CH62045 Module 1 Polymer Basics 2015

CHEMICAL ENGINEERING
PRINCIPLES IN POLYMER
PROCESSING
CH 62045
Prof. Swati Neogi
10/27/15
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
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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.
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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
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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:
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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)
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Course Objective
Learn to use ChE principles to describe polymer processing
Polymer basics
1.What are polymers?
2. How do they differ form other materials ?
3. Why are they different ?
4. Properties
5. Applications
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Module 1
Course Objective
Learn to use CHE. Principles to describe polymer processing
Chemical Engineering principles

(i) Polymer Rheology
(ii) Polymer flow analysis
(iii) Heat transfer & Viscous heat dissipation
(iv) Devolatilisation & Mass transfer
Module 2
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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
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Manufacturing of
polymers is
beyond the scope
& objective
9
Course Overview
Module 1: Fundamentals of Polymer (# of Lectures: 1012)
1.1: Introduction (2)
1.2Molecular characteristics-structure-processing-property
relationship (4)
1.3: Polymer properties (3)
1.5: Polymer additives (1)
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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 devolatilisation during polymer
processing (2)
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Course Overview
Module 3: Polymer Processing Technologies ( # of
Lectures: 18)
3.1: Extrusion (10)
3.2: Injection Molding(6)
3.3: Calendaring , Thermoforming, Others(2)
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Module 1: Course Outline
Introduction of polymer (L2)
Definition
Advantages
Classification of polymer
Applications
Molecular characteristics-structure-propertyprocessing Relationship(L3)
Molecular
Chemical composition
MW/MWD
Macroscopic
Topology
Orientation
Phases
- Crystalline
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- Amorphous
13

Polymer properties (L4)
Thermal Properties
Melting point
Glass transition
Mechanical Properties
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Strength
Modulus
Elongation
Toughness
Impact
Creep
Permeability
14

Chemical Properties
Oxidation
Thermal stability
Degradability
Chemical resistance
Flammability/flame resistance
UV resistance
Melt properties
Flow Characteristics
Viscosity vs. Shear rate
Shrinkage/cooling
Polymer swelling/memory effect
Polymer Additives (L0.5)

Material selection and design guidelines (L0.5)
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Module 1: Fundamentals of Polymer

Section 1.1: Introduction
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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 --------10/27/15
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Processing with
additives
Finished Product
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Polymers
18
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.
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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
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Basic Concept
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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
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Basic Concepts
Compound of hydrogen and carbon, and/or O, N, F and
Si
Low strength compared with metals; lower melting point
Properties can be tailor made by choosing different
monomers, by blending different polymers.
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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
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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
polymers.
Degree of polymerization - number of repeating units
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COMMON MONOMERS AND POLYMERS
Vinyl and Vinyledene monomer and their polymer

Ester forming monomers and Polyester, Polycarbonate
Amide forming monomers and Polyamide
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Common Vinyl and Vinyledene monomers

and Polymers
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Common Ester, Carbonate and Amide

Polymers
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Applications: Packaging
Food wrapping
Bottles
Blister packs
Trash bags and grocery sacks
Shrink wrap
Foam packing
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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
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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
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Applications: Entertainment
Stereo and television components

VCR tapes and housings
Cases for radios, tape players, tapes, and CDs
Toys
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Applications: Textile
Clothing
Carpets
Non-woven fabrics
Diapers and other disposables
Upholstered fabrics for furniture
Draperies and wall paper material
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Applications: Construction and Home
Mouldings
Sprinklers and pipes
Counter tops
Sinks, shower stalls, and plumbing fixtures
Flooring (vinyl and carpeting)
Paint
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Applications: Transportation
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
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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
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Applications: Information Technology
Photo resists for microprocessor fabrication

Interlayer dielectrics for microprocessor
Fabrication
Alignment layers for liquid crystal displays
Lubricants for computer hard disks
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Class Assignment
Write at least two more application of polymer for each
sector from your own observation.
Write structures indication monomer for:
PP
PE
Nylon
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Review of Lecture 1
What are polymers 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 in different areas.
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Classification of Polymer
1.
Based on availability
Synthetic
Adhesives
Fibres
Coatings
Plastics
Rubbers
Natural
Polysaccharides
Adhesives
Fibres
Proteins
Adhesives
Fibres
Polyisoprene
Rubbers
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2. Based on reaction Mechanism
Addition (Chain) Polymer
Break a double bond
PE,PP
Condensation (Step) Polymer
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Elimination of by product (except epoxies and polyurethanes)
PET, PBT, Nylon
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3.
Based on molecular Structure
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Linear Chain
Branched Chain
Network or gel Polymer
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4.
Based on Morphology
5.
Amorphous
Crystalline/semicrystalline
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)
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6.
Based on processing and response to temperature

Thermoplastic: Melts/softens with temperature and can be
reprocessed
Thermoset: Does not melt/soften with heat
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Classification by Application
Plastics
Fibers
Elastomers
Coatings
Adhesives
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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.
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Assignment: Section 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
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Assignment: Section 1.1

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.
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Assignment: section 1.1

5. Name three common vinyl polymer and write down their
structure
6. 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
7. Write the differences between polymer, resin and plastics
8. Write different applications of polymer listing some specific
polymers for specific applications
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Section 1.2 Molecular characteristicsstructure-property-processing Relationship
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Molecular characteristics-structure-property-processing Relationship

Chemistry
(mer
composition)
Molecular
Characteristics
Structure
Size
(molecular weight
distribution)
Shape
Topology
Orientation
Phases
Intermolecular and
Intramolecular forces
Thermal
Mechanical
Rheological
Chemical
Other
Thermal
properties
Rheology
Properties
Processes
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.
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Chemical Composition(contd.)
How much flexibility
Presence of non flexible groups in the backbone such as
amide, p-phenylene,sulfone, Carbonyl.
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Think!!!!!!
How chemical composition will affect following
properties?
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Melting point?
Crystallinity?
Degradation/durability?
Chemical resistance?
Moisture absorption?
Reactivity?
Density?
54
Molecular Weight and Distribution

Molecular weight:
Polymer = (mer)n
n is not a single number. 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
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Molecular Weight Distribution in Polymer
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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
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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
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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.
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Ni: number of molecules with

mass Mi
Pi: number average probablity

of Ni
59
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
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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
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Z Average Molecular Weight
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Comparison of Average Molecular Weights
Mn < Mv < Mw < Mz

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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.
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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
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Polydispersity Index
Ni
Mi
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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.
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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
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Example
NiMi = 260,000
Weight Average Molecular Weight is WiMi = 39,960
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Practice Question
Calculate average Molecular weight of PE with DP of
1000
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Experimental Measurement Technique
The number average molecular weight may be
determined by colligative property measurements:
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Osmometry
Vapor pressure change
Freezing point depression (rare)
Boiling point elevation (rare)
71
MW/MWD
The weight average molecular weight may be
determined experimentally by:
Scattering measurements
Light
X-rays
Neutrons
Sedimentation equilibrium (ultracentrifuge)
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Molecular Weight and Properties

MW ----> Viscosity ----> Processing hardness ---->Part property
Performance properties of finished product and processing
parameters affected by MW
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Tensile strength
Impact strength
Toughness
Creep resistance
Stress-crack resistance
Elongation to break
Reversible elasticity
Melting temperature
Melt viscosity
Difficulty of processing
73
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 Molecular Weight is defined as the MW optimized
for processing and properties.
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Molecular Weight and Properties
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Assignment:
6. Calculate number average molecular weight, weight average molecular weight and polydispersity
index from the following size exclusion chromatography data.
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Number of molecules
Molecular weight
50
1000
45
2000
30
3000
40
5000
80
6000
25
7000
30
8000
20
9000
10
10000
76
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.
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Calculate number average, weight average,

and polydispersity index
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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
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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

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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)/(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
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PDI=531600/500000=1.063
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Problem Statement 4.6

Molecular weight data for some polymer are tabulated
here. Compute:1. The number-average molecular weight, and the weight-average
molecular weight.
2. 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?
3. What is this materials weight-average degree of polymerization?
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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
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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.
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1. 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
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1. 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
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2. 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
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3. 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
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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
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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.
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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
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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 .
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Topology
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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.
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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.
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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.
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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.
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Isomerism
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
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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
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Head to head
98
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.
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Stereoisomerism
Three different form
Atactic (Random configuration)
Isotactic (Same configuration)
Syndiotactic (Alternating configuration)
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Stereoisomerism
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Stereoisomerism
The physical properties of a polymer can have a strong
dependence on tacticity.
Isotactic and Syndiotactic polypropylene have regular
structures, which allow favourable 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 moulded. It is also more soluble in most
solvents.
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Morphology
Polymer morphology is the overall description of polymer
structure including phases
Morphology is determined by
Topology
o linear, branched, cross-linked
Molecular Weight
Phases of polymer
Crystalline phase
Amorphous phase
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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
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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
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Crystalline Phase
Regular polymers forms plate like structure called
lamellar
Usual thickness of the lamella is about 10 to 20 nm
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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
Percentage of the polymer that is
crystalline is called the percent
crystallinity. The percent crystallinity
has an important influence on the
properties of the polymer.
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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
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Spherulite
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Factors Affecting Crystallinity
Structural Regularity
Degree of Polymerization
Intermolecular Forces
Pendant Groups
Processing
Rate of Cooling
Orientation
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Structural Regularity
Structural regularity promotes crystallization
Crystallization is favoured by
Linear structure
High degree of symmetry
o Syndiotactic and or isotactic isomers
Limited crystallization can take place if a small number of
branches are present.
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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.
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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 Terephthalate, contains polar ester
groups. Dipole-dipole forces between the polar groups
hold the PET molecules in strong crystals.
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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.
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PVAc
PVA
116
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.
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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 fibres
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).
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.
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Effect of Crystallinity on Properties
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Section 1.3: Polymer Properties
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Polymer Properties
Thermal Properties
Melting point
Glass transition
Thermal stability
Strength
Modulus
Elongation
Toughness
Impact
Creep
Stress Relaxation
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Polymer Properties
Chemical Properties
Oxidation
Thermooxidative stability
Degradability
Chemical resistance
UV resistance
Melt properties
Polymer Rheology
o Flow Characteristics
o Viscosity vs. Shear rate
Shrinkage/cooling
Polymer swelling/memory effect
Other
Electrical properties
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Thermal Properties
Semicrystalline
polymer
Heat, Tm
Molten
polymer
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Heat, Tg
Glassy
State
123
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
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Change in modulus with Tg
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Factors Affecting Tg
Backbone-Polar groups increases Tg
Molecular Weight
Pendant Group
Cross linking
-Tg in creases with cross link density
Plasticizer
-Plasticizer decreases Tg
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126
Backbone Flexibility
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127
Tg and Molecular Weight
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128
Pendant Group
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129
Cross Linking
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Effect of Plasticizer
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Factors Affecting Melting point

Melting temperature depends on % Crystallinity
Chemical composition
Chain entanglement
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132
Melting Temperature and Chemical

Composition
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Melting Temperature and Crystallinity
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136
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 stress (typical Viscoelastic Properties): time dependent
Stress relaxation: Decrease in stress when a sample is elongated
rapidly to constant strain (typical Viscoelastic Properties): time
dependent
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Effect of T on E
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147
Factors affecting stiffness
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Toughness
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149
Comparison of Toughness
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150
Creep and Stress Relaxation
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Chemical Properties
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156
Chemical Properties
Oxidation
Thermal stability
Chemical resistance
UV resistance
Degradability
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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
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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
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159

Thermal Degradation
Thermo-oxidative Stability
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160
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
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Resistance to UV Light
UV light can cause the degradation of Polymer
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163
UV stabilizer can be added to improve the UV resistance
of polymer
Carbon Black is an excellent UV stabilizer
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164
Ozonolysis
Ozone in atmosphere can cause the degradation of
polymers by breaking the bond
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Resistance to Burning
Polymer mostly being carbon and hydrogen is flammable
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 halogen based additives
Aluminium Trihydroxide (ATH) and Magnesium
Dihydroxides (MDH) are non-halogeneted flame
retardant additives
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Retarding Combustion Process
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Char Formation
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Decomposing Material
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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
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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
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Material Selection-Design
Requirements
Structural/load constraints
Load
Frequency
Worst case scenarios
During manufacturing/shipping/use
Environmental constraints
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Temperature
Humidity
Chemical
Radiation
174
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
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Additives
The reason to add additives, reinforcements, and fillers
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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
176
Additives
Increase properties of plastics
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Strength
Glass fibers
Graphite fibers
Kevlar fibers
Wood fibers
Impact strength
Particles
Talc
177
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
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178
Plastisizers
Increase flexibility
Reduce melt temperature
Lower viscosity
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Water
Mild solvents
Commercial
Dioctyl phthalate
179
UV stabilizers (Carbon black)

UV can break/weaken C-C backbone and many
side groups
Brittle
Weaken
Other additives;
2-hydrocybenzophenone
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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.
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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
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Internal Lubricants
Lubricants
1. Lower external and internal friction
2. No-sticking to the mould
3. Prevent products from adhering to each other
Examples:
Waxes
Metallic soaps
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Antistatic Agents
Attract moisture from the air making the surface more
conductive and then dissipating static charges
Examples:
10/27/15
Amines
Quaternary ammonium compounds
Organic phosphates
Polyethylene glycol
Esters
184

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CH62045 Module 1 Polymer Basics 2015

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CHEMICAL ENGINEERING

Guest Lecture & Field Trip:

No single text book will cover the entire subject. Take

Principles of Polymer Processing by Tadmor & Gogos

Chemical Engineering principles

Module 1: Course Outline

Introduction of polymer (L2)

Molecular characteristics-structure-propertyprocessing Relationship(L3)

Module 1: Course Outline

Module 1: Course Outline

Polymer Additives (L0.5)

Module 1: Fundamentals of Polymer

Some Organic Basics

General name of following series of compounds

write the product of following reaction:

Polymer, Resin, and Plastics

A polymer is any substance made up of many of repeating units,

Polymers are seldom used in their neat form, most often

Frequently, polymers, resins, plastics are used interchangeably.

1868 Cellulose nitrate

Polymer is large molecule having repeating unit

Chemical bonds between chains as in thermoset polymers

COMMON MONOMERS AND POLYMERS

Vinyl and Vinyledene monomer and their polymer

Common Vinyl and Vinyledene monomers

Common Ester, Carbonate and Amide

Stereo and television components

Applications: Construction and Home

Automotive bodies, body panels, trim, and seats

Pipes, valves, and tanks

Applications: Information Technology

Photo resists for microprocessor fabrication

Break a double bond

Condensation (Step) Polymer

Elimination of by product (except epoxies and polyurethanes)

PET, PBT, Nylon

Based on molecular Structure

Based on molecular composition

Alternate Copolymer: ABABAB

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

Based on processing and response to temperature

Lessons learned in Section 1.1

Assignment: Section 1.1

Assignment: Section 1.1

Assignment: section 1.1

Module 1: Fundamentals of Polymer

Molecular characteristics-structure-property-processing Relationship

Molecular Weight and Distribution

Molecular Weight Distribution in Polymer

Average Molecular Weights

Average Molecular Weights

Number Average Molecular Weight

Ni: number of molecules with

Pi: number average probablity

Weight Average Molecular Weight

Viscosity Average Molecular Weight

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

MWD: Polydispersity Index

Number Average Molecular Weight:

Number Average Molecular Weight: