2010-2011 S1

MP2004, MP2304, MP3104, MP3304

Manufacturing & Materials

A/P Zhou Wei

Web:
http://www3.ntu.edu.sg/home/mwzhou
 School of MAE
Research and teaching organized into
Knowledge Domains (KD’s). MP2004 is
aligned with KD of Manufacturing
Engineering Division:
• Materials,
• Forming,
• Joining/assembly,
• Machining.
 Manufacturing & Materials

Mild Steel
Lathe
Interplay
tool between
machining &
materials
 Manufacturing & Materials

Mild
Steel Interplay
Arc between
Welding
seam welding &
materials
 Materials

Metals Metal-Polymer
Metal-Ceramic
Composites
Composites

Ceramics Polymers

Ceramic-Polymer Composites
 Lecture 1

Revision of
key concepts
 Allotropic - Polymorphic
Carbon.

Buckminster
Graphite Diamond
- fullerene
Periodic Table
 Bonding
Three types of primary bonding:
(1) Ionic (I) – metals – nonmetals
(2) Covalent (C) – nonmetals-nonmetals,
(3) Metallic (M) – metals.

Secondary bonding
(1) Van der Waal’s (VDW)
(2) Dipolar (D)
(3) Hydrogen –Bonding (HB).
Nobel Gases – energetically stable
Gases Electron Orbits Electrons per shell
4 2 (K-shell)
2 He e -

e- 10 (K, L-shells)
20
10 Ne

e- 18 (K, L, M-shells)
40
18 Ar
 Primary Bonding
(Ne) (Ar)
(1) I

Na Cl Na+ Cl-
Strong electrostatic force
(Ne) (Ne)

(2) C
O O O2
 Primary Bonding Valence e-

(3) M

Na Na Na Na

Valence e-
(Ne) (conduction e-)
 Secondary Bonding
(1) VDW
As atoms vibrate may temporarily loose
electrical symmetry → dipole.

+ -
(2) D
Permanent dipoles due to asymmetry.
HCl

+ -
 Secondary Bonding
(3) HB
• Strongest secondary bonding type.
• Occurs when H covalently bonded to F, O,
and N.
• High melting point of H20 due to HB.
+
+
-
-
+
+
 Defects

Unit
cell

For effective bonding atoms (ions) need to

be surrounded by maximum number of
nearest neighbors.
 ∞ Single Crystal, defect free

Each atom has max. no. of nearest neighbors &

optimum separaration. (no strain ). Min. energy.
 Single Crystal - defects
Surface Vacancy Interstitial Substitution

Dislocation

⊥
High
energy
Poly-Crystalline -diffusion

Grain
boundary

High
energy
Boundary Energy
Solid
Solution

•Atoms without
max. no. of
nearest
neighbors in state
of high energy.
•Also elastic
strain.
Boundary Energy
Ordered
Phase at
30 °C

Boundary area
=69 units
Boundary Energy
Ordered
Phase at
120 °C
Boundary area
=35 units

Boundary energy
decreases since
originally high.
Boundary Energy
Coherent
Phase at
30 °C
Boundary area
=69 units
Boundary Energy
Coherent
Phase at 120 °C

Boundary area
=69 units

Boundary energy
unchanged since
originally low.
 Stress (σ) – Strain (ε)

Toughness
σ σ Toughness
×
TS
×

ε ε
Brittle Ductile
 Plastic Deformation
Actual strength of metals less than
theoretical strength. Why?
 Plastic Deformation
σ

Slip
plane

σ
Six bonds break at same time!
 Dislocations
σ σ Slip plane

σ σ
Only one bond break!
 Plastic Deformation
Two main deformation mechanisms:
(1) Dislocation motion
(2) Twinning
 Crystallography
• Seven crystal systems.
• Metals mainly Body Centered Cubic (BCC),
Face Centred Cubic (FCC), or Hexagonal Close
Packed (HCP).
• Ceramics rarely simple structures.

BCC FCC HCP c

a a
a
 Slip Systems
• Generally, dislocations move in directions
where atom separation is small.
• All permutations of these “easy”
directions - part of slip system.
• Greater number of (active) slip systems,
greater ductility of material.

BCC – [111]
 Ductile or Brittle?
• Energy required to move dislocation
depends exponentially on distance moved.
• Almost all FCC metals are ductile (many
active slip-systems).
• Almost all HCP metals are brittle (few
active slip-systems).
• For BCC it depends on temperature and
metal.
Binary Phase Diagram Revision

A Cu-60wt% Ag alloy is prepared.

• What phases present at RT?

• What are phase compositions?
• What are relative amounts of each
phase present?
 L
1000
Temperature (°C)

α α+L
800 β+L
8.0 71.9 91.2 β

600

400 α+β

200
×
0 20 40 60 80 100
Composition (wt % Ag)
 L α=8 wt% Ag - 92 wt% Cu
1000 β=91.2 wt %Ag – 8.8 wt% Cu
Temperature (°C)

α α+L
800 β+L
8.0
× 71.9 91.2
β

600

400 α+β

200
0 20 40 60 80 100
6 wt% Ag Composition (wt % Ag) 95 wt% Ag
 L  91.2 − 60 
1000
%α =   = 38%
 91.2 − 8 
Temperature (°C)

α α+L
800 β+L
8.0
× 71.9 91.2
β

600

400 α+β

200
0 20 40 60 80 100
6 wt% Ag Composition (wt % Ag) 95 wt% Ag
 Summary
β−phase
. α + β phases present at RT
. α=8 wt% Ag, β=91.2 wt % Ag.
. α=38%, β=62%
∀≡ phase (takes as long
as is necessary)
• Almost no diffusion
in solid state.

α-phase
 Anisotropy
Polycrystalline metal with equal sized grains
(equiaxed) – isotropic.

Isotropic Anisotropic
 Fracture Toughness, KIC
KIC - materials susceptibility to brittle
fracture.
σ
Critical stress material can withstand
c
before fracture:
K IC
σc≤
2a 1.1 π a
a
KIC-Steel ~90, KIC-Al ~25, KIC-Glass~0.8, KIC-
σc
plastic ~1 MPa√m
 What is creep?
• Creep - time-dependent (permanent)
deformation of materials subjected to
constant stress.

• Limiting factor in lifetime of devices.

• Important for metals when operating-

temperature > 0.4 Tm (Tm =absolute melting
temperature).
 What is creep?
.
ε Rupture
×

Secondary Tertiary

Primary time

Operation preferred in secondary (steady-

state) creep.
 What is creep?
Creep reduce by:

1. Increasing Tm.
2. Increasing elastic modulus, E.
3. Increasing grain-size.
4. Alloys - have substitutional impurities
with low-diffusivity at high-
temperatures (such as W).
 Metastable
E E

Stable Metastable
Examples
• Fe3C (cementite),
• Martensite,
• Amorphous materials.
Lecture 2

Polymers
How Plastic Bottles are Made

http://www.youtube.com/watch?v=T01i_vp2mJE
 Polymer Molecules
• Atoms bonded by covalent bond.
• Gigantic molecules made from repeating
structural units.
Monomer unit

H H H H H H H H H H H H
| | | | | | | | | | | |
-c-c-c-c-c-c-c-c-c-c-c-c-
| | | | | | | | | | | |
H Cl H Cl H Cl H Cl H Cl H Cl
Polymer
 Polymer Molecules
H
|
H – C - H 5-atoms
|
H

Small-Molecule (CH4)

H H H H H H H H H H H H H
| | | | | | | | | | | | |
– C - C– C - C – C - C– C - C – C - C– C - C – C -
| | | | | | | | | | | | |
H Cl H Cl H Cl H Cl H Cl H Cl H

Macro-Molecule (PVC) 10,000-atoms

 Monomers
Monomers must have multi-functional reactive
bonds or chemical groups (minimum functionality
is two, i.e. di-functional)

• Mono-functional:
– Ethanol CH3CH2-OH
• Di-functional:
– Ethylene diol HO-CH2CH2-OH
• Tri-functional
– Glycerol HO-CH2-CH(OH)-CH2-OH
 Condensation Reaction

HO-CH2CH2-OH + HO-CH2CH2-OH→
HO-CH2CH2-O-CH2CH2-OH + H2O

HO-CH2CH2-OH + HO-CH2CH2-O-CH2CH2-OH →
HO-CH2CH2-O-CH2CH2-O-CH2CH2-OH + H2O

Small molecule eliminated (e.g. H2O).

 Plastics?
Plastics fall into two categories.

(1) Pure polymer (e.g. high density

poly-ethylene).
(2) Multiple-blends with fillers,
additives, etc.
 Mers
H H
C C
H R
General vinyl polymer – Poly vinyl mer

Cl
when R is →
Polyvinyl chloride (PVC)
H C H
H
H
Polyethylene (PE)
Polypropylene (PP)
Polystyrene (PS)
 Morphology
Materials categorized according to their
morphologies.
Amorphous
No long-range order, i.e. random coils or
irregular packing of chains.
 Morphology
Perfectly Crystalline

Regular 3-D arrangement of molecular

chains.
 Morphology
Semi-Crystalline

Regions of amorphous & perfectly crystalline

in co-existence.
crystallite
 (1) Linear

• Repeat units held by strong covalent

bonds.
• Chains long & flexible (1-D).
• Different molecules held together by
weaker secondary forces.
Examples PE, PVC, PS, PMMA.
 (2) Branched
•Introduced during side
polymerisation.
•Chains packing efficiency ↓
due to steric (size) effects.
•Polymer density ↓
 Thermoplastics
• Polymers soften upon heating & made to
flow when a stress is applied.
• When cooled, they will solidify to a solid
or rubbery solid.

heating
Solid Liquid (melt)
cooling

Can be recycled.
 Forming Processes
•Widely used in manufacturing plastic
products by
•Injection molding
•Thermoforming
•Extrusion
(3a) Cross-linked
• Adjacent linear chains joined
to one another by strong
covalent bonds.
• Achieved by growth at high
temperature (irreversible).

Example Rubber elastic material

cross-linked by a method known
as vulcanization.
(3b) Network
• Tri-functional (or
more) monomer units
form three or more
covalent bonds resulting
in a 3-D networks.
• Achieved by growth at
elevated temperature.

Example: Epoxies.
 Thermoset
• Polymers which become hard and rigid
upon heating (irreversible).
• Chain motion restricted by high degrees
of cross-linking.
• Harder, stronger, more brittle but with
better dimensional stability compared
with Thermoplastic Polymers.
 Elastomers
• Mechanical properties like natural rubber.
• Linear or cross-linked.
• Chains extended upon deformation but are
prevented from flow by cross-links or physical
domains.
•Returns to original shape on removal of σ.

Linear
Chain
Domain
 Classification

Homopolymer:
• One type of monomer (A) used to build
polymer.
• Structure can be represented by multiple
repetition of a single repeat unit.
A A A A
A n

Examples : PE, PTFE, PS, PVC, ...

 Copolymer
• Polymer structure made up of two (or more)
monomer units.
•Polymer has combined properties of various
monomers.
Types of Copolymer
Random Copolymer - poly(A-ran-B) :

Two different units (A and B) randomly dispersed

along chain
ABAABAAABBAAAB
 Copolymer
Alternating Copolymer - poly(A-alt-B):

ABABABABABABAB

Block Copolymer - polyA-block-polyB :

AAABBBBBAAABBBBB
 Copolymer
Graft Copolymer:
• chains of one kind are attached to backbone
of different polymer.
B B B
B B B
B B B
AA AAA AAA A
B B
B B
B B

• known as polyA-graft-polyB.
 Lecture Theatre
• Distribution of students, ages 19-29 years.
• Can talk about number fraction of
students with age in range 23-25. i.e.
number of students in this age range /
total number of all students present.
• Alternatively, can talk about weight
fraction of students in age range 23-25. i.e.
weight of students in this age range / total
weight of all students present.
 Molar Mass
• Measures size (or weight) of polymer
molecule.
• Defined as an average value with a wide
distribution of polymer chain size.
• Represents statistical nature of
polymerization.
Main averages:
• Number-average molar mass, Mn
• Weight-average molar mass, Mw
Number versus weight average
Distribution of molecular weight
Mn
Amount of Polymers

Mw

Molecular weight
 Poly-Dispersity
Ratio of two measures of molecular weight
called Poly-Dispersity (PD):
MW
PD =
Mn
• PD=1.0 - all molecules have same weight!
Unusual for polymers.
• ↑ in poly-dispersity ⇒ ↑ width of
molecular weight distribution
 Significance of Molar Mass
• Chain ends considered as defects in
polymers since they have no covalent bond to
transmit strength.
↑ in molecular weight
↑ in chain length

↓ in chain ends

∴ as molecular weight ↑, tensile strength ↑

 Example
Molecular xi wi
Weight Range
(g/mol)
8,000-16,000 0.05 0.02
16,000-24,000 0.16 0.10
24,000-32,000 0.24 0.20
32,000-40,000 0.28 0.30
40,000-48,000 0.20 0.27
48,000-56,000 0.07 0.11
Calculate:
(a) Mn, (b) Mw, and (c) nw (weight
averaged Degree of Polymerization.
 (a) Calculate Mn

Molecular wt Range Mean,Mi xi xiMi

8,000-16,000 12,000 0.05 600
16,000-24,000 20,000 0.16 3,200
24,000-32,000 28,000 0.24 6,720
32,000-40,000 36,000 0.28 10,080
40,000-48,000 44,000 0.20 8,800
48,000-56,000 52,000 0.07 3,640

Mn = ΣxiMi = 33,040 g/mol

 (b) Calculate Mw
Molecular wt.
Range Mean,Mi wi wiMi
8,000-16,000 12,000 0.02 240
16,000-24,000 20,000 0.10 2000
24,000-32,000 28,000 0.20 5600
32,000-40,000 36,000 0.30 10,800
40,000-48,000 44,000 0.27 11,880
48,000-56,000 52,000 0.11 5720

Mw = ΣwiMi = 36,240 g/mol

 H H
(c) Calculate nw C C
H H C H
For PP, molar mass of repeat unit H

= 3(mC) + 6(mH)

= (3×12 g/mol) + (6×1 g/mol) = 42 g/mol

Mw
And since nw = , nw = 863
m
 Configurations & Conformations
Geometric detail of how each unit is added & shape
of chain are important factors.

Chain Configurations:
- Refers to placement of successive repeat units
into chain
Chain Conformations:
- Chain can take on ∞ number of shapes by
rotation about backbone bonds, this gives rise to
different conformations.
 Molecular Configuration
Arrangements of atoms fixed by covalent
bonds in molecule & cannot be altered
unless bonds are broken.
Configurations:

• Order (head-to-head, head-to-tail, tail-to-

tail)
• Stereoisomerism (Isotactic, Syndiotactic,
Atactic)
 Order in Molecules
Considering vinyl molecule
H H
Head C C Tail
H R

Three ways adjacent bonds can be formed :

• Head-to-Head
• Head-to-Tail
•Tail-to-Tail
 Order in Molecules

Tail-to-Tail Head-to-Tail Head-to-head

H H H H H H H H H H H H
C C C C C C C C C C C C
H R R H H R H R R H H R

• Head-to-tail - more energetically favourable

due to lack of steric effects & polar repulsion
from similar side groups.
• HT configuration dominates (never 100%).
 Stereoisomerism
Isotactic Syndiotactic
R groups lie on same R groups alternate
side of zig-zag plane. around plane.
R R R R R H R H
H H H H H H H
H
C C C C C C C C
C C C C C C C C
H H H H H R H R
H H H H H H H H

R H R R
Atactic H H H H

R groups on random C C C C
C C C C
position, no regularity H R H H
H H H H
 Tacticity of PS

Isotactic Syndiotactic Atactic

Never 100 % tactic - in a given polymer
chain, usually a combination of configurations!
 Molecular Shape
• Once polymer molecule formed, its
configuration is fixed but single polymer
bonds not “rigid”.

Some degree of freedom :

•Rotation
•Bending

Molecule shape will affect thermal +

mechanical properties.
 Rotation & Bending
0 9 °
1

Rotation

C-C bond length, d=0.154nm

Bending
 Bending & Rotation
Rotation & bending depends on :
(1) Type of bond
• single bond - can rotate C C C C
• double/triple bond - rigid
(2) Type of main chain

• bulky main chain O C O C

restricts rotation
 Bending & Rotation
(3) Type of side group

• bulky side groups act as stearic (size)

hindrance.
• restricts rotation.

C C C C
 Shape
• Each single bond capable of rotation.
• Chain length less useful to characterise
polymer shape.

r
Shape
End-to-End distance, r = d N ,
where N – number of C atoms in polymer
backbone
• for linear flexible chains, distance
separating chain ends is end-to-end
distance, r.

• More useful descriptor for polymer shape

as it describes both size & shape of chain.
 Man in the Mirror

http://www.youtube.com/watch?v=KtT78oI3zDw
Lecture 3

Polymers
 Crystalline Polymer

In very large molecules (polymers), ability

to crystallise depends on

•Regularity of structure

•Intermolecular bonding groups.

Single Crystals
Single Crystal
of PE:

5 µm

• Requires very special growth conditions.

• Engineering polymers not single crystal.
 Amorphous Polymer
• Polymer that is completely non-
crystalline.

• Structure can be thought of as simply

frozen polymer liquids.

• Many engineering polymers are

amorphous.

Examples: are rubber, atactic PS, epoxies.

 Semi-Crystalline (SC) Polymers
• Most polymer molecules partially crystallize due
to size, stereo-regularity, geometrical reason.
• Crystalline regions mixed within amorphous
material.
Amorphous
Most
engineering
polymers SC.
Crystallite
 SC Polymers
• Bulk polymers - generally partially
crystalline.
• Consist of small crystalline regions
(crystallites) & amorphous regions.

Reasons:
• Polymer are macromolecules (long chains), hence
low diffusion rates.
• Macromolecules highly entangled in melt & do
not have time to disentangle during solidification.
 SC Polymers - spherulites
• 10 nm thick radial layers.
• Chains oriented ⊥ to radius of structure.

Nucleus

Amorphous Crystallite
 Polymer Crystalinity
Amorphous SC Crystalline
polymer polymer polymer
↑ in crystallinity
Density : crystalline polymer > amorphous
polymer (chains closely packed in crystalline
polymer).
% Crystallinity =
(
ρc ρs− ρa
× 100
)
ρ s(ρ c − ρ a)
s, c & a refer to specimen, totally crystalline polymer &
totally amorphous polymer.
 Melting Temperature
• Melting - transformation of polymer
crystal from solid with highly ordered
structure of aligned molecular chains to a
viscous liquid with highly random molecular
chains.
• Occurs at melting temperature, Tm.
• Takes place over range of temperatures,
not possible to define single melting
temperature for a polymer.
 Melting Characteristics
Characteristics of polymer melting
different from other materials :
• Melting depends upon specimen history &
temperature of crystallization.
• Melting depends upon rate at which
specimen is heated.
• Differences due to peculiar morphology of
polymer crystals.
 Annealing
Annealing : temperature below melting point of
material
T(°C)
Crystallite

0 time
Amorphous
 Melting Characteristics
• Crystallites very thin.
• Strong dependence of Tm on crystal thickness.
• Surface energy ↑ with decreasing crystallite size.
• Tm ↓ with decreasing size
25%
5% chain
chain
unbonded
unbonded
Melting Melting
 Annealing
Annealing : as crystallites grow, their melting
points increase
T(°C)
Crystallite

0 time
Amorphous
 Effect of Heating Rate
(a) has lower melting point compared to (b) due
to annealing. This is very unusual behavior.
T(°C)
T(°C)

0.1 hrs t 10 hrs t

(a) (b)
 Effect of Heating Rate
Melting dependent on heating rate since
annealing takes place when crystalline polymer
heated and melted.
Decrease in heating rate
• Increase in annealing effect
• Increase in lamellae thickness
• Increase Tm
Annealing : heat treatment providing movement
of polymer chains by diffusion (depends on
temperature & time).
 Glass Transition
• As polymer is cooled it becomes rubbery,
then a relatively hard and/or elastic
polymer glass is obtained!
• Temperature at which polymer changes
from rubber to glass is Glass Transition
Temperature, Tg.
•Polymers that can easily deform will have
low Tg.
 Polymer Crystallinity
Ability of polymer to crystallize depends
on molecular ordering of polymer chains.
Factors affecting chain alignment:

(1) Side group (bulky, polar, branches)

(2) Molecular structure (type of polymer,
isomerism)
(3) Thermal history (cooling rate) and applied
stress.
 Side Groups
Chains with bulkier side groups will have
less tendency towards crystallization.

CH CH2 PS difficult to
crystallize

H H F F
C C C C Crystallize easily
H H F F
PE PTFE
 Side Groups
Chains with hydrogen bonding promote
crystallization.
Nylon
Repeat unit
H O H

N CH2 CH2 C CH2 CH2 CH2 N CH2

CH2 C CH2 CH2 N CH2 CH2 CH2 C
O H O

H O H

N CH2 CH2 C CH2 CH2 CH2 N CH2

CH2 C CH2 CH2 N CH2 CH2 CH2 C
O H O
 Molecular Structure
Crystallinity ↑ with increasing regularity (i.e.
reduced randomness) in structural
arrangement.
• Linear Polymers → Crystallizes easily

•Branched Polymers → Partially crystalline

•Network & Cross-linked Polymers →

Amorphous
 Molecular Structure
Isomerism:
• isotactic & syndiotactic polymer -
crystalline.
• atactic polymers - amorphous.
Copolymer:
More irregular & random monomer
arrangement is less crystalline.
• Alternating & Block copolymer →
Crystallisation
• Random & Graft copolymer → Amorphous
 Important Point

•Tm only relevant to Crystalline

Polymers

•Tg only relevant to Amorphous

Polymers.

•If both Tg & Tm are observed, polymer

must be Semi-crystalline.
 Factors affecting Tm
High melting points associated with
• highly regular structures
• rigid molecules
• close packing capability
• strong inter-chain attraction
Examples
• Aromatic polyesters: high Tm because of
relatively high chain stiffness.
• Polyamides: high Tm because of inter-chain
HB.
 Factors Affecting Tm
• At Tm, whole polymer chains are able to
translate from one position to another.
• Factors affecting interaction between
chains will affect Tm.
Tm dependent on:
(1) Molecular Weight
(2) Backbone
(3) Side groups
 Molecular Weight
↓ molecular weight ⇒ ↓ chain length
↑ in chain ends ⇒ ↑ in defects ⇒ ↓ in Tm

High Tm Low Tm
 Backbone
Most important factor affecting Tm.
Chemical Structure:

(1) Nature of backbone

• Determines stiffness of main polymer
chain.
• Controls ease at which rotation can occur
about chemical bonds along chain.
 Backbone
Flexibility increasing groups:
O , O O , CO O
⇒ ↓ Tm
Flexibility decreasing groups:

• Bulky main chain: phenyl

• Unsaturated bonds: diene C C C C

• Polar groups: amide NHCO ⇒ ↑ Tm

 Backbone

Repeat Unit Tm/K

CH2 CH2 410
CH2 CH2 O 340
CH2 CH2 CO O 395

CH2 CH2 670

CH2 CH2 CO NH 603
 Side Groups
Type & size of side groups affects rotation
about bonds in main chain.
Consider vinyl polymer:
CH2 CHR

If R = H, (a flexible group) i.e PE,

(CH2CH- H)-
 Side Groups
Flexibility restricting groups:

CH3

Bulky side groups

Cl CN

Polar side groups

⇒ ↑ Tm
 Side Groups
Repeat Unit Side group (R) Tm/K
CH2 CHR H 410
CH3 460
Not as clear cut: 398
CH2 CH3
balance between
CH2 CH2 CH3 351
flexibility and size
CH2 CH(CH3)2 508
450
 Chain Branching
Increase in branching
• ↑ in defects (↓ in packing)
• ↓ in intermolecular forces between
polymer chains
• ↓ in Tm
Example: HDPE has a higher Tm than LDPE.
 Glass Transition, Tg
• Tg depends upon rate at which
temperature is changed, i.e. rate of heating
/cooling.
• Lower heating rate, lower Tg
•At Tg, polymer chains frozen in position
become free to rotate & translate.
• Factors that affect chain rotation
(molecular rigidity) & move will affect Tg.
 Effect of Heating Rate
(a) has higher Tg compared to (b). This is very
common behavior.
T(°C)
T(°C)

0.1 hrs t 10 hrs t

(a) (b)
 Factors affecting, Tg
Tg depends on:
(1) Backbone
(2) Side groups
(3) Molecular weight
(4) Molecular structure (Isomerism and
type of polymer)
(5) Additives
 Nature of Backbone
• Chain flexibility governed by nature of
chemical groups which constitute main
chain (similar to Tm).
• Groups that reduce ease of rotation will
increase Tg.
Repeat Unit Tg/K
CH2 CH2 140-270
CH2 CH2 O 206
O 357
CH2 CH2 353
 Side Groups
(i) Bulky side group:
• Large side groups give greatest stiffening
effect.
• Flexible side groups have less stiffening effect.
(ii) Secondary bonding:
• Polar groups increase Tg because of restriction
in rotation due to dipole interactions.
Tg(PVC)>Tg(PP)

• HB & VDW forces between chain ↓ flexibility &

increase Tg.
 Side Groups
Repeat Unit Side group (R) Tg/K
CH2 CHR CH3 250
CH2 CH3 249
CH2 CH2 CH3 233
Not as clear cut: CH2 CH(CH3)2 323
balance between 373
flexibility and size Cl 354
OH 358
CN 370
 Branching
Small number of branches

• Small number of branches tend to ↓ Tg

• Increase in free volume ⇒ increase in
rotation
 Branching
Generally
• Long branches tend to ↑ Tg
• Long branches hinder rotation ⇒ ↑ in chain
rigidity ⇒ increase Tg
 Molecular Weight
• Polymer of low molecular weight have
greater number of chain ends in given
volume compared to high molecular weight.

• Since chain ends are less restrained, they

have greater mobility at a given
temperature.

↑ in molecular weight ⇒ ↑ in Tg
 Molecular Structure
Cross-linking
• Slight cross-linking will have no effect on
chain rigidity.

• High density of cross-links results in

decrease in chain flexibility ⇒↑ Tg

•T may not occur in highly cross-linked

 Plasticisers
• Small molecules which get in between
polymer chains.
• Molecules that space out chains from one
other ⇒Tg is lowered by use of
plasticizers.
•How do plasticizers affect Tm?
Lecture 4

Polymers
 σ-ε of Brittle Polymer
Typical σ-ε curve for glassy polymer, e.g.
PS:
Stress

Compression
Tension

Strain
 σ-ε of Tough Polymer
Typical σ-ε curve of PP (in tension):
Elastic Deformation:
• Initially elastic deformation, σ proportional ε.
• Hooke’s law obeyed. Yield Pt

Stress
Yield:
σ increase with ε up to
yield point.

Strain
Yield of polymers is ~ 5 – 10 % (metals ~ 0.1 %)
 σ-ε of Tough Polymer
Plastic Deformation:
• Deformation cannot be fully recovered.
• Cold drawing (extension at constant stress)
• Polymer strain hardens and ruptures.
Tensile
Strength
Strain
hardening
Stress

Cold draw

Strain
 σ-ε of Elastomers
• Mechanical properties controlled by molecular
structure.
• Material made up of network of cross-linked
polymer chains with individual lengths of chain in
random conformations.

Stress
σ-ε curve (in tension):
• Elastomeric
• Rubber-like elasticity
• Large recoverable ε at Strain
low σ level.
 Deformation of Single Phase
Polymer Crystals
(1) Polymer glasses: (Modulus ~106 Nm-2)

Elastic Deformation

Involves bending & stretching of strong

covalent bonds on polymer backbone as well
as displacement of adjacent molecules which
is opposed by relatively weak secondary
(VDW) bonding.
 Deformation of Single Phase
Polymer Crystals
(2) Polymer crystals:
(Modulus ~1011 Nm-2 // to chain direction,
Modulus ~106 Nm-2 ⊥ to chain direction)

•Elastic Deformation
// to chains:
• Deformation involves stretching of strong
covalent bonds and changing of bond angles.
 Deformation of Single Phase
Polymer Crystals
(2) Polymer crystals:
(Modulus ~1011 Nm-2 // to chain direction,
Modulus ~106 Nm-2 ⊥ to chain direction)

⊥ to chains:
• Deformation opposed only by weak
secondary VDW or HB.
 Deformation of Single Phase
Polymer Crystals
Plastic Deformation
• Polymer molecules remain relatively
undistorted.
• Deformation involves sliding of molecules
in directions // or ⊥ to chain axis (breaking
only VDW forces).
 Deformation of Single Phase
Polymer Crystals
(3) Elastomers: (Modulus ~106 Nm-2)
Elastic Deformation
Amorphous polymer (>Tg) will behave like viscous
liquid & normally flow under its own weight.

Unstressed state:
Elastomer is amorphous & composed of molecular
chains that are highly twisted, kinked and coiled.
 Deformation of Single Phase
Polymer Crystals
Upon application of load:
• Partial uncoiling, untwisting, straightening &
elongation of chains in stress direction.
• Viscous flow takes place by uncoiling of chains in
cross-linked network & extent of flow depends on
degree of cross-linking.
• Properties controlled by nature of cross-linked
network.
 Deformation of Multi-Phase
Polymers – SC Polymers
• Most SC polymers behave like composites (two-
phase materials)

• Increase in modulus due to combined effect of

amorphous & crystalline regions.

• Effective crystal modulus depends on (a)

proportion of crystalline material, (b) size, (c)
shape & (d) distribution of crystals.
 Fracture
Mode of Fracture:

• Thermoset - Brittle (covalent bonds in

network/cross-linked structure
severed.)
• Thermoplastic - Ductile & brittle

Ductile-to-brittle transition occurs when:

• ↓ in temperature (significantly < Tg)
• ↑ in strain rate
 Mechanical Properties
Depend on:
(1) Polymer structure
(Molecular weight, cross-linking, chain
stiffness)
(2) Processing
(Mechanical & thermal treatment)
(3) Application / Testing conditions
(temperature & strain rate dependence)
 Degree of Crystalinity
• Crystalline regions ⇒ chains aligned
• Extensive secondary bonding (intermolecular
bonding)

• Amorphous regions ⇒ Chains misaligned

• Secondary bonding less prevalent.

Semi-crystalline polymers:
• TS ↑ with ↑ degree of crystallinity
 Degree of Cross-linking
Cross-linking involves formation of strong
covalent bonds between individual polymer
chains.
Natural Rubber: Raw X-linked
Property Rubber Rubber
Tensile Strength 300 3000
Elongation at break (%) 1200 800

Cross-linking ↑ strength of rubber

 Chain Stiffening
Polymers with stiff chains are stronger than
those with flexible chains.
Stiffen methods:
1.Stiff backbone
• Double or triple bonds
• Bulky group on backbone

2.Side Groups
• Bulky side groups
• Polar bonds
 Testing Conditions
Plastic deformation - strong dependence on
testing rate & temperature.
Temperature:
At constant ε˙ , yield stress decreases with
↑ temperature because chains flow/slip.

↑ in temperature
• reduction in tensile strength
• enhancement of ductility
• decrease in elastic modulus
Temperature:
Testing
For amorphous polymer, yield stress falls ~ linearly
to zero at Tg (polymer glass becomes rubber)
Rubbery
Log Modulus plateau
SC polymer:
SC
• Above Tg,
Cross-linked
material gains
strength from Amorphous
crystalline
regions. Tg Tm Temperature
• Yield stress → 0 at Tm for SC polymer.
 Testing
Strain Rate:

At constant temperature, ↑ in ε˙ will lead to ↑

in yield stress due to ↓ in response time for
chains.

Other:
Environment such as water, oxygen, organic
solvents, etc.
 Viscoelasticity
• Viscoelasticity distinctive to polymers.
• Mechanical behaviour in between that of an
elastic solid and a viscous liquid.

Low temperature or high strain rates:

→ Elastic
High temperature or low strain rates:
→ Viscous
 Creep Loading
Constant σ applied to a polymer at time t = 0 & ε
increase rapidly at first, slowing down over longer
time period.
ε Polymer Viscous liquid
σ

Elastic solid

time time

Stress system Strain system

 Stress Relaxation
ε in polymer held constant & σ decays slowly
with time.
ε σ Elastic solid

Polymer

time time
Viscous liquid

Strain system Stress system

 Viscoelastic Stress Relaxation
• σ required to maintain a constant ε found to
decrease with time.
• Under isothermal condition, at constant ε0.
time dependent stress relaxation modulus given
by: σ (t)
Er ( t ) =
ε0
Size of σ relaxation modulus dependent on
temperature & time:

• E(t) decreases with increasing t.

• E(t) decreases with increasing T.
 Viscoelastic Creep
• Deformation significant even at room
temperature & under modest σ < yield strength.
• Under isothermal condition, constant stress
applied, σ0, time dependent creep modulus given
by:

σo
Ec ( t ) =
ε (t) time dependent strain
 Viscoelastic Creep
Creep modulus dependent on:

Temperature - Ec(t) → 0 with ↑ temperature

⇒ creep ↑

Crystallinity – Ec(t) ↑ with ↑ crystallinity

⇒ creep ↓
Temperature Dependency of Er
Five regions:
(1) Glassy
• At lowest T, material glassy & brittle.
• Er ~ equal to elastic modulus.
(2) Leathery (Glass transition)
• Er ↓ by 103 in 20 oC.
• Deformation is time dependent & not totally
recoverable on release of applied load.
 104 Glassy
103
Leathery
10 2

10
Er

1
Rubbery
Rubber flow
10-1

10-2
Tg Viscous flow (L) Tm
10-3

10-460 80 100 120 140 160 180 200

Temperature (°C)
 Temperature Dependency
(3) Rubbery Plateau
• Deforms in rubbery manner.
• Consist of viscous & elastic components
(4) Rubbery Flow
• Gradual transition into soft rubbery state
(5) Viscous Flow
• Modulus ↓ dramatically with ↑ temperature
• Chain segment vibration is independent of
rotational motion.
 Example 1
Is it possible to have a PolyMethyl
MethAcrylate (PMMA) homopolymer with
the following molecular weight data and a
weight-average degree of polymerization of
585? Please justify your answer.
Example 1
 Example 1
MW Range Mi wi Mi wi
(g/mol)
8,000-20,000 14,000 0.01 140
20,000-32,000 26,000 0.05 1,300
32,000-44,000 38,000 0.12 4,560
44,000-56,000 50,000 0.25 12,500
56,000-68,000 62,000 0.27 16,740
68,000-80,000 74,000 0.21 15,540
80,000-92,000 86,000 0.09 7,740

Σ M i wi
= 58,520 g / mol
Σ wi
 Example 1
Weight-average degree of polymerisation is
585, ∴molecular weight of this polymer mer
is 100 g/mol.

M w 58,520
m= = = 100 g / mol
nw 585
 Example 1
Examine the mer.

m= ( (12 × 5) + (1× 8) + (16 × 2) )

= 100
Yes, possible!
 Example 2
An experimental poly-propylene sample has
only ten polymer chains present. Four
molecules have a degree of polymerization
of 2, three molecules have a degree of
polymerization of 3, and three molecules
have a degree of polymerization of 7.
 Example 2
Sketch the mer unit.
C

Weight of one PP mer

is (12g/mol × 3) + (1g/mol × 6) = 42 g/mol
 Example 2
Calculate number average molecular weight.
two mers
 Example 2
Calculate number average molecular weight.
Mean Molecular Weight, Number xiMi
Mi Fraction, xi
2 × 42 g/mol = 84 g/mol 0.4 33.6
3 × 42 g/mol= 126 g/mol 0.3 37.8
7 × 42 g/mol= 294 g/mol 0.3 88.2
∑ xiMi = 159.6 g/mol
 Lecture 5

CERAMICS
 Ceramics
Metal-Nonmetal Compounds

Oxides nitrides carbides

borides silicates

Insulator of Resistant to high Hard but

heat & electricity temperature very brittle
and corrosion

Atomic Bonding: Ionic, Ionic+Covalent, Covalent

 Ceramic Structure
Amorphous
• Composed of at least two elements.
• Bonding: ionic to covalent (very strong)
• More complex than metals.

Crystalline
 Crystal Structure
Ceramics with Metallic ions (+) - Cation
ionic bonding
Nonmetallic ions (-) - Anion

(1) Magnitude of electrical charge

(positive = negative charges
Two to maintain electrically neutral)
Factors:
(2) Relative size of cations to anions
(Cation must make contact with
surrounding anions)
 Crystal Structure
Examples: (1) Charge effect
(reflected in chemical formula)

CaF2 Ca2+ Al2O3 2Al3+

2F- 3O2-

Electroneutrality must be maintained

in a ceramic material
 Crystal Structure
(2) Size Effect: Cation contact with
surrounding anions
(a) Ionic radius: Cation rC < Anion rA
(b) Cation has maximum contacting anion
neighbors
Examples:
A A A A A A

A A A A A A

Unstable Stable Stable

 Crystal Structure

(c) larger cation radius, more contacting

anions. Smaller anion radius, more
contacting cation
(d) rC/rA ratio: determines Coordination
Number (CN)
 CN & rC/rA Ratio
CN rC/rA Geometry CN rC/rA Geometry

2 < 0.155
6 0.414 -
0.732
3 0.155-
0.225

8 0.732-
4 0.225-
1.000
0.414
 Coordination Number &
rC/rA Ratio

•Consider simple AX-type structure

such as NaCl, MgO, FeO, CsCl,
ZnS, SiC.
•Determining factor: size effect.
Unit cells -2D
 Unit cells -2D
Anion
Unit cell – 1 anion+1 cation

Cation
• Face of unit cell (UC) – shared between two
neighboring units cells.
• Edge – shared 4 UC; Corner – shared 8 UC

1 2

4 3

1 2
 Cesium Chloride - Structure
Ce+ Cl-
Coordination No.= 8;
rC/rA: 0.732-1.0

Simple cubic of Cl-

with Ce+ at body centre

Unit cell:1 formula unit CsCl

 Cesium Chloride - Structure
Ce+ Cl-
Coordination No.= 8;
rC/rA: 0.732-1.0

Simple cubic of Cl-

with Ce+ at body centre

Unit cell:1 formula unit CsCl

 1
8 ion

Unit cell

CsCl crystal
 Rock Salt (NaCl) -Structure
Coordination No. = 6;
rC/rA: 0.414-0.732

Unit cell: 4 Cl- &

4 Na+
(4 formula units)

Na+
e.g. NaCl, MgO, MnS, LiF, FeO Cl-
 Zinc Blende (ZnS) - Structure
Coordination No.= 4; Zn+ S-
rC/rA: 0.225-0.414

All ions
tetrahedrally
coordinated
Unit cell:
4 formula unit

e.g. ZnS, ZnTe, SiC

 AmXp-Type Structure

•Many ceramic compounds have more than

one type of cation (e.g. BaTiO3)

•Crystal structure becomes very complex

•But (1) Charge effect and (2) Size

effect are still determining factors
 Ceramic Density
Formula units Atomic weight of all
in unit cell cations + anions

ρ =
n' ( ∑ AC + ∑ AA )
VC N A

Avogadro’s Number
Unit cell volume
6.023x1023
 Imperfections
Point Defects Interstitials: Cation
Vacancy: Cation & Anion

Anion Vacancy
Cation Vacancy Cation Interstitial
 Imperfections
Cation: Interstitial &
Impurities
Substitutional
(solid solution)
Anion: Substitutional

Anion impurity
Cation impurity Cation Interstitial Impurity
 Point Defects
(1) Frenkel defect: Cation-vacancy/ Cation
interstitial pair
(2) Schottky defect: Cation-vacancy/ Anion
vacancy pair Frenkel Schottky
 Point Defects
Iron Oxide: Fe present in Fe2+ + Fe3+ state;
Wustite-FeO: Fe2+ in perfect structure.

O2-
Fe2+
 Imperfections
Destruction of neutrality: Fe3+ formation
Maintain neutrality: 2Fe3+& 1 Fe2+ vacancy
Fe2+ vacancy

Fe3+
Fe3+
 Imperfections
Electro-neutrality MUST be maintained
Impurities: example, NaCl (Na+, Cl-)

If impurity Ca2+ substitute for Na+, electro-

neutrality disrupted by extra + charge

To maintain neutrality:
(1) Remove 1 Na+ (form a vacancy)
(2) Add 1 Cl- (interstitial): highly unlikely (Cl- too
big)
 ZrO2-CaO
3000

Liquid
Temperature (°C)

2500
C+L L+CaZrO3
Cubic
2000 ZrO2 Cubic ZrO2
+CaZrO3
T C
1500
+
T
CaZr4O9
1000 C+M CaZrO3
M+ +CaZrO3
M
CaZr4O9
500
0 10 20 30
ZrO2 Composition (wt% CaO)
 ZrO2-CaO System
• One eutectic, two eutectoid reactions
• ZrO2: three crystal structures:

Monoclinic
Tetragonal T & % CaO dependent
Cubic

• T → M (on cooling): volume expansion: 4%

→ severe cracking
• Pure ZrO2 is useless.
 ZrO2-CaO System
Crack Prevention: add CaO (or Y2O3 or
MgO) to enable formation of Cubic Phase.
+ 3-7%CaO
C+T: > 1000oC
Partially No M on cooling
stabilising T & C stabilized
Stabilising No cracking

add more CaO

Fully Cubic at high T
stabilising Cubic on cooling
 Partially Stabilised
Zirconia (PSZ)

•Stabilising agents: CaO, MgO, Y2O3

•Very tough: better than other
ceramics
•Transformation toughening – why?
PSZ -Transformation toughening
RT: C-phase + T-phase (Metastable)
T-phase → M-phase by elastic energy causing
expansion & compressive σ – impede crack
growth.
Stress-induced
T → M T
C T C
M

Crack
 Mechanical Properties
•Brittle
•Low fracture toughness (KIC)
Fracture
•KIC < prediction - due to
small flaws (voids, pores, cracks)
Metals
Composites

Plastics
Ceramics
0.1 1 10 100
KIC
 Ceramic Processing
• Ceramics have extremely high melting
points; most not melted and formed (e.g.
casting).
• Many ceramics structures processed from
powder.
• Powder compressed and heated (sintered)
to give net-shape structure with high
density.
 Why are ceramics brittle?
• Presence of voids, defects, cracks.
• Complex crystallography and small
number of slip systems.
• Very strong ionic (or covalent)
bonding.
• Energetically expensive for
dislocations to move.
 Example 1

It is possible for ceramic to have more

than one type of cation (represented by
A and B) with their chemical formula
designated as AmBnXp. Determine m, n,
and p for barium titanate (BamTinOp) by
examination of the unit cell.
 Example 1
There’s
1 Ti ion,
1 Ba ion
3 O ions.
→Must be BaTiO3.
Ti4+

O2- Ba2+