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STRUC TURE STRUC TURE OF OF SILI CATES & SILI CATES & GLASS ESGLASS ES
(SiO(SiO444-4-) Tetrahedron) Tetrahedron
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 (SiO4
4-) 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 StructuresSilicate StructuresSince 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 the form of islands, single chains, double chains, rings, sheets and 3-dimensional networks.
SiO44- Tetrahedron
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The bonding between them may even create a structure that has no specific configuration. Such structures are called amorphous or glassy.
Island silicatesIsland silicatesThe 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 & RingsSilicates 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.
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Double Chain Silicate StructuresDouble 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 StructuresSheet Silicate StructuresSharing of three corners gives an array of SiO4
4- 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.
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 KAl2(OH)2(Si3Al)O10
Sheet of (Si2O5 ) 2 -
Sheet of bonding layer
Silicate NetworksSilicate Networks
Si4+
O2 -
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:
Quartz, Tridymite and Cristabolite
Silicate GlassesSilicate GlassesThe fundamental subunit of silica based glasses also is SiO4
4- 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.
Sp
ecif
ic V
olu
me
Temperature
Shrinkage due to freezing
TMTG
Crystalline Solid
Liquid
Glass
Supercooled Liquid
Glass Transition TemperatureGlass Transition Temperature
STR UCTURSTR UCTURE O F E O F
POLY MER SPOLY MER S
C
H
H
C
H
H
C
H
H
C
H
H
C
H
H
C
H
H
…
n
Polymerization of EthylenePolymerization of Ethylene
Double Covalent Bond
Single Covalent Bonds
Half Covalent Bond or Free Electron
C
H
H
C
H
H
Heat, Pressure Catalyst
Ethylene Monomers
Degree of Polymerization
Polyethylene
C
H
H
C
H
H
Molecular Structure of Molecular Structure of PolyethylenePolyethylene
Since the covalent bonding angle between single carbon-carbon covalent bonds is ~ 109.5o, a short length of the polyethylene molecule takes on a zig-zag configuration.
… …
109.5o
Bending and Twisting of Long Bending and Twisting of Long Polyethylene Molecular ChainsPolyethylene 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 STRUCTURE OF LONG POLYETHYLENE CHAINSPOLYETHYLENE 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.
C
H
H
C
H
Cl CH3
C
H
H
C
H
Some Other Simple PolymersSome Other Simple Polymers
n n
Polyvinyl Chloride Polypropylene
Some Other Simple PolymersSome Other Simple Polymers
n
C
H
H
C
H
Polystyrene Polyacrylonitrile
n
C
H
H
C
H
C N
n
C
H
H
C
CH3
Polymethyl Methacrtlate
(PMMA)
Polymethyl Acetate
n
C
H
H
C
H
O CO
CH3
C
O
OCH3
Some Other Simple PolymersSome Other Simple Polymers
Folded Chain StructuresFolded Chain Structures
100 Carbon Atoms
Crystalline
Amorphous
Microstructures of Polymers
Homopolymers & CopolymersHomopolymers & 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
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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 COPOLYMER ARCHITECTURESARCHITECTURES
Random CopolymersRandom Copolymers
AABABBABAAABABAB….
Alternating CopolymersAlternating Copolymers
ABABABABABABAB……
Block CopolymersBlock Copolymers
AAA…BBB…AAA...BBB…
Graft PolymersGraft Polymers
…AAAAAAAAAAAAA…BBBB
BBBB