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CHEMICAL ENGINEERING PRINCIPLES

IN POLYMER PROCESSING
CH 62045
Prof. Swati Neogi

Class Guideline
Attendance Policy:
100% attendance is desirable
No unexcused absence
Up to four excused absence

Guest Lecture & Field Trip:


Guest lecture will be arranged from time to time
Field trip to industries will be arranged
Attendance is mandatory

Class Guideline
Assignment and class tests:
Regular homework assignments will be given
Students are expected to maintain a notebook for
assignments and are required to bring the assignment
notebooks everyday in the class
Surprise checking of the assignments will be conducted
Surprise class tests will be taken.

Grading Policy
Assignments, class tests, teachers evaluation: 20%
Theory: weightage 0.75
Mid term:
30%
Final Exam:
50%
-----------------------------------------------------------------------Total:
80%
Tutorial: weightage: 0.25
Two term paper
Field trip/Guest lecture

Text Book

No single text book will cover the entire subject. Take


class notes. Class notes are prepared based on
several books. Following is the list of books which can
be consulted for the course:

Principles of Polymer Processing by Tadmor & Gogos


Polymer Processing:Principles and modeling, by Agassant,
Avenas, Sergent, & Carreau
Plastics Engineering by R, J Crawford

Course Information

Credit: 3-1-0
Course Objective (Handout)
Course outline (Handout)
Tentative Lecture Schedule (Handout)

Course Objective
Learn to use CHE. Principles to describe polymer
processing
Polymer Basics
(i) What are polymers
(ii) How do they differ form other materials
(iii) Why are they different
(iv) Properties
(v) Applications

Module 1

Course Objective
Learn to use CHE. Principles to describe polymer
processing
Chemical Engineering principles
(i) Transplant Equations Polymer Rheology
(ii) Polymer flow analysis
(iii) Heat transfer & viscous heat dissipation
(iv) Devolatiligation & mass transfer

Module 2

Course objective

Learn to use CHE. Principles to describe polymer processing


Polymer processing technology
(i) Extrusion
(ii) Injection molding
(iii) Blow molding
(iv) Calendaring
(v) Thermoforming
(vi) Spinning

Module 3

Manufacturing
of polymers is
beyond he
scope &
objective

Course Overview
Module 1: Fundamentals of Polymer (# of Lectures: 10)
1.1: Introduction ( 2)
1.2: Characterizing parameters (4)
1.3: Polymer properties (3)
1.5: Polymer additives (1)

Course Overview
Module 2: Chemical Engineering Principles for Polymer
Processing (# of lectures: 14)
2.1: Introduction to polymer processing (1)
2.2: Polymer Rheology (3)
2.3: Mass and Momentum equations for isothermal polymer
flow analysis (5)
2.4: Heat transfer and viscous heat dissipation in polymer
processing (3)
2.5: Mass transfer, diffusivity and devolatilization during
polymer processing (2)

Course Overview
Module 3: Polymer Processing Technologies ( # of
Lectures: 18)
3.1: Extrusion (10)
3.2: Injection Molding(6)
3.3: Calendaring , Thermoforming, Other(2)

Module 1: Course Outline

Introduction of polymer (L2)

Definition

Advantages

Classification of polymer

Applications
Characterization parameters L(3)

Molecular

Chemical composition

MW/MWD

Macroscopic

Topology
Orientation
Phases

Crystalline
Amorphous

Module 1: Course Outline

Polymer properties (L4)

Thermal Properties

Melting point
Glass transition

Mechanical Properties

Strength
Modulus
Elongation
Toughness
Impact
Creep
Permeability

Module 1: Course Outline

Chemical Properties

Melt properties

Oxidation
Thermal stability
Degradability
Chemical resistance
Flammability/flame resistance
UV resistance
Flow Characteristics
Viscosity vs. Shear rate
Shrinkage/cooling
Polymer swelling/memory effect

Polymer Additives (L0.5)


Material selection and design guidelines (L0.5

Module 1: Fundamentals of Polymer


Section 1.1: Introduction

Some Organic Basics


Name following organic compounds and write down the
structure.
CH4, C2H6,C2H2, C3H8, C2H4

General name of following series of compounds


RCOOH, R-NH2, HO-R, HO-R-OH

write the product of following reaction:


RCOOH +RNH2 --------RCOOH +HOR -------------RCOOH + HO-R-OH ---------

Processing with
additives
Finished Product

Polymers

Polymer, Resin, and Plastics


A polymer is any substance made up of many of
repeating units, building blocks, called mers.
When in form ready for further working, they are called
resins.
Polymers are seldom used in their neat form, most often
compounded with various additives. The resulting
material is usually referred to as a plastic.
Frequently, polymers, resins, plastics are used
interchangeably.

Development of Plastics

1868 cellulose nitrate


1909 phenol-formaldehyde
1927 cellulose acetate and polyvinyl chloride
1929 urea formaldehyde
1931 Duprene
1935 ethyl cellulose
1936 acrylic and polyvinyl acetate
1938 nylon
1942 polyester and polyethylene terephthalate
1943 silicone
1947 epoxy and polypropylene

Basic Concept

Basic Concept

Polymer is large molecule having repeating unit


Repeating structural units joined by covalent bonds
Molecular weight can be up to 10000
Monomers should have reactive functional group or
double bond
Basic linear chain is called backbones
Molecular weight can be up to 10000
Extensive formability and ductility
Light weight, low cost
Higher chemical reactivity

Basic Concept
Compound of hydrogen and carbon, and/or O, N, F and
Si
Low strength compared with metals; lower melting point
Properties can be tailormade by choosing different
monomers, by blending different polymers

Forces In Polymer
Primary force
Covalent bonds within chain

Secondary Force:
Vander walls force between chains
Hydrogen bonding
Dipole-dipole interactions

Chemical bonds between chains as in thermoset


polymers

Nomenclature

Monomer - molecule with minimum functionality of two


that reacts to form the structural units of the polymer
Oligomer - short chain synthesized from reaction of
several monomers (dimer, trimer, tetramer . . .)
Polymer - macromolecule generated through sequential
reaction of a small number of elementary units
Repeating unit - structure composed of the minimum
number of structural units necessary to generate the
polymer
Degree of polymerization - number of repeating units

COMMON MONOMERS AND POLYMERS

Vinyl and Vinyledene monomer and their polymer


Ester forming monomers and Polyester, Polycarbonate
Amide forming monomers and Polyamide

Common Vinyl and Vinyledene monomers


and Polymers

Common Ester, Carbonate and Amide


Polymers

Monomers Among Top 50 chemicals

April 10, 1995 Chemical and Engineering News

Production of Thermoplastics

Polyethylene
Low density (<0.940 g/cm3): 7,578
Linear low density (<0.940 g/cm3): 7,227
High density (>0.940 g/cm3): 12,924

Polyvinyl chloride and copolymers: 14,502


Polypropylene: 13,825
Styrene polymers
Polystyrene: 6,327

Acrylonitrile-butadiene-styrene: 3,086
*1998 (106 lb)

Production of Thermosets
Phenolic 3,940

Urea: 2,581
Unsaturated polyester: 1,713
Epoxy: 639
Melamine: 290

*1998 (106 lb)

Production of Synthetic Fibers


Noncellulosic fibers

Polyester :3,911
Nylon :2,847
Olefin :2,800
Acrylic :346

Cellulosic fibers
Acetate and rayon :365
*1998 (106 lb)

Production of Synthetic Rubber


Styrene-butadiene rubber: 960
Polybutadiene: 580
Ethylene-propylene: 321
Nitrile: 89
Polychloroprene: 72
*1998 (106 lb)

Applications: Packaging
Food wrapping
Bottles
Blister packs
Trash bags and grocery sacks
Shrink wrap
Foam packing

Applications: Medical
Catheters
Hip joint replacements
Artificial limbs (legs, feet, arms)
Artificial organs (heart, blood vessels, valves)
Dental fillings, bridges, and coatings
Disposable surgical clothes and instruments
Eyeglass frames and lenses

Applications: Recreational
Boat hulls, Boat hulls, masts, kayaks, surfboards, and
sails
Rackets, golf clubs, vaulting poles, and oars
Bobsleds, dune buggies, and automobiles
Athletic shoes
Skis, ski poles, ski boots, and ski lift chairs
Golf ball covers and golf club shafts
Bicycle parts, helmets, and pads

Applications: Entertainment
Stereo and television components
VCR tapes and housings
Cases for radios, tape players, tapes, and CDs
Toys

Applications: Textile
Clothing
Carpets
Non-woven fabrics
Diapers and other disposables
Upholstered fabrics for furniture
Draperies and wall paper material

Applications: Construction and Home


Moldings
Sprinklers and pipes
Counter tops
Sinks, shower stalls, and plumbing fixtures
Flooring (vinyl and carpeting)
Paint

Applications: Transportation
Automotive Automotive bodies, body panels, trim, and
seats
Aerospace components
Train, monorail, and light rail cars
Seat covers and dashboard covers
Truck bed liners
Gas tanks

Applications: Industrial
Pipes, valves, and tanks
Gears and housings
Adhesives and coatings
Vibration damping pads
Electrical circuit boards
Wire insulation and connector devices
Gaskets and sealants

Applications: Information Technology


Photoresists for microprocessor fabrication
Interlayer dielectrics for microprocessor
fabrication
Alignment layers for liquid crystal displays
Lubricants for computer hard disks

Class Assignment
Write at least two more application of polymer for each
sector from your own observation
Write structures indication mponomer for
PP
PE
Nylon

Review of Lecture 1
What is polymer and plastics
Characteristics of polymer
Characteristics of monomer required to undergo
polymerization
Types of monomer
Examples of polymers using each type of monomers
Application of polymers-different areas

Classification of Polymer
1.

Based on availability

Synthetic

Adhesives

Fibres

Coatings

Plastics

Rubbers
Natural

Polysaccharides

Proteins

Adhesives
Fibres
Adhesives
Fibers

Polyisoprene

Rubbers

Classification of Polymer
2.

Based on reaction Mechanism


Addition (Chain) Polymer

Break a double bond

PE,PP

Condensation (Step) Polymer

Elimination of by product (except epoxies and polyurethanes)

PET, PBT, Nylon

Classification of Polymer
3.

Based on molecular Structure

Linear Chain
Branched Chain
Network or gel Polymer

Classification of Polymer
4.

Based on Morphology
Amorphous
Crystalline/semicrystalline

5.

Based on molecular composition


Homopolymer
Copolymer

Alternate Copolymer: ABABAB


Block Copolymer:AAAAAABBBBBBBAAAAAAABBBBB

SBS (styrene-Butadiene-Styrene)

Graft Copolymer:
B
B
B

AAAAAAAAAAAAA

-High Impact Polystyrene, HIPS(Polystyrene with grafted polybutadiene)

Classification of Polymer
6.

Based on processing and response to temperature


-thermoplastic
-melts/softrens with temperature and can be reproccessed
-thermoset
-does not melt/softened with heat

Classification by Application

Plastics
Fibers
Elastomers
Coatings
Adhesives

Lessons learned in Section 1.1

What is polymer
Different monomer and their polymer
Unique characteristics of polymer
Terms related to polymer such as monomer, oligomer,
polymer, plastics, resins
Applications of polymers
Classification of polymers: different scheme of
classification

Assignment: Section 1.1


1. 1. Write down the abbreviation, chemical structure of monomer and chemical
Structure of polymer formed. Classify these polymers based on reaction
mechanism.
i. Polystyrene
ii. Polyethylene
iii. Polymethylacrylate
iv. Polymethylmethacrylate
v. Polypropylene
vi. Polyethylene terepthalate
vii. Polyvinyledene fluoride
viii.Polycarbonate
ix. Nylon 6,6

2. Write the classification scheme of polymers with Examples


3. Name three common vinyl polymer and write down their structure
4. Find at least 10 polymers from your surroundings and everyday use and write the
name of polymer and chemical structure and classification and basis of
classification

Assignment: section 1.1


3. Name three common vinyl polymer and write down their
structure
4. Find at least 10 polymers from your surroundings and
everyday use and write the name of polymer and
chemical structure and classification and basis of
classification
5. Write the differences between polymer, resin and
plastics
6. Write different applications of polymer listing some
specific polymers for specific applications

Module 1: Fundamentals of Polymer


Section 1.2: Characterizing Parameters

Characterizing Parameters
Molecular
Chemical composition
MW/MWD

Macroscopic
Topology
Orientation
Phases
Crystalline structure
Amorphpous Structure

Chemical Composition

Chemical composition:
Chemical nature of the monomers and the resulting nature of backbones
Chemical Composition Determines
Strength of the covalent bond
Intermolecular forces. Determines strengths
Dipole-dipole force as in PVC, Polyester
Hydrogen Bonding when polymer contains OH and NH groups
How closely they are packed. Determines morphology
Pendant groups such as Benzene ring, bulky side chains

Chemical Composition(contd.)
How much flexibility
Presence of non flexible groups in the backbone such as
amide, p-phenylene,sulfone, Carbonyl

Think!!!!!!
How chemical composition will affect following
properties?

Melting point?
Crystallinity?
Degradation/durability?
Chemical resistance?
Moisture absorption?
Reactivity?
Density?

Molecular Weight and Distribution


Molecular weight:
Polymer = (mer)n
n is not a single numebr. It has a range. Theoretically, n can
vary from zero to Infinity
Single polymer contains number of molecules with varying
weights.
Usually the molecular weight of a polymer is characterized by
average molecular weight and a range of distribution
The molecular weights of polymers are much larger than the
molecules usually encountered in organic chemistry
Molecular weight and its distribution affects the properties
significantly

Molecular Weight Distribution in Polymer

Average Molecular Weights


Different average values can be defined depending on
the statistical method that is applied. The weighted mean
can be taken with the weight fraction, the mole fraction
or the volume fraction:

Weight average molar mass or Mw


Number average molar mass or Mn
Viscosity average molar mass or Mv
Z average molar mass or Mz

Average Molecular Weights


Average Molecular weight based on Degree of
Polymerization(DP)
DP is the number, n, of repeating units in the polymer chain.
The molecular weight of a particular polymer molecule is a
product of the degree of polymerization and the molecular
weight of the repeating unit.
DP based on average molecular weight
DP based on number average molecular weight

Number Average Molecular Weight


Number-Average Molecular
Weight
The number average is the
simple arithmetic mean,
representing the total weight of
the molecules present divided
by the total number of
molecules.

Ni: number of molecules with


mass Mi

Pi: number average probablity


of Ni

Weight Average Molecular Weight


Weight-average emphasizes the mass of the
molecules so that the heavier molecules are
more important.
Pi : weight average probability of molecule Ni
with mass Mi

Viscosity Average Molecular Weight


One of the oldest methods of measuring the average
molecular weight of polymers is by solution viscosity. The
viscosity-average molecular weight lies somewhere
between the number average and the weight average

a is constant that depends on the polymer-solvent pair and on temperature

Z Average Molecular Weight

Comparison of Average Molecular Weights

Mn < Mv < Mw < Mz

MWD: Polydispersity Index


Molecular weight distribution also plays important role in
determining the properties along with the average
molecular weight
The weight-average molecular weight is larger than or
equal to the number-average molecular weight.
The ratio of the weight-average and number-average
molecular weights, is a measure of the polydispersity of
a polymer mixture

MWD: Polydispersity Index


Polydispersity Index indicates how widely distributed the
range of molecular weights are in the mixture.
A ratio that is around 1.0 indicates that the range of
molecular weights in the mixture is narrow; a high ratio
indicates that the range is wide. With rare exceptions, all
synthetic polymers are polydisperse

Polydispersity Index

Ni

Mi

Number Average Molecular Weight:


Example
Example :
Size exclusion chromatographic data of a new polymer shows the
following molecular weight distribution.
Number of Molecules
Mass of each molecule
5
10,000
3
30,000
2
60,000
Calculate the number average (Mn) and the weight average (Mw)
molecular weights of this polymer.

Number Average Molecular Weight:


Example
Multiply the weight of the polymer molecule by the number of
polymer molecules of that weight

NiMi would be: 5(1000) + 3(30,000)+ 2(60,000) = 260,000


Ni would be: 5+3+2 = 10
Therefore, Number Average Molecular Weight Mn
= 260,000 / 10 = 26,000

Number Average Molecular Weight:


Example

NiMi = 260,000
Weight Average Molecular Weight is WiMi = 39,960

Experimental Methods For Molecular Weight


Determination

Calculate average Molecular weight of PE with DP of 1000

Number Average Molecular Weight:


Experimental Measurement Technique
The number average molecular weight may be
determined by colligative property
measurements:

Osmometry
Vapor pressure change
Freezing point depression (rare)
Boiling point elevation (rare)

MW/MWD
The weight average molecular weight may be
determined experimentally by
Scattering measurements
Light
X-rays
Neutrons
Sedimentation equilibrium (ultracentrifuge)

Molecular Weight and Properties


MW ----> Viscosity ----> Processing hardness ---->Part property
Performance properties of finished product and processing
parameters affected by MW

Tensile strength
Impact strength
Toughness
Creep resistance
Stress-crack resistance
Elongation to break
Reversible elasticity
Melting temperature
Melt viscosity
Difficulty of processing

Threshold and Working Molecular Weight


Below a certain molecular weight, known as threshold
molecular weight, polymer does not exhibit its properties
for a particular application
Threshold MW depends on the Application.
For adhesive, threshold MW is relatively low
For high strength shaped plastic products, Threshold MW is quite
high

With MW strength and other properties increases but


Viscosity increases due to chain entanglement
High viscosities create processing problems
Working is defined as the MW optimized for processing
and properties

Molecular Weight and Properties

Assignment:
6. Calculate number average molecular weight, weight average molecular weight and polydispersity
index from the following size exclusion chromatography data.

Number of molecules

Molecular weight
50

1000

45

2000

30

3000

40

5000

80

6000

25

7000

30

8000

20

9000

10

10000

Assignment 3: Molecular characterization


and molecular weight
1. Why polymer characterization is so important for a
polymer engineer? List characterization parameters.
2. What is pendant group? Name and write the formula of
two polymers which has the pendant group identifying
pendant groups.
3. Write the formula for number average molecular weight,
weight average molecular weight and polydispersity
index.

Calculate number average, weight average,


and polydispersity index
Number of Molecules

Mass of each Molecule

800,000

750,000

700,000

650,000

10

600,000

13

550,000

20

500,000

13

450,000

10

400,000

350,000

300,000

250,000

200,000

Number Average Molecular Weight


Number of Molecules, Ni

Mass of Each Molecule, Mi

Total Mass of Each Type of Molecule, NiMi

800,000

800,000

750,000

2,250,000

700,000

3,500,000

650,000

5,200,000

10

600,000

6,000,000

13

550,000

7,150,000

20

500,000

10,000,000

13

450,000

5,850,000

10

400,000

4,000,000

350,000

2,800,000

300,000

1,500,000

250,000

750,000

200,000

200,000

Ni = 100

NiMi = 50,000,000

Number average Molecular weight=5,00,000

Weight Average MW & PDI


Number of Molecules

Mass of Each Molecule

Total Mass of Each


Type of Molecule

Weight Fraction
Type of Molecule

(Ni)

(Mi)

(NiMi)

NiMi)

(WiMi)

800,000

800,000

0.016

12,800

750,000

2,250,000

0.045

33,750

700,000

3,500,000

0.070

49,000

650,000

5,200,000

0.104

67,600

10

600,000

6,000,000

0.120

72,000

13

550,000

7,150,000

0.143

78,650

20

500,000

10,000,000

0.200

100,000

13

450,000

5,850,000

0.117

52,650

10

400,000

4,000,000

0.080

32,000

350,000

2,800,000

0.056

19,600

300,000

1,500,000

0.030

9,000

250,000

750,000

0.015

3,750

200,000

200,000

0.004

800

WiMi = 531,600

PDI=531600/500000=1.063

Problem Statement 4.6

Molecular weight data for some polymer are tabulated here.


Compute
(a) the number-average molecular weight, and
(b) the weight-average molecular weight.
(c) If it is known that this materials number-average degree of
polymerization is 477, which one of the polymers listed in Table 4.3
is this polymer? Why?
(d) What is this materials weight-average degree of polymerization?

Problem Statement 4.6


Molecular Weight Range (g/mol)

xi

wi

8,000-20,000

0.05

0.02

20,000-32,000

0.15

0.08

32,000-44,000

0.21

0.17

44,000-56,000

0.28

0.29

56,000-68,000

0.18

0.23

68,000-80,000

0.10

0.16

80,000-92,000

0.03

0.05

xi versus wi
xi the number fraction
The number of polymer chains that fall within a certain molecular
weight range divided by the total number of polymer chains.

wi the weight fraction


The mass of polymer chains that fall within a certain molecular
weight range divided by the total mass.

(a) Number-average molecular weight.


Mi (g/mol)

xi

xi*Mi (g/mol)

14,000

0.05

700

26,000

0.15

3900

38,000

0.21

7980

50,000

0.28

14000

62,000

0.18

11160

74,000

0.10

7400

86,000

0.03

2580

Mn=xiMi

=47720 g/mol

(b) Weight-average molecular

weight

Mi (g/mol)

wi

wi*Mi (g/mol)

14,000

0.02

280

26,000

0.08

2080

38,000

0.17

6460

50,000

0.29

14500

62,000

0.23

14260

74,000

0.16

11840

86,000

0.05

4300

Mw=wiMi

=53720 g/mol

(c) Identify polymer using number-average degree


of polymerization
nn = number-average degree of polymerization
Average number of mer units per polymer chain
nn = Mn / m, where m is the molecular weight of a mer unit
nn = 477 and Mn = 47720 g/mol, therefore m = 100.042 g/mol

(c) Identify polymer using number-average degree


of polymerization
Molecular weight of each mer unit can be found by
summing molecular weights of constituent atoms
In this case well ignore the molecular weight
contributions of the terminal groups

Mer Unit Molecular Weights


Polymer

Atoms in Mer

Mer Unit MW

PE

4H+2C

28.054 g/mol

PVC

3H+2C+Cl

62.499 g/mol

PTFE

4F+2C

100.014 g/mol

PP

5H+2C

29.062 g/mol

PS

8H+8C

104.152 g/mol

PMMA

8H+5C+2O

100.117 g/mol

Bakelite

9H+9C+1O

133.17 g/mol

Nylon 6,6

6H+4C+2O+2N

114.104 g/mol

PET

8H+10C+4O

192.17 g/mol

Polycarbonate

14H+16C+3O

254.285 g/mol

(c) Identify polymer using number-average degree


of polymerization
Most likely PTFE (Teflon) or PMMA (Plexiglass)
Differentiate by color
Teflon white
PMMA clear

Unlikely to use this procedure to identify a polymer in


real life

(d) Weight-average degree of polymerization

nw = weight-average degree of polymerization


Average number of mer units per polymer chain
nw = Mw / m, where m is the molecular weight of a mer unit
m = 100.042 g/mol and Mw = 53720 g/mol, therefore nw = 537

Different from nn because calculated using different average


molecular weight, Mw vs Mn

Topology
Molecular topology is a description of
molecules which includes their stereo-chemical
arrangement, branching, formation of helices
and network/looping/entanglement
characteristics
Physical properties of chain depends on interactions
between its chains.
Interactions between chains depend on the shape of the
chain making up the backbone

Topology

Topology

Topology
Linear Polymers:
Can form close packed structure
Nonlinear (Branched) Polymers
Some polymers, such as low density polyethylene
(LDPE), have branches of different sizes irregularly
spaced along the chain. Such polymers are said to be
nonlinear
Polymers with pendant groups, such as the methyl
group in polypropylene, are considered to be linear
The branches prevent the nonlinear molecules from
packing as closely as the linear, reducing their density

Topology
Cross linked and Network Polymers
Some polymers have cross-links between polymer chains creating
three-dimensional networks
A high density of cross-linking restricts the motion of the chains and
leads to a rigid material
Different structure give rise to very different properties
linear polyethylene has a melting point 20C higher than branched
polyethylene. Unlike linear and branched polymers, network polymers do
not melt and will not dissolve in solvents.
The effect of structure on polymer properties is called the StructureProperty Relationship.

Isomerism

Regularity of polymer chains decides the morphology


Highly irregular chains form amorphous polymer
Highly regular structure promotes crystalline growth
Some isomeric forms of polymer chains decrease the
regularity of chains reducing the probability of forming
crystalline structure

Isomerism
Isomers are molecules
with same molecular formula
Different arrangement of the atoms in space

Different arrangements which are simply due to the molecule rotating as a


whole, or rotating about particular bonds is not considered as isomers
Three forms of isomerism in polymers
Monomer orientation
Head-to-tail
Head-to-head
Geometric
Cis isomerism
trans isomerism
Stereoisomerism or tacticity
Isotactic
Syndiotactic
Atactic

Monomer Orientation
Monomers with pendant groups can attach in two ways.
head-to-tail
head-to-head

The usual arrangement is head-to-tail with the pendant


groups on every other carbon atom in the chain

Head to tail

Head to head

Geometric Isomerism
Double bonds in the polymer chain can show cis- or
trans-isomerism. When a monomer with two conjugated
double bonds, such as isoprene, undergoes chain
polymerization one double bond can remain in the chain.

Stereoisomerism
Three different form
Atactic (Random configuration)
Isotactic (Same configuration)
Syndiotactic (Alternating configuration)

Stereoisomerism

Stereoisomerism
The physical properties of a polymer can have a strong
dependence on tacticity.
Isotactic and syndiotactic polypropylene have regular
structures, which allow favorable polymer-polymer packing
Atactic polyprop. has an irregular structure and poor packing
Isotactic and syndiotactic forms have higher melting
temperatures (~165 and 130 C) and are poorly soluble in
many solvents.
Atactic has lower melting temp (< 0 C), is soft, rubbery, and
can be molded. It is also more soluble in most solvents.

Morphology
Polymer morphology is the overall description of polymer
structure including Phases
Morphology is determened by
Topology
Linear, branched, crosslinked
Molecular Weight

Phases of polymer
Crystalline phase
Amorphous phase

Amorphous Phase
Polymer chains with branches or irregular pendant
groups cannot pack together regularly enough to form
crystals. These polymers are said to be amorphous
Amorphous polymers are
Softer
have lower melting points
penetrated more by solvents

Crystalline Phase
Polymer chains without branches or bulkier pendant
groups can pack together regularly enough to form
crystals. These polymers are called crystalline polymers
Polymers are semi crystalline
Highly crystalline polymers

rigid
high melting,
less affected by solvent penetration
strong but with low impact resistance

Polymer Molecules form lamella

Crystalline Phase
Regular polymers forms plate like structure called
lamellar
Usual thickness of the lamella is about 10 to 20 nm

Semi-Crystalline Polymers

Semi-crystalline polymers have


both crystalline and amorphous
regions
When crystals are formed from the
melt, chain entanglements are
extremely important. Polymer
chains meandering in and out of
ordered crystalline portions
The crystalline portion is in the
lamellae; the amorphous portion is
outside the lamella

Semi-Crystalline Polymers
Ppercentage of the polymer that is crystalline is called
the percent crystallinity. The percent crystallinity has
an important influence on the properties of the polymer.

Spherulites

When a molten crystallizable


polymer cools, the crystals
grow from individual nuclei and
radiate out like the spokes of a
bicycle wheel
The crystalline portions
actually radiate out in in three
dimensions, forming spheres
that are called spherulites
In a sample of a crystalline
polymer there are billions of
spherulites

Spherulite

Factors Affecting Crystallinity

Structural Regularity
Degree of Polymerization
Intermolecular Forces
Pendant Groups
Processing
Rate of Cooling
Orientation

Structural Regularity
Structural Regularity promotes crystallization
Crystallization is favoured by
Linear structure
High degree of symmetry
Syndiotactic and or isotactic isomers

Limited crystallization can take place if a small number of


branches are present.

Degree of Polymerization
Relatively short polymer chains form crystals more
readily than long chains, because the long chains tend to
be more tangled.
High crystallinity generally means a stronger material,
but low molecular weight polymers usually are weaker in
strength even if they are highly crystalline
Low molecular weight polymers have a low degree of
chain entanglement, so the polymer chains can slide by
each other and cause a break in the material.

Intermolecular Forces
Crystallinity is favoured by strong inter backbone forces
The presence of polar and hydrogen bonding groups
favours crystallinity because they make possible dipoledipole and hydrogen bonding intermolecular forces
Polyethylene terepthalate, contains polar ester groups.
Dipole-dipole forces between the polar groups hold the
PET molecules in strong crystals.

Pendant Groups
Regular polymers with small pendant groups crystallize
more readily than do polymers with large, bulky pendant
groups
Poly vinyl alcohol (PVA) is made by the hydrolysis of poly
vinyl acetate ) (PVAc). PVA crystallizes more readily than
PVAc because of the bulky acetate groups in PVAc. The
-OH groups in PVA also form strong hydrogen bonds.

PVAc

PVA

Processing : Cooling Rate

Major difference between small molecules and polymers is that the


morphology of a polymer is dependent on its thermal history
The crystallinity of a polymer can be changed by cooling the
polymer melt slowly or quickly, and by "pulling" the bulk material
either during its synthesis or during its processing
When they are processed industrially, polymers often are cooled
rapidly from the melt. In this situation, crystallization is controlled
by kinetics rather than thermodynamics
There may not be time for the chains, which are entangled in the
melt, to separate enough to form crystals, so the amorphous nature
of the melt is "frozen into" the solid
A polymer is more likely to have a higher percent crystallinity if it is
cooled slowly from the melt.

Processing: Orientation
Crystallinity can be enhanced by stretching the bulk
material either when it is synthesized or during its
processing
Induced crystallization due to orientation is common for
both films and fibers
When a film is formed the small crystallites tend to be
randomly oriented relative to each other. Drawing
(stretching) the film pulls the individual chains into a
roughly parallel organization
Films can either be uniaxially oriented (oriented in only one
direction) or biaxially oriented (oriented in two directions).

Processing: Orientation
Fibers normally are drawn so that they are oriented in
one direction. Unstretched nylon fibers are brittle, for
example.. When the fibers are stretched the oriented
fibers are strong and tough.

Effect of Crystallinity on Properties

Module 1: Fundamentals of Polymer


Section 1.3: Polymer Properties

Polymer Properties
Thermal Properties
Melting point
Glass transition
Thermal Stability

Mechanical Properties

Strength
Modulus
Elongation
Toughness
Impact
Creep
Stress Relaxation

Polymer Properties
Chemical Properties

Oxidation
Thermooxidative stability
Degradability
Chemical resistance
Flammability/flame resistance
UV resistance

Melt properties
Polymer Rheology
Flow Characteristics
Viscosity vs. Shear rate
Shrinkage/cooling
Polymer swelling/memory effect

Other
Electrical properties

Thermal Properties
Amorphous Polymer

Heat, Tg

Glassy State

Crystalline Polymer

Heat, Tm

Molten State

Thermal Properties
Semicrystalline
polymer
Heat, Tm

Molten
polymer

Heat, Tg

Glassy
State

Glass Transition temperature


Above Tg polymers are rubbery whereas below Tg,
polymers are glassy
Rubbery behavior due to polymers ability to change its
conformation at high temperature
Glassy behaviour due to lack of ability to change
conformation at low temperature

Change in modulus with Tg

Factors Affecting Tg

Polarizing group
Polar groups increases Tg
Cross linking
Tg in creases with cross link density
Plasticizer
Plasticizer decreases Tg

Factors Affecting Tg

Polarizing group
Polar groups increases Tg
Cross linking
Tg in creases with cross link density
Plasticizer
Plasticizer decreases Tg

Tg and Molecular Weight

Backbone Flexibility

Pendant Group

Pendant Group

Pendant Group

Pendant Group

Pendant Group

Polar Molecules
Polar Molecules

Cross Linking

Effect of Plasticizer

Effect of Stereochemistry

Factors Affecting Melting point


Melting temperature depends on % Crystallinity
Chemical composition
Chain entanglement

Melting Temperature and chemical


composition

Melting Temperature and Crystallinity

Mechanical Properties
The mechanical properties of a polymer involve its
behavior under stress

How strong is the polymer? How much can you stretch it before it breaks?
How stiff is it? How much does it bend when you push on it?
Is it brittle? Does it break easily if you hit it hard?
Is it hard or soft?
Does it hold up well under repeated stress?

Mechanical Properties

Tensile strength:Resistance to stretching


Compressive strength:Resistance to compression
Flexural strength:Resistance to bending(flexing)
Impact strength:Resistance to sudden stress, like a hammer
blow
Fatigue:Resistance to repeated applications of tensile,
flexural, or compressive stress
Creep:Increase in strain when a polymer sample is subjected
to a constant (typical Viscoelastic Properties): time dependent
Stress relaxation:Decrease in stress when a sample is
elongated rapidly to constant strain (typical Viscoelastic
Properties): time dependent

Strain=elongation=L/L0

Youngs Modulus = Stress/Strain

Effect of T on E

Factors affecting stiffness

Factors affecting stiffness

Typical Stress Strain Curve for Plastic

C
B
A

A: Linear elastic
region
B: Yield Point
C: Failure point

Toughness

Comparison of toughness

Creep and Stress Relaxation

Chemical Properties

Chemical Properties

Oxidation
Thermal stability
Chemical resistance
UV resistance
Flammability/flame resistance
Degradability

Resistance to Oxidation and Thermal


Degradation
Oxygen in the atmosphere and high heat can cause the
can polymer degradation
Tertiary carbon atoms are more vulnerable for this type
of degradation
Usually Antioxidants(polymer additives) are added to
improve the oxidaive properties of polymers

Resistance to Oxidation and Thermal


Degradation
Polymer degrades at high temperature. Two things happen
when polymer is heated to a very high temperature:

Processing temperature is well below than the degradation temperature

Resistance to Oxidation and Thermal


Degradation
Thermo-oxidative Stability

Chemical Resistance
Chemicals can break the bond
Can extract additives and antioxidants
Can fill up of void and cause for swelling. Swelling reduces
mechanical strength
Chemical resistance varies among polymers
Chemical resistance of polymers can be increased by
modifying the polymers
Crystalline polymers are more resistant than Amorphous
polymers
Crosslinking increases chemical resistance
Most of the polymers are better chemical resistant than metals

Resistance to UV Light
UV light can cause the degradation of Polymer

Resistance to UV Light

Resistance to UV Light
UV stabilizer can be added to improve the UV
resistance of polymer
Carbon Black is an excellent UV stabilizer

Ozonolysis
ozone in atmosphere can cause the degradation of
polymers by breaking the bond

Resistance to Burning
Polymer mostly being carbon and hydrogen is flamable
Additives can be added to improve the flame retardant
properties of polymer
Halogens are excellent flame retardants. Most of the flame
retardant additives are halogen based
European countries does not allow halogen because of the
toxicity of the aloen based additives
Aluminium trihydroxide (ATH) and Magnesium di hydroxides
(MDH) are non alogeneted flame retardant additives

Resistance to Burning

Resistance to Burning

Retarding Combustion Process

Char Formation

Decomposing Material

Durability
How long polymer will last in service condition?
Durability usually is determined by the combined effect
of environments and chemicals
To predict the service lifetime usually accelerated aging
test is conducted in a simulated service condition such
as heat, chemicals, moisture and mechanical tension

Flow/Melt Properties

To process the polymer, polymer needs to be melted


Viscosity of molten polymer is an important parameter for
processing
Polymer is highly non Newtonian fluid and polymer rheology is very
complex
Thermal history and memory effect also very important for process
engineers and to determine how the polymer will respond to
processing condition

Material Selection-Design
Requirements

Structural/load constraints

Load
Frequency
Worst case scenarios
During manufacturing/shipping/use

Environmental constraints

Temperature
Humidity
Chemical
Radiation

Material Selection-Design
Requirements

Regulation/standards constraints

Trade groups
Governmental
Need to identify all
Range from materials to design

Marketing constraints
Costs
Esthetic
Use models

Durability

Additives
The reason to add additives, reinforcements, and fillers

To improve process ability


To reduce costs
To reduce shrinkage
To improve surface finish
To change thermal & electrical properties
To prevent degradation
To provide desirable color
To improve mechanical properties
To lower the coefficient of friction

Additives
Increase properties of plastics

Strength
Glass fibers
Graphite fibers
Kevlar fibers
Wood fibers
Impact strength
Particles
Talc

Additives
Increase properties of plastics
Flame retardants
Stability (UV and chemical)
Mold release

Antioxidants
Oxidation of plastics breaking of bonds in polymers
Effects on plastics: chain scission
How to overcome: Add antioxidants

Primary antioxidant: stop oxidative reactions


Secondary antioxidant: neutralize reactive materials
Examples:
Plastics: PP &PE
Primary: Phenolic, Amine
Secondary: Phosphite, Thioesters

Plastisizers

Increase flexibility
Reduce melt temperature
Lower viscosity

Water
Mild solvents
Commercial
Dioctyl phthalate

UV stabalizers (Carbon black)


UV can C-C backbone and many side groups
Brittle
Weaken

Other additives;
2-hydrocybenzophenone

Flame retardant

Ammonium phosphate
Chlorinated hydrocarbons
Chemicals of bromine, chlorine,antimony
Effects:
Emit fire-extinguishing gas (CO2 +N2)
Form an insulation barrier against heat and flame.

Foaming Agents
Foaming agents
Physical: -decompose at specific temperatures, releasing gases
Chemical: -release gases due to a chemical reaction

Uses:
Polyurethane pads
seats for cars,trucks
sofas

Internal Lubricants

Lubricants
1. Lower external and internal friction.
2. No-sticking to the mold.
3. Prevent products from adhering to each other.

Examples:
Waxes
Metallic soaps

Antistatic Agents
Attract moisture from the air making the
surface more conductive and then dissipating static
charges
Examples:
Amines Quaternary ammonium compounds
Organic phosphates Polyethylene glycol
esters