Silicones

Introduction
Definition
• Silicone resins are made up of a chain of alternating
silicon and oxygen atoms like oils, but in the form of a
3-D network. It can be liquid, powder or be dissolved
into an aromatic solvent.
• Silicones are a family of materials that include siloxanes
& silanes.
• Silicones derive ultimately from silicon, as contained in
sand & other minerals. It is the second most common
element in the Earth’s crust.
• Silicones are sophisticated products that are extremely
versatile & can be manufactured in more than 2,000
different forms, within the general categories of silanes,
fluids, elastomers & resins.
• Silicones have important chemical & physical qualities
derived from their molecular structure.
• Depending on requirement these include longevity,
thermo stability, chemical, electrical & ultraviolet
resistance, enduring elasticity, tensile strength
,inertness & microbial resistance.
• They can be formulated either to resist or absorb water.
They are much valued for their purity, especially for
advanced electrical devices & for their cleanliness.
• Silicones are durable, reliable & often employed to
enhance or to confer specific performance properties.
• They promote sustainable development by making
other materials last longer-reducing society’s
consumption of basic raw materials to ensure their
availability for future generations.
•Silicones or polysiloxanes are a class of
synthetic compounds, the molecules of which
consist of polymer chains of alternately
connected silicon and oxygen atoms.
•Silicone resins are a type of silicone material
which is formed by branched,
cage-like oligosiloxanes with the general
formula of RnSiXmOy,
•where R is a non reactive substituent,
usually Methyl (Me) or Phenyl (Ph), and X is a
functional group Hydrogen (H), Hydroxyl
group (OH), Chlorine (Cl) or Alkoxy group (OR).
•These materials consist of an inorganic
silicon-oxygen backbone (...-Si-O-Si-O-Si-O-...)
with organic side groups attached to the silicon
atoms, which are four-coordinate.
• These groups are further condensed in many
applications, to give highly crosslinked,
insoluble polysiloxane networks.
• Silicone (Q) resins are man-made elastomers that
combine high-heat resistance with good cold
performance to produce a material that has many
advantages over natural rubber.
• Silicone resins are relatively low molecular weight
polymers with a three-dimensional branched-chain
structure.
• These organopolysiloxanes are very stable due to the
strength of the Si-O bond. Silicone resins can be
combined with many organic polymers, and this makes
it possible to tailor a large number of properties to the
intended application, e.g. curing behavior, flexibility,
adhesion, and resistance to weathering.
• With excellent thermal stability their many properties
make them suited for use as binders in paints, varnishes
and impregnating products.
 Manufacturing
•Silicon does not exist on its own in nature. Most of it is bound with oxygen in
materials like sand and quartzite and granite rock.
•The silicon-oxygen bond in quartz is so stable it can only be broken by white heat!
•Silicon producers reduce high-grade quartz sand to elemental silicon via a
carbo-thermic smelting process:
SiO₂ + 2C Si + 2CO
•Sand(silica ) carbon Silicon carbon monoxide
•This reaction occurs in an electric furnace at <1,400°C (<2,600°F).
•The carbon monoxide gas (g) leaves the furnace so the silicon cannot react with the
carbon to form silicon dioxide.
•The molten elemental silicon, which is about 99 percent pure, is then cooled and
broken into lumps.
•When used in silicone production, the silicon is ground into a fine powder to
increase the surface area available for reactions
• The diagram below shows the way the value chain works. This is a
highly simplified representation of a system which, in real life, is
sophisticated, complex & covers many more products than the
examples shown.
• Silicones’ chemical structure allows them to be produced in a
number of variations.
• By using siloxane units with different valences, products can
be made with oily, polymeric, resinous or cross linked
properties.
• At the same time, the organic groups bound to the silicon
pave the way for a diverse range of modifications.
• It is this variability that makes possible the impressive variety
of silicone products: greases, release agents, antifoam
agents, paint additives, paper coatings, hydrophobizing
agents, high or room-temperature vulcanizing silicone
rubbers, and many, many more.
 Chemical Structure
• Resins have very varied structures depending on the quantity of
tri-functional T groups or sometimes quadri-functional Q groups
that are introduced into the polymer during manufacture.
• Also, on the type of non-reactive and reactive groups that are
bonded to the silicon atoms.
• Two of the most common types of non-reactive groups found in
the siloxane chain also have a great influence on the resin's
characteristics:
• methyl groups impart water repellency, release properties and
surface hardness, whilst phenyl groups impart resistance to
temperature and weathering, especially by UV-radiation, flexibility
at high temperatures and compatibility with organic products.
• Two types of resins can be distinguished: methyl resins and
methyl phenyl resins.
• Three types of reactive groups allow the resin to crosslink.
• Hydroxy groups are the most common type. They enable crosslinking to occur
by a condensation reaction at room temperature either in the presence of a
catalyst or in alkaline systems. The use of a catalyst and higher temperatures,
especially in the case of methyl phenyl resins, generally accelerates the cure
rate.
• Alkoxy groups hydrolyse to give hydroxy groups at room temperature and in
the presence of humidity. Curing then occurs as above. These resins are more
stable when stored.
• Vinyl groups react at moderate temperature by an addition reaction in the
presence of platinum, as in RTV’s (Room Temperature Vulcanisation), or
sometimes at high temperature in the presence of peroxides as in HCR’s
(Heat-Cure Rubber).
• Resins are generally available diluted in an aliphatic or aromatic solvents,
emulsified into water, or diluted in silicone polymers to reduce their viscosity.
 Typical Properties
• Silicone is usually tetravalent but can assume hexavalent characteristics
• Silicon is more electropositive than carbon and hence silicon-carbon
bonds are polar
• Moulded silicones are characterized by the following points :
o Good dimensional stability at high temperature
o Good electrical and dielectric properties over wide frequent &
temperature ranges
o Low water absorption
o Good flow properties
o Long curing time in comparison with other moulding compounds
o Limited shelf life
o Average level of mechanical properties
o High cost
• Resistance to Chemicals : Dilute mineral acid & alkaline solutions,
sea water, methanol, glycol & formic acid but not resistant to
aromatic hydrocarbons, numerous solvents & concentrated acids
& alkalis
• Weathering resistance : The weathering resistance of silicone
resin mouldings is same as other thermo set compounds such as
epoxy, phenol formaldehyde & unsaturated polyesterstyrene
mouldings
• Flammability : Silicone exhibits a higher temperature than other
plastics. It burns so long as an ignition source is present,
developing a characteristic silica smoke.
• Toxicological Assessment: Silicone resins not usually used for
utensils which come in contacts with food, although the silicones
are basically physiological inert.
Processing
• Compounded rubbers are suitable for normal processing
techniques employed in rubber technology e.g
Extrusion, calendaring and compression moulding.
 Applications
• Silicone fluids are ideal for use as hydraulic or transformer
oils, damping liquids, diffusion pump fluids, thermally
resistant lubricants, dielectrics, defoamers and release
agents for photocopiers and laser printers.
• Used for hydrophobic treatment of glass and mineral wool.
• Special silicone fluids can be processed into impregnating
agents for textiles and leathers.
• They are also used in very small amounts as paint additives.
Other important applications are to be found in cosmetics,
pharmaceuticals and medicine.
• Silicone resins as pure products, solvent-based and
solvent-free systems, emulsions, but also powders.
• With their excellent thermal resistance, silicone resins are
first class binders for all heat-resistant coatings.
• Silicone resins with reactive groups are principally used for
modifying alkyd, epoxy and acrylic coatings. Such modified
coatings offer excellent weathering resistance and elasticity
(e.g. for coil coating).
• In the plastics industry, silicone resins are also used as
heat-resistant moulding compounds and release coatings.
• Silicone resins’ excellent heat resistance and
outstanding range of properties are also very much in
demand for electrical applications, such as binders for
fiberglass laminates and cements for incandescent lamp
base.
• In addition, they are useful as water repellents in
masonry protection or as binders in silicone resin facade
paints.
Silicones and construction
• Silicones bond with most materials, from concrete, glass, granite
and marble to aluminum, steel and plastics.
• They are extremely durable and can resist decay caused to other
materials by rough weather conditions, moisture or sunlight.
• Silicone sealants can prevent humidity and hot or cold air from
coming through joints and cracks, thereby making buildings more
energy efficient. Their flexibility can also reduce damage from
small to medium-scale earthquakes.
• These unique properties silicones are essential not only in
residential and office buildings, but also in bridges, oil rigs,
industrial plants and pipelines.
Silicones and transport
• Silicones are used in almost all aspects of car assembly, from the
tires to the engine, windows and sun-roof.
• They insulate electronic parts, reduce tire rolling resistance, bond
lightweight materials together, and seal windows and doors.
• The same can be said about silicones’ uses in airplanes, trains, and
even space vessels.
• Silicone-based paints and coatings are safer alternatives to
traditional marine coatings and paints.
• By applying these silicone products to hulls of ships and boats, the
build-up of dirt and film is dramatically reduced, thereby
improving fuel efficiency enormously.
• For large cargo ships, this improvement is particularly
important because ships’ fuel consumption is quite
significant. This fact makes the benefit of silicones in this
application all the more impressive – fuel savings
outweigh CO2 emissions from production of the silicone
product 182 times!
Silicones and healthcare
• Silicones are well tolerated by the human skin and body.
• They can facilitate healing, improve the appearance of
existing scars, and reduce discomfort. This makes silicones
an integral part of innovative medical treatments and care.
• Medical applications and infant care products with silicone
can satisfy the highest quality standards demanded by health
care professionals and their patients.
• Resistant to bacteria, silicones are easy to sterilize and are
excellent for sensitive applications, such as respiratory
tubing and topical medications.
• Silicones do not react with other materials and do not
irritate the body.
• They are also hypoallergenic so can be used safely for
skin contact use as well as intravenously.
• Of course silicones used in medical applications are
subject to thorough testing and regulations to ensure
their safety