Presented by Dr Rinu Sharma 1st year PG resident Dept of Prosthodontics & Maxillofacial Prosthetics

Contents
Introduction

Chemistry & manufacturing process

History of Maxillofacial prosthetic material Silicone elastomers

Classification
Properties Advantages/ disadvantages

Common problems associated

Conclusion
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Introduction
Silicon
Chemical element with the symbol Si
Atomic number 14

Rarely occurs as pure free element but in its combined form

accounts for about 25% of earths crust

Elemental silicon is dark grey in color with metallic shine
It is hard & brittle octahedric material.
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 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

in which silicon is surrounded by oxygen atoms.

Silicone
Not to be confused with metalloid element silicon. Silicone includes silicon together with carbon, hydrogen,

oxygen & sometimes other chemical elements.

Silicon to oxygen bond forms the

backbone & in addition bonded to organic group typically methyl.

Thus , silicones are combination of

organic & inorganic compounds

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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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Manufacturing Process ( Silicon to Silicone)

1. Silicon from Quartz :
Thermal reduction of quartz(SiO2) with carbon.

SiO2 + C ------------> Si + CO2

Thus obtained silicon is a solid metal and needs to be

crushed into powder for further reaction.

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

the decisive base product.

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3. Silicone from Chlorosilanes

Hydrolysis

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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 Organochlorosilanes react violently with water releasing hydrochloric acid.

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

POLYDIMETH YL -SILOXANE (PDMS)

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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 ,

Higher n = more elastic Lower n = more plastic

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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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 Apart from wide range of Uses in Prosthodontics,

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

with various materials, have been found in Egyptian Mummies.

According to Beder, the first obturator was described

in 1541 by Ambrose pare. It consisted of a simple disc attached to sponge.

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 Tycho Brache (1546-1601), who used an artificial nose

made from gold to replace his own nose.

1600 to 1800:- Pierre Fauchard (1678) fabricated a silver

mask for a French soldier. It was painted with oil paints & margins covered with facial hair.

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 1800 to 1990:- William Morton was credited with

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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 Upham described the fabrication of nasal and

auricular prosthesis made from vulcanite.

In 1905, Ottofy, Baird and Baker all reported using

black vulcanized rubber.

In 1913 Gelatin-glycerin compounds were introduced

for use in facial prosthesis in order to mimic the softness and flexibility.
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 Kazanjian described the use of celluloid prints for

coloring vulcanized rubber facial prosthesis.

From 1940 to 1960:- Acrylic resin was introduced in the

dental profession.
From 1960 to 1970:- The introduction of various kinds

of elastomers resulted in major changes

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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

prosthesis now a days.

Introduced in mid 19th century, but has been used in the

fabrication of maxillo-facial prosthesis only for the past few years. 24

 Silicone elastomer = Silicone polymer + Filler

+ Crosslinker (vulcanizing agent)

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

dihydroxypolydimethylsiloxanes and silicic acid esters Catalyst Tin.

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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

for bulking up silicone rubbers eg. Quartz, diatoms or metal oxide

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 Crosslinking / Vulcanizing agent

Additives / Colorants: organic or inorganic pigments.
eg. Oxidative degradation can be retarded by iron oxides

Catalysts : platinum, tin and titanium complexes etc.

Surfactants / Antioxidants

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Ideal properties of MFP material

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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Why a MFP material ?

Silicone elastomers have been widely used to fabricate

facial prostheses primarily because of their chemical inertness, strength, durability, ease of manipulation, and biocompatibility
Still far from ideal

The chemical combination of the organic groups

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

Methyl groups regularly spaced throughout silicone

macromolecules are non-polar and do not allow electric current to pass through them. Silicones are therefore non-conductive and are excellent electrical insulators.

They are chemically inert after processing.

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 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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 The polymer chains, silica fillers, and the interactions

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

highly acidic / basic chemicals, water and organic solvents.

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 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

capable of wetting most of the surfaces.

Methyl group points outward making it hydrophobic with

good release properties.

Glass Transition Temperature is low i.e. (146 K for

PDMS )
Excellent weatherability
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 Biocompatible
The material has minimal adverse impact on host Hydrophobicity, its chemical & high molecular weight

polymeric nature provides the theoretical basis for lack of toxicity.

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

agents, temperature) and base-polymer viscosity employed , it can be classified as

1.

High Temperature Vulcanizing silicones (HTV)

2. Room Temperature Vulcanizing silicones (RTV)

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(HTV)
Usually white ,opaque material Basically made from reactive silicone gums, or straight

chains with high molecular weight.

Available in semisolid or putty like consistency in 1 or 2

component system

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 Catalyst/vulcanizing agent : dichlorobenzoyl peroxide

or platinum salt depending on type of polymerisation used

Copolymerisation with methyl vinyl or methyl phenyl

siloxy radical varies the relative softness & tear strength

HTV requires milling, packing under pressure & a 30

min heat application cycle at 180 degrees.

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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)

It lacks sufficient elasticity to function in movable

tissue. Low edge strength (nylon can be reinforced) Has opaque & lifeless appearance . Do not readily accept extrinsic coloration

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Room Temperature Vulcanizing (RTV)

Available as single paste system or clear solution Filler : Stannous octoate Cross linking agent: Orthoalkyl silicate Polymerisation by condensation or addition reaction They are used more often than any other maxillofacial

material due to good physical properties & favorable processing characteristics.

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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

Poor edge strength & difficult to color

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Common problems of Maxillo-facial Prosthetic material

Discoloration over time

1. Intrinsic color change of elastomers 2. Intrinsic color change of colorants(pigment flocking)

Discoloration due to loss of external coloration

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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 The degree of the color change observed clinically

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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 Degradation of physical & mechanical properties

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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 Regardless of type of maxillofacial prosthetic material

used in fabrication, The service life time of a facial prosthesis is usually from 6 months to 2 years

The average wearing time of a facial prosthesis is 10 months.

( Chen M, Udagama A, Drane JB : Evaluation of facial prostheses for head
& neck cancer patients. J Prosthet Dent .46: 538 ; 1981 )

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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

surgical considerations. Ishiyaku Euro-American. Inc. Pulblishers.

2. Restorative Dental Materials, Robert G. Craig 11th edition 3. Silicon Biomaterials : History & chemistry , Reprinted from

Biomaterials Science 2nd edition

4. Udita S Maller , Karthik K S , Sudhakara V Maller . Maxillofacial

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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