Classification of Materials

Most materials can be broadly classified into three main groups: metals
ceramics and polymers. In addition, modern engineering materials include
composites, semiconductors, and biomaterials.

Metals
-- normally combinations of metallic elements (alloys), e.g. Cu/Zn and
Pb/Sn.
-- optically opaque
-- strong and ductile
-- good electrical and thermal conductors
-- mainly structural applications.

Ceramics
-- compounds of metallic and non-metallic elements, e.g. oxides and
carbides
-- can be optically transparent
-- hard and brittle
-- heat and corrosion resistant
-- structural and functional applications
1
Polymers
-- organic compounds of carbon, hydrogen and other non-metallic
elements, e.g. polyethylene and polystyrene
-- low density, flexible and formable
-- resistant to chemical attack
-- mainly structural applications

Composites
-- composed of more than one material type, e.g. glass fiber in a polymer
matrix.
-- combines best characteristics of each of the component materials
-- high specific strength and fracture resistant
-- mainly structural applications

Semiconductors
-- electrical properties intermediate between conductors and insulators
-- properties extremely sensitive to minute traces of impurity elements, e.g.
P and B in Si
-- vapor processing of thin planar arrays of doped-Si forms the basis of the
integrated circuit industry
-- functional applications
2

Biomaterials
-- materials that are non-toxic when implanted in the human body
-- used for replacement of diseased or damaged body parts, e.g. hip
implants

Current Materials Challenges
-- reduce energy use in transportation systems by developing (1) low
cost, high performance structural composites for weight reduction,
and (2) ceramic engines for increased operating efficiency.
-- develop materials for sustainable energy production systems, such
as wind turbines and solar cells.
-- improve quality of the environment by (1) developing cleaner
materials refining and processing technologies, and (2) increasing
recycling efforts.
-- develop nanostructured materials and technologies for the next
generation of miniaturized engineered systems.
3
Atomic Bonding in Solids

A. Primary Bonds
Strong bonds (~100 kcal/mol) arising from transfer or sharing of
valence electrons.

1. Ionic bond
-- transfer of valence electrons
-- electron localization (ionic species)
-- non-directional bonding
-- NaCl, ZnO, Li
2
O, etc.
-- extremities of Periodic Table

2. Covalent bond
-- sharing of valence electrons
-- partial electron delocalization (molecular unit)
-- hybridization of electron orbitals
-- highly directional bonding
-- H
2
, H
2
O, CH
4
, graphite, diamond, fullerene, etc.

4
3. Metallic bond
-- complete sharing of valence electrons (free electron gas)
-- complete electron delocalization
-- non-directional bonding
-- no valency restrictions (alloying)
-- Fe, Cu, Fe-Ni, Cu-Zn, etc.

B. Secondary Bonds

Weak bonds (~1 kcal/mol) arising from dipole interactions.
Responsible for bonding between electrically neutral atoms or
molecules

1. Permanent dipole
-- arises when centers of positive and negative charge in a
molecule do not coincide
-- directional
-- asymmetric polar molecules, such as H
2
O, H
2
S, NH
3
, CF
2
H
2
,
etc.

2. Induced dipole
-- arises from permanent dipole in one molecular group inducing
a dipole in a neighboring group
-- directional
5



3. Fluctuating dipole
-- arises from fluctuating charge distribution (no permanent dipole)
-- non-directional
-- inert gases (Ne, Ar, ) and symmetric molecules (CH
4
, CCl
4
, )

C. Hydrogen Bond
Intermediate bond (~5 kcal/mol)
-- arises when H atom forms a bridge between two electronegative
atoms
-- highly directional
-- nylon, cellulose, etc.

D. Addition (or Chain) Polymerization
Polymerization consists of joining a large number of molecules together
-- broken double bond gives two carbon orbitals for bonding
-- directional
-- chain-like structure that is called a polymer
-- polyethylene, polystyrene, etc.
6
Schematics of Secondary Bonds


(a) Electrically symmetric atom
(b) Induced atomic dipole
Hydrogen bonding in hydrogen
fluoride (HF)
Polar hydrogen chloride (HCl)
molecule
7
Ionic Bond
This is easiest to visualize:
-- results from strong electrostatic attraction between
oppositely charged ions
-- stable ionic aggregates due to ions with filled outer
shells
-- non-directional bonding permits close packing
-- combination of elements with low ionization energy
(e.g. Na) and high electron affinity (e.g. Cl)


Ionization Energy is the energy required to remove the least tightly bound
electron from an atom (forms positive ion)

Electron affinity is the energy released when an electron is captured by
an atom (forms negative ion).
8
Figure 1 An example of an ionic bond showing electron transfer
from Na to Cl to form Na
+
cation and Cl
-
anion pair.

The ionization energy of Na Na
+
is 5.14 eV, whereas the electron
affinity of Cl Cl
-
is 4.02 eV. Hence, the net energy (work) required
to create a pair of isolated Na
+
and Cl
-
ions is 1.12 eV.
9
Figure 2 (a) The bond-force curve showing the location of the equilibrium
separation distance x
0
. Note the approximately linear slope of the total force
curve in the vicinity of x
0
. (b) The bond-energy curve for the ionic compound
NaCl showing the location of the equilibrium separation distance x
0.


Interaction Energy

Consider the interaction between two point charges Q
1
and Q
2
separated by
distance r.
10
The interaction energy E is the sum of two terms: attractive energy E
A
and repulsive
energy E
R


E = E
A
+ E
R
(attractive) (repulsive)

= (1)

(negative) (positive)

o
is permittivity of vacuum, b and n are constants, which depend on ion
type; n ~ 8-10.





Rearranging terms

0
dr
dE
* r r
=
=
0
r
nb
r 4
Q Q
dr
dE
) 1 n ( 2
0
2 1
=
tc
=
+
(2)
n
0
2 1
*) r (
b
* r 4
Q Q
n
1
+ =
tc

n
o
2 1
r
b
r 4
Q Q
+
tc
11
(3)
n
0
2 1
b
*) r (
b
* r 4
Q Q
E +
tc
=
Substituting (2) in (3)
Cohesive Energy
Figure 3A unit cell for the rock salt, or
sodium chloride (NaCl) crystal structure.
|
.
|

\
|

tc
=
n
1
1
* r 4
Q Q
E
0
2 1
b
Now from (1)
Na
+
ion has 6 first nearest neighbor Cl
-
ions at r*.
Na
+
ion has 12 second nearest neighbor Na
+
ions at \2 r*.
etc.

By summing the contributions from all ions, it can be shown that the
cohesive energy/mol is



where N is Avogadros number, and A is the Madelung constant, which
depends on structure type.


For NaCl, one electronic charge is involved in transfer of valence electron;
hence Q
1
Q
2
= (+e) (-e) = -e
2






|
.
|

\
|

tc

=
n
1
1
* r 4
A Q Q N
E
0
2 1
|
.
|

\
|

tc
=
n
1
1
* r 4
A Ne
E
0
2
13
Shorter bond distance r* for ZnO reflects stronger interaction energy between
divalent ions.

Since Q
1
Q
2
= (-2e) (+2e) = - 4e
2
for ZnO, the cohesive energy/mol is at least four
times that of NaCl.


Characteristics of Ionic Crystals

Coordination number is defined as number of nearest neighbors at the bond
distance.

-- NaCl has CN = 6

-- other ionic crystals have different values, e.g. CsCl has CN = 8

-- determined by relative size of anion and cation

Substance A r*() n Cohesive energy
(kcal/mol)
Na
+
Cl
-

Zn
++
O
--

1.75
1.64
2.81
1.97
8
8
181
964
14
Ionic Radius is defined as the radius of the hard sphere that represents the
ion.

-- radius of anion is usually larger than that of the neutral
atom.

-- radius of cation is usually smaller than that of the neutral
atom.










CN = 6

Consider NaCl structure (see Table 1), where each Na
+
cation is surrounded
by six Cl
-
anions at the bond distance.
Element Charge at
given radius
Ionic radius
()
Atomic
radius ()
Sodium
Chlorine
Magnesium
Oxygen
+1
-1
+2
-2
0.98
1.81
0.78
1.32
1.86
0.91
1.59
0.60
15

R
A
= ionic radius of anion (Cl
-
)

R
C
= ionic radius of cation (Na
+
)
A A C A
R 2 2 R 8 ) R R ( 2 = = +
| |
2
A
2
A
2
C A
) R 2 ( ) R 2 ( ) R R ( 2 + = +
( )
A C
R 1 2 R =
( ) 414 . 0 1 2
R
R
A
C
= =
16

This is the smallest value of R
C
/R
A
for which all 6 anions touch the cation,
called the critical radius ratio.
-- larger values allowed
-- smaller values not allowed







Figure 4 Stable and unstable anion-cation coordination
configurations; large circles represent anions; small circles
represent cations.
CN = 4

Consider ZnS structure (see Table 1), where each Zn
2+
cation (0.83) is
surrounded by four S
2-
anions (1.74) at the bond distance.
2
3
R R
C A
= + 2 R 2
A
=
17
Table 1. The critical (r/R) ratio for
each coordination number.
( )
2
2 3
R
C

=
( )
2
2 3
R
C

=
( )
2
2 3
R
C

=
= 0.225
( )
2
2 3
=
C
R
1
2
6
R
R
A
C
=
Note that for crystals having
equal numbers of anions
and cations, only CN values
of 2, 3, 4, 6, 8 and 12 satisfy
symmetry requirements.
18
Crystal Structures
We have examined the forces responsible for aggregation of atoms or
molecules. Now we will consider how they are organized or distributed in
space.

Periodic arrays crystalline materials
Random arrays amorphous materials
Combination arrays semicrystalline materials


Crystal lattice is defined as an array of points, infinite in extent, in which
every point has identical surroundings.


Unit cell is the smallest region that completely defines the crystal lattice

-- vertices of unit cell are known as lattice points
-- lengths of unit cell are known as lattice parameters
19
Figure 5 Possible unit cells for a 2-D space lattice: (a)
square, (b) rectangle, and (c) parallelogram.
There are 14 possible arrangements for 3-D lattices, which are
known as Bravais lattices. These can be grouped into 7 crystal
systems, based on edge lengths of unit cell (unit vectors) and the
angles between them.
20
Figure 6 The 14 Bravais lattices grouped into the 7 crystal systems. The
restrictions on the lattice parameters a, b, and c and the angles between
the edges of the unit cell o, , and are listed for each unit cell.
21
Miller Indices
Most common convention used to denote points, directions, and planes
in crystal lattices


Points

Defined as fractional multiples of
the unit cell edge lengths

Right-hand Cartesian coordinate
system used to denote specific
points, e.g. 1,0,0.
Directions

Defined as the line(s) between
two points or vectors

Specific directions denoted by
square brackets, e.g. [111]; families
of directions denoted by angle
brackets, e.g. <111>
22
Angle between directions [h
1
k
1

1
] and [h
2
k
2

2
] is given by:
) k h ( ) k h (
) k k h h (
cos
2
2
2
2
2
2
2
1
2
1
2
1
2 1 2 1 2 1


+ + + +
+ +
= u
23
Planes
Defined as the reciprocals of the intercepts on the coordinate axes
Specific planes denoted by parenthesis, e.g. (111).
Families of planes denoted by braces, e.g. {111}.
24
Structures of Metals
Three main types:

-- body centered cubic (bcc)

-- face centered cubic (fcc)

-- hexagonal close packed (hcp)
25
fcc and hcp structures formed by different stacking sequences of close-packed
planes.
ABABABA.hcp Both have
ABCABCA.fcc CN = 12
Figure 7 Close packed stacking sequence (ABCABCA) for fcc structure
26
Figure 8 Close packed stacking sequence (ABABABA) for
hcp structure.

Density
Calculate the density of fcc aluminum: atomic mass =
26.98; a = 4.04 x 10
-8
cm; A
0
= 6.02 x 10
23
mol
-1



27
Packing Factor
Calculate packing factor (PF) for bcc, fcc and hcp structures.
(PF = volume of atoms/volume of unit cell)

3
24
23
cm / g 72 . 2
10 x 94 . 65
10 x 93 . 17
v
m
= = =

28
Actual measured density is 2.70 g/cm
3
bcc structure
0.68
= = t
8
3
bcc
PF
Since a
o
=
3
4r
( )
3
0
3
3
4
2
a
r
PF
bcc
t
=
fcc structure
29
hcp structure

Same as for fcc, since both structures are ideally close-packed, with
CN = 12.

PF
hcp
= 0.74
=
t
=
2 3
PF
fcc
( )
3
0
3
fcc
a
r
3
4
4 PF
t
=
2
r 4
Since a
0
=
0.74
30
Interstitial Sites

The locations of the largest holes in bcc, fcc and hcp structures are
known as interstitial sites

fcc structure

Largest hole in an fcc structure is located at the center of the unit cell.
-- known as an octahedral site, since the polyhedron connecting
nearest neighbor atoms has 8 sides
-- there are 12 equivalent octahedral sites located at edge
centers of the unit cell
-- each edge site is shared by four unit cells, hence there are 4 =
[(12 x ) + (1 x 1)] octahedral sites per unit cell
-- if hole radius is k, then the radius ratio k/r = 0.414
-- hence, atoms about 40% of the size of the host atoms can fit
into octahedral sites

The fcc structure also contains tetrahedral sites, located at , , -type
positions in the unit cell.
-- there are 8 equivalent tetrahedral sites that lie completely
within the unit cell
31

-- the radius ratio, k/r, for a tetrahedral site is 0.225
-- hence, atoms about 20% of the size of the host atoms can fit into
tetrahedral sites

Thus, there are twice as many tetrahedral sites as octahedral sites, and
each tetrahedral site is about one-half the diameter of an octahedral site.

bcc structure

This structure also contains both octahedral and tetrahedral sites
-- octahedral sites are located at face centers and edge centers of
the unit cell, giving a total of 6 sites per unit cell and k/r = 0.155.
-- tetrahedral sites are located at , , 0 type positions, giving a
total of 12 tetrahedral sites per unit cell and k/r = 0.291.

Thus, there are twice as many tetrahedral sites as octahedral sites, and
each tetrahedral site is about twice the diameter of an octahedral site.

hcp structure

Similar to fcc, as indicated in Table 2.
32
Table 2. The size and number of tetrahedral and octahedral interstitial
sites in the BCC, FCC, and HCP crystal structures. The sizes of the
interstitial sties are given in terms of the radius ratio (k/r) where k is the
radius of the largest atom that can fit into the interstitial position and r
is the radius of the host atoms. The number of interstitial sites is given in
terms of both the number of sites per cell and, in parentheses, the
number of sites per host atom.
Crystal
Structure
Size of
tetrahedral
sites
Size of
octahedral
sites
Number of
tetrahedral sites
per unit cell (per
host atom)
Number of
octahedral sites
per unit cell (per
host atom)
BCC
FCC
HCP
k/r = 0.291
k/r = 0.225
k/r = 0.225
k/r = 0.155
k/r = 0.414
k/r = 0.414
12 (6)
8 (2)
12 (2)
6 (3)
4 (1)
6 (1)
33
Figure 9 The locations of the interstitial sites in the common crystal
structures: (a) octahedral sites in FCC, (b) tetrahedral sites in FCC, (c)
octahedral sites in BCC, (d) tetrahedral sites in BCC, (e) octahedral
sites in HCP, and (f) tetrahedral sites in HCP.
34
Structures of Ceramics

The structures of many ceramic crystals can be visualized in terms of
stacking of close-packed planes of anions, with interstitial sites occupied
by the cations.
Two types of interstitial sites:
-- tetrahedral (CN=4)
-- octahedral (CN=6)
Crystal structures determined by:
-- stacking sequence (fcc vs. hcp)
-- manner in which interstitial sites are occupied
Figure 10 -- The stacking of one
plane of close-packed spheres
(anions) on top of another:
tetrahedral and octahedral
positions between the planes
are designated by T and O,
respectively
Example NaCl structure
-- fcc array of close-packed anions of the {111} type
-- cations reside in octahedral sites, each with 6 nearest neighbor anions
-- all octahedral sites are occupied
35
*Other ionic structures can be understood in similar manner.
Figure 11 A section of the rock salt
crystal structure from which a corner
has been removed. The exposed plane
of anions (dark spheres inside the
triangle) is a {111}-type plane: the
cations (light spheres) occupy the
interstitial octahedral positions. Density

( )
A c
A c
N V
A A n

+
'
=
n = number of formula units within unit cell
EA
c

= sum of at. wt. of cations
EA
A
= sum of at. wt. of anions
V
c
= volume of unit cell
N
A
= Av. number
Density

36
Calculate the density of NaCl.
n =4
EA
C
= A
Na
= 22.99 g/mole
EA
A
= A
Cl
= 35.45 g/mole
V
C
= a
3
( ) | |
23
3
8 8
10 023 . 6 10 81 . 1 10 02 . 1 2
) 45 . 35 99 . 22 ( 4
+
+
=

3
cm / . g 14 . 2 =
81 . 1 r
Cl
=

1.02 r
Na
=
+
( )
3
Cl Na
3
c
r 2 r 2 a V
+
+ = =
+
+ =
Cl Na
r 2 r 2 a


37
The experimental value is 2.16 g/cm
3
AX-Type Crystal Structures

Equal numbers of cations and anions, known as AX compounds.
NaCl
(CN = 6)
CsCl
(CN = 8)
38
39
A
m
X
P
-Type Crystal Structures

When charges on cations and anions are not the same, a compound with
the formula A
m
X
P
can exist, e.g. CaF
2
RC/RA = 0.8, so that CN = 8

half of center positions only are occupied
by Ca
2+
ions
A
m
B
n
X
P
-Type Crystal Structures

Compounds that have more than one type of
cation (A and B)formula for barium titanate is
BaTiO
3
(perovskite structure).

40
Silicate Ceramics

The basic building block of all silicate ceramics (amorphous and crystalline)
is the tetrahedron.
-- each silicon atom is tetrahedrally bonded to four oxygen atoms
-- since each oxygen atom requires an extra electron to achieve a stable
electronic structure, a charge of 4 is associated with every tetrahedron.
Figure 12 A silicon-oxygen (SiO
4
)
4-
tetrahedron.
Si
4+
= 0.39 Hence r
Si (ion)
/r
O (ion)
= 0.3
O
2-
= 1.32
41
This value is within the stability range 0.225 s r/R < 0.414 (Table 3) for
tetrahedral coordination (CN=4). Since the Si-O bond is mixed ionic and
covalent (about 50:50), the tetrahedron satisfies the bonding
requirements of both ionic radius ratio and covalent directionality.

Various silicate ceramics arise from the different ways in which the
(Si0
4
)
4-

units combine into one-, two-, or three-dimensional structures.
Because of the high charge on the Si
4+
ion, the tetrahedral units are
seldom joined edge to edge and never face to face, but almost always
share corners, with no more than two tetrahedra sharing a corner.
Figure 13 Effect of corner edge, and face sharing on cation-cation
separation. The distances S
1
:S
2
:S
3
are in the ratio 1:0.58:0.33; that is,
cation-cation repulsion increases on going from left to right, which
tends to destabilize the structure.
42
43
Silica

Silicon dioxide or silica (SiO
2
) has a three-dimensional structure, such that
every corner oxygen atom in each tetrahedron is shared by adjacent
tetrahedra.

-- most common crystalline forms are quartz, cristobalite and tridymite.
-- relatively open structures of low density
-- high melting points, due to strength of Si-O bonds
Figure 14 2-D representations of (a) silica glass, (b) crystalline silica.
44
Silica glass

Also known as vitreous silica, silica glass has a highly disordered
structure, i.e. it lacks the long-range order characteristic of crystalline
silica, Fig. 14.
-- Oxides, such as B
2
O
3
and GeO
2
, which readily form glassy
structures, are referred as network formers. When added to a
silica glass, they substitute for the silicate tetrahedra, so that the
long-range order is retained.
45

-- Oxides, such as Na
2
O and K
2
O, which are incapable of forming glassy
structures, are referred as network modifiers. When added to a silica
glass, they break-up the tetrahedral network and create a more
disordered structure.

-- Oxides, such as TiO
2
and Al
2
O
3
, in which the cations substitute for
silicon and help to stabilize the network, are called intermediates.

The addition of modifiers and intermediates lowers the melting point and
viscosity of the glass, making it easier to form into useful shapes. Thus,
glass containers and windows are made from low melting point soda-lime-
silica glasses, while furnace tubes are made from high melting point vitreous
silica.

Pyrex, a glass composition containing the network formers SiO
2
and B
2
O
3
,
and the network modifiers Na
2
O and CaO, has properties intermediate
between those of soda-lime-silicate glass and vitreous silica, e.g. it has about
three times the thermal shock resistance of silica glass, but does not require
the high processing temperature of vitreous silica.
46
Layered silicates

A two-dimensional sheet is formed by sharing of three oxygen atoms in
a planar array of tetrahedra.

-- formula unit is (Si
2
O
5
)
2-
-- a negative charge is associated with the unbonded oxygen
atoms projecting out of the plane.
Figure 15 Schematic
representation of the two-
dimensional silicate sheet
structure having a repeat unit
formula of (Si
2
O
5
)
2-
.
Such a negatively charged sheet can bond with an equivalent positively
charged sheet to form an electrically neutral structure.

-- sheet or layered silicate structures are characteristic of clays
and other minerals
47
-- bonding within a two-layered sheet is strong (ionic-covalent),
whereas bonding between adjacent sheets is relatively weak (van
der Waals).

Clays

Aluminosilicates that contain chemically bound water.

-- crystal structures are relatively complicated

-- when water is added, clays become very plastic; so-called
hydroplasticity

-- can be fired at relatively low temperature to form a dense and
strong ceramic

Kaolinite

Compound is formed by bonding between Al
2
(OH)
4
2+
and (Si
2
O
5
)
2-
layers.

-- formula unit is Al
2
(OH)
4
Si
2
O
5
-- crystalline kaolinite is composed of many such double layers,
stacked one upon the other

-- additive to paper products
48

Figure 16 The structure of
kaolinite clay.
Talc

Compound comprises 1 sheet of Mg
3
(OH)
2
4+
+ 2 sheets of (Si
2
O
5
)
2-

-- formula unit is Mg
3
(OH)
2
(Si
2
O
5
)
2
-- slips easily, like graphite

-- absorbs water
49
Glass Properties


Glass transition temperature

For an amorphous or non-crystalline material, the glass transition
temperature (Tg) is the critical temperature that separates glassy
behavior from rubbery behavior, in the time scale of the experiment.

-- most easily detected via measurements of changes in
specific volume (1/ = v/unit mass) associated with heating
or cooling a material

-- upon heating, the material undergoes a transition from
the glassy state to the supercooled liquid state, and then
to the fully liquid state.
50
Figure 17 Specific volume as a function of temperature for a series of
materials. (a) The liquid-to-crystalline solid transformation. A
discontinuous change in volume occurs at the melting temperature T
m
. (b)
The liquid-to-glass transformation (the liquid-to-crystal curve is shown for
reference). The temperature range in which the slope of the liquid-glass
curve changes is the glass transition temperature T
g
. (c) Specific volume
versus temperature for a semicrystalline material. The discontinuous
change in volume occurs at T
m
, and a change in slope occurs at T
g
. 51
Viscosity-temperature behavior

The temperature dependence of the viscosity of a glassy material is the
key to proper selection of processing parameters.

-- melting point (viscosity 100 P) is the temperature where the glass is
fluid enough to be considered a liquid.

-- working point (viscosity 10
4
P) is the temperature where the glass is
easily deformed.

-- softening point (viscosity 4 x 10
7
P) is the maximum temperature
where glass can be handled without distortion.

-- annealing point (viscosity 10
13
P) is the temperature were any
residual stress in the glass can be eliminated.

-- strain point (viscosity 3 x 10
14
P) is the temperature where fracture
occurs before plastic deformation.

Most glass-forming operations are carried out in the working range,
which is between the working and softening temperature.
52
Figure 18 Logarithm of viscosity versus temperature for fused
silica and several silica glasses.
53
Structures of Polymers
Hydrocarbon molecules

Most polymers are derived from hydrocarbon precursors. It is instructive,
therefore, to consider the structures of some typical hydrocarbon
molecules.
All four valence electrons in carbon participate in bonding. Moreover,
hybridization of s and p orbitals of the valence electrons gives directional
bonding.
-- 4 equivalent sp
3
orbitals, as in methane and ethane
-- 3 equivalent sp
2
orbitals, as in ethylene
-- 2 equivalent sp
1
orbitals, as in acetylene
54
single bond -- formed by overlapping sp
3
orbitals with the orbitals of
other atoms
double bond -- formed by overlapping sp
2
orbitals with the orbitals of two
different carbon atoms
triple bond -- formed by overlapping sp
1
orbitals with the orbitals of two
different carbon atoms

Saturated hydrocarbons

sp
3
orbitals of both CH
4
and C
2
H
6
directed towards the corners of a
regular tetrahedron
55
Unsaturated hydrocarbons


56
-- Activator (catalyst) is needed to start process of polymerization. For
example, ethylene gas can be transformed into polyethylene solid by
heating under pressure in the presence of a catalyst.

-- Polymerization process begins when an active mer is formed by
reaction of an ethylene gas molecule with a catalyst species (R).
Polymer chain is then formed by the sequential addition of
polyethylene monomer units. In so doing, the active site is
transferred to each end-unit monomer as it is linked to the growing
chain.
Polymer molecules

Directional nature of covalent bonds enables carbon atoms to form long-chain
molecules.
57
n
H H
C C
H H
|
|
|
|
.
|

\
|

| |
| |
Figure 19 For polyethylene, (a) a schematic representation of mer and
chain structures, and (b) a perspective of the molecule, indicating the
zigzag backbone structure.

Hence, the formula unit for a polyethylene molecule may be
represented as follows, where n is the number of ethylene molecules
(monomers) that bond together to form the long chain molecule.
58
The final result, after successive additions of ethylene monomer
units, is a long chain polyethylene molecule. Carbon atoms form a
zig-zag backbone in the molecule, with an angle of 109 between the
bonds; the C-C bond length is 0.154 nm.
Mer structures for some common polymeric
materials
59
The molecular structures of PTFE, PVC and PP are shown in Figure 20. In
PTFE, all the hydrogen atoms in polyethylene have been replaced by
fluorine atoms, whereas in PVC and PP every fourth hydrogen atom along
the chain has been replaced by Cl or CH
3
(methyl group).
Figure 20 Mer and chain structures for
(a) polytetra-fluoroethylene, (b) polyvinyl
chloride, and (c) polypropylene.
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Molecular shape
Long chain molecules are capable of rotation and bending in three
dimensions. This is because any carbon atom in a chain can lie at any
point on the cone of revolution (109 angle) with the bond of the
preceding carbon atom, Figure 21. Thus, a long chain molecule typically
has a very complex shape, involving many bends, twists and kinks.
Figure 21 Schematic representations of how polymer chain shape is
influenced by the positioning of backbone carbon atoms (solid circles).
For (a), the rightmost atom may lie anywhere on the dashed circle and
still subtend a 109 angle with the bond between the other two atoms.
Straight and twisted chain segments are shown in (b) and (c),
respectively.
61
Polymer crystallinity
The crystalline state of a polymer is more complex than that of a metal or
ceramic, because of the difficulty of aligning the long chain molecules in
a regular close-packed structure. However, it does occur readily in
molecules, such as PE and PTFE, where the atoms are arranged
symmetrically along the carbon backbone. Polyethylene can be
crystallized with the orthorhombic structure, Figure 22, which represents
the closest packing of the long chain molecules.


Figure 22 Arrangement of
molecular chains in a unit
cell for polyethylene.
62
-- degree of crystallinity may range from completely amorphous up to
about 95% crystalline

-- density of a crystalline polymer is greater than its amorphous
counterpart because of the closer packing of molecules in the
crystalline state

-- degree of crystallinity achieved by a polymer depends on the cooling
rate from the liquid state

-- many bulk polymers that are crystallized from the melt form
spherulites, Fig. 23, which are considered to be the polymer
equivalents of grains in polycrystalline metals and ceramics,
Figure 23 A transmission photo-
micrograph (using cross-polarized
light) showing the spherulite
structure of polyethylene. Linear
boundaries form between adjacent
spherulites, and within each
spherulite appears a Maltese
cross. 525 .
63
Polymer characteristics

1. Side groups
-- clusters of atoms that are attached to the carbon backbone

2. Degree of polymerization
-- defines average chain size of a polymer

3. Cross linking
-- joining of two chains together by an atom, group of atoms or another
chain

4. Elastomers
-- polyisoprene experiences large elongations under load, and returns to its
original shape upon unloading
-- trans-poly on opposite sides (rigid solid)
-- cis-poly on same side (steric hindrance) causes kinking, i.e. chains to
coil.

5. Vulcanization
-- cross-linking process in elastomers; non-reversible reaction at
elevated temperatures using sulfur compounds
-- automobile tires have 3-5% S and are elastic
-- battery cells have more S and are more rigid

64
65
Elastomers
Polyisoprene experiences large elongations under load, and returns to
its original shape upon unloading
trans-poly on opposite sides
(rigid solid)
cis-poly on same side (steric
hindrance) causes kinking, i.e.
chains to coil (flexible solid)

Vulcanization
Cross-linking process in elastomers; non-reversible reaction at elevated
temperatures using sulfur compounds

6. Stereoisomerism
-- same composition but different structure
isotactic all on one side
syndiotactic alternating side groups
atactic randomly on opposite sides

7. Thermoplastic polymer
-- softens when heated and hardens when cooled (reversible process),
as in polyethylene
-- due to breaking and reforming of weak secondary bonds between
chains

8. Thermosetting resin
-- decompose before they soften because of extensive cross linking, as
in epoxy resin

9. Conformation
-- this refers to the outline or shape of the long chain molecule
-- can be modified by a simple bond rotation

10. Configuration
-- this refers to the arrangement of atoms positions along the chain
-- can be altered only by breaking and reforming primary bonds


66
67
Stereoisomerism



Isotactic R groups all on one
side






Syndiotactic R groups
alternating on opposite sides





Atactic R groups randomly on
opposite sides

Same composition but different atomic arrangement:

Melting and crystallization


Carbon backbone of a long chain polymer is strong, since it is
composed of a chain of C-C primary bonds. In the crystallized state,
the close-packed segments of the long chain molecules are held
together by weak secondary bonds


It follows that when a crystalline polymer is heated, thermal energy
can easily disrupt the regular periodicity of the crystalline domains,
thereby forming a disordered network of long chain molecules. As in
ceramics, melting and solidification occurs over a temperature range,
T = Tm Tg.


Fig. 24 shows this effect for three different cooling rates from the
fully molten state, leading to a glassy solid (fast), semi-crystalline
solid (intermediate), and crystalline solid (slow)
68
Polyethylene readily crystallizes by slow cooling from the melt, whereas
polystyrene does not, due to the presence of bulky side groups (benzene
rings)

-- abrupt changes in elastic stiffness, heat capacity and thermal expansion
coefficient occur at Tg

-- processing of thermoplastic polymers is carried out within the critical
temperature range T = Tm Tg, where the material is in its softened,
rubber-like state.
Figure 24 Specific volume
versus temperature, upon
cooling from the liquid melt, for
totally amorphous (curve A),
semicrystalline (curve B), and
crystalline (curve C) polymers
69
Structures of Carbon
Elemental carbon exists in three distinct polymorphic forms:
-- diamond
-- graphite
-- fullerene
Diamond Graphite C
60
Fullerene
Graphite

A stable form of carbon, graphite consists of layers of strong, covalently-
bonded carbon atoms, with weak Van der Waals bonding between the layers.
Hence, the properties of graphite are anisotropic.
-- good solid lubricant, because of ease of interplanar cleavage

-- high in-plane strength and good stability at high temperature

-- high in-plane electrical and thermal conductivity
70
In addition, graphite has high resistance to thermal shock, high absorption
of gases, and good machinability. Applications include heating elements,
rocket nozzles, electrical contacts, battery electrodes, and air purification
devices.

Diamond
A metastable form of carbon, diamond is composed entirely of strong
covalently-bonded carbon atoms, with tetrahedral coordination. The
properties of diamond are exceptional in many respects.
-- hardest known material

-- very low electrical conductivity

-- unusually high thermal conductivity

-- optically transparent in the visible and infrared

-- high index of refraction

Synthetic diamonds are produced commercially by a high pressure-high
temperature process. Industrial grade diamond grits are used for grinding
and cutting operations, and polycrystalline diamond compacts are used for
rock drill bits and machine tools.

Thin films of diamond are also manufactured by a Chemical Vapor
Deposition (CVD) process. Such films are used as wear resistant coatings
on drills, bearings, dies, and lenses.
71

Fullerenes
Discovered in 1985, C
60
fullerene is a molecular form of carbon that
consists of a hollow spherical cluster of sixty carbon atoms.

-- same symmetry as that of a soccer ball

-- composed of 20 hexagons and 12 pentagons, such that no two
pentagons share a common side

-- named after Buckminster Fuller, inventor of the geodisic dome;
each C
60
molecule is a molecular analogue of such a dome.

-- other molecular forms with larger numbers of carbon atoms
have been found

-- properties of these fullerene molecules are being investigated

Recently, methods have been found to produce nanoscale tubular and
polyhedral structures. Carbon nanotubes display very high specific
strengths.

Many structural applications for this new class of superstrong carbon
fibers are envisioned.
72
73
Additional notes
US joining top in energy resources
Directional and deep drilling, fracking
NATURAL GAS
Tungsten carbide cobalt used for drills
Transition from coal-> natural gas
Directional: mud motor uses drilling fluid to
turn, sensors guide the motor.
74