and
pressed together until cured to a single
reinforced structure
04/11/16
124
Molding
Contact molding - A single mold is used;
reinforcing material is placed on the mold,
impregnated with resin, and allowed to cure in
air
Bag molding bag or blanket is used to apply
low pressure to the open surface of the material
Spray-up techniques resin and sometimes
chopped glass are sprayed onto the mold
surface
04/11/16
125
Properties of Unsaturated Polyester

Resins
Ease of handling
Rapid curing with no volatiles evolved
Light colour
Dimensional stability
Good physical and electrical properties
04/11/16
126
Applications of glass-reinforced
polyester resins
Boat hulls
Passenger car parts and bodies
Truck bodies
Luggage
Chairs
Fishing rods
Missile and radome uses
04/11/16
127
04/11/16
128
Oil and Gas

The cost of oil and gas have
risen significantly over the
last few years.
Sustainability is increasingly
driving both corporate and
personal decision making.
Alternatives to using oil or
natural gas exist or are
being developed today.
04/11/16
129
Production of Polymers
Feedstock (Carbon Source)

(such as Natural Gas, Oil, Corn, Soybeans, Sugar Cane)
Monomer
(such as Ethylene, Propylene, Lactic Acid)
Polymer
(such as Polyethylene, Polypropylene, Polylactic acid)
Package
(such as Bottle or Pouch)
04/11/16
130
Bio-based and Bio-degradable

Bio-Based or Bio-Sourced means that the
product has been made from a biological (living)
or renewable source, such as corn or sugar
cane.
Bio-Degradable means the product may be
broken down by other living organisms, such as
bacteria, that exist in nature.
Being bio-based does not mean a material is
bio-degradable. Being bio-degradable does not
mean a material is bio-based.
04/11/16
131
04/11/16
132
04/11/16
133
04/11/16
134
04/11/16
135
04/11/16
136
04/11/16
137
04/11/16
138
Applications
Performance
Fit for use in numerous applications
Clarity and optics
Form and stiffness provide opportunity to downgauge
UV Stable
Printability
Limited heat stability (105 F)
Emotional: Appeal to Consumer
Makes them feel good about purchase decision
Plant origins
Environmental
Made from plants
Purchased renewable energy credits
New disposal/recovery options
04/11/16
139
04/11/16
140
04/11/16
141
04/11/16
142
04/11/16
143
04/11/16
144
04/11/16
145
04/11/16
146
04/11/16
147
CoPolymers
A polymer that is built from one type of
monomer is a homopolymer.
CoPolymers contain two different
monomer types, and terpolymers contain
three monomer types.
CoPolymers bring together the favorable
properties of two distinctly different
polymers.
04/11/16
148
CoPolymers
Alternating Copolymer has two monomers
joined in alternating order:
ABABABABAB
Random Copolymer has no particular
order:
AABABBAABAB
Block CoPolymer has monomers in
specified blocked groupings:
AAABBBAAABBB
04/11/16
149
CoPolymers
Graft CoPolymers:
AAAAAAAAAAA
B
B
B
B
B
B
B
B
04/11/16
150
04/11/16
151
04/11/16
152
Orientation
When a polymer melt cools without any external forces
acting on it, the orientation of molecules tends to be
random.
To orient polymer molecules permanently, the material is
physically stretched at a temperature below its glass
transition.
The general effect of aligning polymer chains is increase
in tensile strength, barrier qualities, and melting
temperature
Orientation can be monoaxial or biaxial. Unoriented
polypropylene film is soft, has high elongation and low
tensile strength. Biaxially oriented film is stiff, has low
elongation, and its tensile strength increases three or
four fold
04/11/16
153
04/11/16
154
04/11/16
155
04/11/16
156
Isotactic
Syndiotactic
Random
04/11/16
157
Polystyrene
Benzene ring, or phenol group:
Cheap, clear plastic

drink cups
04/11/16
158
Polystyrene
Styrene (vinyl benzene) is made from benzene
and ethylene
Ethylene is passed into liquid benzene under
pressure, in the presence of aluminum chloride
catalyst
The resulting ethylbenzene is dehydrogenated to
styrene by passing it over an iron oxide or
magnesium oxide catalyst at 600C
The styrene is then refined by distillation
04/11/16
159
Polymerization of Styrene
Most polystyrene is made by suspension
polymerization or polymerization in bulk
Bulk polymerization starts in a
prepolymerizer, a small stirred vessel
styrene is polymerized (with a peroxide
initiator) until the reaction mixture is
concentrated (30% polymer)
04/11/16
160
Polymerization of Styrene Cont.

The syrupy mixture then enters a cylindrical
tower (40 ft long x 15 ft diameter)
By cooling the upper part of the tower and
heating the lower part, polymerization is
controlled to prevent runaways
Pure molten polymer is obtained at the bottom.
The melt is discharged through spinnerets or
into an extruder producing small diameter rod
that is chopped, after cooling, into short lengths
to provide the finished molding powder
04/11/16
161
Polystyrene Properties
Clear
Transparent
Easily coloured
Easily fabricated
Linear polymer
Amorphous
Atatic product
04/11/16
162
High-Impact Polystyrene (HIPS)

HIPS is a polystyrene copolymer that has
been modified with elastomeric molecules
such as butadiene to form a material with
significantly improved impact qualities
04/11/16
163
Expanded Polystyrene (EPS)

EPS formed by incorporating a blowing
agent with the PS.
Blowing agents (pentane, isopentane,
chlorinated fluorocarbons) are liquids that
boil away to form gases at about the
softening point of PS.
When heated, the expanding gases give a
cellular structure to the PS
04/11/16
164
Molded EPS
A measured charge of PS beads along
with blowing agent is placed into a mold
and steam is injected to heat both the PS
and the blowing agent.
The blowing agent gases cause the heatsoftened PS to expand and conform to the
mold shape
Used to make cups, food trays,
containers, insulating materials
04/11/16
165
Polystyrene applications
Polystyrene/EPS/, is used in home insulation, as
a packaging material, for many cushioning and
insulation foam packaging applications.
It is also used for sound insulation and thermal
insulation of buildings.
Its many uses include electrical and thermal
insulation, translucent window panels, storage
window panels, storage-battery cases, and toilet
articles
04/11/16
166
Polymerization techniques
Homogeneous systems
Bulk polymerization
Solution polymerization
Heterogeneous systems
Suspension polymerization
Emulsion polymerization
Precipitation polymerization
Polymerization in solid state
Polymerization in the gas phase
04/11/16
167
04/11/16
168
Bulk Polymerization
The polymerization reaction is carried out
within the monomer itself.
The reaction is catalyzed by additives or
under the influence of heat or light.
Polymer is obtained as a powdery porous
solid.
The polymer formed is usually pure
Examples vinyl chloride, vinyl acetate,
and acrylic esters
04/11/16
169
04/11/16
170
Bulk polymerization
Polymerization of the undiluted monomer. Viscosity increases
dramatically during conversion. Heat removal and hot spots
Advantages
Disadvantages
* Pure products * heat control
* Simple equipment
* dangerous
* No organic solvents * molecular weights
very disperse
Applications
Polymers through step reactions (nylon 6)
PMMA-plates
04/11/16
171
Solution Polymerization
When both the monomer and the polymer
produced are soluble in a suitable solvent,
the polymerization reaction is carried out
with the monomer in solution.
Solution polymerization is mainly applied
when solutions of polymers are required
(for ready made use) for technical
applications, e.g. as lacquers, paints,
adhesives.
04/11/16
172
Solution polymerization
Monomer dissolved in solvent, formed polymer stays
dissolved. Depending on concentration of monomer the
solution does not increase in viscosity.
Advantages
* Product sometimes
directly usable
* Controlled heat
release
Disadvantages
* Contamination
with solvent
* Chain transfer to
solvent
* Recycling solvent
Applications
Acrylic coating, fibre spinning, film casting
04/11/16
173
04/11/16
174
Precipitation Polymerization
In such a polymerization reaction, the monomer
is soluble in the solvent, and the polymer
precipitates out as a result of polymerization
(polymer being insoluble in solvent).
The so precipitated polymer can be separated in
the form of a gel or powder by centrifugation or
simple filtration.
Polyethylene, polyvinyl esters, polyacrylic esters
are obtained commercially with hydrocarbons as
solvents. Polyacryonitrile is prepared using
water as solvent.
04/11/16
175
Suspension Polymerization
The monomer containing initiator, modifier etc. is
dispersed in a solvent (generally water) by
vigorous stirring.
For a stable suspension of monomer in the
solvent, some stabilizers are added.
The polymerization takes place within the
dispersed (or suspended) monomer particles and
the agglomeration of which is prevented by
stabilizer.
After the reaction is completed, the polymer is
separated by centrifugation or filtration, washed,
and dried.
04/11/16
176
Suspension polymerization
Water insoluble monomers are dispersed in water.
Initiator dissolved in monomer.
Stabilization of droplets/polymer particles with nonmicelle forming emulsifiers like polyvinylalcohol or Nacarboxymethylcellulose.
Equivalent to bulk polymerization,
small droplets dispersed in water.
Product can easily be separated,
particles 0.01-1mm.
Pore sizes can be controlled by adding a combination of
solvent (swelling agent) and non-solvent.
Viscosity does not change much.
04/11/16
177
Suspension Polymerization
Advantages
Disadvantages
* Heat control simple * Contamination with
* Product directly
stabilizing agent
usable
* Coagulation possible
* Easy handling
Applications
Ion-exchange resins, polystyrene foam, PVC
04/11/16
178
04/11/16
179
04/11/16
180
04/11/16
181
04/11/16
182
04/11/16
183
Emulsion Polymerization
The liquid monomer is dispersed in an
insoluble liquid, which in turn gives an
emulsion (usually in water).
So the monomer in water emulsion,
containing catalyst and stabilized by
emulsifying agents (e.g. by surface active
agents), is then used as the polymerizing
mixture.
04/11/16
184
Polymerization takes place within the surfactant
micelles (size about 10 nm) which grow in size
at the expense of the dispersed monomer
droplets (size about 1000 nm).
In the end, a latex (or a polymer colloid) with
dispersed polymer (size about 100 nm) is left.
The polymer is then isolated by evaporation of
water in spray dryer, or by coagulation of the
polymer latex, filtration and drying.
04/11/16
185
04/11/16
186
A micelle forming emulsifier is used.
Initiator is water soluble.
The formed latex particles are much smaller
than suspension particles (0.05-2 m).
Kinetics differ considerable from other
techniques.
Polymer is formed within the micelles
and not in the monomer droplets.
04/11/16
187
Advantages
Disadvantages
* Low viscosity even * Contamination of
at high solid contents
products with additives
* Independent control
* More complicated
of rate and molecular weight in case of water
soluble
monomers
* Direct application of
complete reactor contents
04/11/16
188
04/11/16
189
04/11/16
190
04/11/16
191
04/11/16
192
04/11/16
193
04/11/16
194
04/11/16
195
04/11/16
196
04/11/16
197
04/11/16
198
04/11/16
199
Solid State Polymerization

Solid State Polymerization (SSP) is a process in which the
polymer chain lengths are increased by heat in the absence of
oxygen and water, by means of either vacuum or purging with
an inert gas to drive off the by-products of reactions. The
reaction is driven by temperature, pressure, and the diffusion
of by-products from the interior of the pellet to the surface.
SSP is an important step frequently used after meltpolymerization for the purpose of enhancing the mechanical
and rheological properties of polymers before injection blow
molding or extruding. The SSP technique is widely applied in
industrial manufacture of bottle-grade PET, films, and superior
industrial fibers.
04/11/16
200
Solid State Polymerization

Higher molecular weights may be reached by Solid State
Polymerization (SSP) at temperatures between the glass
transition and the onset of melting. Polycondensation
progresses through chain end reactions in the amorphous
phase of the semicrystalline polymer, which in most cases is
in the form of flakes (mean diameter>1.0 mm) or powder
(mean diameter<100 m); reaction by-products are removed
by application of vacuum or through convection caused by
passing an inert gas. The advantages of SSP include low
operating temperatures, which restrain side reactions and
thermal degradation of the product, while requiring
inexpensive equipment, and uncomplicated and
environmentally sound procedures. Disadvantages of SSP
focus on low reaction rates, compared to melt phase
polymerization, and possible solid particle processability
problems arising from sintering.
04/11/16
201
Polymerization techniques
Sometimes for one monomer several
techniques of polymerizing are available.
Choice of a specific technique depends on a
number of factors:
Kinetic / mechanistic factors related to chain
length, chain composition
Technological factors e.g. heat removal, reaction
rate, viscosity of the reaction mixture,
morphology of the product
Economic factors; production costs,
environmental aspects, purification steps etc.
04/11/16
202
Step-growth polymerization refers to a type
of polymerization mechanism in which bi-functional or
multifunctional monomers react to form first dimers, then trimers,
longer oligomers and eventually long chain polymers.
Many naturally occurring and some synthetic polymers are produced
by step-growth polymerization,
e.g. polyesters, polyamides, polyurethanes, etc.
Due to the nature of the polymerization mechanism, a high extent of
reaction is required to achieve high molecular weight.
The easiest way to visualize the mechanism of a step-growth
polymerization is a group of people reaching out to hold their hands
to form a human chain each person has two hands (= reactive
sites).
There also is the possibility to have more than two reactive sites on a
monomer: In this case branched polymers are produced.
04/11/16
203
Step-Growth Polymerization
04/11/16
204
Microwaveable Plastics
Safety aspects:
They must not further react
They must not decompose into the food
They must not leach out components into the food.
Safe Microwaveable plastics are:
Type I polyethylene terephthalate (PET)
Type 2 High density Polyethylene (HDPE)
Type 5 Polypropylene (PP)
Unsafe plastics are:
Type 3 polyvinyl alcohol (PVC)
Type 4 low density polyethylene (LDPE)
Type 6 polystyrene (PS)
Type 7 polycarbonate , plasticizers leach out, like bisphenol-A.
04/11/16
205
Microwaveable Rubbers
Two important criteria polarity, conductivity of the rubber

Polar rubbers which can be used in the microwave are :
Nitrile
Chloroprene
Hypolen
Fluorinated Elastomers
Acrylic Rubber
Polyurethanes
Ethylene-Propylene Rubber
Ethylene Propylene Diene (EPDM)
The other option is to add some fillers and promoters and additives like carbon black,
silica, zinc oxide, diethylene glycol to nonpolar rubber compounds to absorb
microwave energy.
04/11/16
206
Classes of step-growth polymers - Polyester
Polyester has high glass transition temperature

Tg and high melting point Tm, good mechanical
properties to about 175 C, good resistance to
solvent and chemicals. It can exist as fibers and
films. The former is used in garments, felts, tire
cords, etc. The latter appears in magnetic
recording tape and high grade films.
04/11/16
207
Polyamide
Polyamide (nylon) has good balance of
properties: high strength, good elasticity
and abrasion resistance, good toughness,
favorable solvent resistance. The
applications of polyamide include: rope,
belting, fiber cloths, thread, substitute for
metal in bearings, jackets on electrical
wire.
.
04/11/16
208
Polyurethane
Polyurethane can exist as elastomers with
good abrasion resistance, hardness, good
resistance to grease and good elasticity,
as fibers with excellent rebound, as
coatings with good resistance to solvent
attack and abrasion and as foams with
good strength, good rebound and high
impact strength
04/11/16
209
Polyurea
Polyurea shows high Tg, fair resistance to
greases, oils, and solvents. It can be used
in truck bed liners, bridge coating, caulk
and decorative designs.
04/11/16
210
Polysiloxane
Polysiloxane are available in a wide range
of physical statesfrom liquids to
greases, waxes, resins, and rubbers. Uses
of this material are as antifoam and
release agents, gaskets, seals, cable and
wire insulation, hot liquids and gas
conduits, etc.
04/11/16
211
Polycarbonate
Polycarbonates are transparent, selfextinguishing materials. They possess
properties like crystalline thermoplasticity,
high impact strength, good thermal and
oxidative stability. They can be used in
machinery, auto-industry, and medical
applications. For example, the cockpit
canopy of F-22 Raptor is made of high
optical quality polycarbonate.
04/11/16
212
Polysulfides
Polysulfides have outstanding oil and
solvent resistance, good gas
impermeability, good resistance to aging
and ozone. However, it smells bad, and it
shows low tensile strength as well as poor
heat resistance. It can be used in gasoline
hoses, gaskets and places that require
solvent resistance and gas resistance.
04/11/16
213
Polyether
Polyether shows good thermoplastic
behavior, water solubility, generally good
mechanical properties, moderate strength
and stiffness. It is applied in sizing for
cotton and synthetic fibers, stabilizers for
adhesives, binders, and film formers in
pharmaceuticals.
04/11/16
214
Phenol-Formaldehyde
Phenol formaldehyde resin (Bakelite) have good heat
resistance, dimensional stability as well as good
resistance to most solvents. It also shows
good dielectric properties. This material is typically used
in molding applications, electrical, radio, televisions and
automotive parts where their good dielectric properties
are of use. Some other uses include: impregnating
paper, varnishes, decorative laminates for wall
coverings.
04/11/16
215
Design Project
Develop a polymer compound and processing method for a component of your
choice.
1. Define engineering and aesthetic qualities.
2. Identify synthesis route
3. Propose a compounding recipe that will satisfy these
requirements.
4. Recommend appropriate processing techniques for
manufacturing the product.
5. Evaluation of the product properties, tests
04/11/16
PSE Students 2014

CH002 Rohan Ahir contact lens
CH003 Paras Akbari medical catheter
CH005 Viraj Bhatti biodegradable
packaging
CH006 Parag Chauhan artificial joint
CH012 Arjun Desai high-performance
tire tread
CH013 Piyush Donda ropes
04/11/16
217
PSE 2014
CH014 Deep Doshi adhesive
CH015 Ankit Gamit stain resistant paint
CH017- Brijesh Gujarati biodegradable
sutures
CH021 Jatin Kajavadara sporting
equipment
CH022 Sharad Kajavadara clothing
04/11/16
218
PSE 2014
CH023 Jaydeep Kapadia automobile
panel
CH024 Gaurav Kavar Bottles
CH025 Archit Kedia Blister packages
CH026 Yatin Lad Luggage suitcase
CH027 Bhavesh Machhi chair
CH034 Ashish Parmar gasket
04/11/16
219
PSE 2014
CH037 Ashish Patel heart valves
CH038 Darpan Patel membrane for
dialysis
CH039 Gaurav Patel syringe
CH040 Harsh Patel bucket
CH041 Keval Patel car windshield
glass
CH046 Samir Patel garbage bag
04/11/16
220
PSE 2014
CH049 Sanjay Rabari petrol tank

CH050 Rahul Prasad bullet-proof glass
CH051 Nirav Raiyani insulation cable
CH053 Ravi Rana microwaveable
container
CH054 Bhavuk Shah goggles
CH057 Nisarg Shah surgical gloves
CH058 Romit Shah helmets
04/11/16
221
PSE 2014
CH060 Jatin Suthariya coat and pant
suit and tie
CH064 Vijay Vala toy
CH065 Khushal Vekariya toothbrush
04/11/16
222
Molecular Weight and Molecular

Weight Distribution
Molecular weight is a measure of chain
length.
Larger the molecular weight, longer is the
polymer chain.
There is a distribution in any finite sample
of polymer.
Thus the experimental measurement of
molecular weight gives only an average
value.
04/11/16
223
Molecular Weight:
Number Average
Weight Average
04/11/16
224
Find out the Number-average molecular weight , the Weight average molecular weight,
and Polydispersity from the distribution given below.
No.
1
2
3
Tota
l
04/11/16
Weight
10,000 g/mol
1,000 g/mol
100 g/mol
Number
10 mol
10 mol
80 mol
100 mol
225
04/11/16
226
Find out the Number-average molecular weight , the Weight average molecular weight,
and Polydispersity from the distribution given below.
No.
1
2
3
Tota
l
04/11/16
Weight
50,000 g/mol
5,000 g/mol
500 g/mol
Number
10 mol
50 mol
40 mol
100 mol
227
Polydispersity
The quantity Mw/Mn is a useful measure of
the breadth of the molecular weight
distribution curve.
Typical values of Mw/Mn are:
Hypothetical monodisperse polymer M w/Mn
= 1.0
Polymers made by addition polymerization
Mw/Mn = 1.5
04/11/16
228
Polydispersity
Polymers made by condensation polymerization
Mw/Mn = 2
High conversion vinyl polymers Mw/Mn = 2-5
Addition polymers made by coordinate
polymerization Mw/Mn = 8-30
Branched polymers Mw/Mn = 20-50
In any given polymer sample, wide distribution of
molecular weights, not just one molecular weight
(ie. not just one chain length)
04/11/16
229
Polydispersity
Because heavier molecules contribute
more to Mw than light ones, Mw is always
greater than Mn, except for a hypothetical
monodisperse polymer.
04/11/16
230
Determination of molecular weight
a. Absolute method :
mass spectrometry
colligative property
end group analysis
light scattering
ultracentrifugation.
b. Relative method : solution viscosity
c. Fractionation method : GPC
04/11/16
231
POLYMER CHEMISTRY
SOLUTION VISCOSITY
Solution viscosity is used as a measure of
polymer molecular weight. It is basically a
measure of the size or extension in space of
polymer molecules.
Measurement of solution viscosity is made by
comparing the efflux time required for a specific
volume of polymer solution to flow through a
capillary tube with the corresponding efflux time
of the solvent. Measurement at a series of
concentrations are made and extrapolation is
made at c=0.
04/11/16
232
FIGURE 2.8. Capillary viscometers : (A) Ubbelohde, and (B) Cannon-Fenske.
04/11/16
233
FUNCTIO
NALCHEMISTRY
PO LYMERS LAB
POLYMER
Nomenclature of Solution Viscosity

Relative viscosity: r = /o = t/to
Specific viscosity: sp = (-o)/o
Reduced viscosity: red = sp/c
Inherent viscosity: inh = (ln r)/c
Intrinsic viscosity: [] = (sp/c)c=0
04/11/16
234
Huggins Equation
Viscosity data as a function of
concentration are extrapolated to infinite
dilution
sp/c = [] + k[]2c
k is a constant for a series of polymers of
different molecular weights in a given
solvent
04/11/16
235
INTRINSIC VISCOSITY-empirical
correlation
[] = KMa
Where [] = intrinsic viscosity
M=molecular weight
K and a are constants determined from a double
logarithmic plot of intrinsic viscosity and molecular weight
04/11/16
236
TABLE 2.3. Representative Viscosity-Molecular Weight Constantsa

Polymer
Solvent
Polystyrene
(atactic)c
Cyclohexane
Cyclihexane
Benzene
Decalin
Polyethylene
(low pressure)
Poly(vinyl chloride)
Polybutadiene
98% cis-1,4, 2% 1,2
97% trans-1,4, 3% 1,2
Polyacrylonitrile
Benzyl
alcohol
Cyclohexano
ne
Toluene
Toluene
Poly(methyl methacrylate-co-DMFg
DMF
styrene)
30-70 mol%
71-29 mol%
Poly(ethylene terephthalate) 1Chlorobutane
Nylon 66
1Chlorobutane
a
Value taken from Ref. 4e. M-Cresol
b
See text for explanation of these
constants.
M-Cresol
c
Atactic defined in Chapter 3.
d
temperature.
e
Weight average.
f
Number average.
g 04/11/16
N,N-dimethylformamide.
Temperature,Molecular Weight
o
C
Range 10-4
35 d
8-42e
50
4-137e
25
3-61f
135
3-100e
155.4d
20
4-35e
7-13f
30
30
25
25
5-50f
5-16f
5-27e
3-100f
30
30
25
25
5-55e
4.18-81e
0.04-1.2f
1.4-5f
Kb 103
80
26.9
9.52
67.7
ab
0.50
0.599
0.74
0.67
156
13.7
0.50
1.0
30.5
29.4
16.6
39.2
0.725
0.753
0.81
0.75
17.6
24.9
0.77
240
0.67
0.63
0.95
0.61
237
POLYMER CHEMISTRY
2.4.1 Light Scattering

B. Light source
High pressure mercury lamp and laser light.
C. Limitation of molecular weight( ) : 104 107
FIGURE 2.7.
Schematic of a laser
light-scattering
photometer.
04/11/16
238
FUNCTIO
NALCHEMISTRY
PO LYMERS LAB
POLYMER
2.4 Measurement of Weight Average Molecular Weig

A. The intensity of scattered light or turbidity() is depend on following fa

a. size
b. concentration
c. polarizability
d. refractive index
e. angle
f. solvent and solute interaction
g. wavelength of the incident light
04/11/16
239
POLYMER CHEMISTRY

= HcMW
32
H= 3
No2(dn/dc)2
4No
Hc = 1 + 2A C
2
MP()
C : concentration
no: refractive index of the solvent
: wavelength of the incident light
No : Avogadro's number
dn/dc : specific refractive increment
P() : function of the angle,
A2 : second virial coefficient
Zimm plot (after Bruno Zimm) : double extrapolation of concentration
and angle to zero (Fig 2.6)
04/11/16
240
POLYMER CHEMISTRY
FIGURE 2.6. Zimm plot of light-scattering data.
Hc
1
Mw
C=0
Experimental
Extrapolated
sin2/2 + kc
04/11/16
241
FUNCTIO
NALCHEMISTRY
PO LYMERS LAB
POLYMER
04/11/16
242
04/11/16
243
04/11/16
244
FIGURE 2.2 Schematic representation of a membrane

osmometer.
04/11/16
245
2.3.2 Membrane Osmometry

A. According to van't Hoff equation
RT
)C=0 =
+ A2C
c
Mn
limitation of : 50,000 2,000,000

The major error arises from low-molecular-weight species diffusing
through the membrane.
FIGURE 2.3 Automatic membrane osmometer [Courtesy of Wescan Instruments
04/11/16
246
FIGURE 2.4. Plot of reduced osmotic pressure (/c) versus concentration (c).
/c
RT
Mn
Slope = A2
04/11/16
247
POLYMER CHEMISTRY
04/11/16
248
Cryoscopy and Ebulliometry

A. Freezing-point depression (Cryoscopy)
RT2
Tf
+ A2C
(
)C=0 =
Hf Mn
C
Tf : freezing-point depression,
C : the concentration in grams per cubic
centimeter
R : gas constant
T : freezing point
Hf: the latent heats of fusion
04/11/16
249
POLYMER CHEMISTRY
04/11/16
250

B. Boiling-point elevation (Ebulliometry)
RT2
Tb
+ A2C
(
)C=0 =
C
HvMn
Tb : boiling point elevation

H v : the latent heats of vaporization
We use thermistor to major temperature. (110-4 )
limitation of Mn : below 20,000
04/11/16
251
POLYMER CHEMISTRY
04/11/16
252
2.3.4 Vapor Pressure Osmometry

The measuring vapor pressure difference of solvent and solution
drops.
RT2
T = (
)m
100
solvent
: the heat of vaporization per gram of

m : molality

Calibration curve is needed to obtain molecular weight of polymer
sample
Standard material : Benzil
04/11/16
253
POLYMER CHEMISTRY
04/11/16
254
Molecular Weight Distribution

2.6.1 Gel Permeation Chromatography (GPC)
A. GPC or SEC (size exclusion chromatography)
a. GPC method is modified column chromatography.
b. Packing material: Poly(styrene-co-divinylbezene),
glass or silica bead swollen and porous surface.
c. Detector : RI, UV, IR detector, light scattering detector
d. Pumping and fraction collector system for elution.
e. By using standard (monodisperse polystyrene), we can obtain
04/11/16
255
POLYMER CHEMISTRY
Mn
04/11/16
256
04/11/16
257
04/11/16
258
04/11/16
259
FIGURE 2.9. Schematic representation of a gel permeation

chromatograph.
04/11/16
260
POLYMER CHEMISTRY
FIGURE 2.10. Typical gel permeation chromatogram. Dotted lines represent volu
Detector
response
04/11/16
Baseline
Elution volume (Vr) (counts)
261
POLYMER CHEMISTRY
FIGURE 2.11. Universal calibration for gel permeation chromatography. THF, tetra
Log([]M)
109
Polystyrene (linear)
Polystyrene (comb)
Polystyrene (star)
Heterograft copolyner
Poly (methyl methacrylate)
Poly (vinyl chloride)

Styrene-methyl methacrylate graft copolymer
Poly (phenyl siloxane) (ladder)
Polybutadiene
107
108
106
105
04/11/16
18
20
22
24
26
Elution volume ()5 ml counts, THF solvent)
28
30
262
POLYMER CHEMISTRY
FIGURE 2.12. Typical semilogarithmic calibration plot of molecular weight versus

retention volume.
Molecular weight (M)
106
105
104
103
Retention volume (Vr) (counts)
04/11/16
263
POLYMER CHEMISTRY
Polymer Categories: Price

Commodity
<Rs. 100/kg
Engineering
Rs. 150-500/kg
Specialty
> Rs 500/kg
04/11/16
264
Bacteria-Produced Polyesters
In 1982, Imperial Chemical Industries, Ltd. (ICI)
in England began product development on a
new type of thermoplastic polyester.
The polymer was to be manufactured by a largescale fermentation process not unlike the
brewing of beer.
In this case, it involved the production of the
polyester inside of the cells of bacteria grown in
high densities and containing as much as 90%
of their dry weight as polymer.
04/11/16
265
Biopol
The bacterium capable of performing this
feat was Wautersia eutropha, and the
commercial polyester was trade named
Biopol, now produced by Metabolix, Inc.
Biopol is a copolyester containing
randomly arranged mers of R-3hydroxybutyrate, HB, and R-3hydroxyvalerate, HV:
04/11/16
266
Biopol
04/11/16
267
The natural polymer in many species of bacteria is

poly(3-hydroxybutyrate).
The polymer serves as a reserve source of food for the
bacteria..
However, the above copolymer could be made by
feeding the bacteria a mixture of glucose and propionic
acid.
The composition of the copolymer can be controlled by
the diet fed to the bacteria, providing a convenient route
to controlling the melting temperature for better
processing.
04/11/16
268
In fact, it is now known that many species of

bacteria produce a range of polyesters, some
with fairly long side chains.
These copolymers are all 100% biodegradable,
since they are natural products.
The HB-HV copolymers can be melt processed
into a wide variety of consumer products
including plastics, films, and fibers.
As a special type of fiber, the copolymer
provides absorbable sutures for surgery.
04/11/16
269
Production
Bacteria actually produce the polymer,
much as humans make and store fat.
Normally, the bacteria use the polymer for
their own energy needs.
But the bacteria can be "harvested" before
using the polymer they've stored, and it
can be used by people.
04/11/16
270
Polymer Production
"You grow bacteria in vats, using the same
fermentation process that creates beer".
"You feed them sugar, oils, or starch, wait a few
days, then harvest the polymer grown inside the
bacteria."
Nuclear magnetic resonance spectrometer can
be used to determine the best harvest time and
to measure how much and what kind of polymer
the bacteria create.
04/11/16
271
Material Properties
Processability, impact strength and flexibility
improves with a higher percentage of valerate in
the material.
PHB is similar in its material properties to
polypropylene (PP), has a good resistance to
moisture and aroma barrier properties.
Polyhydroxybutyric acid synthesized from pure
PHB is relatively brittle and stiff.
PHB copolymers, which may include other fatty
acids such as beta-hydroxyvaleriate acid, may
be elastic.
04/11/16
272
Limitations
"Biodegradable plastics are already widely used
in Europe and Japan, because they're much
more environmentally conscious".
And although these polymers are more
expensive than traditional plastics, it's not price
that keeps them from the world market.
A law requiring companies to prove their
products decompose in any environment in
which they might be left "has made it virtually
impossible to market biodegradable products in
the USA."
04/11/16
273
Biodegradation
Fastest in anaerobic sewage and slowest in
seawater
Depends on temperature, light, moisture,
exposed surface area, pH and microbial activity
Degrading microbes colonize polymer surface
& secrete PHA depolymerases
PHA CO2 + H2O (aerobically)
PHA CO2 + H2O + CH4 (anaerobically)
04/11/16
274
Blood-Contacting Polymers
04/11/16
275
Polymers: Biomedical Applications

UHMWPE: acetabular caps in hip implants
and patellar surface of knee joints
HDPE used as pharmaceutical bottles,
fabrics
Others used as bags, pouches, tubes etc.
04/11/16
276

Polymethylmethacrylate (PMMA, lucite,
acrylic,plexiglas)
acrylics
transparency
tough
biocompatible
Used in dental restorations, membrane for

dialysis, ocular lenses, contact lenses, bone
cements
04/11/16
277

Polyvinylchloride (PVC)
Cl side chains
amorphous, hard and brittle due to Cl
metallic additives prevent thermal degradation
Used as blood and solution bags,

packaging, IV sets, dialysis devices,
catheter, bottles
04/11/16
278

Polypropylene (PP)
properties similar to HDPE
good fatigue resistance
Used as syringes, oxygenator membranes, sutures,

fabrics, vascular grafts
Polyesters (PE)
hydrophobic (beverage container PET)
molded into complex shapes
Used as vascular grafts, sutures, heart valves, catheter

housings
04/11/16
279

Polyurethanes
block copolymer structure
good mechanical properties
good biocompatibility
tubing, vascular grafts, pacemaker lead

insulation, heart assist balloon pumps
04/11/16
280
04/11/16
281
Paints
Paint is any liquid, liquefiable, or mastic
composition which after application to a
substrate in a thin layer is converted to an
opaque solid film.
It is most commonly used to protect, color
or provide texture to objects.
04/11/16
282
Paint Components
Pigment
Binder
Solvent
Additives
04/11/16
283
Colors
Salts of Lead white, yellow

Fe and Mg Red
Oxides of cobalt Blue
Copper Green
Iron Oxides yellow, red or brown
Chromium oxide green
Lead oxide red
Chromates of lead, zinc, nickel yellow,
orange
04/11/16
284
Binder, vehicle, or resins

The binder, commonly referred to as the
vehicle, is the actual film forming
component of paint.
It is the only component that must be
present;
other components listed are included
optionally, depending on the desired
properties of the cured film
04/11/16
285

The binder imparts adhesion, binds the
pigments together, and strongly influences
such properties as gloss potential, exterior
durability, flexibility, and toughness.
04/11/16
286

Binders include synthetic or natural resins
such as cement, alkyds, acrylics, vinylacrylics, vinyl acetate/ethylene (VAE),
polyurethanes, polyesters, melamine
resins, epoxy, or oils.
04/11/16
287
Polymeric Binders
Alkyd resins
Polyester resins
Acrylic resins
Amino resins
Epoxy resins
Urethane resins
04/11/16
288
04/11/16
289

Binders can be categorized according to
drying, or curing mechanism.
The four most common are:
simple solvent evaporation,
oxidative crosslinking,
catalyzed/cross linked polymerization,
coalescence.
04/11/16
290

Note that drying and curing are two different
processes.
Drying generally refers to evaporation of the
solvent or thinner, whereas curing refers to
polymerization of the binder.
Depending on chemistry and composition, any
particular paint may undergo either, or both
processes.
Thus, there are paints that dry only, those that
dry then cure, and those that do not depend on
drying for curing
04/11/16
291
Lacquers (Simple solvent

evaporation)
Paints that dry by simple solvent evaporation
and contain a solid binder dissolved in a solvent
are known as lacquers.
A solid film forms when the solvent evaporates,
and because the film can re-dissolve in solvent,
lacquers are not suitable for applications where
chemical resistance is important.
Performance varies by formulation, but lacquers
generally tend to have better UV resistance and
lower corrosion resistance than comparable
systems that cure by polymerization or
coalescence
04/11/16
292
Latex (simple solvent evaporation

and coalescence)
Latex paint is a water-borne dispersion of sub-micrometre polymer

particles.
The term "latex" in the context of paint simply means an aqueous
dispersion; latex rubber (the sap of the rubber tree that has
historically been called latex) is not an ingredient.
These dispersions are prepared by emulsion polymerization
Latex paints cure by a process called coalescence where first the
water, and then the trace, or coalescing, solvent, evaporate and
draw together and soften the latex binder particles and fuse them
together into irreversibly bound networked structures, so that the
paint will not redissolve in the solvent/water that originally carried it.
04/11/16
293
Oxidative crosslinking
Paints that cure by oxidative crosslinking are
generally single package coatings.
When applied, the exposure to oxygen in the air
starts a process that crosslinks and polymerizes
the binder component.
Classic alkyd enamels would fall into this
category.
Oxidative cure coatings are catalyzed by metal
complex driers such as cobalt naphthenate.
04/11/16
294
Catalyzed Polymerization
Paints that cure by "catalyzed" polymerization are
generally two package coatings that polymerize by way
of a chemical reaction initiated by mixing resin and
curing agent/hardener, and which cure by forming a hard
plastic structure.
Depending on composition they may need to dry first, by
evaporation of solvent.
Classic two package epoxies or polyurethanes would fall
into this category.
The word catalyst is a misnomer as catalyst should not
be part of the polymer. Cobalt driers are catalysts, iso
cyanates and epoxy adducts are not
04/11/16
295
Solvent
The main purposes of the solvent are to adjust the curing
properties and viscosity of the paint.
It is volatile and does not become part of the paint film. It
also controls flow and application properties, and affects
the stability of the paint while in liquid state.
Its main function is as the carrier for the non volatile
components.
In order to spread heavier oils (i.e. linseed) as in oilbased interior housepaint, a thinner oil is required.
These volatile substances impart their properties
temporarilyonce the solvent has evaporated or
disintegrated, the remaining paint is fixed to the surface
04/11/16
296
Solvent water based

Water is the main diluent for water-borne
paints, even the co-solvent types.
04/11/16
297
Solvent oil based

Solvent-borne, also called oil-based, paints can
have various combinations of solvents as the
diluent, including aliphatics, aromatics, alcohols,
ketones and white spirit.
These include organic solvents such as
petroleum distillate, esters, glycol ethers, and the
like.
Sometimes volatile low-molecular weight
synthetic resins also serve as diluents.
Such solvents are used when water resistance,
grease resistance, or similar properties are
desired.
04/11/16
298
Additives
Besides the three main categories of ingredients, paint
can have a wide variety of miscellaneous additives, which
are usually added in very small amounts and yet give a
very significant effect on the product.
Some examples include additives to modify surface
tension, improve flow properties, improve the finished
appearance, increase wet edge, improve pigment
stability, impart antifreeze properties, control foaming,
control skinning, etc.
Other types of additives include catalysts, thickeners,
stabilizers, emulsifiers, texturizers, adhesion promoters,
UV stabilizers, flatteners (de-glossing agents), biocides to
fight bacterial growth, and the like.
04/11/16
299
Condensation Reaction
04/11/16
300
Amino Resins
Condensation products of formaldehyde
with urea/melamine
Clear and colorless
Adhesives for plywood and furniture
Melamine resins have better properties
than urea resins but are higher in price
04/11/16
301
Epoxy Resin
Epoxy resin is made by condensing
epichlorohydrin with bisphenol A
Epoxy resins are cured by polyamines,
polyamides, polysulfides, urea-and
phenol- formaldehyde, acids, acid
anhydrides, through coupling or
condensation reactions
04/11/16
302
Unsaturated Polyester Resins Formulation
43 lbs of phthalic anhydride

19 lbs of maleic anhydride
38 lbs of propylene glycol
Total 100 lbs
To this 100 lbs, formulator will add about 70
lbs of styrene for crosslinking
Typically, around 100-300 lbs of glass-fiber
filler will be added, depending upon end
use
04/11/16
303
Major Applications of Epoxy Resins

Surface-Coating materials
Combine toughness, flexibility, adhesion,
and chemical resistance to a nearly
unparalled degree
04/11/16
304
04/11/16
305
Other polymer backbones

Some linear polymers have more
complex
Nylon
backbones:
Fabrics, ropes,
structural plastics
Polycarbonate, PC
Shatter-resistant
clear plastic
04/11/16
306
Polyurethanes
Formed by a reaction between diisocynate
and glycol
Contain the group NHCOO Thermoset types, cured by the presence of
moisture, are used as adhesive and coating
base resins
Polyurethanes can be blown in foams of
various densities, used as protective
packaging
04/11/16
307
Polyurethanes - Foams-in-place
Metering-Mixing-Delivery systems
Two reacting chemicals are mixed just
prior to being sprayed around an object to
be protected
The mixed components foam up within
seconds to totally encapsulate the item
04/11/16
308
Chemical Class
A popular classification scheme amongst chemists is based on polymer
functionality.
Polyesters:
poly(ethylene terephthalate) - Dacron
Polyamides:
poly(caprolactam) - nylon 6
Urethanes:
carbamate linkages through reaction
O
C O
of diisocyanates and diols.
H O on
Another (!) classification scheme, again favoured by chemists is based
differences between the polymer and constituent monomer(s). N C
Condensation polymers: synthesis involves elimination of some small molecule (H 2O in
the preparation of nylon)
Addition polymer: formed without loss of a small molecule i.e. ethylene polymerization to
generate poly(ethylene)
H O
04/11/16
N C O1.309
04/11/16
310
04/11/16
311
Alkyd resins
Alkyd resins are modified with a number of oils including
soya, linseed, dehydrated castor, and coconut.
They in turn can be combined with such resins as
acrylics, vinyl toluene, silicones, and amino-resins.
The latitude of compatibility of the oil-modified resins
makes them popular for use in industrial coatings.
They are fairly inexpensive and they have a variety of
properties.
Alkyds can be prepared directly from oil (triglyceride), a
polyol, or an acid.
The percentage of oil contained in an alkyd classifies the
end use of the alkyd and affects such properties as
speed of drying, flexibility, durability, and so forth.
04/11/16
312
04/11/16
313
Polyester resins
Polyester resins are typically used in heatcured coatings that need to be high in
paint solids and low in solvent content.
They have extremely good color retention
that provides good over-bake protection
and very good UV resistance, and they
can be applied using a wide range of
spray equipment.
04/11/16
314
Acrylic resins
In the coatings and plastic fields, the term acrylic resin applies to
the polymers and copolymers of the esters of methacrylic and
acrylic acids.
Copolymers of these esters with nonacrylic monomers such as
styrene, butadiene, or vinyl acetate are also referred to as acrylic
resins.
Acrylic resins are very versatile and popular for industrial liquid
coatings. They provide toughness, good weathering ability, and
resistance to abrasion and chemical attack.
They are also considered to be better than alkyd resins for gloss
retention.
Acrylic thermosetting resins that are cross-linked with epoxy or
amino resins are used in the appliance industry because of their
excellent physical and chemical properties.
04/11/16
315
Amino resins
Amino resins are generally used in baked
coatings as cross-linking agents.
They are used in proportions up to 50% of
the total vehicle binder.
They can be used with alkyds, polyesters,
epoxies, thermosetting acrylics, phenolics,
and other heat reactive resins.
Melamine and ureaformaldehyde are the
most common examples of this resin.
04/11/16
316
Epoxy resins
Epoxy resins are known for their excellent
corrosion and chemical resistance.
Because of their tendency to fade and
chalk when exposed to sunlight, they are
used for interior topcoat applications or as
primer for exterior applications.
04/11/16
317
Epoxy resins
Excellent corrosion resistance can be obtained with film
thickness as low as 0.5 mil.
The epoxy resin is usually cross-linked with melamine or
urea resin at curing temperatures of 350425F.
Epoxy coatings are characterized by excellent adhesion,
a high degree of impact and abrasion resistance, and
resistance to chemicals and solvents.
This combination of properties makes the epoxy
formulas a good fit for chemical laboratory furniture and
similar applications.
They also have good insulating properties, making them
a good fit for the electrical industry, and they can provide
excellent wear on tools.
04/11/16
318
Urethane resins
Urethane is the accepted description for a group
of polymers that are sometimes called
polyurethanes.
Urethane resins are very popular with
formulators, providing a combination of chemical
resistance, toughness and abrasion resistance,
and exterior durability.
Effective application on plastics has led to
substantial growth in urethane technology.
04/11/16
319
Urethane resins
Urethanes are the reaction products of isocyanates with
materials that have hydroxyl groups.
They contain a significant number of urethane groups
regardless of what the rest of the molecule may be.
The basic chemistry of isocyanates and urethanes has
been known for over a hundred years.
In 1848,Wurtz prepared methyl and ethyl isocyanates by
reacting potassium cyanate and alkyd iodides.
He also found that ethyl isocyanate reacted with ethyl
alcohol to form ethyl carbamate, which was later named
urethane.
04/11/16
320
Colour changing paint

Various technologies exist for making paints that
change color.
Thermochromic paints and coatings contain
materials that change conformation when heat is
applied, and so they change color.
Liquid crystals have been used in such paints,
such as in the thermometer strips and tapes
used in fishtanks.
Photochromic paints and coatings contain dyes
that change conformation when the film is
exposed to UV light, and so they change color.
These materials are used to make eyeglasses
04/11/16
321
Colour changing paint

Electrochromic paints change color in response
to an applied electric current.
Car manufacturer Nissan has been reportedly
working on an electrochromic paint for use in its
vehicles, based on particles of paramagnetic
iron oxide.
When subjected to an electromagnetic field the
paramagnetic particles change spacing,
modifying their color and reflective properties
04/11/16
322
Painting as Art
Since the time of the Renaissance, siccative
(drying) oil paints, primarily linseed oil, have
been the most commonly used kind of paints in
fine art applications; oil paint is still common
today.
However, in the 20th century, water-based
paints, including watercolors and acrylic paints,
became very popular with the development of
acrylic and other latex paints.
04/11/16
323
Painting as Art
Milk paints (also called casein), where the medium is
derived from the natural emulsion that is milk, were
popular in the 19th century and are still available today.
Egg tempera (where the medium is an emulsion of egg
yolk mixed with oil) is still in use as well, as are encaustic
wax-based paints.
Gouache is a variety of opaque watercolor which was
also used in the Middle Ages and Renaissance for
manuscript illuminations. The pigment was often made
from ground semiprecious stones such as lapis lazuli and
the binder made from either gum arabic or egg white.
Gouache, also known as 'designer color' or 'body color' is
commercially available today.
04/11/16
324
Paint Application
Paint can be applied as a solid, a gaseous
suspension (aerosol) or a liquid.
Techniques vary depending on the
practical or artistic results desired
04/11/16
325
Paint Application - Solid

As a solid (usually used in industrial and
automotive applications), the paint is applied as
a very fine powder, then baked at high
temperature.
This melts the powder and causes it to adhere
(stick) to the surface.
The reasons for doing this involve the
chemistries of the paint, the surface itself, and
perhaps even the chemistry of the substrate (the
overall object being painted).
This is commonly referred to as "powder coating"
an object.
04/11/16
326
Paint Application - Gas

As a gas or as a gaseous suspension, the
paint is suspended in solid or liquid form in
a gas that is sprayed on an object. The
paint sticks to the object.
This is commonly referred to as "spray
painting" an object.
04/11/16
327
Paint Application - Liquid

In the liquid application, paint can be
applied by direct application using
brushes, paint rollers, blades, other
instruments, or body parts such as fingers
04/11/16
328
Paint Application - Liquid

Rollers generally have a handle that allows for
different lengths of poles which can be attached
to allow for painting at different heights.
Generally, roller application takes two coats for
even color.
A roller with a thicker nap is used to apply paint
on uneven surfaces.
Edges are often finished with an angled brush.
04/11/16
329
Spray painting
Paint application by spray is the most popular
method in industry.
In this, paint is atomized by the force of
compressed air or by the action of high pressure
compression of the paint itself, which results in
the paint being turned into small droplets which
travel to the article which is to be painted.
Alternate methods are airless spray, hot spray,
hot airless spray, and any of these with an
electrostatic spray included. There are numerous
electrostatic methods available
04/11/16
330
Clean-up
Water-based paints tend to be the easiest
to clean up after usingthe brushes and
rollers can be cleaned with soap and
water.
04/11/16
331
Paint Disposal
Proper disposal of left over paint is a challenge.
Sometimes it can be recycled: Old paint may be usable
for a primer coat or an intermediate coat, and paints of
similar chemistry can be mixed to make a larger amount
of a uniform color.
To dispose of paint it can be dried and disposed of in the
domestic waste stream provided that it contains no
prohibited substances (see container).
Disposal of liquid paint usually requires special handling
and should be treated as hazardous waste, and
disposed of according to local regulations
04/11/16
332
Primer
Primer is a preparatory coating put on
materials before painting.
Priming ensures better adhesion of paint
to the surface, increases paint durability,
and provides additional protection for the
material being painted.
It can also be used to block and seal
stains, or to hide a color that is to be
painted over.
04/11/16
333
Emulsion Paint
Emulsion paint is a water-based paint
used for painting interior or exterior
surfaces.
04/11/16
334
Varnish
Varnish and shellac provide a protective
coating without changing the color.
They are paints without pigment.
04/11/16
335
Wood Stain
Wood stain is a type of paint that is very
"thin," that is, low in viscosity, and
formulated so that the pigment penetrates
the surface rather than remaining in a film
on top of the surface.
Stain is predominantly pigment or dye and
solvent with little binder, designed
primarily to add color without providing a
surface coating.
04/11/16
336
Lacquer
Lacquer is usually a fast-drying solventbased paint or varnish that produces an
especially hard, durable finish.
04/11/16
337
Enamel
An enamel paint is a paint that dries to an
especially hard, usually glossy, finish.
Enamel paints sometimes contain glass
powder or tiny metal flake fragments
instead of the color pigments found in
standard oil-based paints.
Enamel paint is sometimes mixed with
varnish or urethane to increase shine as
well as assist its hardening process.
04/11/16
338
Glaze
A glaze is an additive used with paint to
slow drying time and increase
translucency, as in faux painting and Art
Painting
04/11/16
339
Roof Coating
A roof coating is a fluid applied membrane
which has elastic properties that allows it
to stretch and return to their original shape
without damage.
It provides UV protection to polyurethane
foam and is widely used as part of a roof
restoration system
04/11/16
340
Inks
Inks are similar to paints, except they are
typically made using finely ground
pigments or dyes, and are designed so as
not to leave a thick film of binder.
04/11/16
341
Anti-fouling paint
Anti-fouling or bottom paint, prevents
barnacles and marine organisms from
adhering to the hulls of ships
04/11/16
342
Failure of a paint
The main reasons of paint failure after
application on surface are the applicator
and improper treatment of surface.
While there have been cases of paint also,
but they are rare.
04/11/16
343
Contamination
Foreign contaminants added without the
manufacturers consent which results in
various film defects
04/11/16
344
Dilution
This usually occurs when the dilution of
the paint is not done as per manufacturers
recommendation.
There can be a case of over dilution and
under dilution, as well as dilution with the
incorrect diluent.
04/11/16
345
Peeling/Blistering
Most commonly due to improper surface
treatment before application and inherent
moisture/dampness being present in the
substrate.
04/11/16
346
Chalking
Chalking is the progressive powdering of
the paint film on the painted surface.
The primary reason for the problem is
polymer degradation of the paint matrix
caused by attack by UV radiation in
sunshine.
04/11/16
347
Cracking
Cracking of paint film is due to the unequal
expansion or contraction of paint coats.
It usually happens when the coats of the
paint are not allowed to cure/dry
completely before the next coat is applied.
04/11/16
348
Blistering
Blistering is due to improper surface
exposure of paint to strong sunshine
04/11/16
349
Erosion
Erosion is very quick chalking.
It occurs due to external agents like air,
water etc.
04/11/16
350
Volatile Organic Compounds

(VOCs) in paint are considered harmful to the
environment and especially for people who work with
them on a regular basis. Exposure to VOCs has been
related to organic solvent syndrome, although this
relation has been somewhat controversial.
In the United States, environmental regulations,
consumer demand, and advances in technology led to
the development of low-VOC and zero-VOC paints and
finishes. These new paints are widely available and meet
or exceed the old high-VOC products in performance
and cost-effectiveness while having significantly less
impact on human and environmental health.
04/11/16
351
Families based on an ethenic backbone are vinyl

polymers or vinylydines
Polyethylene
PE
Polypropylene
PP
04/11/16
352
Polypropylene
Propylene gas is recovered from cracked
gas streams in olefin plants and oil
refineries
Polymerization of propylene gas utilizes a
coordination catalyst prepared as colloidal
diepersion by reacting an aluminium alkyl
and TiCl4 in heptane
04/11/16
353
Polypropylene Properties
Density: 0.905; lightest major plastic
Melting point: 165C
High cyrstallinity gives high tensile strength,
stiffness, and hardness
High strength to weight ratio
Less stable than PE to heat, light and oxidative
attack
To overcome brittleness, random and block
copolymers with ethylene are made with good
impact resistance
04/11/16
354
PP Properties Tailored By
Catalyst selection
Copolymerization
Molecular weight control
Isotatic product in commercial use
04/11/16
355
Isotactic
Syndiotactic
Random
04/11/16
356
Polypropylene Applications
Injection molded uses automotive and
appliances
Filament rope, cordage, webbing
Filament and staple for carpeting
04/11/16
357
Orienting PP improves
Tensile strength
Stiffness
Moisture and grease-barrier properties
Low temperature durability
Clarity
Gloss
04/11/16
358
Biaxially Oriented Polypropylene

Biaxially oriented polypropylene is the
backbone of snack-food and confection
packaging
04/11/16
359
Poly(ethylene terephthalate)
An ester is the reaction product of an
organic acid and an organic base.
PET formed by reacting ethylene glycol
(base) and terephthalic acid
Condensation polymerization reaction
Largest use in injection blow molded
carbonated beverage bottles (2 liter
bottles)
04/11/16
360
04/11/16
361
PET polyester fibers

Garments made from PET polyester fibers
are resistant to wrinkling
Garments can be washed repeatedly
without ironing
Wash and Wear concept
Polyester fibers are often blended with
cotton or wool
04/11/16
362
Polyamides (Nylon)
Polyamide or nylon is formed by condensation
polymerization reaction of a diamine and a
dibasic acid
Polyamides also formed by polymerization of
certain amino acids
Polyamides identified by number representing
the number of carbon atoms in the basic amino
acid (nylon type 6)
Polyamides identified by number of carbon
atoms in reacting diamine and dibasic acid
(nylon type 66)
04/11/16
363

complex
Nylon
backbones:
Fabrics, ropes,
structural plastics
Polycarbonate, PC
Shatter-resistant
clear plastic
04/11/16
364
04/11/16
365
Nylon 66
Condensation polymerization reaction of
hexamethylenediamine and adipic acid
Nylons developed by W.H. Carothers in
1928 at DuPont
04/11/16
366
Polymamides
The key chemical in production of both Nylon 6
and Nylon 66 is cyclohexane
Cyclohexane produced by catalytic
hydrogenation of benzene
About 70% cyclohexane converted to adipic acid
by oxidation, and the rest converted to
caprolactum
In turn, portion of the adipic acid converted to
hexamethylenediamine via the ammonium salt,
adipamide, and adiponitrile
04/11/16
367
Ring Opening Polymerization

Some polymers can be prepared by reactions involving
ring opening. Few typical examples of monomers for
ring-scission polymerization are cyclic ethers, cyclic
anhydrides.
The polymerization of ethylene oxide leading to a high
molecular weight polyethylene oxide (PEO) can be
accomplished by ring opening polymerization.
The monomer is added to form a chain (chain
polymerization), the polymer growth is through step wise
addition, and thus molecular weight of the polymer
increases during the course of reaction
(polycondensation).
04/11/16
368
04/11/16
369
04/11/16
370
Polymerization of Nylon 6
The polymerization of caprolactum is carried out
by adding water to open the rings, and removing
the water again at elevated temperatures, where
linear polymer forms
An autoclave or continuous reactor can be used
Polycaprolactum is in equilibrium with 10% of
the monomer which must be washed away
before polymer can be spun
04/11/16
371
Polymerization of Nylon 66
Hexamethylenediamine and adipic acid form a
1:1 salt that is isolated because of its low
solubility in methanol
The salt is dissolved in water and added to
autoclave with 1% mol acetic acid as viscosity
stabilizer
As temperature is raised, steam generated
purges air from the vessel
Pressure is kept at 250 psi as temperature is
raised to 275C
04/11/16
372
Polymerization of Nylon 66 Cont.

Pressure is then reduced, and vacuum may be
applied
After a total time of 3-4 hours, nitrogen pressure
is used to extrude the nylon as a ribbon through
a valve in the bottom of the autoclave
The ribbon is then cut into cubes, the finished
product
For fiber use, the lower molecular weight
polymer is melt spun
04/11/16
373
Properties of Nylons
Specific Gravity: 1.14

High strength
Good elasticity
Good toughness
Good abrasion resistance
Good solvent resistance
04/11/16
374
Fiber Applications of Nylons

Housing related, especially carpets
Apparel (clothes and garments)
Tire cords
04/11/16
375
Plastics Applications of Nylons

Engineering materials substitute for
metal in bearings, gears, cam, rollers,
slides
Ability to be injection-molded to close
dimensional tolerances, plus light weight,
gives the plastic a cost advantage in
appliances
04/11/16
376
Reinforced Grade Nylons

Increased strength, stiffness, and creep
resistance
Fillers consist of continuous mat or
chopped glass, various minerals and
glass, and minerals alone
04/11/16
377
Other Polyamides from DuPont

Nomex nonflammable; industrial
applications where unusual heat
resistance is required
Kevlar liquid crystalline polyamide;
outstanding strength to weight ratio; bulletproof vests; Kevlar cable can match the
strength of steel at the same diameter and
20% of the weight
04/11/16
378
Polycarbonates (PC)
Polycarbonate is made from carbonic acid
and bisphenol A.
Tough plastic, one with the highest impact
resistance
High use temperatures
Clarity equals that of glass replacement
for glass
Returnable large water bottles and milk
jugs
04/11/16
379

Nyloncomplex
backbones:
Fabrics, ropes,
structural plastics
Polycarbonate, PC
Shatter-resistant
clear plastic
04/11/16
380
04/11/16
381
Vinyl chloride is a gas (b.p. -14C)
produced by the dehydrochlorination of
ethylene dichloride, made by reacting
ethylene with chlorine
PVC is produced by suspension (over
80%) polymerization (rest by emulsion
polymerization) of vinyl chloride.
04/11/16
382
Structure of PVC
PVC differs from polyethylene in having a
chlorine atom replace one hydrogen atom
Syndiotactic configuration
04/11/16
383
Compounding of PVC
PVC are compounded with a wide range
of additives including plasticizers, slip
agents, pigments, waxes, fillers, stabilizers
making it a versatile material with
properties ranging from hard and rigid to
the softest of cling films
04/11/16
384
Applications of PVC
Pipes water supply and distribution,
agricultural irrigation, chemical processing,
drain, waste, vent pipe, sewer systems
Conduits electrical and telephone cables
Building construction window frames,
gutters, flooring, wire and cable insulation,
upholstery, shower curtains
04/11/16
385
04/11/16
386
04/11/16
387
04/11/16
388

In a substance where all molecules are small
and have similar molecular weight, properties
such as melting point are sharply defined.
Water, for example goes from a solid state to a
liquid state at exactly 0oC (32oF) at I atm.
Polymer molecules are large, entangled, having
different molecular weights, and restricted in
their movements, so do not have a sharp
transition point and there is no clearly visible
phase change.
04/11/16
389

Glass transition temperature (Tg) is the
temperature at which a polymeric material
changes from a rigid solid state to a soft, rubbery,
or elastic state.
Tg is related to the point where there is sufficient
energy (i.e. temperature) for segments of the
polymer molecules to move with respect to one
another.
As the temperature increases, the plastic will
enter a melt phase at the melt transition point Tm.
04/11/16
390
04/11/16
391
04/11/16
392
Stress-strain behavior of Polymers
04/11/16
393
Stress-Strain Behavior of Polymers

A reinforced or crystallizable rubber exhibits a
relative low value of breaking stress, but high
elongation
A ductile plastic like polyethylene exhibits
yielding, drawing, and at high elongations some
strengthening due to orientation
A brittle plastic such as polystyrene does not
yield much and breaks at low elongation
A fiber exhibits the highest strength, high
stiffness, and low elongation
04/11/16
394
Elastic
A metal spring illustrates elasticity.
It elongates with the application of a load.
When the load is removed, the spring will
return to its original shape (providing that
its elastic limit was not exceeded).
The application rate and duration of the
load (time) have little influence on the end
result.
Such behavior is said to be elastic.
04/11/16
395
Viscous Fluid
Application of force causes the material to
flow and permanently deform.
Unlike a spring, a material with viscous
properties will not return to its original
shape when the load is removed.
Also, the rearrangement of molecules
characterized by viscous flow is time
dependent.
04/11/16
396
Viscoelastic Polymers
Viscoelastic materials combine elastic and
viscous properties.
Accordingly, rapid application of a load to
a plastic will cause it to bend, and if that
load is quickly released, the plastic will
return to its original shape: It behaves like
an elastic or a spring.
04/11/16
397
Viscoelastic Polymers
However, the same load applied over a long time
period allows viscous flow to take place.
Polymer molecules will flow and rearrange
themselves in new orientations that reduce the
internal stress caused by the load.
When the load is released, the plastic will not go
back to its original shape.
This deformation of plastics under load is
referred to as creep or cold flow.
04/11/16
398
POLYMER RHEOLOGY
RHEOLOGY IS THE SCIENCE OF
DEFORMATION AND FLOW OF MATERIALS.
THE STRESS APPLIED IS PROPORTIONAL TO
THE DEFORMATION PRODUCED. VISCOSITY
IS DEFINED AS THE RATIO BETWEEN THE
SHEAR STRESS AND THE VELOCITY
GRADIENT (RATE OF SHEAR) . IF VISCOSITY
IS INDEPENDENT OF THE RATE OF SHEAR,
THE BEHAVIOR IS NEWTONIAN
FOR NON-NEWTONIAN FLUIDS, VISCOSITY
IS A FUNCTION OF SHEAR RATE AND TIME
04/11/16
399
Newtonian Fluids
All gases, and most simple liquids and
solvents, including water are Newtonian
fluids
Materials upto molecular weight of 5000
behave as Newtonian fluids
04/11/16
400
Newtonian Behaviour
THE STRESS APPLIED IS PROPORTIONAL
TO THE DEFORMATION PRODUCED.
VISCOSITY IS DEFINED AS THE RATIO
BETWEEN THE SHEAR STRESS AND THE
VELOCITY GRADIENT (RATE OF SHEAR) .
IF VISCOSITY IS INDEPENDENT OF THE
RATE OF SHEAR, THE BEHAVIOR IS
NEWTONIAN
04/11/16
401
Newtons Law of Viscosity

A plot of yx versus (dvx/dy) for a given
fluid should give a straight line through the
origin, and the slope of the line is the
viscosity of the fluid at the given
temperature and pressure
04/11/16
402
Non-Newtonian Fluids
Many paints, pastes, slurries, and high
polymers, polymer melts, polymer
solutions do not obey the Newtons law of
viscosity
Non-Newtonian flow is a subdivision of the
science of rheology
04/11/16
403
Rheology
Rheology is the science of deformation
and flow
Rheology includes Newtonian fluid
mechanics at one end of the spectrum
and Hookean elasticity at the other
The region in between concerns the
deformation and flow of all sorts of gunky
and gooey materials
04/11/16
404
04/11/16
405
SHEAR-THINNING & SHEAR

THICKENNING
IN SHEAR THINNING MATERIALS, THE
VISCOSITY DECREASES WITH INCREASING
SHEAR RATE AND THE BEHAVIOR IS
TERMED PSEUDOPLASTIC (MOST POLYMER
MELTS, SOLUTIONS, AND DISPERSIONS).
IN SHEAR THICKENNING MATERIALS, THE
VISCOSITY INCREASES WITH INCREASING
SHEAR RATE, THE BEHAVIOR IS TERMED
DILATANT (HIGHLY CONCENTRATED
SUSPENSIONS OF FINE POWDERS)
04/11/16
406
04/11/16
407
Bingham Model
yx = -o dvx/dy o, if lyxl > o
dvx/dy = 0 if lyxl < o
Bingham Plastic it remains rigid when shear
stress is less than the yield stress o, but flows
somehow like a Newtonian fluid when the shear
stress exceeds o
Accurate for many fine suspensions, pastes,
tomato ketchup
04/11/16
408
Oswald-de Walde Model or Power

Law
= m .n-1
This two-parameter model is known as power
law
For n =1, it reduces to Newtons law of viscosity
with m =
Thus, the deviation of n from unity indicates the
degree of deviation from Newtonian behaviour
For values of n less than unity, the behaviour is
pseudoplastic
For values of n greater than 1, the behaviour is
dilatent
04/11/16
409
Non-Newtonian fluids
Under constant shear stress:
Thixotropic fluids: viscosity decreases with
time
Rheopectic fluid: viscosity increases with time
04/11/16
410
04/11/16
411
04/11/16
412
04/11/16
413
04/11/16
414
Basic rheological ideas

Summary
Viscosity - the viscous sample flows on the surface until surface
tension stops further flow (surface tension > gravitational force)
Elasticity - the elastic sample will bounce at contact with table
Plasticity - the plastic sample will deform at impact with surface.
Deformation will depend on the yield stress (yield stress compared
with gravitational force)
Viscoelasticity - the viscoelastic sample will initially bounce upon
contact with surface (short time scales). After longer times the
sample will come to rest on surface and will start to flow (long time
scales)
04/11/16
415
Measuring Viscosity
Poiseuille Law
Stokes Law
Efflux time
Torque for shear rate
Concentric cylinders
04/11/16
416
Capillary Viscometers
04/11/16
417
Falling Ball Viscometers
04/11/16
418
Rotational Viscometers
04/11/16
419
04/11/16
420
Non-Newtonian Fluids
04/11/16
421
04/11/16
422
Steady Simple Shear Flow

We consider steady shear flow between a
pair of parallel plates, where the velocity
profile is given by vx = .y, the other velocity
components being zero
The quantity ., here taken to be positive, is
called the shear rate.
For a Newtonian fluid, the shear stress
yx =-dvx/dy
Normal stresses xx, yy, zz are all zero
04/11/16
423

For incompressible non-Newtonian fluids,
the normal stresses are nonzero and
unequal.
It is conventional to define three material
functions as follows:
yx = -dvx/dy
xx yy = -1 (dvx/dy)2
yy zz = -2 (dvx/dy)2
04/11/16
424

is the non-Newtonian viscosity
1 is the first normal stress coefficient
2 is the second normal stress coefficient
, 1, and 2 are all functions of the shear rate .
and 1 are positive (fluid behaves as if under
tension in the flow x direction)
2 is almost always negative (fluid is under
tension in the transverse z direction)
For Newtonian fluid, =; 1=0; 2=0
04/11/16
425
04/11/16
426

The positive 1 is responsible for the
Weissenberg rod-climbing effect
Because of the tangential flow, there is
tension in the tangential direction, and this
tension pulls the fluid towards the rotating
rod, overcoming the centrifugal force
The negative 2 can be shown to explain
the convex surface shape in the
semicylindrical tilted-trough experiment
04/11/16
427
The Aim of Rheometry
Using rheological studies, one can mimic different processes and

predict the influence on product properties or changes in
formulations. The measurements can be used to study material
structure, for raw-material or process control and for application
properties, such as consistency, shear- or storage stability against
sedimentation.
Every application requires its own practical tests, but very often it is
difficult to optimize and to see small differences in performance
using only these tests. Rheology measurements can reveal these
small variations.
These measurements can also be of help in the development of
new products, giving better understanding of the processes
governing the final properties.
04/11/16
428
Newtonian
versus
Polymeric fluids
04/11/16
429
04/11/16
430
Steady state laminar flow in circular

tubes
Newtonian Fluid:
Vz/Vz max = 1 (r/R)2
<vz>/Vz max =
Po P L ~ Q
Polymeric Fluid:
- vz/vz max = 1 (r/R) (1/n) + 1
- <vz>vz max = (1/n) + 1 / (1/n) + 3
- Po P L ~ Q4
- n is a positive parameter characterizing the fluid,
usually with a value less than unity.
04/11/16
431
04/11/16
432
04/11/16
433
04/11/16
434
04/11/16
435
04/11/16
436
04/11/16
437
Drag-reducing agents
With only ppm of some polymers (drag
reducing agents), the friction loss in
turbulent pipe flow can be lowered by 3050%!
Used by fire departments to increase the
flow of water
Used by oil companies to lower the cost of
pumping crude oil over long distances
04/11/16
438
Small Amplitude Oscillatory Motion

Sample is kept between two parallel plates
Top plate moves back and forth in sinusoidal
fashion, and with a tiny amplitude
If the plate spacing is extremely small, and the
fluid has a very high viscosity, then the velocity
profile will be nearly linear, so that
Vx(y,t) = .oy cos wt, in which .o gives the
amplitude of the shear rate excursion
x y
04/11/16
439
Small-Amplitude Oscillatory Motion

The first (in-phase) term is the viscous
response, and the second (out-of-phase)
term is the elastic response
Polymer chemists use the curves of (w)
and (w) (or the storage and loss moduli;
G=w and G=w) for characterizing
polymers, since much is known about the
connection between the shapes of these
curves and the chemical structure
04/11/16
440
Small-Amplitude Oscillatory Motion

For the Newtonian Fluid,
=
= 0
04/11/16
441
04/11/16
442
04/11/16
443
G
G
W
04/11/16
444
04/11/16
445
Chemical Gelation
04/11/16
446
Gel Point
04/11/16
447
04/11/16
448
04/11/16
449
04/11/16
450
04/11/16
451
04/11/16
452
STRESS RELAXATION
In a stress relaxation experiment the sample is
rapidly stretched to the required length, and the
stress is recorded as a function of time.
The length of the sample remains constant, so
there is no macroscopic movement of the body
during the experiment.
Usually the temperature remains constant also
04/11/16
453
04/11/16
454
04/11/16
455
Creep Experiments
Creep experiments are conducted in the
inverse manner.
A constant stress is applied to a sample,
and the dimensions are recorded as a
function of time.
Of course, these experiments can be
generalized to include shear motions,
compression, and so on.
04/11/16
456
04/11/16
457
04/11/16
458
Molecular Basis of Stress

Relaxation and Creep
Chain Scission
Bond Interchange
Viscous flow
Thirion relaxation
Molecular relaxation near Tg
04/11/16
459
Chain Scission
04/11/16
460
Bond Interchange
While this is not a degradation in the sense that
the molecular weight is decreased, chain
portions changing partners cause a release of
stress.
Examples of stress relaxation by bond
interchange include polyesters and
polysiloxanes.
Bond interchange is going on constantly in
polysiloxanes, with or without stress.
In the presence of a stress, however, the
statistical rearrangements tend to reform the
chains so that the stress is reduced.
04/11/16
461
Viscous Flow
Caused by linear chains slipping past one
another, this mechanism is responsible for
viscous flow in pipes and elongational flow
under stress.
An example is the pulling out of Silly
Putty.
04/11/16
462
Thirion Relaxation
This is a reversible relaxation of the
physical crosslinks or trapped
entanglements in elastomeric networks.
Usually an elastomeric network will relax
about 5% by this mechanism, most of it in
a few seconds.
It must be emphasized that the chains are
in constant motion of the reptation
04/11/16
463
Molecular Relaxation
Molecular relaxation, especially near Tg.
It was pointed out that near Tg the chains relax
at about the same rate as the time frame of the
experiment.
If the chains are under stress during the
experiment, the motions will tend to relieve the
stress.
It must be emphasized that more than one of the
relaxation modes above may be operative
during any real experiment.
04/11/16
464
Polymer Processing
Extrusion rods, tubes, profiles
Injection Molding buckets, containers,
articles, snap-on parts
Blown-film making of films and plastic
bags
Blow Molding making of bottles
04/11/16
465
Fabrication
Polymer Processing fabricating the
polymer into useful articles and shapes
04/11/16
466
Fabrication Considerations
Rheology and flow properties

Thermoplastic or thermosetting
Softening temperature
Stability
Size and shape of the final product
04/11/16
467
Common steps
Handling of particulate solids

Melting
Pressurization and pumping
Mixing
Devolatilization and stripping of undesired
components
Forming the final shape
04/11/16
468
Molding
Molding processes are those in which a
finely divided plastic is forced by the
application of heat and pressure to flow
into, fill, and conform to the shape of a
cavity (mold).
04/11/16
469
Extrusion
04/11/16
470
04/11/16
471
04/11/16
472
Extrusion
In the extrusion process, polymer is
propelled continuously along a screw
through regions of high temperature and
pressure where it is melted and
compacted, and finally forced through a
die shaped to give the final product
04/11/16
473
Final shapes by extrusion
Rods
Channels
Other structural shapes
Tubing
Hoses
Sheeting up to several feet wide and thick
Films of small thickness (few thousandths of an
inch)
04/11/16
474
Coextrusion
Films or sheets consisting of two or more
different polymers can be produced by
mixing the molten streams from a like
number of extruders in a multimanifold die
This process can be used to combine
materials to provide combinations of
properties that cannot be obtained in a
single polymer
04/11/16
475
Co-extrusion
04/11/16
476
Coextrusion
For example, a film for packaging food
may consist of three layers imparting,
respectively, high strength, low oxygen
permeability, and heat sealability
04/11/16
477
04/11/16
478
Modern trends in extruder usage

Twin Screw or multiple screw extruder
Two screws turn side by side in opposite
directions providing more working of the melt
Vented Extruder
Having an opening or vent at some point
along the screw that can be opened or led to
vacuum to extract volatiles from the polymer
melt
04/11/16
479
Sheet extrusion
The product from a sheet die is passed
between rolls that control its thickness and
apply a desired surface finish by polishing
and embossing
04/11/16
480
Wire and cable extrusion

Employs dies through which bare copper
or aluminum wire is passed, and in which
it is coated with plastic insulation
Extrusion rates can be as high as 8000
ft/min.
04/11/16
481
Injection molding machine
04/11/16
482
Injection Molding
Injection molding is probably the most extensively used
method for processing short-fiber reinforced
thermoplastics.
The fiber/resin mixture, whether it is preblended or fed as
a physical mixture, is fed into the hopper and transferred
into the heated barrel.
The material softens by the heat transfer from the barrel
wall.
At the same time, the screw rotates to apply high-shear
process to further heat the material and fill the barrel.
The molten material is collected in front of the screw by
the rotation of the screw, and then injected with a high
pressure into the mold cavity through the runner and the
gate.
04/11/16
483
Injection Molding
The mold is cooled below the solidification
temperature of the resin in case of
thermoplastics composites.
The level of automation of this method is the
highest among many processing methods.
Due to the intensive mixing with high-shear and
passage through a narrow gate, extensive fiber
damage occurs, therefore, injection molding for
composite materials is suitable only with short
fiber reinforced or particulate-filled polymers.
04/11/16
484
04/11/16
485
Film extrusion
In the blown film process, a tubular die is used,
from which a hollow tube of product is extruded
vertically upward towards a film tower.
The tube is blown into a thin cylindrical film by
air introduced through the die and trapped in the
film bubble.
At the top of the tower, the bubble (now cool) is
collapsed, and subsequently slit into a flat film.
04/11/16
486
04/11/16
487
04/11/16
488
Blow Molding
A section of molten polymer tubing
(parison) is extruded into an open mold.
By means of compressed air or steam the
plastic is then blown into the configuration
of the mold
Widely used for the manufacture of bottles
and similar items
04/11/16
489
Compression molding press
04/11/16
490
Reaction injection molding machine
04/11/16
491
Reaction Injection Molding

Starts with unreacted components that lead to a
polymer product
They are pumped in predetermined amounts
into a mixing head, where they are thoroughly
mixed and injected into a warm (65oC) mold
under relatively low pressures (50-100 psi).
Polymerization takes place in the mold
Meanwhile, the mixing head is cleaned, with
unused monomers being recycled
Molding of polyurethanes
04/11/16
492
04/11/16
493
Calendering
04/11/16
494
04/11/16
495
Transfer Molding
The resin is placed in a separate chamber,
called the pot, preheated to just below
cure temperature
It is then injected or transferred into the
heated mold where cure takes place
Used for thermosetting resins
04/11/16
496
04/11/16
497
Casting
In casting processes, a liquid material is poured
into a mold and solidified by physical (e.g.
cooling) or chemical (e.g. polymerization) means
And the solid object is removed from the mold
Casting utilizes low cost equipment (molds can
be made out of soft, inexpensive materials such
as rubber and plaster) but is a relatively slow
process
04/11/16
498
Film Casting
Films, including photographic film and
cellophane, are made by flowing a solution
of the polymer onto an extremely smooth
surface in the form of a large polished
wheel or occasionally, a metal belt or band
After the solvent has evaporated (or, in the
case of cellophane, the polymer has
coagulated) the film is stripped from the
casting surface.
04/11/16
499
Composite
A composite is a heterogeneous substance consisting of
two or more materials which does not lose the
characteristics of each component.
This combination of materials brings about new desirable
properties.
Naturally occurring composites include tendon, bone,
bamboo, rock, and many other biological and geological
materials.
For composite engineering applications, we restrict
ourselves to synthetic polymer matrices which are used
with naturally occurring mineral fillers such as
wollastonite, silica, mica, and calcium carbonate, and
synthetic fibers like glass fibers and carbon fibers.
04/11/16
500
Study of Composites
In the subject of composite processing, we will learn how
to make the best use of these available materials
through the understanding of
chemical interaction of ingredients,

structural changes during processing,
suitable processing methods for desired product shapes
and the resultant consequence on the mechanical and physical
properties.
Therefore, we will deal with interdisciplinary subjects

including rheology, chemistry, mechanics, machinery,
and sometimes, economy.
04/11/16
501
04/11/16
502
04/11/16
503
Advantages of Composite Materials
Composites have many engineering advantages over synthetic

polymers and copolymers.
Some of these advantages are:
i. Reinforcement of the resin resulting in increased tensile strength,
flexural strength, compression strength, impact strength, rigidity and
combination of these properties.
ii. Increased size stability.
iii. Improved fire retardancy.
iv. Corrosion protection.
v. Improved electrical properties
vi. Coloring.
vii. Improved processibility; controlled viscosities, good mixing,
controlled orientation of fibers.
04/11/16
504
Composite Applications
Polymer Matrix Composites (PMC) are
used for manufacturing: secondary loadbearing aerospace structures, boat
bodies, canoes, kayaks, automotive parts,
radio controlled vehicles, sport goods (golf
clubs, skis, tennis racquets, fishing rods),
bullet-proof vests and other armor parts,
brake and clutch linings.
04/11/16
505
04/11/16
506
Graphite Fibers-Epoxy Resin Matrix

PAN (polyacrylonitrile) pyrolyzed at 15002500C (to drive off all atoms but carbon)
to get graphite fibers
Graphite fiber-epoxy resin matrix has
tensile strength and stiffness of steel, with
one-quarter the weight
04/11/16
507
Hand lay-up operation
04/11/16
508
Hand Lay-up Molding
Hand lay-up molding is the method of laying down fabrics made of

reinforcement and painting with the matrix resin layer by layer until
the desired thickness is obtained.
This is the most time and labor consuming composite processing
method, but majority of aerospace composite products are made by
this method in combination with the autoclave method.
Due to the hand assembly involved in the lay-up procedure, one can
align long fibers with controlled orientational quality.
Another advantage of this method is the ability to accommodate
irregular-shaped products.
Such advantages are utilized in low performance composites
including fiber-glass boat and bath tub manufacturing.
04/11/16
509
Spray-up molding
04/11/16
510
Spray-up molding
Spray-up molding is much less labor intensive than the
hand lay-up method by utilizing a spray gun and a fiber
cutter.
However, only short fiber reinforced composites can be
made.
A continuous fiber is fed into the cutter and chopped.
The chopped fiber is sprayed upon a mold with the
stream of resin mist and catalyst delivered through
separate nozzles.
The sprayed mixture of fiber and resin soon cures on the
mold at room temperature and the product is produced.
Because of the spraying operation, large and complexshaped objects can be easily made.
04/11/16
511
Pultrusion
04/11/16
512
Pultrusion
Pultrusion is used only for polymer composite processing.

A bundle of fiber rovings is passed through a wet resin bath,
squeezed into a desired shape, passed through a heated die, and
cured into a final composite.
The solidified composite, typically reinforced unidirectionally with
continuous fibers or sometimes bidirectionally, is pulled by a puller
to continuously feed the uncured portion of the wet fibers into the
hot die, thus the name, "pultrusion".
This is one of very few continuous processing methods for
continuous fiber reinforced composites.
Only constant cross-sectional products can be made; the shape of
the cross-section does not necessarily have to be the same,
however.
04/11/16
513
Pultrusion
Excess resin is removed by a forming
guide, and the mix is then pulled through a
heated mold that shapes and cures it.
04/11/16
514
Filament winding machine
04/11/16
515
Filament Winding
Filament winding is also a unique processing method for polymer

composite processing with a continuous reinforcing fiber.
Resin-wet rovings are wound with a certain pattern around a
mandrel.
The wound mandrel is then placed into an oven and cured to a solid
composite.
Due to the controlled tension, squeezing action and controlled
winding pattern, the fiber content can be very high to produce
composites with one of the highest mechanical properties.
The winding process is time consuming and is the cause of low
productivity.
However, due to its very high mechanical properties with automated
operation, it is actively evaluated by aerospace industries.
04/11/16
516
04/11/16
517
04/11/16
518
04/11/16
519
04/11/16
520
04/11/16
521
04/11/16
522
04/11/16
523
04/11/16
524
04/11/16
525
04/11/16
526
04/11/16
527
04/11/16
528
04/11/16
529
04/11/16
530
04/11/16
531
04/11/16
532
04/11/16
533
04/11/16
534
04/11/16
535
04/11/16
536
Fiber
Fiber (also spelled fibre) is a class of
materials that are continuous filaments or
are in discrete elongated pieces, similar to
lengths of thread.
One common definition of fiber requires
that its length be at least 100 times its
diameter.
04/11/16
537
Polymer fibers
Polymer fibers are a subset of man-made fibers,
which are based on synthetic chemicals (often
from petrochemical sources) rather than arising
from natural materials by a purely physical
process. These fibers are made from:
04/11/16
polyamide nylon,
PET or PBT polyester
phenol-formaldehyde (PF)
polyvinyl alcohol fiber (PVA) vinylon
polyvinyl chloride fiber (PVC) vinyon
polyolefins (PP and PE) olefin fiber
538
Polymer Fibers
Acrylic polyesters, pure polyester PAN
fibers are used to make carbon fiber by
roasting them in a low oxygen
environment.
Traditional acrylic fiber is used more often
as a synthetic replacement for wool.
Carbon fibers and PF fibers are noted as
two resin-based fibers that are not
thermoplastic, most others can be melted.
04/11/16
539
Polymer fibers
Aromatc polyamides (aramids) such as Twaron,
Kevlar and Nomex thermally degrade at high
temperatures and do not melt. These fibers have
strong bonding between polymer chains
polyethylene (PE), eventually with extremely long
chains / HMPE (e.g. Dyneema or Spectra).
Elastomers can even be used, e.g. spandex although
urethane fibers are starting to replace spandex
technology.
polyurethane fiber
04/11/16
540
Suitable properties of fiber for

textiles
High softening point to allow ironing
Adequate tensile strength over a wide
temperature range
Solubility or meltability for spinning
High modulus or stiffness
Good textile qualities comfort, long lasting
04/11/16
541
Types of fibers
Long Continuous filaments
Staples made by cutting continuous
filament into short lengths
04/11/16
542
Denier
The denier of a fiber, a measure of its size,
is defined as the weight in grams of 9000
meters of the fiber.
It is thus proportional to the density of the
fiber and to its cross sectional area
04/11/16
543
Tenacity
The tensile strength of a fiber is usually
expressed in terms of tenacity.
Tenacity is defined as the strength per unit
size number, such as the denier, where
the size number is expressed as a weight
per unit length.
Tenacity is thus a function of the density of
the fiber as well as its tensile strength
04/11/16
544
Making of Fibers
Melt-spinning (polyester, nylon)
Dry-spinning (cellulose acetate from
acetone; PAN from dimethyl formamide;
aramid fibers from dimethyl acaetamide)
Wet-spinning (viscose, cellulose, Spectra)
04/11/16
545
Spinning of fibers
The conversion of the spun polymer melt
or solution to a solid fiber involves:
A) melt spinning cooling
B) dry spinning solvent evaporation
C) wet spinning coagulation (solvent is
removed by leaching out into another
liquid which is miscible with the spinning
solvent but is not itself a solvent for the
polymer)
04/11/16
546
04/11/16
547
Spinning
The spinneret may consist of a 2- to 3- inch
diameter steel disk about one-quarter inch thick
with 50-60 countersunk holes 0.010 in or less in
diameter
The denier of the filament is determined not by
the diameter of the holes, but the rate at which
the polymer is pumped through the spinneret
and the rate at which the filaments are wound up
(about 2500 ft/min)
04/11/16
548
Drawing
A separate drawing step is necessary to
produce the orientation of the crystallites
necessary for optimum physical properties
The drawing step utilizes two set of rolls;
one to feed the undrawn yarn from a
supply package at velocity v1 and the
other moving about four times as fast, to
collect the drawn yarn at velocity v2
04/11/16
549
Spun fiber properties

Melt spun fiber uniform properties,
circular cross section
Dry spun fibers elliptical cross section
Wet spun fibers highly convoluted cross
sections
04/11/16
550
04/11/16
551
Rate-controlling step
Melt spun fiber cooling of a fine filament is
normally very rapid and can be controlled
Dry spun fiber solvent evaporation involves
simultaneous outward mass transfer and inward
heat transfer, the rate controlling step invariably
being outward diffusion of solvent
Wet spun fiber coagulation involves two-way
mass transfer, the coagulating acid (e.g. acid)
diffusing inward, and the products of coagulation
(e.g. salts, H2S) diffusing out.
04/11/16
552
04/11/16
553
04/11/16
554
04/11/16
555
04/11/16
556
Elastomers (Rubbers)
Ability to stretch and retract rapidly; exhibit high
modulus and strength while stretched and
recover fully on release of the stress
Contain a network of crosslinks to restrain gross
mobility of the chains process by which
network of crosslinks is introduced is
vulcanization (sulphur curing reaction)
Reinforced with carbon black increases tensile
strength, abrasion resistance, and tear
resistance
Automobile, truck, bus tires; hose, gaskets,
rubber shoe soles, tubes, gloves
04/11/16
557
Elastomer Characteristics
Elastomers must be amorphous when
unstretched
Must be above their glass transition
temperature to be elastic
04/11/16
558
Vulcanization
Process by which a network of crosslinks
is introduced into an elastomer is called
vulcanization
Vulcanization process discovered by
Goodyear in 1839
Vulcanization transforms an elastomer
from a weak thermoplastic mass without
useful mechanical properties into a strong,
elastic, tough rubber
04/11/16
559
Vulcanization Cont.
For a long time, vulcanization was done by
heating rubber with small amounts of sulfur
Rubber can be vulcanized (or cured) without
heat by the action of sulfur chloride
A large number of compounds that do not
contain sulfur can vulcanize rubber: oxidizing
agents (organic peroxides); generators of free
radicals (azo compounds); and phenolic resins
Neither heat nor sulfur is essential to the
vulcanization process
04/11/16
560
Definition of Vulcanization
Vulcanization may be defined as any
treatment that decreases the flow of an
elastomer, increases its tensile strength
and modulus, but preserves its
extensibility
These changes are due primarily to
chemical crosslinking reactions between
polymer molecules
04/11/16
561
Reinforcement
Inert fillers like clay make the rubber
easier to handle before vulcanization, but
have no effect on physical properties
Reinforcing fillers like carbon black
improve the tensile strength, stiffness,
abrasion resistance, and tear resistance
04/11/16
562
Preparation of Carbon Black

Carbon black made by burning oil or gas in a
furnace in limited air
Removing the carbon from the off-gases by a
centrifugal and electrostatic precipitation
Range of 200-500 Angstroms in particle size
The colloidal forms of carbon (water slurry)
constitute the most important reinforcing filler for
rubber
04/11/16
563
Natural Rubber
Natural rubber is a high molecular weight
polymer of isoprene
Obtained from the tree Hevea Brasilliensis
Rubber is obtained from a latex that
exudes from the bark of the Hevea tree
when it is cut
04/11/16
564
04/11/16
565
Natural Rubber
Material is processed
04/11/16
566
Natural Rubber
Latex is then dried, sorted and smoked
04/11/16
567
Natural rubber latex

Latex is an aqueous dispersion of rubber, containing 2540% rubber hydrocarbon stabilized by small amount of
protein material and fatty acids
The latex is gathered, coagulated, washed, and dried
Crepe rubber results if sodium bisulfite is added to
bleach the rubber. The coagulum is rolled out into
sheets 1 mm thick and dried in air at 50C
For smoked sheets, bleach is omitted, thicker sheets are
rolled, and dried in smokehouses at 50C in smoke from
burning wood or coconut shells
04/11/16
568
Natural Rubber
The difficulties with natural rubber
Strength
Availability
Bacterial breakdown
Creep
04/11/16
569
Properties of natural rubber

Rapid extensibility to great elongations
High stiffness and strength when stretched
Rapid and complete retraction on release
of the external stress
04/11/16
570
Cis and trans 1, 4 polyisoprenes
04/11/16
571
Synthetic Polyisoprene or Isoprene

Rubber
Need
Supply of natural rubber disrupted during
WWI and WWII
Used in tires for bicycles and early cars
Used the Ziegler-Natta catalyst system to
improve properties
The trans- or cis- nature of the rubber could be
controlled up to 90% in either direction
04/11/16
572
Synthetic Polyisoprene
Structure-properties close to natural
rubber
Two processes one based on
coordination polymerization using catalyst
of titanium tetrachloride and aluminum
alkyl such as triisobutyl aluminum
Other process is anionic polymerization
with butyl lithium as the catalyst
04/11/16
573
Butadiene Rubber (BR)
How is this polymer different from natural rubber?
04/11/16
574
Butadiene Rubber (BR)

No cis or trans isomers
Lower mechanical strength because of no
of pendant methyl group but also more
flexibility
Lower cost (all synthetic from cheap
monomer)
Improvement of low-temp flexibility
Compatibility with other polymer materials
04/11/16
575
Styrene-Butadiene Rubber
Made by emulsion polymerization at -10 to
5C.
Random copolymer
Majority application automobile tires
Other applications rubber shoe soles,
belting, hose, molded goods, flooring
04/11/16
576
Styrene Butadiene Rubber (SBR)
04/11/16
577
Polychloroprene (Neoprene)
Good oil resistance
Made by emulsion polymerization
Vulcanization is by zinc oxide and
magnesium oxide
No carbon black reinforcement needed
Used in cable and wire coatings, hoses
and belts
04/11/16
578
Other Synthetic Elastomers

Polyisobutylene and Butyl rubber inner
tubes for tires
04/11/16
579
Oil-Resistant Elastomers
NBRNitrile Butadiene Rubber
Copolymerization of butadiene and
acrylonitrile
More expensive than SBR or BR
CRChloroprene rubber (neoprene)

Thermal stability
Non-flammable
04/11/16
580
Thermoplastic Elastomers
Materials that have elastomeric properties
at ambient temperature, but process like
thermoplastics
No need for vulcanization step to develop
rubberlike elasticity
Examples: block copolymers of styrene
with butadiene; polyurethanes;
copolyesters; ethylene-propylene
copolymers
04/11/16
581
Properties of Elastomers
Property
Natural
Rubber
SBR
Butyl
Neoprene
Nitrile
Tensile
strength
(psi)
4000
3500
3000
4000
4000
Elongation
(%)
700
700
700
700
600
Modulus
(psi)
2500
2500
1000
1000
1500
Lower use T
C
-50
-50
-50
-50
-50
Upper use T
C
80
110
100
100
120
Weather
resistance
Fair
Fair
Excel
Excel
Poor
Oil
resistance
Poor
Poor
Poor
Fair
Ecel
Electrical
04/11/16
properties
Excel
Fair
Excel
Good
Fair
582
Thermoplastic Elastomers (EPM

and EPDM)
Many of the properties of thermoset elastomers
Resiliency
Elasticity
More easily processed

Injection molding, extrusion and other standard
thermoplastic processes
Highly compatible with polyolefins
EPDM is crosslinked very lightly and may not be
capable of being melted
04/11/16
583
Thermoplastic Olefin Elastomers

(TPO)
Block tripolymers (such as SBS) with hard
and soft domains
Poor compatibility with other rubbers
Melt processible
04/11/16
584
TABLE 1.8 Principal Types of Synthetic Rubber

Type
Description
Styrene-butadiene Copolymer of the two monomers in various proportions depending on

properties desired; called SBR for styrene-butadiene rubber
Polybutadiene
Consists almost entirely of the cis-1,4 polymer
Ethylenepropylene
Often abbreviated EPDM for ethylene-propylene-diene monomer;

made up principally of ethylene and propylene units with small amounts
of a diene to provide unsaturation
Polychloroprene
Principally the trans-1,4polymer, but also some cis-1,4 and 1,2 polymer;
also known as neoprene rubber
Polyisoprene
Nitrile
Butyl
Mainly the cis-1,4 polymer; sometimes called synthetic natural rubber

Copolymer of acrylonitrile and butadiene, mainly the latter
Copolyner of isobutylene and isoprene, with only small amounts of the
Latter
Contains inorganic backbone of alternating oxygen and methylated silicon
atoms; also called polysiloxane
Elastomers prepared by linking polyethers through urethane groups
Silicone
Urethane
04/11/16
585
Copolymerization & Copolymers

The process of polymerising two or more than
two monomers together is copolymerisation
and the polymer formed copolymer
The term copolymer is better referred to
addition polymers.
The copolymers often possess the properties
shown by the homopolymers made from the
constituent monomers of the copolymer.
04/11/16
586
Why Copolymers?
Practical Importance
Variety of copolymers by varying nature and
amounts of each monomer
Produce properties not available with
Homopolymers
04/11/16
587
Types of copolymers
AABBBAAABABBAAABBA
Random
ABABABABABABABA
Alternating
AAAAAAAAABBBBBBBAAAAAABBBB
Block
AAAAAAAAAAAAA
Graft
04/11/16
B
BBBBBBBBBBBBB
588
Diblock copolymers
Triblock copolymers
Block Copolymer:
Macromolecule, that is composed of
at least two different monomers
in a block-like structure.
(AB, ABA, ABC...)
ABC=(A)x(B)y(C)z
ABA=(A)x(B)Y(A)z
ABC=(A)x(B)y(C)z
04/11/16
show
phase-separation
in the solid-state,
in selective solvents,
on surfaces.
589
Block Copolymer Properties

change
With the type of structure Di, Tri, Multi, Radial..
With the total molecular weight and % Block
With the different monomers used in making
blocks
Thus there is need for tailor-made polymers
04/11/16
590
Block copolymers have

become important in recent
years
Advances in polymerization techniques
Newer applications in green chemistry,
nanoscience and biotechnology
04/11/16
591
Block Copolymer Characterization

Type,Total mol wt, % Blocks, Microstructure,
Spectroscopy
Thermal analysis
Light scattering
Chromatography
04/11/16
NMR &IR
DSC&TGA
SLS,DLS,SAXS,SANS
GPC
592
Properties in Solution
Adsorption characteristics on to
surfaces
Aggregation in solution
Distinct structural moieties in block
copolymers make them behave like
surfactants ( Amphiphiles)
04/11/16
593
Hydrophilic- Hydrophobic Copolymers

or
Amphiphilic Block Copolymers
04/11/16
594
A Hydrophilic-Hydrophobic Block Copolymer
PMMA
(polymethylmethacrylate)
PS
(polystyrene)
Negative charge on the
Neutral hydrocarbons
oxygen makes it hydrophilic.
make it hydrophobic.
04/11/16
595
Phase Diagram of a Diblock Copolymer

Hydrophilic + Hydrophobic
Data
Interaction Strength
Theory
Volume Fraction
04/11/16
596
Triblock Copolymers:
Even more Options
04/11/16
597
Various Block Copolymer Phases
Cylinders (or vertical sheets)

04/11/16
Spheres (or vertical cylinders)

598
Block copolymer adsorption

Water soluble copolymeric surfactants like
pluronics adsorb at air/water interface and
significantly reduce surface tension.
Water insoluble copolymeric surfactants
form insoluble monolayers that can have
different phases.
Block copolymers can efficiently adsorb on
to the solid/liquid or liquid/liquid surfaces,
thus sterically stabilize sols, latexes and
emulsions.
04/11/16
599
Amphiphiles at Interfaces e.g. Air / Water

CMC = critical micelle
conc.
KP = Krafft point
cmc
Micellar Characteristics:
- size
(3-5 nm)
(sphere, rod,..)
- shape
- agg number (20-...)
(s to ms)
- dynamics
- amphiphiles reduce surface energy
-hydrophobic effect = entropy

loss of oriented water-molecules
around the hydrophobic tail
04/11/16
600
Aggregation behaviour
In selective solvent , block copolymers
aggregate to form micelle
Hydrophilic-hydrophobic block copolymers
form micelle in water.
PEO-PPO-PEO ( Pluronics) block
copolymers form micelle in water and are
commercially available surfactants
04/11/16
601
Surfactant Aggregates
Unimers
Normal micelles
Cylindrical
Spherical
Inverted hexagonal phase
Reverse micelles
Bilayer lamella
4 nm
04/11/16
602
Aggregation in solution
Apart from spherical and rod like micelles,
concentrated copolymers solutions form
different liquid crystalline phases that control
the rheology of solutions.
Micelle shape and size and the existence of
lc phases depends on the molecular
characteristics of copolymer and external
factors like temperature, pressure, pH ,
presence of additives etc.
04/11/16
603
Phase Diagram of an Oil/Water/Amphiphile Mixture
04/11/16
604
APPLICATIONS
Block Copolymers
Several commercial products are
available as thermoplastic elastomers
(e.g. styrene- diene block polymers as
Solprene Philips; Kraton; Shell.
04/11/16
605
The use of styrene- butadiene and styrene-isoprene

block copolymer as thermoplastic elastomers in
footwear is well known.
The other thermoplastic elastomers are polyetherpolyester and polyether-polyamide.
Thermoplastic elastomers combine the properties of
a rubber and the processing characteristics of a
thermoplastic which make these materials of great
industrial importance.
04/11/16
606
Styrene-diene and styrene-hydrogenated

diene triblock copolymers are reportedly
good pressure sensitive adhesives and are
used for bitumen modification.
The interfacial characteristics make block
copolymers useful materials as polyblends,
as adhesives, sealants, binders for laminates,
as constituent of coating materials, surface
modifiers for fillers and fibers.
Blending of block copolymers with other
polymers provides new polymeric materials
with desired properties. Some grades of high
impact polystyrene are such systems
04/11/16
607
04/11/16
Surfactant based applications of block

copolymers are as colloid stabilizers,
in dispersion polymerization in
aqueous and nonaqueous media ,
in emulsion stabilization,
in microemulsion polymerization
in polymeric emulsions.
608
EO/PO block copolymers find numerous

applications in medical, pharmaceutical,
textile, cosmetic, detergents and pesticidal
formulations.
Their reversible thermorheological feature
makes them potential candidates for
controlled release.
04/11/16
609
Block Copolymer:
Macromolecule, that is composed of at least two different
monomers
in a block-like structure.
(AB, ABA, ABC...)
Diblock copolymers
Triblock copolymers
ABC=(A)x(B)y(C)z
ABA=(A)x(B)Y(A)z
ABC=(A)x(B)y(C)z
04/11/16
610
Block Copolymer properties depends on
1. Change in the structure (Di, Tri, Multi, Radial, .. etc.
2. Change in the molecular weight and the % block.

3. Different monomers used in making the block.
04/11/16
611
PEO-PPO-PEO (Pluronic)
CH 3
HO
C H 2C H 2O
CH CH 2O
m/2
CH 2CH 2O H
n
m/2
PEO hydrophilic and PPO hydrophobic

Form core shell micelle in dilute solutions. Micellization strongly
concentration and temperature dependent
Show reversible thermorheological behaviour and various LC
phases in concentrated solutions
Prepared by the reaction of preformed polypropylene glycol and
ethylene oxide.
04/11/16
612
Typical mol mass of PPO group
4000
3625
3250
2750
2250
2050
1750
1450
1200
950
04/11/16
10
20
30
40
50
% PEO
60
70
80
613
Pluronics: Applications
Dispersant/emulsifier/solubilizer/ and for rheology

control in different industries.
Surface modification of biocolloids
In making mesoporous silica
Controlled release of bioactive molecules, for artificial
blood
04/11/16
614
The performance based properties of Pluronics can

be enhanced in presence of various stimulies.
Temperature
Concentration
Salts
Surfactants
Hydrotropes
Urea and its derivatives.
04/11/16
615
Block Copolymer Basics

MOST polymers DO NOT mix
(like oil and water).
Polymer A
04/11/16
Lets consider the
Polymer B
fundamentals of mixing
616
04/11/16
617
Rubinstein, M. and Colby, R. H. Polymer Physics, Oxford University Press, 2003.
Microphase Separation
Most polymers are immiscible
Block Copolymer Basics

The chemically different segments of a block
copolymer cannot completely phase
separate, because they are covalently
bound (frustrated separation).
The propensity of two different polymers to
phase separate can lead to interesting
solid-state and solution morphologies.
Lets consider the parameters affecting

04/11/16
phase
separation in diblock copolymers
619
The radial polymer is a star-like polymer in which the arms are of

polymer chains which are attached to a common centre.
For Pluronics, temperature and dilution of micelles is the main route

of drug release. With increase in temperature, the micelles will
collapse due to dehydration at some temperature, the same can be
tuned by the polymer structural properties and salt conditions.
Similarly, with dilution, micelles will be broken and converted back to
monomers, simultaneously releasing the drug molecules.
04/11/16
620
04/11/16
621
Diblock Morphologies (TEM)

Spheres
PS-b-PI
fPS = 0.16
100 nm
Han, C. D.; Vaidya, N. Y.; Kim, D.; Shin, G.; Yamaguchi, D.; Hashimoto, T.;
Macromolecules 2000, 33(10), 3767-3780.
04/11/16
622

Cylinders
(Dendritic Benzyl Ether)-b-PS
Stained w/ RuO4
Pochan, D. J.; Pakstis, L.; Huang, E.; Hawker, C.; Vestberg, R.;
Pople, J.; Macromolecules 2002, 35(24), 9239-9242.
200 nm
04/11/16
624
Lamellae
PS-b-PI fPS = fPI
Stained with OsO4
Bailey, T.S.; Pham, H. D.; Bates, F. S.
Macromolecules 2001, 34, 6994-7008.
04/11/16
50 nm
625
PS-b-PI
Same magnification
Same volume fraction
Left: MW = 104
Right: MW = 105
04/11/16
626
PS-b-PI
45% PS
Differences in
TEMs?
discrete block copolymer
tapered block copolymer
Copolymerization Kinetics
Homo-propagation
Cross-propagation
Cross-propagation
Homo-propagation
Styrene = M1
Bd = M2
r1 = k11 / k12 = 0.04

r2 = k22 / k21 = 26
For free radical r2 >>1 and r1 < 1 gives.?

For living polymerization r2 >>1 and r1 < 1 gives.?
Block Copolymer Uses

Unique properties of triblocks
04/11/16
629
04/11/16
630
Triblock Morphologies
04/11/16
631
Bates, F.S., 1999 MSRI Lecture notes: http://www.msri.org/publications/ln/msri/1999/materials/fbates/1/banner/03.htm,

accessed 9/2003.
04/11/16
632
TEM of PI-b-PS-b-PDMS
04/11/16
633
Bates, F.S., 1999 MSRI Lecture notes: http://www.msri.org/publications/ln/msri/1999/materials/fbates/1/banner/03.htm,
accessed 9/2003.
Phase Separation in
PS-b-(PE-co-PB)-b-PMMA
0.5m
04/11/16
634
Breiner, U.; Krappe, U.; Thomas, E. L.; Stadler, R. Macromolecules 1998, 31, 134-141.
Order-Disorder Transition
S ~ 1/N
04/11/16
Micro-phase separation
635
Diblock Copolymer Morphology

From M. Matsen
04/11/16
Morphology not sensitive to chain architecture
636
Phase Diagram of Diblock

Copolymers
Two parameters:
f and N
Mean Field Theory
04/11/16
M. Matsen and W. Schick, Phys. Rev. Lett, 72, 2660(1994).
637
Complex Block Copolymers
From G. H. Fredrickson and F. S. Bates
04/11/16
Rich and variety chain architectures
638
Triblock Copolymers
A
C
C
A
A
04/11/16
Block Sequence
Chain Architecture
Parameter space increases 18-fold
639
A Challenge
Can we effectively predict

new morphologies and their
stability?
YES!
Self-Consistent Field Theory
04/11/16
640
Influence of Chain Architecture

C
C
VS
A
P. Tang, F. Qiu, H. D. Zhang, Y. L. Yang, J. Phys.

Chem. B, 108, 8434(2004).
04/11/16
641
Phase Diagrams of ABC

Triblocks
A
04/11/16
AB= BC= AC = 35
642
3D Structures
04/11/16
643
Polymer Additives and

Compounding
It is relatively rare for an article to be made from
polymer alone.
Most are polymer compounds, consisting of a
mixture of polymer and various additives.
04/11/16
644
Polymer Additives and

Compounding
Fillers
Colorants
Stabilizers thermal, oxidative, UV
Plasticizers
Flame retardants
Lubricants
Others
04/11/16
645
Fillers
Particulate silica, sand earth, mica, talc
Fibrous cellulose, nylon, polyester,
carbon, PVC
Enhanced properties dimensional
stability; impact resistance; tensile and
compressive strength; abrasion
resistance; thermal stability
04/11/16
646
Fillers
To strengthen a polymer by restricting
chain mobility
Inert materials are used, e.g., short fibercellulose and asbestos
04/11/16
647
Fillers
Fillers: solid additives used to modify physical
properties.
Dilution - talc
Reinforcing - carbon black in tires
Toughening - rubber in ABS plastic
04/11/16
648
Fillers
Phenolic and amino resins are always
filled with substances like wood flour,
short-fiber cellulose or powdered mica.
Glass fiber as a reinforcing filler for
polyester resins
Calcium carbonate fillers dominate the
market
04/11/16
649
Filler Reinforcement
Inert fillers like clay make rubber easier to
handle before vulcanization, but have no
effect on physical properties
04/11/16
650
Filler Reinforcement
Inert fillers like clay make rubber easier to
handle before vulcanization, but have no
effect on physical properties
04/11/16
651
Plasticizers
Benefits: improve flow; improve processability;
reduce brittleness of the product.
Achieved by lowering the glass transition
temperature below room temperature, thus
achieving a change in properties from hard,
brittle, glasslike solid to soft, flexible, tough
material
Examples: phthalate esters; glycol derivatives
04/11/16
652
Plasticizers
To soften a polymer
Blending with a low-molecular weight
polymer
04/11/16
653
Plasticizers
Plasticizers: non-volatile solvents added to
improve flexibility
Dialkyl phthalates in poly(vinylchloride)
04/11/16
654
Plasticizers requirements
Basic requirements to be met by a
plasticizer are compatibility and
permanence.
The plasticizer must be miscible with the
polymer
Similarity in the intermolecular forces
active in the two components
04/11/16
655
Plasticizers requirements
Permanence requirements demand low
vapor pressure and a low diffusion rate of
the plasticizer within the polymer.
04/11/16
656
Efficiency of plasticization
The efficiency of the plasticizer in bringing
about the desired changes in properties is
important for its proportion
04/11/16
657
Evaluation of plasticizer efficiency

Amount of nonsolvent needed to cause phase separation
when added to polymer-plasticizer solution (dilution ratio)
Viscosity of dilute solutions of the polymer in the
plasticizer
Polymer-solvent interaction constants measured on
these solutions
Depression of the glass transition temperature
Melt viscosity of the plasticized polymer
Electrical or mechanical properties of the plasticized
polymer
Molecular size, shape, and viscosity of the plasticizer
04/11/16
658
Various plasticizers
Phthalate esters
Phosphate esters
Adipates, azelates, oleates
Epoxy plasticizers
Fatty acid esters
Glycol derivatives
Sulfonamides
Hydrocarbon and hydrocarbon derivatives
serving as secondary plasticizers
04/11/16
659
Stabilizers
To reduce polymer degradation, e.g. to
retard the room temperature oxidation by
adding complex phenol group
04/11/16
660
Antioxidants
Preventing or inhibiting the oxidation of the
polymer
Preventing degradation of the polymer
Examples phenols, aromatic amines
04/11/16
661
Antioxidants
Preventing or inhibiting the oxidation of the
polymer
Preventing degradation of the polymer
Examples phenols, aromatic amines
compounds that reduce polymer degradation
through intervention in free radical reactions
04/11/16
662
Antioxidant
The antioxidant may itself be readily
oxidized, or it may combine with the
oxidizing polymer to form a stable product
04/11/16
663
04/11/16
664
Flame retardant
To reduce the inherent combustibility
Halogens, e.g. Cl atoms, by terminating
free-radical chain reaction
Antimony Trioxide
Phospahte ester plasticizers reduce
flammability in vinyl resins
04/11/16
665
Factors in reducing the flammability

of materials
A) Elimination of volatile fuel, as by
cooling
B) Production of a thermal barrier, as by
charring, thus eliminating fuel by reducing
heat transfer
C) Quenching the chain reactions in the
flame, as by adding suitable radical
scavengers
04/11/16
666
Polymer Additives
04/11/16
667
Colourants
Colourants: additives used to change product
aesthetics
Pigments - soluble colourants
Dyestuffs - insoluble additives
04/11/16
668
Colourants
To provide colour to a polymer
Pigments (insoluble), and dyes (soluble
and provide transparent colour)
04/11/16
669
Organic pigments
Organic pigments such as
phthalocyanines are molecularly
dispersed (oil soluble dyes) and have
small particle size and a refractive index
near that of the plastic and lead to
transparent coloured products
04/11/16
670
Inorganic pigments
Impart opacity to the plastic

White titanium dioxide and barium sulfate
Phthalocyanine blue and green
Ultramarine blue
Chrome greens
Quinacridone reds
Molybdate orange
Cadmium reds and yellows
Carbon black
Flake aluminum for silver metallic effect
Lead carbonate or mica for pearlescence
04/11/16
671
Blending
The coloring of plastics is normally carried
out by
adding the colourants to the powdered plastic
Tumbling
Compounding on hot rolls or in an extruder
04/11/16
672
PMMA
Coloured castings of poly(methyl
methacrylate) PMMA are produced by
dissolving or dispersing the colourants in
the syrup before polymerizing.
04/11/16
673
Colour Concentrates
Colour concentrates, consisting upto 70%
pigment in resin, that can be let down
with upto 200 times as much uncolored
resin by the plastics processor.
04/11/16
674
Stabilizers
Use of carbon black to prevent
photochemical degradation (by excluding
light) in polyethylene
Ultraviolet light absorbers, such as
hydroxybenzophenones, to improve the
light stability of both plastics and their
colourants
04/11/16
675
Compounding
Selection of additives to modify the
properties of a polymer
To their incorporation with the polymer to
give a homogeneous mixture, in a form
suitable for efficient use in subsequent
processing or fabrication step
04/11/16
676
Traditional Compounding Device

Two Roll Mill
By proper selection of temperatures and
speed of rotation, the plastic is made to
adhere to the front roll, except as it is cut
off by the operator
The compounding ingredients are added
to the plastic mass as it passes between
the rolls
04/11/16
677
Modern Compounding Device

Compound or mixer extruder
Function of the mixing section of the screw
is emphasized
Advantages: contamination is reduced;
inert atmosphere or vacuum may be
utilized; continuous processes are more
readily achieved
04/11/16
678
Other Compounding Devices

Internal mixers:
Kneaders
Masticators
Paddle blenders
Tumblers
blenders
04/11/16
679
Determination of molecular weight
a. Absolute method :
mass spectrometry
colligative property
end group analysis
light scattering
ultracentrifugation.
b. Relative method : solution viscosity
c. Fractionation method : GPC
04/11/16
680
POLYMER CHEMISTRY
SOLUTION VISCOSITY
Solution viscosity is used as a measure of
polymer molecular weight. It is basically a
measure of the size or extension in space of
polymer molecules.
Measurement of solution viscosity is made by
comparing the efflux time required for a specific
volume of polymer solution to flow through a
capillary tube with the corresponding efflux time
of the solvent. Measurement at a series of
concentrations are made and extrapolation is
made at c=0.
04/11/16
681
FIGURE 2.8. Capillary viscometers : (A) Ubbelohde, and (B) Cannon-Fenske.
04/11/16
682
FUNCTIO
NALCHEMISTRY
PO LYMERS LAB
POLYMER
Nomenclature of Solution Viscosity

Relative viscosity: r = /o = t/to
Specific viscosity: sp = (-o)/o
Reduced viscosity: red = sp/c
Inherent viscosity: inh = (ln r)/c
Intrinsic viscosity: [] = (sp/c)c=0
04/11/16
683
Huggins Equation
Viscosity data as a function of
concentration are extrapolated to infinite
dilution
sp/c = [] + k[]2c
k is a constant for a series of polymers of
different molecular weights in a given
solvent
04/11/16
684
INTRINSIC VISCOSITY-empirical
correlation
[] = KMa
Where [] = intrinsic viscosity
M=molecular weight
K and a are constants determined from a double
logarithmic plot of intrinsic viscosity and molecular weight
04/11/16
685
TABLE 2.3. Representative Viscosity-Molecular Weight Constantsa

Polymer
Solvent
Polystyrene
(atactic)c
Cyclohexane
Cyclihexane
Benzene
Decalin
Polyethylene
(low pressure)
Polybutadiene
98% cis-1,4, 2% 1,2
97% trans-1,4, 3% 1,2
Polyacrylonitrile
Benzyl
alcohol
Cyclohexano
ne
Toluene
Toluene
Poly(methyl methacrylate-co-DMFg
DMF
styrene)
30-70 mol%
71-29 mol%
Poly(ethylene terephthalate) 1Chlorobutane
Nylon 66
1Chlorobutane
a
Value taken from Ref. 4e. M-Cresol
b
See text for explanation of these
constants.
M-Cresol
c
Atactic defined in Chapter 3.
d
temperature.
e
Weight average.
f
Number average.
g 04/11/16
N,N-dimethylformamide.
Temperature,Molecular Weight
o
C
Range 10-4
35 d
8-42e
50
4-137e
25
3-61f
135
3-100e
155.4d
20
4-35e
7-13f
30
30
25
25
5-50f
5-16f
5-27e
3-100f
30
30
25
25
5-55e
4.18-81e
0.04-1.2f
1.4-5f
Kb 103
80
26.9
9.52
67.7
ab
0.50
0.599
0.74
0.67
156
13.7
0.50
1.0
30.5
29.4
16.6
39.2
0.725
0.753
0.81
0.75
17.6
24.9
0.77
240
0.67
0.63
0.95
0.61
686
POLYMER CHEMISTRY

B. Light source
High pressure mercury lamp and laser light.
C. Limitation of molecular weight( ) : 104 107
FIGURE 2.7.
Schematic of a laser
light-scattering
photometer.
04/11/16
687
FUNCTIO
NALCHEMISTRY
PO LYMERS LAB
POLYMER
2.4 Measurement of Weight Average Molecular Weig

A. The intensity of scattered light or turbidity() is depend on following fa

a. size
b. concentration
c. polarizability
d. refractive index
e. angle
f. solvent and solute interaction
04/11/16
688
POLYMER CHEMISTRY

= HcMW
32
H= 3
No2(dn/dc)2
4No
Hc = 1 + 2A C
2
MP()
C : concentration
no: refractive index of the solvent
: wavelength of the incident light
No : Avogadro's number
dn/dc : specific refractive increment
P() : function of the angle,
Zimm plot (after Bruno Zimm) : double extrapolation of concentration
and angle to zero (Fig 2.6)
04/11/16
689
POLYMER CHEMISTRY
FIGURE 2.6. Zimm plot of light-scattering data.
Hc
1
Mw
C=0
Experimental
Extrapolated
sin2/2 + kc
04/11/16
690
FUNCTIO
NALCHEMISTRY
PO LYMERS LAB
POLYMER
04/11/16
691
04/11/16
692
04/11/16
693
FIGURE 2.2 Schematic representation of a membrane

osmometer.
04/11/16
694
2.3.2 Membrane Osmometry

A. According to van't Hoff equation
RT
)C=0 =
+ A2C
c
Mn
limitation of : 50,000 2,000,000

The major error arises from low-molecular-weight species diffusing
through the membrane.
FIGURE 2.3 Automatic membrane osmometer [Courtesy of Wescan Instruments
04/11/16
695
FIGURE 2.4. Plot of reduced osmotic pressure (/c) versus concentration (c).
/c
RT
Mn
Slope = A2
04/11/16
696
POLYMER CHEMISTRY
04/11/16
697

A. Freezing-point depression (Cryoscopy)
RT2
Tf
+ A2C
(
)C=0 =
Hf Mn
C
Tf : freezing-point depression,
C : the concentration in grams per cubic
centimeter
R : gas constant
T : freezing point
Hf: the latent heats of fusion
04/11/16
698
POLYMER CHEMISTRY
04/11/16
699

B. Boiling-point elevation (Ebulliometry)
RT2
Tb
+ A2C
(
)C=0 =
C
HvMn
Tb : boiling point elevation

H v : the latent heats of vaporization
We use thermistor to major temperature. (110-4 )
04/11/16
700
POLYMER CHEMISTRY
04/11/16
701
2.3.4 Vapor Pressure Osmometry

The measuring vapor pressure difference of solvent and solution
drops.
RT2
T = (
)m
100
solvent
: the heat of vaporization per gram of

m : molality

Calibration curve is needed to obtain molecular weight of polymer
sample
Standard material : Benzil
04/11/16
702
POLYMER CHEMISTRY
04/11/16
703
Molecular Weight Distribution

2.6.1 Gel Permeation Chromatography (GPC)
A. GPC or SEC (size exclusion chromatography)
a. GPC method is modified column chromatography.
b. Packing material: Poly(styrene-co-divinylbezene),
glass or silica bead swollen and porous surface.
c. Detector : RI, UV, IR detector, light scattering detector
d. Pumping and fraction collector system for elution.
e. By using standard (monodisperse polystyrene), we can obtain
04/11/16
704
POLYMER CHEMISTRY
Mn
04/11/16
705
04/11/16
706
04/11/16
707
04/11/16
708
FIGURE 2.9. Schematic representation of a gel permeation

chromatograph.
04/11/16
709
POLYMER CHEMISTRY
FIGURE 2.10. Typical gel permeation chromatogram. Dotted lines represent volu
Detector
response
04/11/16
Baseline
Elution volume (Vr) (counts)
710
POLYMER CHEMISTRY
FIGURE 2.11. Universal calibration for gel permeation chromatography. THF, tetra
Log([]M)
109
Polystyrene (linear)
Polystyrene (comb)
Polystyrene (star)
Heterograft copolyner
Poly (methyl methacrylate)
Poly (vinyl chloride)

Styrene-methyl methacrylate graft copolymer
Poly (phenyl siloxane) (ladder)
Polybutadiene
107
108
106
105
04/11/16
18
20
22
24
26
Elution volume ()5 ml counts, THF solvent)
28
30
711
POLYMER CHEMISTRY
FIGURE 2.12. Typical semilogarithmic calibration plot of molecular weight versus

retention volume.
Molecular weight (M)
106
105
104
103
Retention volume (Vr) (counts)
04/11/16
712
POLYMER CHEMISTRY
One dimensional polymer

Since the days of Staudingers enunciation of the
Macromolecular Hypothesis in 1920, people
have been increasingly aware of the long chain
structure of most polymers.
Most of these polymers consist of long chains of
carbon atoms with various amounts of hydrogen,
oxygen, nitrogen, or other atoms and groups
attached to the backbone.
Basically, these chains can be considered to be
one dimensional in that the chain structure can
be written in a straightforward line.
04/11/16
713
Crystalline
Example: Polyethylene
04/11/16
714
Two- and three- dimensional

polymers
Polymers based entirely on carbon exist, however,
with no other element present.
Scientists have long been familiar with graphite, a
two-dimensional planar structure of carbon.
By simple extension of Staudingers logic, this
should be considered a two-dimensional polymer.
By further extension of Staudingers hypothesis,
diamond is a three-dimensional polymer.
Note that both of these materials are of very high
molecular weight for each molecule, and that both
of these materials are 100% carbon, with no other
atoms required.
04/11/16
715
Graphite and Diamond

It must be noted that while the diamond structure is
composed entirely of carbon-carbon single bonds
spaced at the traditional 109 angle, graphite
constitutes a large planar sheet of aromatic rings,
with the traditional alternating double and single
bonds.
Of course, both of these allotropic forms of carbon
have been known throughout history, but not
necessarily recognized as polymers.
However, graphite has long had the derisive
nickname poly(vinyl chicken wire) in honor of its
polymeric nature.
04/11/16
716
Allotropes of carbon
Diamond: consists of carbon atoms that are
tetrahedral bonded to each other through sp 3
hybrid bonds that form a three dimensional
network. Each carbon atom has four nearestneighbor carbons.
Graphite has a layered structure with each layer,
called a graphitic sheet, formed from hexagons
of carbon atoms bound together by sp 2 hybrid
bonds that make 1200 angles with each other.
Each carbon atom has three nearest neighbor
carbons in the planar layer.
04/11/16
717
Allotropes of carbon
Diamond and graphite are two allotropes of carbon: pure forms of the
04/11/16
718
same element that differ in structure.
Contour length
Contour length is a term used in
molecular physics.
The contour length of a polymer chain is
its length at maximum physically possible
extension.
04/11/16
719
Persistence length
The persistence length is a basic
mechanical property quantifying the stiffness
of a polymer.
Informally, for pieces of the polymer that are
shorter than the persistence length, the
molecule behaves rather like a flexible elastic
rod, while for pieces of the polymer that are
much longer than the persistence length, the
properties can only be described statistically,
like a three-dimensional random walk.
04/11/16
720
Kuhn length
The Kuhn length is a theoretical treatment,
developed by Werner Kuhn, in which a real
polymer chain is considered as a collection
of N Kuhn segments each with a Kuhn
length b.
Each Kuhn segment can be thought of as if
they are freely jointed with each other.
For semiflexible chain, Kuhn length equals
two times the persistence length.
04/11/16
721
Chain length
Each segment in a freely jointed chain can
randomly orient in any direction without the
influence of any forces, independent of the
directions taken by other segments.
Thus the real chain consisting of n bonds and with
fixed bond angles and bond lengths is replaced by
an equivalent chain with N connected Kuhn
segments that can orient in any random direction.
The length of a fully stretched chain or the contour
length is L = Nb for the Kuhn segment chain.
04/11/16
722
Random Walk
In the simplest treatment, such a chain follows the
random walk model, where each step taken in a random
direction is independent of the directions taken in the
previous steps, forming a random coil.
The average end-to-end distance for a chain satisfying
the random walk model is < R2 > = Nb2.
Since the space occupied by a segment in the polymer
chain cannot be taken by another segment, a selfavoiding random walk model can also be used.
The Kuhn segment construction is useful in that it allows
complicated polymers to be treated with simplified
models as either a random walk or a self-avoiding walk,
which can simplify the treatment considerably
04/11/16
723
Random Walks
end-to-end distance
a
n 1
R02
r2
an a m
n ,m
2
2
a
Na
nm
n ,m
R0 ~ N
radius of gyration
1 N
R
Ri R
N 1 i 0
2
g
1
Ri R j 2
2 N N 1 i , j
1
2
N
1
R
Ri
N 1 i 0
1
1
N 1 2 Na 2
2
2
ri ri1 ... rj1
i ja
a ~
N N 1 i j
N ( N 1) i j
6
6
In general, we have
R04/11/16
N
~
R
N
~
N
0
g
for a real polymer chain
724
Random walks a chain

model
For a polymer chain model;
Consider random steps of
equal length, a, defined
by chemical bonds
Complications:
Excluded volume effects
Steric limitations
The chain end-to-end vector R

describes a coil made up of N
jump vectors ai.
Random walk
N
R ai
R is made up of N jump vectors ai . The average of all

conformational states of the polymer is <R>=0
i 1
aj
N 1 N
The simplest non-zero average is the meansquare end to end distance <R2>
R 2 Na 2 2a 2 cos ij
i 1 ji 1
(A matrix of dot-products where the

diagonal represents i=j and off axis
elements ij)
For a freely jointed chain the average of the cross terms above is zero
and we recover a classical random walk: <R2>=Na2
The rms end to end distance <R2>1/2=N1/2a

04/11/16
726
A size example:
An ideal polymer chain with 106 repeat units
(not unusual), each unit about 6 will
have:
a rms end-to-end distance R of 600 nm
a contour length of 600 m
The rms end to end distance <R2>1/2=N1/2a
E. Hydrodynamic volume of polymer molecules in

solution.
to be depended on followings
a. polymer-polymer interaction
b. solvent-solvent interaction
c. polymer-solvent interaction
d. polymer structure ( branched or not )
e. brownian motion
r = end-to-end distance
s = radius of gyration
Figure 2.1 Coil molecular shape
r 2 = r o2 2
s 2 = s o2 2
(r2)1/2
=
(ro2)1/2
04/11/16
The greater the value of , the better

the solvent
= 1, 'ideal' statistical coil.
728
Polymer Solutions
F. theta() temperature and theta() solvent
The lowest temperature at which =1 : theta() temperature
The solvent satisfied this condition : theta() solvent point
G. Flory-Fox equation :
The relationship among hydrodynamic volumes,
intrinsic viscosity and molecular weight
[] =
04/11/16
(r2)3/2
M
[] : intrinsic viscosity
M : average molecular weight
: Flory constant (31024/mol)
r : end-to-end distance
729
POLYMER CHEMISTRY
The expansion parameter
r depends on balance between i) polymer-solvent and ii)

polymer-polymer interactions
If (ii) are more favourable than (i)
r < 1
Chains contract
Solvent is poor
If (ii) are less favourable than (i)
r > 1
Chains expand
Solvent is good
If these interactions are equivalent, we have theta condition

r = 1
Same as in amorphous melt
04/11/16
730
The theta temperature

For most polymer solutions r depends on temperature, and
increases with increasing temperature
At temperatures above some theta temperature, the solvent is
good, whereas below the solvent is poor, i.e.,
T>
r > 1
T=
r = 1
T<
r < 1
Often polymers will precipitate out of solution,

rather than contracting
04/11/16
What determines whether or not a polymer is soluble?
731
Random Walks
end-to-end distance
a
n 1
R02
r2
an a m
n ,m
2
2
a
Na
nm
n ,m
R0 ~ N
radius of gyration
1 N
R
Ri R
N 1 i 0
2
g
1
Ri R j 2
2 N N 1 i , j
1
2
N
1
R
Ri
N 1 i 0
1
1
N 1 2 Na 2
2
2
ri ri1 ... rj1
i ja
a ~
N N 1 i j
N ( N 1) i j
6
6
In general, we have
R04/11/16
N
~
R
N
~
N
0
g
for a real polymer chain
732
Polymer Theories
1. Polymer Network Theories
2. Single-Molecule Theories
04/11/16
733
Polymer Network Theories

The network theories were originally
developed for describing the mechanical
properties of rubber.
One imagines that the polymer molecules in
the rubber are joined chemically during
vulcanization.
The theories have been extended to
describe molten polymers and concentrated
solutions 04/11/16
734
Polymer Network Theories

by postulating an ever-changing network
in which the junction points are temporary,
formed by adjacent strands that move
together for a while and then gradually pull
apart.
It is necessary in the theory to make some
empirical statements about the rates of
formation and rupturing of the junctions.
04/11/16
735
04/11/16
736
04/11/16
737
04/11/16
738
Relaxation Times
04/11/16
739
Polymer solutions
Polymers in solutions are a major topic in
polymer science applied as well as theoretical.
Polymer segments in a solution have an
interaction energy with other (near by) segments
apart from covalent bonding: wpp
In a similar way we have an interaction energy
between the solvent molecules: wss
When the polymer becomes disolved we have a
new interaction energy between solvent and
polymer: wps
04/11/16
740
A -parameter for polymer solutions

Following the arguments we derive an expression for the
mixing when new p-s contacts are made and old p-p and
s-s contacts are lost:
z
2w ps w pp w ss
2k b T
The internal energy U will change with the addition of

polymer to a solvent:
U int
04/11/16
N2
k b T 2 3
R
741
The good the bad

and the theta
Combining the new expression for Uint with the previous for
coil swelling:
N2
Frep U int k b T(1 2)
R3
The value of x determines if excluded volume effects are

dominating or whether they are counteracted by the p-s
interaction:
When x=1/2 the two energies cancel and we have a theta
solvent with pure random walk conformation!
When x<1/2 the coil is swollen (A good solvent; Clint E?)
When x>1/2 the coil forms a globule (A bad or poor solvent)
04/11/16
742
Another important characteristics of

polymer solutions which
can be
determined from the value of [ ] is the
overlap
concentration of polymer coils c*
c < c*
Dilute polymer
solutions
c = c*
Overlap
concentration
c > c*
Semidilute
polymer solutions
N
1
R3
3 N 1 2a3
The average polymer concentration in the
solution is equal to that
inside one polymer
coil at the overlap concentration c*. Thus,
c
Since c* N/R3 , and [] R3/N , we have
1
practical
normally c
assumed
04/11/16 estimations it is
[]c* 1. For the

743
Solution Thermodynamics
Part 1
Statistical thermodynamics of a polymer chain
How much space does a polymer chain occupy?
Part 2
Chemical thermodynamics of polymer solutions
What determines solubility of a polymer?
Examine
(i) Models of polymer chain structure in solution
(ii) Interactions between polymers and solvents
04/11/16
744
The freely jointed chain
Simplest measure of a chain is the length along the backbone

For n monomers each of length l, the contour length is nl
l
1
04/11/16
. ..
745
A more useful measure is the

end-to-end distance r
For an isolated polymer in a solvent the end-to-end distance will

change continuously due to molecular motion
But many conformation give rise to the same value of r, and
some values of r are more likely than others e.g.,
Only one conformation with r = nl - a fully extended
chain
Many conformation have r = 0, (cyclic polymers)
Define the root mean square end-to-end distance
r
04/11/16
1
2
746
Key result for a freely jointed chain
04/11/16
1
2 2
nl
1
2 2
749
Bond angles and steric effects
Real chains are not freely jointed

Links between monomers subject to bond angle restrictions
Rotation hindered by steric effects
E.g., n-butane
Each bond angle = 109.5

Different conformations arise from rotation of 1 and 2 about 3-4
bond
Steric interactions between methyl groups not all angles of
rotation have the same energy
04/11/16
750
Valence angle model
Simplest modification to the freely jointed chain model

Introduce bond angle restrictions
Allow free rotation about bonds
Neglecting steric effects (for now)
If all bond angles are equal to ,

(1 - cos )
r 2 fa nl 2
(1 cos )
indicates that the result is for the valence angle model
E.g. for polyethylene = 109.5 and cos ~ -1/3, hence,
r 2 fa 2nl 2
04/11/16
751
Rotational isomeric state theory

Steric effects lead to
1 cos
r 0
1 cos
is defined by = 0 as the planar trans orientation
2
1 cos
nl
1 cos
2
<cos> is the average of cos, based on the probability of each

angle , determined by its associated energy and the Boltzmann
relation
cos 0 r 2
r2
fa
Generally | are the most energetically favourable angles

Steric effects cause chains to be more stretched
What about temperature effects????
04/11/16
752
Steric parameter and the

characteristic ratio
In general
r 2 0 2 nl 2
(1 - cos )
(1 cos )
where is the steric parameter, which is usually determined

for each polymer experimentally
A measure of the stiffness of a chain is given by the
characteristic ratio
C r 2 0 / nl 2
C typically ranges from 5 - 12
04/11/16
753
An equivalent freely jointed chain
A real polymer chain may be represented by an equivalent freely-jointed chain

Comprised of N monomers of length b such that the chains have the same
contour length, i.e., Nb = nl
Normally has fewer, longer joints
N n / C ; b C l
04/11/16
754
Excluded volume
Freely jointed chain, valence angle and rotational isomeric

states models all ignore
long range intramolecular interactions (e.g. ionic polymers)
polymer-solvent interactions
Such interactions will affect

Define
where
04/11/16
r2
r2 r 2
r2
is the expansion parameter
755
The expansion parameter
r depends on balance between i) polymer-solvent and ii)

polymer-polymer interactions
If (ii) are more favourable than (i)
r < 1
Chains contract
Solvent is poor
If (ii) are less favourable than (i)
r > 1
Chains expand
Solvent is good
If these interactions are equivalent, we have theta condition

r = 1
Same as in amorphous melt
04/11/16
756
The theta temperature

For most polymer solutions r depends on temperature, and
increases with increasing temperature
At temperatures above some theta temperature, the solvent is
good, whereas below the solvent is poor, i.e.,
T>
r > 1
T=
r = 1
T<
r < 1
Often polymers will precipitate out of solution,

rather than contracting
04/11/16
What determines whether or not a polymer is soluble?
757
Flory Huggins Theory
Dissolution of polymer increases conformational entropy of system

Molar entropy of mixing normally written as
mix
RV
V0
2
ln 1 ln 2
r2
r1
where i is the volume and volume fraction of each component (solvent =

1 and polymer = 2), ri is approximately the degree of polymerisation of
each component (r1 ~ 1, r2 ~ N)
Note that increasing the r2 decreases the magnitude of Smix
Flory Huggins Theory 2
Enthalpy of mixing
HMix = kT 2N1
where is the dimensionless Flory Huggins parameter.
For dilute solution of high molecular weight polymers, N~N 1
HMix = RT 2
Remember condition for thermodynamically stable solution
GMix = HMix - TSMix < 0
04/11/16
760
Practical Use of Polymer TDs

Fractionation
Consider solution in poor solvent

of two polymers, p1 and p2.
Flory-Huggins tells us that if p2
has higher molecular weight it
should precipitate more readily
than p1
add non-solvent until solution
becomes turbid
heat, cool slowly and separate
precipitate
finite drop in temperature always
renders finite range of molecular
weight insoluble
some p2 will also remain soluble!
1 phase clear solution
1
1
2
N 1
T
2 phase
cloudy p1
p2
2
volume fraction polymer
Summary
A little knowledge goes a long way!
Simple models enable us to predict the size of polymer

chains in solution
Critical to dynamic properties of solutions
Solubility of polymers generally decreases with
increasing molecular weight.
Can exploit this in fractionation procedures to purify
polymers
There are practical limits to how well fractionation can
work
04/11/16
762
Polymer Solutions
A. Process of polymer dissolution : two step
first step : the solvent diffuses into polymer masses to make
a swollen polymer gel
second step : swollen polymer gel breaks up to solution
04/11/16
763
POLYMER CHEMISTRY
Polymer Solutions
B. Thermodynamics of solubility :
Gibb's free energy relationship
G =H - TS
G < 0 : spontaneously dissolve
T and S are always positive for dissolving process.
Conditions to be negative G,
H must be negative or smaller than TS.
04/11/16
764
POLYMER CHEMISTRY
C. Solubility parameter :
Hmix=Vmix
[( E ) -(E ) ]
1
1/2
V1
1/2 2
1 2
V2
1, 2 = volume fraction
E1/V1, E2/V2 = cohesive energy densities
1, 2 = solubility parameter
1, 2 =
(E
V
1/2
Hmix= Vmix(1 2)2 1 2

E = Hvap- RT
1 =
04/11/16
H vap - RT
V
1/2
765
POLYMER CHEMISTRY
if 1= 2, then Hmix= 0
E. Hydrodynamic volume of polymer molecules in

solution.
to be depended on followings
a. polymer-polymer interaction
b. solvent-solvent interaction
c. polymer-solvent interaction
d. polymer structure ( branched or not )
e. brownian motion
r = end-to-end distance
s = radius of gyration
Figure 2.1 Coil molecular shape
r 2 = r o2 2
s 2 = s o2 2
(r2)1/2
=
(ro2)1/2
04/11/16
The greater the value of , the better

the solvent
= 1, 'ideal' statistical coil.
766
Polymer Solutions
F. theta() temperature and theta() solvent
The lowest temperature at which =1 : theta() temperature
The solvent satisfied this condition : theta() solvent point
G. Flory-Fox equation :
The relationship among hydrodynamic volumes,
intrinsic viscosity and molecular weight
[] =
04/11/16
(r2)3/2
M
[] : intrinsic viscosity
M : average molecular weight
: Flory constant (31024/mol)
r : end-to-end distance
767
POLYMER CHEMISTRY
Radius of Gyration of a Polymer Coil

The radius of gyration Rg is defined as the RMS
distance of the collection of atoms from their
common centre of gravity.
R
For a solid sphere of radius R;
2
Rg
R 0.632R
5
For a polymer coil with rms end-to-end distance R ;
1 2
Rg R
6
04/11/16
1/ 2
a 1/ 2
N
6
768
The excluded volume effect

Steric hindrance on short distances limits the
number of conformations
At longer distances we have a topological
constraint the self avoiding walk or the
excluded volume effect:
Instead of <R2>1/2=aN1/2 we will have
<R2>1/2=aN
where v>0.5
Experiments tells us that in general: v~0.6
Why?
04/11/16
769
Excluded volume according to Flory

Consider a cube containing N segments of a polymer
V=r3 where r is the radius of gyration.
The concentration of segments is c~N/r3
Each segment with volume stuffed into the cube reduces the
entropy with kbN/V = -kbN/r3
(for small x; ln(1-x)~lnx)
The result is a positive contribution to F; Frep= kbTN/r3 (expansion
of the coil)
From before; Coiling reduces the entropy; Fel=kbT3R2/2Na
The total free energy F is the sum of the two contributions!
Search for equilibrium!
04/11/16
770
Florys result for the swollen coil:

k b TN 2
k b TR 2
Ftot (R )
3
const
3
2
R
2 Na
dFtot 3k b TN 2 3k b TR
0
4
2
dR
R
Na
R 5 a 2 N 3
a3
R 5 a 5 N3
R aN
04/11/16
3/ 5
771
Polymer melts a simpler case

In dilute polymer solutions the
excluded volume effect is large.
(OBS Theta cond. Later)
When chains start to overlap

the expanding force on a
single coil will be reduced
In a polymer melt the
concentration of segments is
uniform due to space filling. No
swelling!
04/11/16
772
Q1: The tube model and the idea of

reptation
Every segment in the tube have a mobility, seg
restricted by the surrounding resistance.
The tube with N segments have a mobilty, tube= seg/N
Brownian motion within the tubes confinement use
Einstein relation to calculate a Diffusion coefficient =>
A polymer escapes from

its own tube of length L
after a time T
04/11/16
=> Dtube=kbT tube=kbT seg/N
T D tube L2
L2
N3
T
D tube const
Close to the
exp. results!
773
Q2; The rubber plateau and entanglements

In a similar way as we explained the elastic
behaviour at very short times for all simple liquids
as a glassy state we can explain the rubber
plateau in a qualitative way as a signature of
entanglements.
It can be shown that in a rubber, a cross linked polymer,

the elastic modulus depends on the average molecular
mass between cross-links Mx, R ,T and the density :
Adopting an identical relation and treating the
entanglements as temporary cross-links with a lifetime of
the order of T we can calculate an average mass of the
molecular mass between the entanglements (Me).
04/11/16
RT
G
Mx
774
Polymer solutions
polymer: wps
04/11/16
775

z
2w ps w pp w ss
2k b T

U int
04/11/16
N2
k b T 2 3
R
776
The good the bad

and the theta
coil swelling:
N2
R3

interaction:
04/11/16
777
This topic provides a link between

molecular characterisation techniques
concerned with how to measure properties of
polymers
and polymer physics

concerned with understanding how polymers behave
once their characteristics are known
A good starting point are dilute solutions

allows us to consider polymers in isolation
04/11/16
778
Dilute solutions
Chains do not overlap
Can consider that each chain
acts in isolation
Dynamic considerations:
Movement of polymers diffusion
Solutions under flow - viscosity
In semi-dilute solutions
concentration is sufficient for
chains to just overlap
Measuring Diffusion
Dynamic Light Scattering (DLS, PCS, QELS etc)
04/11/16
Light scattered from polymer chains in dilute solution

interferes producing a speckle pattern
Diffusion causes shimmering of speckle pattern as
polymer chains undergo Brownian motion
Can also view this as Doppler shift to frequency of
scattered light
Measure rate of shimmering with autocorrelation function
780
Interpretation of DLS data
Autocorrelation function G() leads to effective hydrodynamic

radius of polymer coil in solution.
I(t)
G 1 exp 2 Dq 2
4
q
sin
kT 1
6 Re
t
G()
where is the viscosity,
Dilute Solution Viscosity
A step towards understanding

dynamics in polymers
A useful practical tool for rapid

measurement of molecular
weights
Important relationship for

relative viscosity:
rel
t0 0
Suspended level dilution

viscometry
B C A
Solution pumped into E from A

with pressure and C closed
Pressure removed from A and C
opened
Solution flows back from E into D
Viscosity determines time for
height of solution to change from x
to y
Measurements can be repeated
for different concentrations by
diluting the solution via A
x
E
y
Ubbelohde Viscometer
Relative, specific, intrinsic
Relative viscosity
rel
solution viscosity
solvent viscosity
Specific viscosity
sp rel 1
Intrinsic viscosity
sp

c
c 0
extrapolated to
zero concentration
Viscosity measures
rel
sp
conc.
04/11/16
slope
=
785
Spheres
Einstein: for a solution of dilute noninteracting spheres

Viscosity increases according to...
0 1 2.5v 2
v2 is the volume fraction of spheres
What is the intrinsic viscosity?
The equivalent sphere

model I
Consider that each polymer chain is

impenetrable to solvent
with an effective hydrodynamic radius, Re
and volume
4
3
Re
3
Ve
For polymer equivalent spheres, Einstein

relation can be rewritten
n2
Ve
V
sp 2.5
Number of molecules/ unit volume
Re

model II
Since the number of molecules per unit

volume is also given by
molecular
weight
n2 cN A
V
M
then the intrinsic viscosity is
sp

c
c 0
Re2
10
NA
3
M
constant (in freely jointed chain models)

model III
From the solution thermodynamics

lecture
R R
2
e
2
e0
and
Re20 M
theta
solvent
good
solvent
Hence intrinsic viscosity
The Mark-Houwink
Relationship
Flory showed that in a good solvent
R M
2
e
theta
solvent
= 0.5
equivalent to
M 0.1
Typically state
KM
So a log [] vs log M plot is normally linear
where 0.5 < < 0.8
good
solvent
=0.8
Highly Branched Polymers
Quite different viscosity / molecular weight properties are seen for

highly branched polymers
Shown here for both dendrimers and hyperbranched
(Hobson & Feast, Chem Comm 1997, p2067)
Intrinsic viscosity begins to fall with increasing Mw at high Mw.
04/11/16
791
Summary
Polymer structure and solvent interactions have a huge
effect on dynamics, even in dilute systems
Light scattering can quantify diffusion and effective size of
polymer chains
Viscometry provides a simple but effective method for
molecular size characterisation
Simple measurements like these can provide a profound
insight into the physical properties of polymers in solution
04/11/16
792
The mean field picture of polymer

solutions
monomer fraction
translational entropy of
polymer chains
Translational entropy
S site

ln 1 ln 1
N N
The entropy of mixing
ln 1 ln 1
793
N
S Stot S 1 1 S 0
04/11/16
mix
translational entropy of
solvent molecules
BIOPOLYMERS
Biopolymers are polymers produced by living organisms.
Since they are polymers, biopolymers contain monomeric units that are
covalently bonded to form larger structures.
There are three main classes of biopolymers based on the differing monomeric
units used and the structure of the biopolymer formed:
1.polynucleotides,
nucleotide monomers;
which are long polymers composed of 4 or more
2.polypeptides, which are short polymers of amino acids; and

3.polysaccharides, which are often linear bonded
carbohydrate structures.
Many of the polysaccharides earlier studies

biopolymers since they have repeating units
04/11/16
Cellulose
most abundant biopolymer
are
polymeric
also
794
Synthetic polymers are much simpler and random in molecular

mass.
This fact leads to a molecular mass distribution that is missing
in biopolymers.
All biopolymers of a type (say one specific protein) are all alike:
they all contain the similar sequences and numbers of monomers
and thus all have the same mass.
monodispersity in contrast to the

polydispersity encountered in synthetic polymers.
This phenomenon is called
As a result biopolymers have a polydispersity index of 1.
04/11/16
795
BIOPOLYMERS AS MATERIALS
polylactic acid (PLA), naturally

occurring zein, and poly-3-hydroxybutyrate can be used as
Some
biopolymers-
such
as
plastics, replacing the need for polystyrene or polyethylene based plastics.
Some plastics are now referred to as being 'degradable', 'oxydegradable' or 'UV-degradable'. This means that they break down
when exposed to light or air, but these plastics are still primarily (as much
as 98 per cent) oil-based and are not currently certified as
'biodegradable' under certain international laws.
Biopolymers, however, will break down and some are
domestic composting.
suitable for
Zein is a class of prolamine protein found in maize. It is usually manufactured as

04/11/16
796
a powder from corn gluten meal.
BIOPOLYMER USES
Biopolymers (also called renewable polymers) are
produced from biomass for use in the packaging industry.
Biomass comes from crops such as sugar beet, potatoes or
wheat: when used to produce biopolymers, these are classified
as non food crops. These can be converted in the
following pathways:
Sugar beet > Glyconic acid > Polyglonic acid

Starch > (fermentation) > Lactic acid > Polylactic acid (PLA)
Biomass > (fermentation) > Bioethanol > Ethene > Polyethylene
Many types of packaging can be made from biopolymers: food
trays, blown starch pellets for shipping fragile goods, thin
films for wrapping.
04/11/16
797
Biopolymers
Nucleic acid polymers (DNA, RNA)

Amino acids polymers (Proteins)
Sugar polymers (Carbohydrates)
Genetic information for the cell: DNA

Structural strength and catalysis: Proteins
Energy source: Carbohydrates
04/11/16
798
Proteins: amino acid monomers
The basic structure of an amino acid monomer
The difference between amino acids is the R group
04/11/16
799
04/11/16
800
Biopolymers: Proteins
The Peptide Bond between Amino Acids in a Protein
Two amino acids react.
N forms the bridge.
See the * orbital

of this double bond
in X-ray absorption
O
N
04/11/16
covalent
(zwitter)-ionic
801
DNA
04/11/16
802
Thymine (T)
The monomers:
Adenine (A)
Cytosine (C)
Guanine (G)
PhosphateSugar (backbone) of
DNA
04/11/16
803
Phosphate-sugar
backbone holds the
DNA macromolecule
together
04/11/16
804
One strand unwinds to

duplicate its
complement via a
polymerization of the
monomers
C, G, A and T
04/11/16
805
Carbohydrates
04/11/16
806
04/11/16
807
04/11/16
808
Cotton fiber is mostly cellulose, and

cellulose is made of chains of the sugar,
glucose linked together a certain way.
04/11/16
809
Glucose
Glucose
Structural formula.
Straight chain
glucose
1
H-C=O
|
2
H-C-OH
|
HO-C-H
| 3
H-C-OH
bends
|
4
H-C-OH
|
CH25OH
Two ring-shape
versions
Glucose
glucose bending
flips
either
way
6
Glucose bends itself into 4 different
shapes millions of times a second
04/11/16
Used in
making
starch
810
alpha-glucose
Used in
making
cellulose
beta-glucose
Biological Polymers
3 Main classes of biological polymers:

Nucleic acid polymers
Linear informational polymers
comprised of 4 nucleotide
monomers
Polysaccharides
Branching storage/structural
polymers comprised of one of a
few select monosaccharide
monomers
Proteins and peptides
Linear informational polymers
comprised of 20 standard amino
acid monomers
General Functions of Biological Polymers

Nucleic Acids
Information storage (genome)
Translational molecules (mRNA
& tRNA)
Biological catalysts (RNA
ribozymes)
Carbohydrates
Energy storage (glycogen)
Structural (cellulose cell walls or
chitin exoskeletons)
Recognition (carbohydrates of
glycoproteins and glycolipids)
Nucleic acids and proteins are

considered informational because the
sequence of monomers in the polymers
is:
Nonrandom
Significant to function
A similar argument can be made for
branched carbohydrates comprised of
04/11/16
different monomers.
Proteins
Structural (fibrous proteins)
Biological catalysts (enzymes)
Recognition (immunoglobulins)
811
The Hierarchal Structure of Proteins
Primary Structure:
Amino acid sequence from N- to Cterminus
Ultimately determines all higher order
structure and function
Driven and stabilized by covalent bonds
Secondary Structure:
Local, spatial interactions between
functional groups of the protein backbone
Driven and stabilized by the hydrogen
bond
Not usually a determinant of function
Tertiary Structure:
Three-dimensional folding of a
polypeptide
Driven and stabilized largely by weak,
hydrophobic interactions
Often dictates biological activity
Quaternary Structure:
Specific interactions between two or
more proteins
Can be driven and stabilized by any
combination of bond types
Figure illustrating the four hierarchal

levels of protein structure
Figure 3-6: Becker et. Al., World of the Cell 6 th Ed.
Structure is a consequence of sequence.

Function is a consequence of structure.
812
04/11/16
813
Protein
Folding
Hierarchy
04/11/16
814
Protein Folding Patterns
-helix
Pleated sheet
Random coil
04/11/16
Hydrogen bonds play a large role.
815
Proteins: condensation polymers

Formed by condensation polymerization of amino acids
Monomers: 20 essential amino acids
NH2
H
General structure of an amino acid

R
CO2H
R is the only variable group
Glycine (R = H) + Glycine
04/11/16
First step toward poly(glycine)

816
Representation of the constitution of a protein
04/11/16
817
Three D representation of the structure of a protein
04/11/16
818
04/11/16
819
04/11/16
820
04/11/16
821
Biopolymers: DNA
Base pairing via hydrogen bonds :
Adenine
Thymine
Cytosine
Guanine
04/11/16
822
04/11/16
823
04/11/16
824
04/11/16
825
04/11/16
826
04/11/16
827
04/11/16
828
04/11/16
829
04/11/16
830
04/11/16
831
04/11/16
832
04/11/16
833
04/11/16
834
04/11/16
835
STRESS RELAXATION
In a stress relaxation experiment the sample is
rapidly stretched to the required length, and the
stress is recorded as a function of time.
The length of the sample remains constant, so
there is no macroscopic movement of the body
during the experiment.
Usually the temperature remains constant also
04/11/16
836
04/11/16
837
04/11/16
838
Creep Experiments
Creep experiments are conducted in the
inverse manner.
A constant stress is applied to a sample,
and the dimensions are recorded as a
function of time.
Of course, these experiments can be
generalized to include shear motions,
compression, and so on.
04/11/16
839
04/11/16
840
04/11/16
841
Modulus and Compliance

We define the modulus of a material as a
measure of its stiffness,
and compliance as a measure of its softness.
Under conditions far from a transition,
E 1/J.
Frequently stress relaxation experiments are
reported as the time-dependent modulus, E(t),
whereas creep experiments are reported as the
time-dependent compliance, J(t).
04/11/16
842
Molecular Basis of Stress

Relaxation and Creep
Chain Scission
Bond Interchange
Viscous flow
Thirion relaxation
Molecular relaxation near Tg
04/11/16
843
Chain Scission
04/11/16
844
Bond Interchange
While this is not a degradation in the sense that
the molecular weight is decreased, chain
portions changing partners cause a release of
stress.
Examples of stress relaxation by bond
interchange include polyesters and
polysiloxanes.
Bond interchange is going on constantly in
polysiloxanes, with or without stress.
In the presence of a stress, however, the
statistical rearrangements tend to reform the
chains so that the stress is reduced.
04/11/16
845
Viscous Flow
Caused by linear chains slipping past one
another, this mechanism is responsible for
viscous flow in pipes and elongational flow
under stress.
An example is the pulling out of Silly
Putty.
04/11/16
846
Thirion Relaxation
This is a reversible relaxation of the
physical crosslinks or trapped
entanglements in elastomeric networks.
Usually an elastomeric network will relax
about 5% by this mechanism, most of it in
a few seconds.
It must be emphasized that the chains are
in constant motion of the reptation
04/11/16
847
Molecular Relaxation
Molecular relaxation, especially near Tg.
It was pointed out that near Tg the chains relax
at about the same rate as the time frame of the
experiment.
If the chains are under stress during the
experiment, the motions will tend to relieve the
stress.
It must be emphasized that more than one of the
relaxation modes above may be operative
during any real experiment.
04/11/16
848
Spring and Dashpot Model

To permit a mathematical analysis of the creep
and relaxation phenomenon, spring and dashpot
elements are frequently used.
A spring behaves exactly like a metal spring,
stretching instantly under stress and holding that
stress indefinitely.
A dashpot is full of a purely viscous fluid. Under
stress, the plunger moves through the fluid at a
rate proportional to the stress. On removing the
stress, there is no recovery.
Both elements may be deformed indefinitely.
04/11/16
849
04/11/16
850
04/11/16
851
Maxwell and Kelvin models

The springs and dashpots can be put together to
develop mathematically amenable models of
viscoelastic behavior.
The simplest two such arrangements, the
Maxwell and the Kelvin (sometimes called the
Voigt) elements.
While the spring and the dashpot are in series in
the Maxwell element, they are in parallel in the
Kelvin element.
In such arrangements it is convenient to assign
moduli E to the various springs, and viscosities
to the dashpots.
04/11/16
852
Maxwell and Kelvin models

In the Maxwell element both the spring
and the dashpot are subjected to the
same stress but are permitted
independent strains.
The inverse is true for the Kelvin element,
which is equivalent to saying that the
horizontal connecting portions are
constrained to remain parallel.
04/11/16
853
As examples of the behavior of

combinations of springs and dashpots, the
Maxwell and Kelvin elements will be
subjected to creep experiments.
In such an experiment a stress, , is
applied to the ends of the elements, and
the strain,, is recorded as a function of
time.
04/11/16
854
Creep Behavior of Maxwell and

Kelvin Elements
04/11/16
855
Maxwell creep test

On application of the stress to the Maxwell
element, the spring instantly responds, as
illustrated by the vertical line.
The height of the line is given by = /E.
The spring term remains extended, as the
dashpot gradually pulls out, yielding the
slanted upward line.
This model illustrates elasticity plus flow.
04/11/16
856
Kelvin creep test

The spring and the dashpot of the Kelvin
element undergo concerted motions, since
the top and bottom bars are constrained to
remain parallel.
The dashpot responds slowly to the
stress, bearing all of it initially and
gradually transferring it to the spring as
the latter becomes extended.
04/11/16
857
04/11/16
858
The Four-Element Model

While a few problems in viscoelasticity can
be solved with the Maxwell or Kelvin
elements alone, more often they are used
together or in other combinations.
Figure illustrates the combination of the
Maxwell element and the Kelvin element in
series, known as the four-element model.
It is the simplest model that exhibits all the
essential features of viscoelasticity.
04/11/16
859
04/11/16
860
Creep and Recovery

On the application of a stress, , the
model undergoes an elastic deformation,
followed by creep.
The deformation due to 3, true flow, is
nonrecoverable.
Thus, on removal of the stress, the model
undergoes a partial recovery.
04/11/16
861
Four-Element Model
The quantities E and of the models shown above are
not, of course, simple values of modulus and viscosity.
However, as shown below, they can be used in
numerous calculations to provide excellent predictions or
understanding of viscoelastic creep and stress
relaxation.
It must be emphasized that E and themselves can be
governed by theoretical equations.
For example, if the polymer is above Tg, the theory of
rubber elasticity can be used.
Likewise the WLF equation can be used to represent
that portion of the deformation due to viscous flow, or for
the viscous portion of the Kelvin element.
04/11/16
862
More complex arrangements of elements are

often used, especially if multiple relaxations are
involved or if accurate representations of
engineering data are required.
The MaxwellWeichert model consists of a very
large (or infinite) number of Maxwell elements in
parallel.
The generalized VoigtKelvin model places a
number of Kelvin elements in series.
In each of these models, a spring or a dashpot
may be placed alone, indicating elastic or
viscous contributions.
04/11/16
863
Relaxation and Retardation times
04/11/16
864
Relaxation time
04/11/16
865
04/11/16
866
Stress Relaxation
04/11/16
867
04/11/16
868
04/11/16
869
Activation Energy
A plot of ln 1 versus 1/T yields Eact/R for
the slope.
An apparent energy of activation of 35
kcal/mol was estimated from such a plot.
Thus a purely chemical quantity can be
deduced from a mechanical experiment.
04/11/16
870
04/11/16
871
Retardation Time
04/11/16
872
04/11/16
873
04/11/16
874
04/11/16
875
Time-Temperature Superposition
04/11/16
876
04/11/16
877
Summary
This chapter has illustrated how stress relaxation, creep,
and rheology in polymers depend on the rate of molecular
motion of the chains and on the presence of
entanglements.
It must be remembered that all macroscopic deformations
of matter depend ultimately on molecular motion.
In the case of high polymers, the chains radius of
gyration is changed during initial deformation or flow.
Thermal motions tend to return the polymer to its initial
conformation, thus raising its entropy.
Clearly, there is a direct relationship between the
mechanical or viscous behavior of polymeric materials
and their molecular behavior.
04/11/16
878
Polyurethanes
TDI Route
MDI Route
04/11/16
879
TDI
TDI Toluene diisocyanate

Organic compound
CH3C6H3(NCO)2.
Two of six possible isomers 2,4-TDI and

2,6-TDI
TDI marketed as 80/20 and 65/35 mixtures
of the 2,4 and 2,6 isomers resp.
World production is 2 billion kg.
04/11/16
880
04/11/16
881
TDI Synthesis
Toluene is doubly nitrated with nitric acid to
give dinitrotoluene determines the isomer
ratio of the ultimate TDI.
Hydrogenation of the dinitrotoluene produces
the isomers of toluene diamine (TDA).
TDA is subjected to phosgenation, treatment
with phosgene to form TDI.
HCl produced as by-product.
04/11/16
882
Phosgene
COCl2
Cobalt Chloride
Greek phos light
genesis birth
RNH2 + COCl2 - RN=C=O + 2HCl
04/11/16
883
TDI Applications
Isocyanate functional groups in TDI react
with a hydroxyl group to form urethane
linkages.
Classified as very toxic.
04/11/16
884
MDI
Methylene diphenyl diisocyanate
Three isomers 2,2 MDI; 2,4 MDI, and 4,4
MDI.
4,4 isomer is most widely used and known as
pure MDI
61% of the global diisocyanate market is
MDI, 40% is TDI.
World production is 5 million tonnes per year.
04/11/16
885
04/11/16
886
MDI
MDI reacts with polyols in the manufacture
of polyurethane.
04/11/16
887
MDI
The first step of the production of MDI is the reaction
of aniline and formaldehyde, using hydrochloric acid
as a catalyst to produce a diamine precursor under the
chemical formulation:
2 C6H5NH2 + CH2O CH2(C6H4NH2)2 + H2O
Then, these diamines are treated with phosgene to
form an MDI. The isomer ratio is determined by the
isomeric composition of the diamine. Distillation of the
MDI mixture give Polymeric MDI (a mixture of
oligomeric polyisocyanates) and an MDI isomer
mixture which has a low 2,4' isomer content. Further
purification entails fractionation of the MDI isomer
mixture.
04/11/16
888
Applications of MDI
The major application of 4,4'-MDI is the production
of rigid polyurethane.
Typically, one tonne of polyurethane foam needs
0.616 tonne of MDI and 0.386 tonne of polyol, with
0.054 tonne pentane as a blowing agent.
These rigid polyurethane foams are good thermal
insulators and used in nearly all freezers and
refrigerators worldwide, as well as buildings.
Typical polyols used are polyethylene adipate (a
polyester) and poly(tetramethylene ether) glycol (a
polyether).
04/11/16
889
MDI Applications
4,4'-MDI is also used as an industrial
strength adhesive, which is available to
end consumers as various high-strength
bottled glue preparations.
04/11/16
890
Polyurethane uses
Over three quarters of the global consumption of polyurethane
products is in the form of foams, with flexible and rigid types
being roughly equal in market size.
In both cases, the foam is usually behind other materials: flexible
foams are behind upholstery fabrics in commercial and
domestic furniture;
rigid foams are inside the metal and plastic walls of most
refrigerators and freezers,
or behind paper, metals and other surface materials in the case
of thermal insulation panels in the construction sector.
Its use in garments is growing: for example, in lining the cups of
brassieres.
Polyurethane is also used for moldings which include door
frames, columns, balusters, window headers, pediments,
medallions and rosettes
04/11/16
891
Polyurethane applications
Formulations cover an extremely wide range of
stiffness, hardness, and densities. These materials
include:
Low-density flexible foam used in upholstery, bedding,
and automotive and truck seating
Low-density rigid foam used for thermal insulation and
RTM cores
Soft solid elastomers used for gel pads and print rollers
Low density elastomers used in footwear
Hard solid plastics used as electronic instrument bezels
and structural parts
Flexible plastics used as straps and bands
04/11/16
892
Density of PU foams
Solid PU Elastomers - 1,500 kg/m3
Microcellular Foams and Elastomers
800 kg/m3
High Density Foams 400 kg/m3
Low Density Foams 6 kg/m3
04/11/16
893
PU Applications
Polyurethanes are used in the manufacture of
flexible, high-resilience foam seating;
rigid foam insulation panels;
microcellular foam seals and gaskets;
durable elastomeric wheels and tires (such as
roller coaster and escalator wheels);
automotive suspension bushings;
electrical potting compounds; high performance
adhesives; surface coatings and surface sealants;
synthetic fibers (e.g., Spandex); carpet underlay;
hard-plastic parts (e.g., for electronic instruments);
hoses and skateboard wheels
04/11/16
894
Other Applications of PU
Furniture
Automobile seats
Houses, sculptures, and decorations
Construction sealants and firestopping
Water vessels
Inflatable boats
Surfboards
Rigid-hulled boats
Boat decks and outdoor marine surface areas
Flexible plastics
Tennis grips
Watch-band wrapping
Textiles
Varnish
Wheels
Automotive Parts
Electronic components
Adhesives
Abrasion resistance
04/11/16
895
Production
Polyurethanes are produced by mixing two or more liquid
streams. The isocyanate is usually added by itself and the
polyol stream is usually more complex, containing catalysts,
surfactants, blowing agents and so on. The two components
are referred to as a polyurethane system, or simply a system.
The isocyanate is commonly referred to in North America as
the 'A-side' or just the 'iso'. The blend of polyols and other
additives is commonly referred to as the 'B-side' or as the 'poly'.
This mixture might also be called a 'resin' or 'resin blend'. In
Europe the meanings for 'A-side' and 'B-side' are reversed.
Resin blend additives may include chain extenders, cross
linkers, surfactants, flame retardants, blowing agents,
pigments, and fillers. Polyurethane can be made in a variety of
densities and hardnesses by varying the isocyanate, polyol or
additives
04/11/16
896
Polyurethanes
Formed by a reaction between diisocynate
and glycol
Contain the group NHCOO Thermoset types, cured by the presence of
moisture, are used as adhesive and coating
base resins
Polyurethanes can be blown in foams of
various densities, used as protective
packaging
04/11/16
897
Polyurethanes - Foams-in-place
Metering-Mixing-Delivery systems
Two reacting chemicals are mixed just
prior to being sprayed around an object to
be protected
The mixed components foam up within
seconds to totally encapsulate the item
04/11/16
898
Reaction Injection Molded (RIM)

Polyurethane
Reaction injection molding is a process
that allows polymerization and crosslinking
to take place simultaneously with forming
a part into its final shape
Mainly used to produce bumper covers
and fenders, and microcellular elastomers
04/11/16
899
Reaction injection molding machine
04/11/16
900
04/11/16
901
Reaction Injection Molding

Starts with unreacted components that lead to a
polymer product
They are pumped in predetermined amounts
into a mixing head, where they are thoroughly
mixed and injected into a warm (65oC) mold
under relatively low pressures (50-100 psi).
Polymerization takes place in the mold
Meanwhile, the mixing head is cleaned, with
unused monomers being recycled
Molding of polyurethanes
04/11/16
902
PU
Polyurethane polymers are formed by
reacting an isocyanate with a polyol.
Both the isocyanates and polyols used to
make polyurethanes contain on average
two or more functional groups per
molecule
04/11/16
903
Polymerization reaction
The polymerization reaction makes a
polymer containing the urethane linkage,
-RNHCOOR'- and is catalyzed by tertiary
amines, such as 1,4diazabicyclo[2.2.2]octane (also called
DABCO or TEDA), and metallic
compounds, such as dibutyltin dilaurate or
bismuth octanoate. This is often referred to
as the gellation reaction or simply gelling.
04/11/16
904
Foams
If water is present in the reaction mixture (it
is often added intentionally to make
foams), the isocyanate reacts with water to
form a urea linkage and carbon dioxide gas
and the resulting polymer contains both
urethane and urea linkages. This reaction
is referred to as the blowing reaction and is
catalyzed by tertiary amines like bis-(2dimethylaminoethyl)ether.
04/11/16
905
Rigid foams
A third reaction, particularly important in
making insulating rigid foams is the
isocyanate trimerization reaction, which is
catalyzed by potassium octoate, for
example.
04/11/16
906
Spandex
Spandex are polyurethane fibers which
can be stretched to 500% elongation
without breaking.
They contain alternating hard and soft
(flexible) segments.
There is stretch countered by resistance
Example is Lycra used by athletes and
swimwear.
04/11/16
907
MDI/TDI Blends
MDI rigid foams
TDI flexible foams
MDI/TDI blends range of foams from
rigid to soft
04/11/16
908
Flory-Huggins Theory
FloryHuggins solution theory is a mathematical
model of the thermodynamics of polymer solutions which
takes account of the great dissimilarity in molecular sizes
in adapting the usual expression for the entropy of
mixing.
The result is an equation for the Gibbs free energy
change for mixing a polymer with a solvent.
Although it makes simplifying assumptions, it generates
useful results for interpreting experiments
04/11/16
909
F-H Theory
Entropy of mixing: The Flory-Huggins theory
Deviation of polymer solutions from ideal
behavior is mainly due to low mixing
entropy.
This is the consequence of the range of
difference in molecular dimensions between
polymer and solvent.

04/11/16
910
F-H Theory
Flory-Huggins theory
Transfer of the polymer chains from a
pure, perfectly ordered state to a state of
disorder
Mixing process of the flexible chains with
solvent molecules
04/11/16
911
Flory Huggins Theory
Dissolution of polymer increases conformational entropy of system

Molar entropy of mixing normally written as
mix
RV
V0
2
ln 1 ln 2
r2
r1
where i is the volume and volume fraction of each component (solvent =

1 and polymer = 2), ri is approximately the degree of polymerisation of
each component (r1 ~ 1, r2 ~ N)
Note that increasing the r2 decreases the magnitude of Smix
Flory Huggins Theory 2
Enthalpy of mixing
HMix = kT 2N1
where is the dimensionless Flory Huggins parameter.
For dilute solution of high molecular weight polymers, N~N 1
HMix = RT 2
Remember condition for thermodynamically stable solution
GMix = HMix - TSMix < 0
04/11/16
913
Practical Use of Polymer TDs

Fractionation
Consider solution in poor solvent

of two polymers, p1 and p2.
Flory-Huggins tells us that if p2
has higher molecular weight it
should precipitate more readily
than p1
add non-solvent until solution
becomes turbid
heat, cool slowly and separate
precipitate
finite drop in temperature always
renders finite range of molecular
weight insoluble
some p2 will also remain soluble!
1 phase clear solution
1
1
2
N 1
T
2 phase
cloudy p1
p2
2
volume fraction polymer
Polymer solutions
polymer: wps
04/11/16
915

z
2w ps w pp w ss
2k b T

U int
04/11/16
N2
k b T 2 3
R
916
The good the bad

and the theta
coil swelling:
N2
R3

interaction:
04/11/16
917
Another important characteristics of

polymer solutions which
can be
determined from the value of [ ] is the
overlap
concentration of polymer coils c*
c < c*
Dilute polymer
solutions
c = c*
Overlap
concentration
c > c*
Semidilute
polymer solutions
N
1
R3
3 N 1 2a3
The average polymer concentration in the
solution is equal to that
inside one polymer
coil at the overlap concentration c*. Thus,
c
Since c* N/R3 , and [] R3/N , we have
1
practical
normally c
assumed
04/11/16 estimations it is
[]c* 1. For the

918
C. Solubility parameter :
Hmix=Vmix
[( E ) -(E ) ]
1
1/2
V1
1/2 2
1 2
V2
1, 2 = volume fraction
E1/V1, E2/V2 = cohesive energy densities
1, 2 = solubility parameter
1, 2 =
(E
V
1/2
Hmix= Vmix(1 2)2 1 2

E = Hvap- RT
1 =
04/11/16
H vap - RT
V
1/2
919
POLYMER CHEMISTRY
if 1= 2, then Hmix= 0
Radius of Gyration of a Polymer Coil

The radius of gyration Rg is defined as the RMS
distance of the collection of atoms from their
common centre of gravity.
R
For a solid sphere of radius R;
2
Rg
R 0.632R
5
For a polymer coil with rms end-to-end distance R ;
1 2
Rg R
6
04/11/16
1/ 2
a 1/ 2
N
6
920
The excluded volume effect

Steric hindrance on short distances limits the number
of conformations
At longer distances we have a topological constraint
the self avoiding walk or the excluded volume effect:
Instead of <R2>1/2=aN1/2 we will have ( solvent)
<R2>1/2=aN
where v>0.5
Experiments tells us that in general: v~0.6 (good
solvent)
Why?
04/11/16
921
Excluded volume according to Flory

Consider a cube containing N segments of a polymer
V=r3 where r is the radius of gyration.
The concentration of segments is c~N/r3
Each segment with volume stuffed into the cube reduces the
entropy with kbN/V = -kbN/r3
(for small x; ln(1-x)~lnx)
The result is a positive contribution to F; Frep= kbTN/r3 (expansion
of the coil)
From before; Coiling reduces the entropy; Fel=kbT3R2/2Na
The total free energy F is the sum of the two contributions!
Search for equilibrium!
04/11/16
922
Florys result for the swollen coil:

k b TN 2
k b TR 2
Ftot (R )
3
const
3
2
R
2 Na
dFtot 3k b TN 2 3k b TR
0
4
2
dR
R
Na
R 5 a 2 N 3
a3
R 5 a 5 N3
R aN
04/11/16
3/ 5
923
This topic provides a link between

molecular characterisation techniques
concerned with how to measure properties of
polymers
and polymer physics

concerned with understanding how polymers behave
once their characteristics are known
A good starting point are dilute solutions

allows us to consider polymers in isolation
04/11/16
924
Dilute solutions
Chains do not overlap
Can consider that each chain acts in
isolation
Dynamic
considerations:
Movement of polymers - diffusion
Solutions under flow - viscosity
In semi-dilute
solutions
concentration is sufficient for chains
to just overlap
Measuring Diffusion
Dynamic Light Scattering (DLS, PCS, QELS etc)
04/11/16
Light scattered from polymer chains in dilute solution

interferes producing a speckle pattern
Diffusion causes shimmering of speckle pattern as
polymer chains undergo Brownian motion
Can also view this as Doppler shift to frequency of
scattered light
Measure rate of shimmering with autocorrelation function
926
Interpretation of DLS data
Autocorrelation function G() leads to effective hydrodynamic

radius of polymer coil in solution.
I(t)
G 1 exp 2 Dq 2
4
q
sin
kT 1
6 Re
t
G()
where is the viscosity,
Dilute Solution Viscosity
A step towards understanding

dynamics in polymers
A useful practical tool for rapid

measurement of molecular
weights
Important relationship for

relative viscosity:
rel
t0 0
Relative, specific, intrinsic
Relative viscosity
rel
solution viscosity
solvent viscosity
Specific viscosity
sp rel 1
Intrinsic viscosity
sp

c
c 0
extrapolated to
zero concentration
Viscosity measures
rel
sp
conc.
04/11/16
slope
=
930
Spheres
Einstein: for a solution of dilute noninteracting spheres

Viscosity increases according to...
0 1 2.5v 2
v2 is the volume fraction of spheres
What is the intrinsic viscosity?

model I
Consider that each polymer chain is

impenetrable to solvent
with an effective hydrodynamic radius, Re
and volume
4
3
Re
3
Ve
For polymer equivalent spheres, Einstein

relation can be rewritten
n2
Ve
V
sp 2.5
Number of molecules/ unit volume
Re

model II
Since the number of molecules per unit

volume is also given by
molecular
weight
n2 cN A
V
M
then the intrinsic viscosity is
sp

c
c 0
Re2
10
NA
3
M
constant (in freely jointed chain models)

model III
From the solution thermodynamics

lecture
R R
2
e
2
e0
and
Re20 M
theta
solvent
good
solvent
Hence intrinsic viscosity
The Mark-Houwink
Relationship
Flory showed that in a good solvent
R M
2
e
theta
solvent
= 0.5
equivalent to
M 0.1
Typically state
KM
So a log [] vs log M plot is normally linear
where 0.5 < < 0.8
good
solvent
=0.8
Highly Branched Polymers
Quite different viscosity / molecular weight properties are seen for

highly branched polymers
Shown here for both dendrimers and hyperbranched
(Hobson & Feast, Chem Comm 1997, p2067)
Intrinsic viscosity begins to fall with increasing Mw at high Mw.
04/11/16
936
Q1: The tube model and the idea of

reptation
Every segment in the tube have a mobility, seg
restricted by the surrounding resistance.
The tube with N segments have a mobilty, tube= seg/N
Brownian motion within the tubes confinement use
Einstein relation to calculate a Diffusion coefficient =>
A polymer escapes from

its own tube of length L
after a time T
04/11/16
=> Dtube=kbT tube=kbT seg/N
T D tube L2
L2
N3
T
D tube const
Close to the
exp. results!
937
Q2; The rubber plateau and entanglements

In a similar way as we explained the elastic
behaviour at very short times for all simple liquids
as a glassy state we can explain the rubber
plateau in a qualitative way as a signature of
entanglements.
It can be shown that in a rubber, a cross linked polymer,

the elastic modulus depends on the average molecular
mass between cross-links Mx, R ,T and the density :
Adopting an identical relation and treating the
entanglements as temporary cross-links with a lifetime of
the order of T we can calculate an average mass of the
molecular mass between the entanglements (Me).
04/11/16
RT
G
Mx
938
04/11/16
939
04/11/16
940
04/11/16
941
04/11/16
942
04/11/16
943
04/11/16
944
04/11/16
945
04/11/16
946
04/11/16
947
04/11/16
948
Swelling and Collapse

of Single Polymer Molecules and Gels
Single polymer molecules
Coil-globule transition
If polymer chains are not ideal, interactions of non-neighboring monomer
units ( the so-called volume interactions ) should be taken into account. If
these interactions are repulsive, the coil swells with respect to its ideal
dimensions. If monomer units attract each other, contraction leads to the
condensation of polymer chain upon itself with the formation of a dense
droplet conformation, which is called a polymer globule.
04/11/16
949
Polymer gels
The gel as a whole is actually one giant three-dimensional molecule.
Swelling
of a gel
Collapse
of a gel
Repulsive interactions Attractive interactions

of monomer units
of monomer units
Advantage of studying gels vs. dilute polymer solutions: possibility of
direct visual observation of conformational transitions.
Main disadvantage: very slow equilibration in macroscopic gel. For
the sample of 1 cm it takes several days. Equilibration time can be
diminished by using smaller size L of the sample, one can show that
~ L2
04/11/16
950
DNA macromolecules
DNA coil and globule

as revealed by fluorescent microscopy
The size of DNA coil and even globule can be of order of the wavelength
of visible light (400-700 nm), therefore conformational changes with DNA
can be seen by optical microscope. Normally in such experiments for
better contrast DNA chain is doped with fluorescent dyes.
04/11/16
951
Single Polymer Chains with Volume Interactions

Main polymer chain models for the considera-tion of volume interactions:
1. Model of beads on a Gaussian filament
Beads of volume
on immaterial filament. The connectivity of beads is
given by a condition that the the probability distribution for a vector
between neighboring beads is
r
3
2
3
3r 2
g (r )
exp
2
2
2a
2a
Comment: chain connectivity
as in the model of beads can be obtained for any
chain by
selecting the dividing points separated by several persistent lengths and
by assigning all the mass of each chain segment to the dividing point.
04/11/16
952
The value of a is the average distance between neighboring beads.

It is possible to have
or
a3
a 3
The beads interact with the interaction potential

U (r ).Typical
interaction po-tential
repulsion due to
self-volume of the
beads (excluded volume)
r
Van-der-Waals
attraction
Note: in principle this potential is renormalized by the presence of
the solvent, so its form can be much more complicated.
04/11/16
953
2. Lattice model
Polymer chain is modeled as a random walk on a lattice. The random

walk cannot visit each site more than once (the excluded volume
condition); the lattice attractive energy is assigned to each pair of
neighbor sites visited by two non-consecutive monomer units of the
chain.
04/11/16
954
Concept of
-temperature
It should be noted that for both models:

1. At high values of T, the ratio / kT << 1 and only repulsion matters. The
coil should swell with respect to the ideal dimensions; this phenomenon
is called the excluded volume effect. In this case the so-called
swelling coefficient of the coil, ,
2 is larger than unity:
2
1
2
R 0
2. At low values of T, the ratio / kT >> 1, and attraction dominates. The
coil should shrink and form a condensed globule
( coil-globule
transition ).
3. At intermediate values of T, the effect of repulsion and attraction
should compensate each other and the coil should adopt ideal-chain
( unperturbed ) size. This happens at the so-called -temperature.
04/11/16
955
The free energy of a coil is the sum of energetic and entropic

contributions:
F E TS
As to the energy E, contrary to the case of the ideal coil, for the present
case it is not equal to zero.
To write down the expression for E we should recall that the
concentration of monomer units inside the polymer coil is very small for
long chains. Therefore, we can write the expression for E in terms of the
expansion in the powers of n:
E NkT ( Bn Cn 2 )
Here B, C, are second, third, virial coefficients; these coefficients

are responsible for binary, ternary, etc. interactions of monomeric units.
These coefficients depend only on the interaction potential between the
units, e.g.
3
1
B (T )
1 exp( U ( r ) kT ) d r
2
04/11/16
956
From the expression for B(T ): at high T

( kT
1with the decrease of T the value of B diminishes,
until it reaches zero at some temperature
At
:
T
, where
T-
T
The characteristic
dependence of the
second virial
coefficient
on temperature
B 0
F TS
At the -temperature
chain adopts the conformation of ideal coil.

At
repulsion dominates, coil swells due to the excluded volume
T
effect
- region
of good solvent.
At
attraction dominates, coil shrinks into globule - region of poor
T
solvent.
04/11/16
957
Remarks:
1. The fact of complete compensation of interactions at the point is a specific polymer property (not valid e.g. for gases)
connected with low polymer concentration in the coil.
2. Repulsion forT
and attraction forT
is valid for the
usual form of the potentialU (r. )

For more complicated forms
the situation may be reverse, or it may be many -points (see
below).
04/11/16
958
The Excluded Volume Problem

Let us consider the polymer coil far above the -point,
in the good solvent region, and let us calculate the swelling of the
coil due to the excluded volume.
F E TS NkTBn TS
3N
3kTR 2
NkTB
const
4 R 3
2 Na 2
For the second term we used the expression for the entropy of a
polymer coil expanded up to the size R (derived earlier).
Excluded volume repulsion (first term) induces the coil
swelling, while entropic elasticity (second term) opposes the
swelling. The balance (minimization of F with respect to R) gives
the equilibrium coil size.
04/11/16
959
The free energy of a coil is

N
3kTR 2
F NkTB 4
3
2 Na 2
3 R
F
Minimization of F with respect to R :
0
R
kTBN
R4
Therefore,
R Ba
kTR
0
Na 2
Also swelling coefficient is
R
N
3
a
1
10
The polymeric coil swells essentially due to the excluded volume. In

spite of the low polymer concentration in the coil, the swelling is large
because of high susceptibility of long polymer chains.
04/11/16
960
Swelling of polymer gels

We will consider the gels synthesized in the presence of a large amount
of solvent. For such gels entanglements between the gel chains are not
important.
A swollen
polymer gel
Since each subchain of a gel swells independently in its own
subvolume:
1. The swelling degree of each subchain is equal to the swelling degree
of the gel as a whole.
2. The swelling degree of each subchain is the same as the swelling
degree of an isolated chain in the good solvent.

04/11/16
a3
1
10
1
961
Coil-Globule Transition
Now let us consider the whole range of temperatures. When the
temperature is lowered below the -point, the coil-globule transition(or
polymer chain collapse) should take place.
T > ; >1
good solvent
T < ; <1
poor solvent
The interest to globular form of macromolecules is induced by molecular

biophysics: proteins-enzymes are polymeric globules. Denaturation of
proteins is sometimes considered to be analogous to the transition from
globule to coil.
04/11/16
962
Summary
Polymer structure and solvent interactions have a huge
effect on dynamics, even in dilute systems
Light scattering can quantify diffusion and effective size of
polymer chains
Viscometry provides a simple but effective method for
molecular size characterisation
Simple measurements like these can provide a profound
insight into the physical properties of polymers in solution
04/11/16
963

PSE

Caricato da

Informazioni sul documento

Copyright

Formati disponibili

Condividi questo documento

Condividi o incorpora il documento

Opzioni di condivisione

Hai trovato utile questo documento?

Questo contenuto è inappropriato?

Copyright:

Formati disponibili

PSE

Caricato da

Copyright:

Formati disponibili

Introduction to Polymer

Science & Engineering

Polymers in Daily Life

We start the day with toothbrush

Raw Material Source for Polymers

The Rise of Polymer Science

Early Industrial Developments

Degree of Polymerization and

Monomer: Vinyl Chloride CH2=CHCl

Measurement of Molecular Weight

Thermoplastic and Thermoset

Amorphous and Crystalline

Chains assume folded

These collect into

Two crystalline morphologies

Spherulite (no shear)

Row Nucleated (shear )

High Density (Linear) Polyethylene

Polyethylene Chain Branching

HDPE Versus LDPE

HDPE Versus LDPE

HDPE Versus LDPE

HDPE Versus LDPE

Nonpolar nature of polyethylene

Gas phase polymerization;

TiCl4 and aluminium alkyl

Heptane or octane added

TiCl4 and aluminium alkyl

Very dense and tight

Electrical insulation, films,

Containers, pails, vessels,

Wrapping; shrink wrap;

Knee-joint and hip joint

Pigments - soluble colourants

Polymer Categories: Price

Natural Product Polymers

Thermal Behavior of Polymers

Thermal Behavior of Polymers

Stress-strain behavior of Polymers

Stress-Strain Behavior of Polymers

The elements that make up the polymer molecule carbon,

Addition (chain reaction)

Ring Opening Polymerization

In radical polymerization we speak about:

Somewhere in the intermediate conversion regime:

This effect is called: gel effect, Trommsdorff effect,or auto-acceleration

In the polymerization of MMA this occurs at relatively low conversion.

Classes of step-growth polymers - Polyester

Polyester has high glass transition temperature

Two important criteria polarity, conductivity of the rubber

Answer: Repeat unit (O--CO)n

Free Radical PolymerizationInitiation

The Chain Transfer

The Chain Transfer

Cationic Polymerization - Initiation

Anionic Polymerization - Initiation

Unsaturated Polyester Resins Formulation

43 lbs of phthalic anhydride

Polyester Resins Fabrication

Properties of Unsaturated Polyester

Oil and Gas

Feedstock (Carbon Source)

Bio-based and Bio-degradable

Benzene ring, or phenol group: