Lecture -V

Inorganic Polymers
• Characteristics of Silicones
• Applications of Silicones
• Polyphosphazines
• Sulphur based polymers
Paints
• Introduction
• Requirements of a Good Paint
• Types of Paints
• Applications of Paints
Date :2078- 02 - 27 1
 Characteristics of Silicones
The physical properties of silicones depend upon the kind and
number of organic groups attached to the silicon backbone whereas
the chemical properties are controlled by Si-O-Si bonds.
Silicones can be obtained in the form of oils, viscous-liquid, resins or
rubber like solids.
Organic
• Water repellant: In silicones the atoms of silicone parts
are surrounded by organic parts. The content of
the organic groups make silicones highly water
repellant. This property is increased by aromatic Organic
parts. parts
n
• Resistance to oxidation: Silicones are resistance to oxidation due to
the organic parts. Aromatic parts enhances the property i.e. the
stability towards oxygen increases by the presence of aromatic
parts.
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 Characteristics of Silicones…
• Toxicity: Silicones are nontoxic.
• Thermal stability: They are stable
towards heat due to stable silica like
arrangement of Si – O– Si and high bond
energy of Si – O bond. Silica like arrangement
• Resistance to Chemicals: Most of mild acids and alkalis do not react
with silicones. However other chemicals react with silicones due to
polar nature of Si – O bond and ability of silicone to expand its
valency due to presence of vacant orbitals.
•They do not melt at high temperature and do not freeze at low
temperature.
•Silicon oils are highly stable non-volatile even on heating.
•The boiling point and viscosity of silicones are highly affected by
chain length
• Since they can withstand high temperature without charring, they
are used for making insulating materials for electric motor and other
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electric appliances.
 Applications of Silicones…
• Silicones oils are used for high temperature oil bath, vacuum pumps
etc. because they are very stable and non- volatile even on heating.
• They are used as low temperature lubricants since they do not
become viscous on cooling.
• They are also used to make Vaseline like grease, which are used as
lubricants in aero plane since they do not freeze at – 40 o C and do
not melt at 200 o C.
• Silicones resins being highly water repellent are used for making
water proof clothes and papers.
• Silicones fluids are mixed with paints, enamels to resist to the
effect of high temperature, sunlight, chemical and damp.
• They are used for making nonstick pans since they are thermally
stable.
• Silicones rubbers are used in transplant surgery for making
artificial heart valves , artificial breasts etc. 4
5
Phosphorous based polymers: Polyphosphazines
Nitrogen and phosphorus have little tendency to
undergo catenation but much more less than carbon
atoms. However nitrogen and phosphorus undergo
catenation resulting in the formation of polymeric
compounds known as Polyphosphazines. The general
formula of the polymer is represented by

R Where, R may be variable

R = - Cl in Polyphosphonitrilic chlorides
P N R = - OCH3 in Polydimethoxy phosphazines
R = - OC2H5 in Polydiethoxy phosphazines
R n 6
Preparation of Polyphosphonitrilic chlorides
By the reaction between phosphorus pentachloride and
ammonium chloride in presence of C6H5Cl or by heating PCl5 with
NH4Cl at 120-150 °C.
N

C6H5Cl Cl + (PCl2N)3 + (PCl2N)4

n PCl5 + n NH4Cl H P N
- 4n HCl

N n
cyclic trimer cyclic
a linear polymer tetramer

The trimeric or tetrameric compounds are easily

separated by distillation method.
7
 Cl Cl
P
N N
Cl
Cl
P P
Cl Cl
N
Trimer Tetramer

Properties of Polyphosphonitrilic chlorides

• They have high elastic properties and can be extended many
times reversibly so called inorganic rubbers.
• When stored in the absence of moisture they do not lose
elastic properties but becomes brittle if stored in moisture
because of reaction with moisture.
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 Properties of Polyphosphonitrilic chlorides…
• Freshly prepared polymers are soluble in chloroform. They are not
soluble in petroleum and ether. The solution on standing slowly
changes to gel and cross linked.
Applications of Polyphosphonitrilic chlorides
• They are used as high stretched rubbers.
• As a catalyst for polymerization of Polysiloxanes from Silanol.

Polydimethoxy phosphazines and Polydiethoxy phosphazines

Preparation
Polydimethoxyphosphazines and Polydiethoxyphosphazines are
prepared by treating Polyphosphonitrilic chloride with sodium
methoxide (CH3ONa) and sodium ethoxide (C2H5ONa) respectively
as follows .
9
Polydimethoxy phosphazines and Polydiethoxy phosphazines…
OCH3 Cl OC2H5

CH3ONa C2H5ONa
P N P N P N

OCH3 n Cl n OC2H5 n
Polyphosphonitrilic Polydiethoxypho
Polydimethoxyp
chloride sphazines
hosphazines
Properties
• They are transparent, colorless and film thermoplastics.
• On heating above 100 °C they slowly changes to cyclic polymers.
Applications
• They are applied as metal coatings and insulations for wire.
• Form flexible plastics which have been used for fuel hoses
(flexible tube for flowing fuel).
• They are used in the manufacture of gaskets.
• Some polymers being water repellant they are used to
water proof thermoplastics. 10
 Sulfur based polymers
Because of ability to form catenation but much less than that of
carbon sulphur can form open or cyclic sulphur based polymer
(Sn).
Types of Sulphur based polymers
• Linear chain polymers (Polymeric sulphur &polymeric
sulphur nitride)
• Network polymers (Chalcogenide glasses)
Polymeric sulphur(PS)
Preparation Ordinary variety of Sulphur

It is prepared by melting the rhombic sulphur at 165- 168 °C.

The molten sulphur is poured into ice water, the polymer
formed is called polymeric sulphur. On heating the rhombic
structure of sulphur (S8) opens up to form free radicals which
combine with other S8 to form long chains. 11
 Polymeric Sulphur (PS)…

free radicals

The product thus formed is purified by washing with carbon

disulphide (CS2) to remove traces of S8. The removal of S8 is
necessary because the transition from polymeric sulphur to
rhombic sulphur is accelerated by the presence of S8.The
removal of S8 by washing the sulphur with carbon disulphide
slows down the transition.
Below the boiling point of sulphur i.e. 114°C the polymeric
sulphur is unstable and changes back to rhombic sulphur S8.
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Uses of Polymeric sulphur
• Used in flame proofing fabric.
• As plasticizers.
• As a catalyst in the manufacture of silicones
Polymeric sulphur nitride (SN) n
Polymeric sulphur nitride consists of nearly planar chains
with S N bonds of approximately bond length (1.16 Å).
The bond angle is 120 o.

Plasticizer -a substance (typically a solvent) added to a synthetic resin to

produce or promote plasticity and flexibility and to reduce brittleness.
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 Polymeric sulphur nitride (SN) n…
Preparation
The preparation of the polymer involves three steps.
• Preparation of tetrasulphur tetra nitride
It is prepared by passing ammonia into warm solution of
disulphur dichloride in dry CCl4.
6 S2 Cl2 + 16NH3 S4 N4 + NH4Cl + 8S

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 Polymeric sulphur nitride (SN) n…

Uses of Polymeric sulphur nitride (SN) n

• For making digital circuit
• Digital computers
• Electric power transition, transformer,
storage devices, electric motors etc.
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Network Polymer of Sulphur (Chalcogenide glasses)
Sulphur based network polymers are cross-linked
polymers formed by reacting polyvalent elements such as
silicone, antimony, arsenic, bismuth, germanium, indium
with chalcogens (S,Se,Te).The resultant binary products
formed are of great variety and complexity - known as
chalcogenide glasses or chalconide glasses.

Examples of Network polymers are (SiS)n,

(As2S3)n. (As2S3)n is best known chalcogenide
containing two elements, the structure of
which can be represented as follows.

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Chalcogenide glasses…

Structure of (As2S3) n

Structure of (SiS2)n 17
 Properties of Chalcogenide glasses
• Have lower softening points and lower tensile strength as
compared to other inorganic polymers.
• Stable to acids but attacked by concentrated alkalis.
• Can be distilled in vacuum without decomposition
• Are deeply colored.
• Change in conductivity reversible from low conductivity to
high conductivity under applied voltage.
• Its resistance is high until certain threshold voltage
gradient is reached. When this voltage gradient is reached
then it abruptly changes into low resistance state.
The softening point is the temperature at which a material softens beyond some
arbitrary softness. The term arbitrary describes a course of action or a decision
that is not based on reason or judgment but on personal will or discretion without
regard to rules or standards.
Tensile strength measures the force required to pull something such as
rope, wire, or a structural beam to the point where it breaks. 18
 Applications of Chalcogenide glasses
• In high energy particle
detector.
• In ultrasonic delay lines
• To make memory devices
for computers.
• For infrared transmitting Optical glasses
windows because most of
them are good infrared
transmitting materials.
• For fabrication of IR
windows for army and civil
optical devices.
The ultrasonic delay line is a thin
layer of piezoelectric material used
to produce a short, precise delay in an Camera lens glasses 19
electrical signal.
The softening point is the temperature at which a material
softens beyond some arbitrary softness.The
term arbitrary describes a course of action or a decision that is
not based on reason or judgment but on personal will or
discretion without regard to rules or standards.

The ultrasonic delay line is a thin layer of piezoelectric material

used to produce a short, precise delay in an electrical signal.

Piezoelectric materials are materials that produce an electric

current when they are placed under mechanical stress.
Energy Particle Detectors can measure the particle energy and
other attributes such as momentum, spin, charge, particle type.
IR Windows are an inspection point that is designed to allow
infrared radiation to transmit to the outside environment so that a
data point can be recorded using a thermal camera.
Tensile strength measures the force required to pull something such as
rope, wire, or a structural beam to the point where it breaks.
Fabrication-the action or process of manufacturing or inventing something.
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 Paints
Paint is a mixture of a pigment and suitable
liquid to form a closely adherent coating when
spread on a surface in a thin coat. In simple
sense, paint is a mixture of pigments and
vehicle.
Mechanism of drying up of the paint
When paints are applied to the surface of base
materials, the paint film dry up by the process of
evaporation of thinner (volatile oil) followed by
oxidation and polymerization of drying oils.
Vehicle: A liquid mixture of volatile and non-volatile
solvent.
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 Requisites of a Good Paint
Paints are mainly used for the protective,
decorative and functional purposes. In order to
fulfill the purposes of the paints, a good paint
should have the following characteristics.
• It should have good adhesive property.
• It should protect the surface from corrosion.
• It should have good texture and glossy and
pleasing appearance.
Glossy-shiny and smooth.
Texture-appearance of a surface or substance.
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 Requisites of a good paint…
• It should form a uniform, impermeable &
tough film when applied onto the surface
area covering property.
• It should be fluid enough to spread over the
surface and should have high surface area
covering property.
• The film should not get cracked on drying.
• The film should be highly stable at the
operating condition.
Impermeable - not allowing fluid to pass
through.
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 Types of Paints
On the basis of the chemical composition
and their effects on the surface of the base
materials, paints are classified into five
groups.

• Varnishes
• Enamels
• Lacquers
• Emulsion paints
• Special paints

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 Types of Paints…
Varnishes
• A homogenous colloidal solution of resin
(natural or synthetic) in drying oil or volatile
solvent or both.
• Used as a protective and decorative coating
of suitable surfaces.
• Dries by evaporation, oxidation and
polymerization of its constituents and forms
a hard transparent and glossy film.
Colloidal solution -a solution in which a material is
evenly suspended in a liquid.
Some of the Examples of Colloidal Solution are gelatin;
muddy water, milk, Butter, blood, Colored Glass. 25
 Solution, Colloid Suspension

The size of solute particles in the 1&1000 nm Particle size greater

solutions is extremely small. It is in diameter than 1000 nm
< 1 nm in diameter.
 Two types of Varnishes
Oil varnish or oleo resinous varnish
• A homogenous colloidal solution of resins in
drying oil and volatile solvent.
• This type of varnish dries up by evaporation
of volatile solvent followed by oxidation and
polymerization of the drying oil.
• The presence of oil reduces the brittleness
of the resin and increases the elasticity of
the varnish film.
Resin -a sticky flammable organic substance,
insoluble in water, exuded by some trees and
other plants. 27
 Two types of Varnishes…
Spirit varnish
• A homogenous colloidal solution made by
dissolving resin in a volatile solvent.
• Spirit varnish dries up rapidly by the process
of evaporation.
• The film so formed is comparatively brittle
and peel off more easily.
• A solution of shellac resin in alcohol is an
example of spirit varnish.
Peel off - remove a thin outer covering or layer.
Shellac - a natural thermoplastic; that is, a material that is
soft and flows under pressure when heated but becomes
rigid at room temperature. 28
 Applications of Varnishes
Varnishes are mainly applied for protection
and decorative purpose. Besides these some
of the main uses of varnishes are as follows.
• Used to give brightening layer to a painted
surface.
• Used to improve the appearance of wood
surfaces.
• To impart effective coating on the metal
surface from corrosion as it forms more
uniform coating layer.

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 Types of Paints…
Enamels
Enamel is a pigmented varnish (the dispersion
mixture of pigments in varnish). It forms a hard
and glossy film on drying. There are two types of
enamels.
• Baking enamel
It dries at elevated temperatures either in the
presence or absence of oxygen.
• Air drying enamel It dries up at room
temperature by oxidation and polymerization.
30
 Types of Paints…
Lacquers
• Lacquer - a colloidal dispersion solution of
resins of cellulose derivative such as
cellulose nitrate or cellulose ester etc. and
plasticizer in volatile solvent.
• It mainly dries up by evaporation and forms
hard, transparent and water- proof film.
Uses of Lacquers
• For giving finishing coats to automobiles
• For paintings of furniture
• Coating cotton fabrics and preparing artificial
leathers. 31
 Types of Paints…
Emulsion paints
• Emulsion paint - a dispersion mixture of rubber like
resin in water and film forming vehicle.
• In addition it also contains some specific additives
such as extender stabilizers, pigments, driers,
antifoaming agents and preservatives.
• When emulsion paint is applied onto the surface,
water evaporates and resinous particle unite to form
uniform, homogenous and clear film.
Emulsion mostly refers to paint used for walls and
ceilings. It is water-based with vinyl or acrylic added
for durability.
Resinous - having the characteristics of pitch or tar. resiny, tarry, pitchy. adhesive -
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tending to adhere.
 Types of Paints…
Uses of emulsion paints
• For coating porous surface because of low
penetration of water solutions.
• Easy to apply due to less odorless and non-
inflammable.
• Can be recoated many times which is not
possible in ordinary paints.

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 Special Paints

The Paints made by

adding special types of
additives which are able
to give the desired
appearance to glass,
wood, plastic, or metal
surfaces.

On the basis of the special effects obtained in

paints using specific types of additives, Special
paints are classified as follows.
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 Fire Retardant Paints

Temperature Indicating Paints

Cement Paints

Cellulose Paints

Distempers
Types of Luminescent Paints
special Paints
Water Repellant Paints

Aluminum Paints

Antifouling Paints

Coal tar Paints

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 Types of Special Paints…

Fire retardant paints-

have polyvinyl chloride
(PVC), chlorinated rubber
etc.
These components break
up at high temperature
producing non-inflammable
gases such as CO2, NH3,
HCl etc. and help to retard
probable firing by diluting
the concentration of
inflammable gases.
36
 Types of Special Paints ….
Temperature Indicating
Paints- Contain a special
additive that undergoes
color change at specific
temperatures.
Such additives usually are
the double salts or amine
salts of Cu,Fe etc. These
paints indicate the
temperature change of
the environment at the
range of 45 – 1450 oC
with 10 % error.
37
38
 Types of Special Paints…

Cement paint - Contains

white cement (70%) +
Calcium hydroxide + fine
sand + pigment + water
repellant compounds.
It is found in powder
form. It is mixed with a
suitable solvent and
makes slurry before use.
It is widely applied to
interior and exterior
coating of the brick –
walls. 39
 Types of Special Paints…

Cellulose paint: the

paint made by
dissolving nitro-
cellulose in thinner.
It dries up by
evaporation leaving
hard glossy and
durable film.
40
 Types of Special Paints…

Distempers: These paints

are water paints made by
mixing chalk powder,
glue, and pigment in
water.
Distempers are generally
used for finishing the
paintings on the surface
of the walls, plastered
surfaces of the walls etc.
41
 Types of Special Paints…
Luminescent paints- contain the
pigments which fluorescence
under the influence of ultra violet
light and these pigments are
called luminophor pigments
which include the compounds
such as zinc sulphide, cadmium
sulphide etc. which absorb UV
light and emit visible radiation
so that they add special
brightness to the paints.
Color modifiers called activators
such as Cu, Ag, Mn may also be
added. 42
43
 Types of Special Paints…
Water repellant paints-
Prepared by hydrolysis
and condensation of
orthoethoxy silanes and
organochloro silanes.
After the application of
this paint, it forms a
highly cross linked film
that is more water
repellant which makes
the paints to be more
durable.
44
 Types of Special Paints…
Aluminum paint: Prepared
by mixing fine aluminum
powder in spirit varnish or oil
varnish. It dries up by
evaporation of thinner
followed by oxidation and
polymerization of drying of oil.
It forms a bright and uniform
coating on the painted
surface.Aluminium paint is
mostly used to paint metal
surfaces since it is less
corrosive and bright in
appearance. 45
 Types of Special Paints…
Antifouling paints- Contain
antifouling agents such as
mercuric oxide , cuprous
oxide etc. Are used in ship
coatings which retard the
fouling of ships due to
marine worms, fungi etc.

Coal tar paint: This paint

is prepared by dissolving
coal tar in spirit or other
solvent. It is always applied
at hot condition and it is
found good for protecting
iron under the ground. 46
 Applications of Paints
• Widely used to coat the metallic surfaces in
order to protect it from the corrosive
environments.
• Modern synthetic paints are used to make the
furniture more attractive in appearance.
• Heat resistant paints are used as finishes of
ovens furnaces, aircraft combustion chambers
etc.
• Cement paints are widely used for finishing the
buildings as they protect as well as decorate
the buildings.
47
 Applications of Paints…
• Varnishes are used to give brightness to the
paints and make uniform protective coatings
over the surface.
• Antifouling paints are used in marine ships
which reduce foul smelling in ships due to
marine worms and fungus attack.
• Some paints have the special characteristic
that they can indicate the temperature change
in environment by change of color.

48
 Constituents of Paints
Paints consist of one or more pigments in a liquid
containing volatile oil, film forming material and
drying oil.
In order to produce desired characteristics into the
paints, specific types of additives are used. On the
basis of the effects produced by the additives into
paints, they are of following types.
Extenders or Fillers- the materials which serve to
fill the gaps in the film and hence to form uniform film
of the paints. Help in the arrangement of pigment
particles, increase the durability of the paints. The
commonly used extenders- BaSO4,CaSO4,CaCO3
49
 Constituents of Paints…
Driers- are the substances which accelerate the
drying of the paint film by oxidation ,
polymerization & condensation. The most effective
driers are resinates, tungstates of Zn,Co,etc.
Thinners- the substances added to reduce viscosity
of the paint to suitable consistency and help to the
drying of the paint.
Commonly used thinners- turpentine, benzene,
kerosene, mineral spirits etc.
Plasticizers-the substances which increase the
elasticity of the paint film. Commonly used
plasticizers- vegetable oils, triphenyl phosphates
50
 Constituents of Paints…
Stabilizers- are the substances which provide
chemical inertness to the emulsion of the paints.
Mostly used stabilizers-proteins like dextrin,caesin
etc., and starch.
Preservatives-the substances added to prevent the
decomposition of proteins and the growth of fungus.
Commonly used preservatives- mercuric chloride.
Antifoaming agents- the materials added to check
the formation of foams especially during the
manufacture and application of the paints.
Pine oil,kerosene etc.-Antifoaming agents.

51
 Constituents of Paints…
Antiskinning agents - the substances added to
prevent gelling and skinning of the paint film.
Most commonly used Antiskinning agents-
polyhydroxy phenols, oximes, quinones
Gelling -set or become more solid.
Skinning - a process in which paint or other form
of coating in a container forms a thin solid layer on
top of or in the liquid paint or coating.
Gelling is caused by using contaminated tools and
water solvents during mixing the paint, which
decreases the viscosity levels.
As the paint on the lid loses moisture, it will start to
dry, forming a film. This film of dry paint on the lid is
referred to as skinning. 52