Documente Academic
Documente Profesional
Documente Cultură
IN POLYMER PROCESSING
CH 62045
Prof. Swati Neogi
Class Guideline
Attendance Policy:
100% attendance is desirable
No unexcused absence
Up to four excused absence
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
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
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)
Definition
Advantages
Classification of polymer
Applications
Characterization parameters L(3)
Molecular
Chemical composition
MW/MWD
Macroscopic
Topology
Orientation
Phases
Crystalline
Amorphous
Thermal Properties
Melting point
Glass transition
Mechanical Properties
Strength
Modulus
Elongation
Toughness
Impact
Creep
Permeability
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
Processing with
additives
Finished Product
Polymers
Development of Plastics
Basic Concept
Basic Concept
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
Nomenclature
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
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
Polyester :3,911
Nylon :2,847
Olefin :2,800
Acrylic :346
Cellulosic fibers
Acetate and rayon :365
*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: 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
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.
PE,PP
Classification of Polymer
3.
Linear Chain
Branched Chain
Network or gel Polymer
Classification of Polymer
4.
Based on Morphology
Amorphous
Crystalline/semicrystalline
5.
SBS (styrene-Butadiene-Styrene)
Graft Copolymer:
B
B
B
AAAAAAAAAAAAA
Classification of Polymer
6.
Classification by Application
Plastics
Fibers
Elastomers
Coatings
Adhesives
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
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?
Polydispersity Index
Ni
Mi
NiMi = 260,000
Weight Average Molecular Weight is WiMi = 39,960
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)
Tensile strength
Impact strength
Toughness
Creep resistance
Stress-crack resistance
Elongation to break
Reversible elasticity
Melting temperature
Melt viscosity
Difficulty of processing
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
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
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
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
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.
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
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
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
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
Isomerism
Isomers are molecules
with same molecular formula
Different arrangement of the atoms in space
Monomer Orientation
Monomers with pendant groups can attach in two ways.
head-to-tail
head-to-head
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
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
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
Spherulite
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
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: 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.
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
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
Backbone Flexibility
Pendant Group
Pendant Group
Pendant Group
Pendant Group
Pendant Group
Polar Molecules
Polar Molecules
Cross Linking
Effect of Plasticizer
Effect of Stereochemistry
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
Strain=elongation=L/L0
Effect of T on E
C
B
A
A: Linear elastic
region
B: Yield Point
C: Failure point
Toughness
Comparison of toughness
Chemical Properties
Chemical Properties
Oxidation
Thermal stability
Chemical resistance
UV resistance
Flammability/flame resistance
Degradability
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
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
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
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
Plastisizers
Increase flexibility
Reduce melt temperature
Lower viscosity
Water
Mild solvents
Commercial
Dioctyl phthalate
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