Structure OF Sili Cat Es & Glass Es

ST RUC TU RE
OF
SILI CAT ES &
GLASS ES
(SiO ) Tetrahedron
4
4-
The Si – O bond in the (SiO44-) has 50%

ionic character and 50% covalent
character.
The radius ratio between Si4+ and O2- ions
is 0.29. This gives rise to tetrahedral
coordination between them.
The basic building block of the silicates
is the (SiO44-) tetrahedron.
Because of the small highly charged Si4+ ion at the
center of the tetrahedron strong bonding forces are
created within a tetrahedron. Units are normally joined
corner-to-corner and rarely edge-to-edge.
Silicate Structures
Since each oxygen ion of the silicate
tetrahedron has one electron available
- for bonding, many different types of
silicate structures can be produced.
- - Structures arising from bonding
between different tetrahedra can be in
-
SiO44- Tetrahedron
the form of islands, single chains,
double chains, rings, sheets and
3-dimensional networks.
The bonding between them may even create a structure

that has no specific configuration. Such structures are
called amorphous or glassy.
Island silicates
The simplest example of silicates is the sand. In technical
terms it is known as OLIVINE which has the basic chemical
formula (Mg, Fe)SiO4. In this situation the number of shared
oxygen ions is zero.
It consists of Fe2+ and Mg2+ ions bonded with SiO44- terahedron.
Since different tetrahedra are not bonded with any strong
primary bond, the structure is said to have an island structure.
Separate island structures can also be

formed as two tetrahedra joined together. In
such a situation the number of oxygen ions
shared between tetrahedra is one. The
example is a mineral called HEMIMORPHITE,
Zn4Si2O7(OH)2.
Silicates as Single Chains & Rings
- - -
- - - - - -
… …
- - -
By sharing two of the tetrahedral oxygen
ions in the structure, we can produce either
a single chain or a ring structure.
The mineral ENSTATITE, MgSiO3 is an
example of the single chain structre.
The mineral BERYL Be3Al2(SiO3)6 is an
example of the ring structure.
Double Chain Silicate Structures
An average sharing of 2.5 corners of the tetrahedra
gives the double chain structure.
Asbestos, Ca2Mg5(OH)2(Si4O11)2, is an example of

double chain structure.
Sheet Silicate Structures
Sharing of three corners gives an array of SiO44- tetrahedra in
the form of sheets. Since there is still one unbonded oxygen
on each silicate tetrahedron, these sheets are able to bond
with each other with other types of structural sheets.
Sheet of (Si2O5 ) 2 -
Sheet of bonding
layer
Ordinary clay, is sheets of (Si2O5)2- bonded with sheets of Al2(OH)42+.

Talc is sheets of (Si2O5)2- bonded with sheets of Mg3(OH)24+.
Mica also has a similar sheet like structure with a complex formula of
KAl (OH) (Si Al)O
Silicate Networks
When all four corners of SiO44 –
tetrahedra share oxygen ions, a
SiO2 network, called silica is
produced.
Crystalline silica exists in

several polymorphic forms that
correspond to different ways in
which the silicate tetrahedra are
arranged with all corners shared.
There are three basic silica
structures:
Si4+
Quartz, Tridymite and
Cristabolite O2 -
Silicate Glasses
The fundamental subunit of
silica based glasses also is
SiO44- tetrahedron.
While SiO44- tetrahedra in
crystalline silica produce a
long range order, in silicate
glasses these tetrahedra are
joined corner-to-corner to
form a LOOSE NETWORK
with no long-range order.
Glasses developed for many
industrial and commercial
applications contain also
glass modifying oxides.
Glass Transition Temperature
Supercooled Liquid
Liquid
Specific Volume
Shrinkage
Glass due to
freezing
Crystalline Solid
TG TM
Temperature
STR UCTUR
E OF
POLY MER S
Polymerization of Ethylene
H H H H H H
…
Half
Covalent
Bond or
C Free
C C C C C Electron
Double Single
Covalent Covalent
H H Bond H H H Bonds H
Ethylene H H Heat, H H Polyethylene

Monomers Pressure
Catalyst
C C C C
Degree of
Polymerization
H H H H n
Molecular Structure of
Polyethylene
Since the covalent bonding
angle between single carbon-
109.5o
carbon covalent bonds is ~
109.5o, a short length of the
polyethylene molecule takes
on a zig-zag configuration.
… …
Bending and Twisting of Long
Polyethylene Molecular Chains
Though the bond
angles in covalently
bonded PE molecules
are fixed, each sub
unit, i.e. a mer is free
to rotate without
violating any of the
bond angle
requirement.
As a consequence, it is very difficult to keep a long

PE chain straight and stiff
STRUCTURE OF LONG
POLYETHYLENE CHAINS
Long chains of polyethylene

molecules therefore remain curled
and twisted. They even get
entangled with each other.
In fact their appearance is like that
of boiled noodles.
Some Other Simple Polymers
H H H H
C C C C
H Cl n H CH3 n
Polyvinyl Chloride Polypropylene

H H H H
C C C C
H n H C N n
Polystyrene Polyacrylonitrile
H H H CH3
C C C C
O O
H O C n H C
n
CH3 OCH3
Polymethyl Acetate Polymethyl

Methacrtlate
(PMMA)
Folded Chain Structures
100 Carbon
Atoms
Microstructures of Polymers
Amorphous
Crystalline
Homopolymers & Copolymers
Homopolymers are polymeric materials that consist of
polymer chains made up of a single repeating unit.
Thus, if A is the repeating unit, a homopolymer chain
will be made up of sequence
…..AAAAAAAAAAAAA……
in the polymeric molecular chain.
In contrast, copolymers consist of polymer chains

made up of two or more chemically different repeating
units. The architecture of copolymers may use
chemically different repeating units in a different ways.
COPOLYMER
ARCHITECTURES
Random Copolymers Alternating Copolymers
AABABBABAAABABAB…. ABABABABABABAB……
Block Copolymers Graft Polymers
AAA…BBB…AAA...BBB… …AAAAAAAAAAAAA…
B B
B B
B B
B B

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ST RUC TU RE

The Si – O bond in the (SiO44-) has 50%

The bonding between them may even create a structure

Separate island structures can also be

Asbestos, Ca2Mg5(OH)2(Si4O11)2, is an example of

Ordinary clay, is sheets of (Si2O5)2- bonded with sheets of Al2(OH)42+.

Crystalline silica exists in

Ethylene H H Heat, H H Polyethylene

As a consequence, it is very difficult to keep a long

Long chains of polyethylene

Polyvinyl Chloride Polypropylene

Polymethyl Acetate Polymethyl

In contrast, copolymers consist of polymer chains

Block Copolymers Graft Polymers

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