Dental Polymers

Three Basic Classes Of Materials In

Dentistry:
Metals Polymers Ceramics

Metals
At the atomic level , the atoms are bonded together by metallic bond. -metallic luster. -excellent electrical and thermal conductivity. -ability to be shaped (malleability). -strength, hardness, and high density. -Opaque

Metals
What is alloy?
Mixture of 2 or more metals

What is metal??

Metals versus alloys in dentistry.

 Types of metals in dentistry:

Noble (gold, pt, Pd, .. Semi-noble ( old term).gold is replaced with silver

Non-noble.

Metals
Preformed metals:
Cohesive gold Amalgam

Wrought wires

Metals
Casting metals

The restoration is fabricated outside the mouth utilizing the lost wax technique.

POLYMERS
They are widely used in dentistry.

Polymers versus plastics??? Plastic is any material cabable to be shaped . Ductile metals considered as plastic

 Polymers:

this term means many parts

Polymerisation: process by which the monomer is converted into polymer.

Polymers
They are bonded by covalent bonding along the backbone, and ionic bonding . Polymers are prepared in form of dough then shaped into desired shapes. They harden by: -physical reaction,(cooling, or evaporation). Waxes, -chemical reaction,

 Types
Impression materials

Cavity Filling Materials

Cements Equipments

Sealants
Temporary Crown & Bridge Restorative Material.

Denture bases

Ceramics
They are made of metallic oxides.
Porcelain. Produced by sintering Glass, produced by melting and fusion of the

oxides.

ceramics
They are bonded by ionic bonds.

No free electron to conduct heat or electricity.

Poor thermal conductor Stable ,biocompatible Transparent Translucency, due to air bubbles Three dimensional crystal structure.

Brittle

Denture Base Resins

Prosthetic Uses

Denture bases Denture teeth Relining Materials Repair of dentures Provisional acrylic partial dentures Custom impression trays Mouth guards

Fluoride and bleaching trays Facing on esthetical crowns Provisional restorations Removable tooth movement devices Orthodontic retainers

Denture

base function

Distributes pressure over a wider area

So reducing bone resorption

Retains artificial teeth
Replaces missing tissue

Forms a seal for retention

Denture Base materials

Carved ivory Carved Wood Vulcanite; dark, opaque (Vulcanised rubber) Highly cross-linked Acrylic resin Other Resin and plastic alternatives

Plastic acrylic teeth

Bind chemically to the denture
Can be adjusted Not cause wear of opposing tooth

Good colour match

Minor resiliency Wear under high force occlusion May stain with time

Other Teeth Materials

Porcelain (high fusing ceramic) composite; X-linked acrylic) Experimental fiber-reinforced teeth

Maxillofacial prosthesis
Needed
After trauma
Surgical defects Birth defects

Other materials
Silicone rubber

Vinyls with plasticizers

Acrylic repair
Materials
Chemically cured acrylic Light cured acrylic

Relining Materials

Provisional partial dentures

Impression trays

Record
Materials

bases

Cold-curing acrylic resin Other material

Shellac Vacuum formed vinyl or polystyrene Baseplate wax.

 Occlusal Splint Night guards Bleaching and fluoride application trays

Mouth guards

Orthodontic applications

Removable tooth movement devices Orthodontic retainers

Facing of crowns Provisional restorations

Other materials:
Polycarbonate Aluminum

Stainless steel
celluloid

Requisites of Dental Resins

Can be processed easily using simple techniques Aesthetics Economical

Charactristics

Biological compatibility Physical properties Ease of manipulation Low cost Chemical stabilty in mouth aesthetics
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POLYMER PRINCIPLES

Terminology

Monomer + monomer = polymer

Monomer1 + monomer2 = copolymer

Oligomonomer= 2-4 monomers

Poly

= many Mono = single Mer = unit Oligo =several

Morphology of spatial

arrangements
Linear or chain polymerisation
Easily manipulated, stretched, bent, thermoplastic, Hard e.g. fitting surface of acrylic teeth- better binding to

denture base

Branched polymerisation
Easily manipulated, stretched, bent, thermoplastic, More

hard

Morphology of spatial arrangements

Cross-linked polymerisation
Strong, stiff, thermoset, wear resistant E.g. Denture base materials, Occlusal

surfaces of actylic teeth

Coiled chains
Flexible e.g. impression materials

Morphology of spatial arrangements

Crystalline polymers
Very regular arrangement in space: strong, stiff, absorb less water.

Amorphous or glassy polymers

Irregular arrangement Behaves as a brittle solid

Plasticizers effects
Added to stiff, glassy uncross-linked polymers Lowers glass transition temperature (Tg) Become
rubber-like,

Flexible
less brittle Eg. pipe

Dimensional and thermal changes

Expansion on polymerization, exothermic Contraction on polymerization
21vol.% If unfilled acrylic resin 6% denture resin 1-3% composites

Expansion on swelling in water Expansion or warpage on thermal change and

reheating

Types and molecular weight

Addition polymerisation:
No by products

Polymer mol. wt = mol. wt monomers

Step Growth or Condensation polymerisation:

By products are produced and lost in the final

product Polymer mol. wt mol. wt monomers

Stages in Addition Polymerization

4 distinct stages
Induction Activation and initiation Propagation Chain Transfer Termination

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Polymethyl methacrylate (PMMA)

MMA Liquid Heat and pressure

PMMA Powder Particle swells PMMA Powder

(entanglements)

MMA Liquid Acrylic dough (Cohesive gel)

Old and new polymer chains Intertwined at the molecular level.

Activation

Initiation Chain Propagation

Termination

Induction
To begin : a source of free radicals R
R generated by activation of radical producing

molecules using a second chemical ,heat or UV light

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Propagation
The resulting free radical monomer complex then

acts as anew free radical center when it approaches another monomer to form a di-mer which also becomes a free radical This reaction continues. The growth of polymer chain ceases when the reactive center is destroyed by number of termination reactions

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Chain Transfer
The active free radical of a growing chain is

transferred to another molecule and a new free radical for further growth is created.

Termination
Most often terminated by direct coupling of two free radical chain ends or by exchange of hydrogen atom from one growing chain to another
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ACRYLIC RESIN TYPES

Ideal properties

Natural appearance Easy processing Easy to clean Easy to repair Inexpensive Biocompatible Resistant to bacterial contamination High strength, stiffness, hardness, toughness, fatigue resistance

Low density Radiopaque High thermal conductivity High modulus of elasticity, impact strength Abrasive resistance Dimensionally stable Accurate reproduction of surface detail

Curing methods
Chemically cured
Tertiary amine ( dimethyl-p-toludine or sulfinic acid)

(accelerator) Benzoyl peroxide (initiator) Hydroquinone (inhibitor)

Heat cured
Heat and pressure control
Avoids porosity Maximizes conversion of monomer to polymer

Light cured
Photo-initiators (camphorquinone), Blue light,

Used for: record bases, custom tray, denture repair

Heat cured acrylic resin

Powder ( can have limitless life)

Beads or granules of polymethyl methacrylate Initiator (benzoyl peroxide) Pigments/dyes (colour vitality as cadmium, iron, organic dyes) Optical opacifiers (tio2/ Zno) Plasticizers (ethyl acrylate (internal), dibutylphthalate (external) to make dough easier) Bead Polymer Synthetic fibres (nylon) Coloured fibres (blood vessels)

Liquid ( in dark bottle, avoid

contamination by powder) Methyl methacrylate monomer Inhibitor (hydroquinone) Crosslinking agent
(diethylene glycol dimethacrylate, (1,4 butylene glycol dimethacrylate)

Chemical cured resin

Cure is initiated by a tertiarv amine (e.g. Dimethyl-ptoluidine or sulfinic acid) Absence of heat:

Lower molecular weight material Lower strength properties Higher residual monomer in the resin Color stability is not as good- yellowing Less contraction on cooling to room temp

Polymer beads are smaller

Faster dissolution in the monomer to produce a dough Doughy stage is reached before the addition curing reaction mix viscosity is high and prevents the adaptation of the mix to the mould walls

or cast -keep readapting

Lowering of the glass transition temperature

Less build-up of internal strain Highly susceptible to creep- distortion when in use.

Light activated materials

Components:
Urethane dimethacrylate { matrix} Acrylic copolymer Silica (filler) to control rheology

Forms
Sheets Ropes

Curing
Light chamber- 400-500 nm Photo-initiators (camphorquinone), Teeth added in a second exposure over the base

 Used for
Record bases Custom tray Denture repair

Hardness and impact strength heat

cured resin Elastic modulus < heat cured resin; deform under mastication Less shrinkage (3%) better fit Less residual monomer

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Auto-polymerizing/cold cure acrylic

Reducing agent (tertiary aromatic amine or barbituric acid

derivative, NN-dimethyl-p-toluidine) reacts with peroxide at room temp. Excellent detail reproduction To be able to pour in mold, balanced size mol. wt, plasticizers and x-link agents Reversible hydrocolloid (agar) mold cant resist teeth movement during pouring Hydro pressure flask reduces air bubbles and monomer porosities Difficult to dewax, less monomer binding to teeth Shortcomings: residual monomer Cross link densities Creep Variety of products

High-impact acrylic
A rubber phase is added (phase inversion)
Uniformly distributed Rubber cored polymer

Types
Butadiene + styrene = polystyrene butadiene rubber Butadiene + MMA PMMA + polystyrene butadiene rubber + poly(2,3-dibromopropyl

methacrylate) for opacity

PMMA = lucitone 199 Lightly xlinked or no cross linking agent is added Rubber has a craze inhibitory effect

Experimental types of acrylic

Added Bis-GMA and fiber
Flexural strength ceramics

Can be used as lingual bars and connectors

Experimental (mwt polyethylene fiber-reinforced)

Neutral color

Low density
Biocompatibility Surface treated to enhance fabrication Time consuming

Types of acrylic
Other (polystyrene,epoxy, SS)

PMMA Adhesion to
Metal- use adhesive primers untreated porcelain teeth with organo silane

compounds

HEAT CURED RESIN

Setting reaction
Mixing of powder and liquid cause monomer diffusion and softening of the surface of the powder producing the following gelling stages: Ratio P/L (2/1 wt %, 1.6 -1 vol %)
Sandy - initial melting of beads

(not used)

Stringy or sticky - entanglements with swollen beads and thickened interstitial monomer (not used)
Dough - gelation

(used)

Rubbery - monomer penetrates to the core of beads, plasticizing them, Tg (not used)

Manipulation issues
P/L
Inadequate filling by monomer

Weak material properties

Porosity

P/L
Excessive polymerisation shrinkage Poor fit

Light color as powder holds the pigments

Manipulation issues
Curing before monomer diffuse to bead (before dough stage)
flexural strength cracks between linear polymerised interstitial gel and cross linked beads More shrinkage contraction by the loss of pressure produced by the dough to

compensate for it

Curing in dough stage

monomer penetrate the beads dissolves beads allows cross-linking agent to penetrate interpenetrating polymer network IPN.

Packing in the rubber stage

Less extrusion of excess acrylic from flask Extra pressure in the mould Fracture the cast less flow around teeth Dislodgment of teeth into mould

Manipulation issues
Control of color
Pigments position Inside beads surface of beads
polymer should be added to the monomer slowly so it will not washed off by too rapidly

Blood vessel resembling Fibers aggregate in the

bottom of bottle
Shake powder well before use

Mould Lining
resin may penetrate rough plaster and adhere a separating medium must be employed solution of sodium alginate tin foil.

Manipulation issues
Control of Processing strains
Shrinkage in restricted mould cause internal strain On release of stress (flask opening) it may give Crazing Warpage Distortion These are reduced by the slightly extra packed material that flow

into shrinkage spaces when temperature is higher than Tg (heated flask) Manipulation further reduces strains by
Using acrylic teeth Cooling the flask slowly

Flasking steps

Flasking Dewaxing Putting a separating medium Placing acrylic dough Packing Heat curing

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Flasking for heat cured resin

Flasking options with acrylic dough:

Trial-packing, trimming, repacking Packing-only Poured resin (e.G., Lucitone fas-por) Injection moulding

Heat and pressure control

Aim to produce radicals and initiate polymerization Reaction is thermally activated and generates heat as well Reaction conversion is about 98 to 99.5% MMA: tbp = 100c (p= 1 atm); 140c (p= 2 atm)

Heat curing cycles

Fast cycle
Cure at 71-72C for 30-90 min 100C for 30 min.

Slow cycle = cure at 71-72c for 10 hrs

[A slow cycle is better with larger amounts of

material.] [Generally, slow cures result in better dimensional accuracy.]

Other cycles are done as recommended

by manufacturers

Heat curing cycles

Rapid heating:
Excess radical release Extra xlinking and branching of interstitial

polymer More residual monomer Reduced toughness Heat builds up from exothermic rxn Porosity

Loss of strength Bad esthetics (opaque and cloudy color) Possible fouling

Heat curing cycles

Slow :
Sufficient radical release Adequate x-linking and branching between high

mol.wt polymer chains Increased toughness Sufficient radical ends increase monomer incorporation in growing chains X-linking agents polymerized, reducing their plasticizing effect (in their non bound state) and reduce creep Produce an annealing effect easing stresses produced from shrinkage, reducing crazing and distortion

Heat curing cycles

Pressure control
Places compressive force Compensates for polymerization shrinkage

Increase flow of dough around teeth, more monomer

wetting and surface dissolution, stronger bond Oozes out excess dough Some hybrid systems begin polymerization from one side to allow dough to cover for shrinkage

Heat curing cycles

Microwave curing
Uses a microwave Flasks are non metalic

Reduced time

DENTURE SHORTCOMINGS

Denture Radiolucency
Problems when accidents displace fractured segments
Lungs

Skull
stomach

Salts and fillers reduce esthetics, strength

Organo-metalics are toxic

Bromine containing organics lack heat stability, must be added in

quantities that plasticize the denture, causing creep and water sorption Phase separating bromo-polymer in beads reduce the previous effects

Mechanical properties
Failure to Moderate strengths:

impact resistant denture is low Low elastic and flexural modulus lack of fracture toughness 30% of denture repairs involve midline fractures which are most prevalent among upper dentures. dropped denture does not necessarily break instantly a crack continue to grow and failure due to flexural fatigue.

Failure due to poor quality processing

Lack of bonding between the resin and the acrylic teeth and

weak interface Crazes due to processing faults or exposure to solvents is another possibility.

Creep

Reduced by cross linking Heat cured < cold cured

Internal denture porosity

Inherent porosity: Not seen by vision 1-2% of residual monomer Leaks Replaced by fluids

Minimized by Use heat cured resin Pack denture under correct pressure Use correct P/L Use the glaze after polishing

Internal denture porosity

Irregular porosity: Seen by vision Not regular on denture surface P/L heterogeneity Air incorporation (spherical pores) Minimized by Use correct P/L Add liquid first Mix well Cover the mix before dough stage Can use the vibrator

External denture porosity

Irregular surface deficiencies: Seen by vision Insufficient pressure Dough was not molded correctly by hand leaving surface blisters and pores Insufficient dough
Minimized by Mold dough by hand into small areas Place sufficient material in flask Pack under correct pressure

External denture porosity

Minimized to by Irregular porosity: Pack under pressure Shrinkage by polymerisation (5-8% vol or 0.2 -0.5% linear) Slight extra denture material can overcome Further shrinkage by cooling shrinkage and maintain to room temperature pressure (single Can compensated for by the packing) Pack in dough stage post dam technique

Internal denture porosity

Minimized by Gaseous porosity Avoid high processing temperatures Seen by vision Avoid extra monomer Volatisation of monomer by recommended for than Localized MMA boiling P/L Common in thicker portions heat slowly and Raise evenly around the flask

Gaseous porosity
Avoid high processing temperatures

160

Temperature 0C

140 120 100 80 60 40 20 0

Incorrect cycle

Correct cycles
10 20 30 40 50 60 70 80 90 10 0

Time (min)

Crazing
Area of localised region of high plastic

deformation which may fill by voids

Crazed region can still support stress As the voids in the crazed region grow, they become separated

Caused by

only by thin fibrils of polymer Fibrils fail and a crack is formed Crack will grow under an externally applied load Cause denture failure by brittle fracture.

CRAZE

CRACK

Internal strains in flask Heat (due to polishing) Differential contraction around porcelain

Reversible

Irreversible

teeth Attack by solvents such as alcohol

Crazing
Avoid internal strain during polymerisation
Slow cooling of the flask Use single trial packing Use cross linked polymer types

Avoid extra stress during function

Use acrylic rather than porcelain teeth Do not overheat on polishing Keep denture away from solvents Avoid denture drying Polish after each adjustment Use glazes for surface
CRAZE CRACK

Reversible

Irreversible

Dimensional changes on processing

Expansion on heating flask; heat evenly

Expansion on polymerization, exothermic

Contraction on polymerization (21vol.%); Contraction on cooling to room temperature;

Expansion on swelling in water;

Expansion on thermal change to 32c.

Net result should be near zero

Warpage on drying
Contraction on evaporation of absorbed water
Dont leave denture outside the mouth dry

Adverse reactions to PMMA

Most common in dental

Irritant contact dermatitis

laboratories Associated with regular contact with monomer when handling the dough Must avoid direct contact Rubber gloves may not provide sufficient protection Barrier creams can help

Adverse reactions to PMMA

Allergic contact dermatitis
of
residual monomer Benzoic acid Types Immediate Delayed hypersensitivity (type IV) Heat cured resin < chemical

Must ensure full cure of denture

Usually associated with release

Avoid relining procedures

May use an extra cycle of

polymerisation but denture

may warp
May need to consider alternative

material such as polycarbonate if

Delayed hypersensitivity

cured

Adverse reactions to PMMA

Thermal properties
Low Thermal conductivity
during denture processing heat cannot escape prone to gaseous

porosity isolates from any sensation of temperature throat burns

High Coefficient of Thermal Expansion

Porcelain teeth may be lost due the differential expansion and

action Warpage if denture is cleaned with hot water

Water Sorption
PMMA will absorb water by polar nature (1.0-2.0% wt) May compensate for processing shrinkage Weeks of continuous immersion in water to reach a

stable weight

Solubility
Solvents (e.G. Chloroform, alcohol) Xlinked are insoluble in most of fluid intakes Weight loss will occur, due to leaching of the
Monomer Pigments and dyes.

Ideal properties achieved?

Natural appearance Easy processing Easy to clean Easy to repair Inexpensive Biocompatible Resistant to bacterial contamination High strength, stiffness, hardness, toughness Low density Radiopaque High thermal conductivity Dimensionally stable Accurate reproduction of surface detail

X
X X X

OTHER DENTURE BASE MATERIALS

Injection molded plastic

Types Advantage:
Polycarbonates Nylon Consistent mwt Substitute acrylics in sensitive patients

Disadvantage

Must use dry mold, slow heating and cooling Under filled molds by inadequate spruing or underheating Low melt temp cause high injection forces, moving teeth in mold

Cost of equipment Difficult to attach to teeth Small market segment Can explode if high heat and wet molds Overheating cause depolymerization, oxidation, porosties
Loss of strength Bad esthetics (opaque and cloudy color) Possible fouling

Polycarbonates
Tough plastic
Injected in dry molds A high melt viscosity

Problems in binding to teeth

May de-polymerize explosively in the presence of heat and water No cross linking

Poor solvent resistance Poor craze resistance

Nylons and polyamides

Polyamide = diacid + diamine
Conventional nylon failed
Excessive water sorption Poor creep resistance Biodegradation

Glass (beads or fibers) reinforced nylon

Less water sorption Fibers better in stiffness( acrylic) than beads Fibers may irritate patient if denture fitting surface was abraded

Cellulose product
Camphor used as plasticiser
Warpage in mouth Camphor leached out
Loss of color Taste Blistering Staining

Phenol Formaldehyde (Bakelite)

Difficult to process
Lost its color with function

Vinyl resins
Low resistance to fracture
Fatigue failure

RELINING MATERIALS

Denture base reprocessing:

Hard and soft tissue changes every 5-8 years
Require modifying denture base:

Relining resurfacing of the tissue surface

Rebasing replacement of entire denture base

Soft denture lining material

Uses:
After surgery
Immediate dentures Sores Undercuts which are not removed by surgery

Ill fitting denture

can be done
In lab Chair side

Ideal lining material properties

Durability: but hardens in short time

(1-4w, 1-3 y) Dimensional stability Resistance to fouling Water absorption Osmotic presence of soluble material Resistance of Biodegradation Could it bond old acrylic Inhibit candida growth

Glassy MMA + high conc. of plasticizers Plasticizers:

Free: diffuse out reducing the resiliency Bound in cured matrix failed clinically
Has lower rate of polymerization Phase separation Water accumulate in plasticizer rich phase Soluble impurities cause more osmotic pressure Swells and distorts

Lining materialsacrylic based

Discoloration Bad taste Exothermic rxn Bad taste

Lining materialsacrylic based

Soft acrylics that have Tg EMA (ethylmethacrylates)
Beads coploymer Ethyl methacrylate + isobutyl methacrylate Ethyl methacrylate + ethoxyethyl methacrylate
Have unpleasant odour

Monomer MMA Tg > room temp Less irritant to patients Isobutyl methacrylate Tg < room temp (polished after placing in iced water), Dimensional instability

Plasticizer in monomer trapped in beads (25-50%)

Phthalate ester leach out by time Avoid heat, strong bleaching agents that reduce resilience

Lining materialsacrylic based

Soft acrylics that have Tg
Hydroxy EMA
Water is the plasticizer Swelling of liner may make it distort Ions enter and may crystallize inside matrices thus hardening

the liner

Polymerisable plasticisers
Beads ploymer Ethyl methacrylate + isobutyl methacrylate or

Monomer Alkyl maleate or Alkyl itaconate + Tridecyl methacrylate + 2-diethylhexyl maleate, ethylene glycol dimethacrylate

Tissue conditioners
Differ from soft lining material by the following
Different viscoelastic properties Flowable on insertion responding to
Masticatory forces Lingual forces Border moulding forces

Increase viscosity on setting Flows slowly responding to persistent heavy masticatory forces after setting
Useful to fill space after tissue swellings resolve Can be used as a functional impression

Reaction Gel formation not polymerization Alcohol swells beads and their Tg Beads become tacky by entanglements and cohesive strength

Tissue conditioners
Differ from soft lining material by the following
Composition
Old- plasticine Old- chewing gum Ethyl methacrylate copolymers Or small mwt polymers

Plasticisers:

ethyl alcohol or aromatic esters (butylphthalyl butylglycolate)

hemical cleaning damages the liner

Use plain soap and water

Tissue conditioners
Differ from soft lining material by the following
Alcohol problems:

Leak and replaced by water- so harden days up to 14 days High conc. Can give a sting sensation Can give a false positive on breathalyser test

Reduce leach of plasticisers by glazing or semiset MMA

Very susceptible to infection
Incorporate antimicrobials as silver zeolite itraconazole

Chemical cleaning damages the liner

Use plain soap and water

Silicon - RTV
Room temperature vulcanizing silicones (RTV)
Polymethyl siloxane polymer It sets by crosslinking of existing polymers Heat Tetraethyl silicate

Condensation minimal xlinking

Poor tear resistance Poor abrasion resistance Poor adhesion to denture Use adhesive or coupling agent Osmotic pressure effects Buckling and swelling with water Poor resistance to cleansers Biocompatible Dimensional stability May foul by Candida

Silicon Heat cured

More xlinking Poor tear resistance Adequate adhesion to denture
Can use siloxane methacrylate as a binder to heat cured additional silicon

Resistant to aqueous environment and Osmotic

pressure effects
better resistance to cleansers

Poor tear resistance

Poor abrasion resistance

Denture base hygiene

1. Clean with toothbrush and warm soap-and-water 2. Use low abrasive cleaners 2. Avoid oxidizing or Cl-containing materials

Bleaching the color Reduces strengths of denture Reduces fatigue resistance

Diligently clean both the top and tissue-borne surfaces 4. Clean with benzalkonioum
3.