Contents
Introduction
Classification
Properties Advantages/ disadvantages
Introduction
Silicon
Chemical element with the symbol Si
Atomic number 14
Silicon and oxygen have a strong chemical affinity. Occurs naturally only in stable form of Si-O
compounds such as calcium, magnesium and iron silicates. As well as silicon dioxide (silica) as sand and quartz.
The tetravalent structure is common to all compounds
Silicone
Not to be confused with metalloid element silicon. Silicone includes silicon together with carbon, hydrogen,
Chemistry
Chemically Silicone is :
Polydimethylsiloxane (PDMS)
The basic repeating unit is known as siloxane. Polymerized siloxane or polysiloxane with chemical formula [R2SiO]n, where R is an organic group eg. methyl .
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Rochow Process
2. Chlorosilanes from Silicon
Most commercially important reaction . Finely ground and well mixed Silicon is reacted with Methyl chloride in gaseous form in presence of copper catalyst & certain promoters to form Methylchlorosilanes.
300 Cent 2 CH3-Cl + Si ---------------> Me2SiCl2 Catalyst (Mueller-Rochow synthesis)
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Produces a silane mixture According to the number of chlorine atoms on the basic silane molecule, Mono-, di-, tri- or other silane units with Si-O bonds.
The predominant material obtained is dimethyldichlorosilane (approx. 80% by weight). All silicone fluids, emulsions and rubbers are based on dimethyldichlorosilane. This is therefore
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The reaction of the dimethyldichlorosilanes with water (hydrolosis) or methanol (methanolysis) produces siloxane.
Linear siloxanes with OH groups as well as Cyclic siloxanes with normally between three and six chain units are formed.
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Using HCl catalysis, thus formed siloxane directly leads to formation of further reacted oligomers or
polymer siloxanes.
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QUARTZ
CHLOROSILANES
SILOXANE
SILICON
DIMETHYL DICHLOROSILANES
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Polydimethylsiloxane (silicone)
Polydimethylsiloxane (PDMS) is the most commonly
available silicone.
By adjusting -Si-O- chain lengths, the functionality of
the side groups and the cross-linking between molecular chains, silicones can be synthesized into almost infinite variety of materials.
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Polydimethylsiloxane
Wherein n is an integer ,
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Grades of silicone
Fluids Emulsions Resins Elastomers Silicone elastomers, or rubbers, are made from linear polymers that bear hydroxyl, vinyl or other reactive side chains. They can be cross-linked in various ways to yield highly elastic, more or less open-pored structures.
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Most importantly,
Silicone Elastomers are used as Maxillofacial Prosthetic Material for Rehabilitation of patients with Oral or Facial defects.
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History
Auricular, nasal, and even ocular prosthesis fabricated
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mask for a French soldier. It was painted with oil paints & margins covered with facial hair.
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fabrication of a nasal prosthesis using enameled porcelain to match the complexion of a patient.
In 1880:- Kingsley described a combination of a nasal
palatal prosthesis in which the obturator portion was an integral part of the nasal prosthesis.
In 1900 to 1940:- In the nineteenth century, vulcanite
rubber was widely used in dental profession and was also adopted for use in facial prosthesis.
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for use in facial prosthesis in order to mimic the softness and flexibility.
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dental profession.
From 1960 to 1970:- The introduction of various kinds
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1960 to 1970
Barnhart was the first to use silicone rubber for
construction and coloring of facial prosthesis by combining silicon rubber base material with acrylic resin polymer.
Tashma used dry earth pigments dispersed in colorless
acrylic resin polymer powder for intrinsic coloring of a silicon facial prosthesis. Thus , silicon elastomers came into practice.
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Silicone elastomers
Probably the most widely used material for facial
Thus, Silicone elastomers are crosslinked linear silicone (fluids or gums )with a three-dimensional structure.
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Cross-linking of Silicones
There are three different types of cross-linking reactions: Peroxide (-initiated) curing --where polymer contains vinyl groups.
Addition curing --where polymer contains vinyl groups
and crosslinking agent contains Si-H groups catalyst- platinum , palladium , rhodium etc
Condensation curing between
Classification
Silicones are classified into 4 groups according to their applications:
Class I: - Implant grade, which requires the material to
undergo extensive testing and must meet FDA requirements. Class II: - Medical grade, which is approved for external use. This material is used for fabrication of maxillofacial prosthesis. Class III: - Clean grade Class IV: - Industrial grade commonly used for industrial applications.
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Composition
Inorganic
silicon , carbon, oxygen ,hydrogen
Organic
methyl / phenyl / vinyl group
Fillers
1. Reinforcing fillers :
- Pyrogenic -
(fumed) silicas Modifies properties( Modulus, Tensile strength or Elongation at break ) Reinforcing fillers:
2. Non
-Needed
Surfactants / Antioxidants
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Ideal Physical and Mechanical Properties: - High edge strength. - High elongation. - High tear strength. - High tensile strength - Softness, compatible to tissue. - Translucent. - Low coefficient of friction - Low glass transition temperature - Low specific gravity
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Ideal Biological Properties: - Non-allergenic. - Cleansable with disinfectants. - Color stability. - Dimensionally stable - Inert to solvents and skin adhesives. - Resistance to growth of microorganisms. -Resistance to environmental discoloration
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facial prostheses primarily because of their chemical inertness, strength, durability, ease of manipulation, and biocompatibility
Still far from ideal
attached to the polysiloxane backbone leads to products with outstanding chemical and physical properties.
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Properties of Silicones
Thermally stable :
The thermal stability of silicones stems from the Si-O and
Si-CH3 bonds which are themselves thermally stable.
(standard grades of silicone elastomers can handle temperatures ranging from -40 to 200C/-40 - to 392F)
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Electric insulation
macromolecules are non-polar and do not allow electric current to pass through them. Silicones are therefore non-conductive and are excellent electrical insulators.
Tensile strength
Measurement of resistance resulting from stretching
till it breaks. Measured as pounds per square inch(psi). Depends on amount & type of filler used. High elongation is desirable when peeling prosthesis from tissue surface
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between these two components affect the overall silicone strength and bonding .
(Muhanad M. Hatamleh, David C. Watts . Mechanical properties and bonding of maxillofacial silicone elastomers. Dent Mater 2 6 ( 2 0 1 0 ) 185191.)
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Tear strength :
Measurement of material by pulling until it tears.
Measured as (psi) Silicone elastomers posses high tear resistance due to cross-linking of material. This property helps to overcome adhesive resistance & allows the fabrication of thin margins.
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Viscosity
Measured as internal resistance of material to flow. Measured in centipois(cps) or millipascals(mPas). Lower the viscosity, higher the flow. Can be increased with both cross linker & fillers.
Adhesion
Posses excellent adhesion properties Silicon based adhesives & sealants can withstand
Hardness:
Measure of flexibility Measurement of hardness is done by instrument
Durometer. Shore A Scale most common (0-100) Higher the value , harder is the rubber. Similar hardness to missing facial tissue desired (shore A 5-20).
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Surface tension PDMS have a low surface tension (20.4 mN/m) & are
PDMS )
Excellent weatherability
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Biocompatible
The material has minimal adverse impact on host Hydrophobicity, its chemical & high molecular weight
Biodurable
The Host has minimal side effects on the material Related to exceptional thermal & chemical stability
properties.
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Silicone elastomers
According to the type of vulcanisation (crosslinking
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(HTV)
Usually white ,opaque material Basically made from reactive silicone gums, or straight
component system
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Advantages
Pigments are milled into these material so intrinsic
color can be achieved. Better color stability than RTV. It exhibits better mechanical strength and can be used at temperatures ranging from -50C to +300C. hence thermally stable It is chemically & biologically inert Better Ageing Resistance & photo-oxidative stability
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Disadvantages
Requirement of a milling machine & a press Metal mold is normally used & fabrication of mold is
a lengthy procedure (stone mold increases risk of damage to the material during de-flasking)
tissue. Low edge strength (nylon can be reinforced) Has opaque & lifeless appearance . Do not readily accept extrinsic coloration
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Advantages:
Can be polymerised by artificial stone molds but more
durable molds can be made from epoxy resins or metals Original RTV silicone are biologically inert & retain their physical & chemical properties at wide temperature ranges. Excellent resistance to weathering
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Disadvantages:
Not as strong as HTV & generally monochromatic
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1. loss of adhesion of extrinsic coloration to prosthesis 2. primers & adhesives 3. Poor patient handling 4. Staining 5. Medical adhesives & cleansers
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in maxillofacial prostheses may result from staining rather than aging of the polymers or pigments.
(RG.C.raig, k Koraann d R. Yu. Elastomers for maxillofacial applications, Review. Biomaterials 1980, Vol 1)
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1. Tear at margins ( tear strength , fatigue) 2. Change in surface texture 3. Elongation at margins 4. Compatibility with medical adhesives 5. Weakening of margins by colorants, adhesives, solvents, cleansers(colorants do not adhere chemically) 6. Deterioration of static & dynamic mechanical properties.
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used in fabrication, The service life time of a facial prosthesis is usually from 6 months to 2 years
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Conclusion
Polydimethylsiloxane, commonly known as Silicone
are used in many applications including Maxillofacial prosthesis. The ultimate challenge of a maxillofacial prosthetic material lies in 1. Improving physical & mechanical properties so that it will behave more like human tissue & increase service life of prosthesis 2. Finding color stable coloring agents & developing sceintific method of color matching to human skin.
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References
1. John Beumer III, Maxillofacial rehabilitation: prosthodontics and
Prosthetic Materials - Past and Present Trends. JIADS VOL -1 Issue 2 April - June,2010 |25|
5. Muhanad M. Hatamleh, David C. Watts . Mechanical properties and bonding of maxillofacial silicone elastomers. Dent Mater 2 6 ( 2 0 1 0 ) 185191.
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THANK YOU
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