Carbon

Carbon

Carbon

Carbon/Diamond/Fullerenes/ Nanotubes
Read => p399-403
http://www.nas.nasa.gov/Groups/SciTech/nano/

Principles of Ceramic Architecture:

Size relationships Cation to Anion

Electrical Neutrality of the overall structure

Crystallographic Arrangements

Stoichiometry Must Match

ANNOUNCEMENTS
Reading: Callister Chapter 4.1-4.10

Solve all problems

POLYMERS

Ancient Polymers
Originally natural
polymers were used:
Wood
Rubber
Cotton
Wool
Leather
Silk
Oldest known use:

Rubber balls used by Incas

Noah used pitch (a natural polymer) for the ark

Noah's pitch
Genesis 6:14 "...and cover it inside and
outside with pitch."

gum based resins

extracted from pine
trees

Naturally occurring polymers

Proteins

Nucleic acids

Cellulose

Rubber

Synthetic polymers

Nylon

Dacron

Lucite

Polymer Building Blocks

Carbon (key)
Hydrogen
Oxygen
Nitrogen
Fluorine
Silicon
Sulfur
Chlorine

Carbon Is Key
Atomic number: 6
Valence: 2s22p2
Hybrid orbital- sp
Will share up to four electrons,
Catenation, tetrahedral arrangement

Polymer Composition
Most polymers are hydrocarbons
i.e., made up of H and C
Saturated hydrocarbons
Each carbon singly bonded to four other atoms
Example:
Ethane, C2H6
H

H
C

H
C
H

H
Tetrahedral
arrangement
of C-H
13

Unsaturated Hydrocarbons
Double & triple bonds somewhat unstable
Thus, can form new bonds
Double bond found in ethylene or ethene - C2H4

H
C C

Triple bond found in acetylene or ethyne - C2H2

H C C H
How these are formed?

14

Tetrahedral
arrangement
of C-H

Unsaturated Hydrocarbons
Double & triple bonds relatively reactive can form new
bonds
Double bond ethylene or ethene - CnH2n

H
C C

4-bonds, but only 3 atoms bound to Cs

Unsaturated Hydrocarbons
Triple bond acetylene or ethyne - CnH2n-2
H C C H

Unsaturated Hydrocarbons
Benzene, C6H6, is the simplest and first recognized
aromatic hydrocarbon

An aromatic hydrocarbon (abbreviated as AH) or arene is a

hydrocarbon, of which the molecular structure incorporates one or
more planar sets of six carbon atoms that are connected by
delocalised electrons numbering the same as if they consisted of
alternating single and double covalent bonds

Chemistry and Structure of Polyethylene

Ethylene
Ethene

Adapted from Fig.

14.1, Callister &
Rethwisch 8e.

Note: polyethylene is a long-chain hydrocarbon

- paraffin wax for candles is short polyethylene

19

Examples of monomers and polymers

Monomer
CH2

Polymer

CH2

CH2

CH2CH2

CHCl

CH2CH2
Cl

O
H2C

CH2

CH2CH2O

CH2CH2O

HOCH2CH2OH

HO

CO2H

Repeating unit n For a polymer, if n =10000, and molecular wt of one molecule

(monomer ) is 120, then the total molecular wt of this polymer will be 120, 0000

Functionality
The functionality of a molecule is the number of sites available for bonding to
other molecules under the specific conditions of the polymerization reaction.
1. Use of the term functionality here is not the same as in organic chemistry
where a carbon-carbon double bond, for example, is classified as a single
functional group.
2. Functionality refers in general to the overall reaction of monomers to yield
products. It is not used in connection with the individual steps in a reaction
sequence.
Functionality is defined only for a given reaction. A glycol, HOROH, has
a functionality of 2 in esterification or ether-forming reactions, but its
functionality is zero in amide-forming reactions. The same is true of 1,3butadiene. which may have a functionality of 2 or 4, depending on the particular
double-bond addition reaction.

. Alfred Rudin, The Elements of Polymer Science & Engineering,

23

Classification of Polymers
1. Thermal Behavior
2. Polymerization Mechanism
3. Polymer Structure

Polymer Types: Based on Thermal Behavior

Thermoplastics

Those which soften on heating and then harden again on cooling

These are called thermoplastic polymers because they keep their plastic
properties
These polymer molecules consist of long chains which have only weak
bonds between the chains
The bonds between the chains are so weak that they can be broken when
the plastic is heated
The chains can then move around to form a different shape
The weak bonds reform when it is cooled and the thermoplastic material
keeps its new shape

Polymer Types: Based on Thermal Behavior

Thermosets

Extensive cross-linking formed by covalent bonds.

Bonds prevent chains moving relative to each other.
What will the properties of this type of plastic be like?
Thermosets are generally stronger than thermoplastics due to this three
dimensional network of bonds (cross-linking)
Better for high-temperature applications up to the decomposition
temperature.
More brittle.
Since they are "set" (non-reformable), they tend not to be recyclable.

Classification of Polymers: Polymerization Mechanism

Addition (Chain) Polymerization

An addition polymer is a polymer which is formed by an addition reaction, where

many monomers bond together via rearrangement of bonds without the loss of any atom
or molecule.

Initiation

Catalyst

Propagation
Termination

28

Chain growth: High molecular wt polymers formed in early stage of reaction and % of
monomer conversion increase with time

Some Common Addition Polymers

Classification of Polymers: Polymerization Mechanism

Condensation (Step) Polymerization

condensation polymer is formed by a condensation reaction where a molecule, like
water, is lost during the formation.

Step growth: High-molecular wt polymers yield near the end of

reaction, ~ 98% conversion

30

Condensation Reaction

Some Condensation Polymers

Molecular Shape (or Conformation) Molecular

orientation can be changed by rotation around the
bonds
note: no bond breaking needed

Angle =109o

Classification of Polymers: Structures of Polymers

Sequence of monomer linking: Homopolymer and Copolymer
If formed from one monomer (all the repeat units are
the same type) this is called a homopolymer
If formed from multiple types of monomers (all the
repeat units are not the same type) this is called a
copolymer

Homopolymer and Copolymer

Homopolymer is a polymer made up of only one type of monomer

( CF2

CF2 )n

Teflon

( CH2

CH2 )n

( CH2

Polyethylene

CH )n

Cl
PVC

Copolymer is a polymer made up of two or more monomers

( CH

CH2

CH2

CH

CH

CH2 )n

Styrene-butadiene rubber

Terpolymer: 3 different unit monomers

Classification of Copolymers
two or more monomers
polymerized together
depending on reactivity
random A and B randomly
positioned along chain
alternating A and B alternate
in polymer chain
block large blocks of A units
alternate with large blocks of B
units
graft chains of B units grafted
onto A backbone

Adapted from Fig.

4.9, Callister &
Rethwisch 3e.

random

alternating

block

graft

37

Classification based on Steriochemical configuration

(how atoms are arranged ?) of Polymers

R groups on same side of chain

Isotactic

Tetrahedral
arrangement
of C-H

R groups alternate from side to side Syndiotactic

R groups disposed at random Atactic

Classification scheme for

the characteristics of
polymer molecules
isomerism different molecular
configurations for molecules (polymers)
of the same composition
Stereoisomerism
Geometrical Isomerism

Molecular configurations
Vs conformation ?

POLYMER MICROSTRUCTURE
Covalent chain configurations and strength:

Direction of increasing strength

Adapted from Fig. 14.7, Callister 6e.
2

Linear polymers
polymers in which the mer units are connected endto-end along the whole length of the chain
These types of polymers are often quite flexible
Van der waals forces and H-bonding are the two
main types of interactions between chains
Some examples polyethylene, teflon, PVC,
polypropylene

Branched polymers
Polymer chains can branch:

Or the fibers may aligned parallel, as in fibers and some

plastic sheets.
chains off the main chain (backbone)
This leads to inability of chains to pack very closely
together
These polymers often have lower densities

These branches are usually a result of side-reactions during

the polymerization of the main chain
Most linear polymers can also be made in branched forms

Crosslinked polymers
Molecular structure
adjacent chains attached via covalent bonds
Carried out during polymerization or by a non-reversible
reaction after synthesis (referred to as crosslinking)
Materials often behave very differently from linear polymers
Many rubbery polymers are crosslinked to modify their
mechanical properties; in that case it is often called
vulcanization
Generally, amorphous polymers are weak and cross-linking adds
strength: vulcanized rubber is polyisoprene with sulphur crosslinks:

Network polymers
polymers that are trifunctional instead of bifunctional
There are three points on the mer that can react
This leads to three-dimensional connectivity of the
polymer backbone
Highly crosslinked polymers can also be classified as
network polymers
Examples: epoxies, phenol-formaldehyde polymers

Polymer states
The polymer chain layout determines a lot of material properties:
Amorphous:

Crystalline:

Crystallinity in Polymers
Polymers can be crystalline (i.e.
have long range order)

Adapted from Fig.

4.10, Callister &
Rethwisch 3e.

Ordered atomic arrangements

involving molecular chains
Crystal structures in terms of unit cells

Example shown
polyethylene unit cell:

Orthorhombic
However, given these are
large molecules as
compared to atoms/ions
(i.e. metals/ceramics) the
crystal structures/packing
will be much more
complex

47

Polymer Crystallinity (cont.)

Polymers rarely 100% crystalline
Difficult for all regions of all chains to
become aligned
crystalline
region

Degree of crystallinity

expressed as % crystallinity.
-- Some physical properties
depend on % crystallinity.
-- Heat treating causes
crystalline regions to grow
and % crystallinity to
increase.
Adapted from Fig. 14.11, Callister 6e.
(Fig. 14.11 is from H.W. Hayden, W.G. Moffatt,
and J. Wulff, The Structure and Properties of
Materials, Vol. III, Mechanical Behavior, John Wiley
and Sons, Inc., 1965.)

49

Polymer Crystallinity
Polymer crystals
Chain folded-model
Many polymers crystallize as very thin platelets (or lamellae)
Idea the chain folds back and forth within an individual plate
(chain folded model)

Semicrystalline Polymers
Some semicrystalline
polymers form spherulite
structures
Alternating chain-folder
crystallites and amorphous
regions

Adapted from Fig. 4.13, Callister & Rethwisch 3e.

51

Structures of Polymers
Polymer crystals
More commonly, many polymers that crystallize from a melt form
spherulites
One way to think of these the chain folded lamellae have
amorphous tie domains between them
These plates pack into a spherical shape
Polymer analogues of grains in polycrystalline metals/ceramics

Photomicrograph Spherulites in Polyethylene

Cross-polarized light used
-- a maltese cross appears in each spherulite

Adapted from Fig. 4.14, Callister & Rethwisch 3e.

53

Structures of Polymers
Polymer crystallinity
(One of the) differences between small molecules and
polymers
Small molecules can either totally crystallize or
become an amorphous solid
Polymers often are only partially crystalline
Why? Molecules are very large
Have crystalline regions dispersed within the
remaining amorphous materials
Polymers are often referred to as semicrystalline

Structures of Polymers
Polymer crystallinity
Another way to think about it is that these are two phase
materials (crystalline, amorphous)
Need to estimate degree of crystallinity many ways
One is from the density

c s a
%crystallin ity
100
s c a
s = overall density of the sample

c = density of the crystalline part

a = density of the amorphous part

Problem
The density and associated crystallinity of 2 polypropylene
materials are as follows
Density(g/cc)
0.904
0.895

Crystallinity(%)
62.8
54.4

(a) Compute density of the totally crystalline and totally

amorphous polypropylene
(b) Determine density of the polypropylene of 74.6% crystallinity

We are asked to compute the densities of totally crystalline and totally amorphous
polypropylene (c and a)
Let C=%crystallinity/100

In which s1= 0.904 g/cm3, s2= 0.895 g/cm3, C1= 0.628, and C2= 0.544. Solving the
above two equations for a and c leads to

(b) Now we are asked to determine the density of a specimen

having 74.6% crystallinity. Solving for s by using a and c which
were computed in part (a) yields

Polymer crystallinity
What influences the degree of crystallinity?

Rate of cooling during solidification: Slower cooling

rates from the melt favor higher crytallinity - giving time for ordered
configurations)

Molecular chemistry structure matters

Linear Polymers Crystallization easily accomplished, since no restriction to chain
alignment
Branched polymers NEVER highly crystalline . Side branches interfere with
crystallization
Network Polymers AMORPHOUS
Polyisoprene

Polyethylene

Stereoisomers atactic hard to crystallize

(why?);
isotactic, syndiotactic easier to crystallize

COPOLYMERS ?
More Irregular and random mer less crystallinity

Alternating and block copolymers likelihood of crystallization.

Random and Graft copolymers Normally Amorphous

Crystalline thermoplastic (TP) polymers have Tm only and

Semicrystalline TP polymers have both Tg and Tm. For TS polymers
generally no Tm.
Tg: glass transition temperature

A: Amorphous polymers

Tm: melting temperature

T < Tg glass
T > Tg rubbery / liquid melt
B: Semi-crystalline polymers

Rubbery

T < Tg semi-crystalline solid

Tg<T<Tm rubbery
T > Tm liquid melt

C: Crystalline polymers
T < Tm crystals
T > Tm liquid melt
From Fig. 14.18
Callisters Materials Science and Engineering,
Adapted Version.

61

Melting vs. Glass Transition Temp.

For P melting/solidification occurs over a range of T

What factors affect Tm and Tg?

Is glass solid or liquid?

Both Tm and Tg increase with

increasing chain stiffness
Chain stiffness increased by
1. Bulky side groups
2. Polar groups or sidegroups
3. Double bonds or aromatic
chain groups

Regularity effects Tm only

1. Impurity/imperfection
decrease Tm
2. Tm/Tg influence workablity,
procedure,
From Fig. 14.18

Callisters Materials Science and Engineering, Adapted Version.

62

2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning is a trademark used herein under license.

The effect of temperature on the structure and

behavior of thermoplastics.

64

ALL here are thermoplastic

t02_14_pg514

At RT hard, brittle

At RT Soft, rubbery
ductile

TYPE OF TP POLYMERS
AMORPHOUS POLYMERS
EX

POLYSTYRENE (PS)
POLY(METHYL METHACRYLATE) (PMMA)

POLYBUTADIENE (PB)

(SEMI) - CRYSTALLINE POLYMERS

EX

HIGH DENSITY POLYETHYLENE (HDPE)

LOW DENSITY POLYETHYLENE (LDPE)
POLYPROPYLENE (PP)
POLY(ETHYLENE TEREPTHALATE) (PET)
POLYHEXAMETHYLENE ADIPAMIDE (PA6,6 or NYLON 6,6)

Group Problem 3 (29/01/2016): Marks 2. Each group 2

Please mention the following point in your answer sheet

Name
ID
group problem number
Date

Write down coordinate positions of all C in diamond structure.

Molecular Weight of Polymers

Molecular weight, M:

Mass of a mole of chains.

low M

high M

Not all chains in a polymer are of the same length

i.e., there is a distribution of molecular weights

68

Molecular weight
The properties of a polymer depend on its length
synthesis yields polymer distribution of lengths
Define average molecular weight
Two approaches are typically taken
Number average molecular weight (Mn)
Weight-average molecular weight (Mw)

MOLECULAR WEIGHT DISTRIBUTION

Adapted from Fig. 4.4, Callister & Rethwisch 3e.

total wt of polymer
Mn
total # of molecules

M n x i M i
M w w i M i

Mi = mean (middle) molecular weight of size range i

xi = number fraction of chains in size range i

wi = weight fraction of chains in size range i
70

Molecular weight
Are the two different? Yes, one is essentially based on
mole fractions, and the other on weight fractions
They will be the same if all the chains are exactly of the same
MW! If not Mw > Mn

Get Mn from
this

Get Mw from this

Degree of Polymerization, DP
DP = average number of repeat units per chain

Mn
DP
m
where m repeat unit molecular weight

Consider M n = 21,150
for PVC: m = 2(carbon) + 3(hydrogen) + 1(Clorine)
(from front of book)

= 2(12.011) + 3(1.008) + 1(35.45)

= 62.496 g/mol

DP = 21,150 / 62.496 = 338.42

72

Problem
Below, molecular weight data for a polypropylene material are
tabulated. Compute (a) the number-average molecular weight,
(b) the weight-average molecular weight, and (c) the degree of
polymerization.
Molecular Weight
Range (g/mol)

Xi

Wi

8,00016,000

0.05

0.02

16,00024,000

0.16

0.10

24,00032,000

0.24

0.20

32,00040,000

0.28

0.30

40,00048,000

0.20

0.27

48,00056,000

0.07

0.11

Part a

Molecular wt

Step 1
Mean Mi

xi

Step 2
xiMi

8,000-16,000

12,000

0.05

600

16,000-24,000

20,000

0.16

3200

24,000-32,000

28,000

0.24

6720

32,000-40,000

36,000

0.28

10,080

40,000-48,000

44,000

0.20

8800

48,000-56,000

52,000

0.07

3640

Range

M n = xi M i = 33,040 g/mol

Part b
Molecular
Range

Part c

wt.
Mean M

w M
i i

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
48,000 - 56,000

44,000

0.27

11,880
5720

52,000

0.11

M w = wi M i = 36,240 g/mol

m = 3(AC) + 6(AH)
= (3)(12.01 g/mol) +
(6)(1.008 g/mol) = 42.08

g/mol

Mn
33,040 g/mol
DP =
=
= 785
m
42.08 g/mol

Polymer Chain Lengths

Many polymer properties are affected by the length of
the polymer chains. For example, the melting
temperature increases with increasing molecular
weight.
At room temp, polymers with very short chains
(roughly 100 g/mol) will exist as liquids.
Those with weights of 1000 g/mol are typically waxy
solids and soft resins.
Solid polymers range between 10,000 and several
million g/mol.
The molecular weight affects the polymers properties
(examples: elastic modulus & strength).
76

The Top 10 Bulk or Commodity

Yield stress (sy) stress at which plastic deformation becomes noticeable

78

Mechanical Properties
i.e. stress-strain behavior of polymers: Typically 3 types
brittle polymer: deform eleastically

Examples of Polymers
A: brittle

sFS of polymer ca. 10% that of metals

- PS
B: plastic

plastic
elastic modulus
less than metal

elastomer

Large recoverable strain at low stress

- PE

- PP
C: highly rubbery
- Natural rubber (NR)

- PB

Strains deformations > 1000% possible

(for metals, maximum strain ca. 10% or less)

Adapted from Fig. 14.1, Callisters

Materials Science and
Engineering, Adapted Version.

79

Tensile Response: Brittle & Semicrystalline Thermoplastic

Near Failure

s (MPa)

fibrillar
structure

x brittle failure

near
failure

onset of necking

plastic failure

x
Initial
unload/reload

e
aligned, networked
crosscase
linked
case

crystalline
regions
slide
semicrystalline
case

amorphous
regions
elongate

crystalline
regions align

Stress-strain curves adapted from Fig. 14.1. Inset figures along plastic response curve adapted from Figs. 14.12 &
14.13, Callisters Materials Science and Engineering, Adapted Version.
(Figs. 14.12 & 14.13 are from J.M. Schultz, Polymer Materials Science, Prentice-Hall, Inc., 1974, pp. 500-501.)

80

81

T and Strain Rate: Thermoplastics

Decreasing T...

-- increases E
-- increases TS
-- decreases %EL

s(MPa)
80

Data for the

semicrystalline
polymer: PMMA
(Plexiglas)

4C

60

20C

40

40C

20
60C
0
0

0.1

0.2

to 1.3
0.3

From Fig. 14.3

Callisters Materials Science and Engineering, Adapted Version.
(Fig. 14.3 is from T.S. Carswell and J.K. Nason, 'Effect of Environmental
Conditions on the Mechanical Properties of Organic Plastics", Symposium
on Plastics, American Society for Testing and Materials, Philadelphia, PA,
1944.)

82

Effects of Strain Rate and Temperature

Increasing strain rate -- same effects as decreasing T

stress

Increasing
strain rate

Increasing temp

strain

Ductile Thermoplastic Fracture at Different

Strain Rates
A

e A< e B< e C
B
C

Tensile Response: Elastomer Case

s(MPa)
x brittle failure

plastic failure

elastomer

e
initial: amorphous chains are
kinked, cross-linked.

final: chains
are straight,
still
cross-linked

Stress-strain curves
adapted from Fig. 14.1,
Inset figures along
elastomer curve (green)
adapted from Fig. 14.15,
Callisters Materials
Science and
Engineering, Adapted
Version.
(Fig. 14.15 is from Z.D.
Jastrzebski, The Nature
and Properties of
Engineering Materials,
3rd ed., John Wiley and
Sons, 1987.)

Deformation
is reversible!

Compare to responses of other polymers:

-- brittle response (aligned, cross-linked & networked polymer)

-- plastic response (semi-crystalline polymers)
85

Predeformation by Drawing
Drawing(ex: monofilament fishline)

-- stretches the polymer prior to use

-- aligns chains in the stretching direction
Results of drawing:
-- increases the elastic modulus (E) in the
stretching direction
-- increases the tensile strength (TS) in the
stretching direction
-- decreases ductility (%EL)
Annealing after drawing...
-- decreases alignment
-- reverses effects of drawing.

From Fig. 14.13, Callisters Materials

Science and Engineering, Adapted
Version.
(Fig. 14.13 is from J.M. Schultz, Polymer
Materials Science, Prentice-Hall, Inc.,
1974, pp. 500-501.)

Compare to cold working in metals!

86

Polymer Fracture
A phenomenon that frequently precedes fracture in some glassy and
semicrystalline thermoplastics. Associated with crazes are regions of
very localized yielding, which lead to the formation of small and
interconnected microvoids.
alligned chains

fibrillar bridges

microvoids

crack

A craze showing microvoids

A craze followed by a crack
and fibrillar bridges
From Fig. 14.9
Callisters Materials Science and Engineering, Adapted Version.

87

Effect of M.Wt on Strength

Polyethylene

Annealing causes crystalline regions to grow.

91

Viscoelastic behavior of polymer

Elastic

Viscoelastic

Viscoelastic behavior: depends on time and temperature

Viscous

Stress relaxation test:

-- strain to eo and hold.

-- observe decrease in stress with

time.
tensile test
eo

strain

s(t)
time
Relaxation modulus:

E r (t )

s(t )
eo

Relaxation Modulus is the time dependent

change in stress w.r.t maintained constant strain.

94

Crystalline isotactic PS

Lightly x-linked atactic PS

decompose

Amorphous PS

f08_14_pg498

Plastic Recycling Symbols

In 1988 the Society of the Plastics Industry developed a
numeric code to provide a uniform convention for
different types of plastic containers.
These numbers can be found on the underside of
containers.
1.
2.
3.
4.
5.
6.

PET; PETE (polyethylene terephthalate): plastic water and soda

bottles.
HDPE (high density polyethylene): laundry/dish detergent
V (Vinyl) or PVC: Pipes, shower curtains
LDPE (low density polyethylene): grocery bags, sandwich bags
PP (polypropylene): Tupperware, syrup bottles, yogurt cups,
PS (polystyrene): Coffee cups, disposable cutlery

7.

Miscellaneous: any combination of 1-6 plastics

96