POLYMERS

(synthetic RESIN THAT FORMS THE DENTURE BASE including many

other things)
Synthetic resin used in variety of dental applications
(dentures bases, liners, artificial teeth, impression materials, sealants, resin based cements)
Dental resins solidify when they polymerize are often called plastics as they can be formed into complex shapes (by
application of heat and pressure)

 Polymer
A chemical compound formed by many repeating smaller functional monomeric units to form a large molecular weight
compound
Eg: Acrylic resins, Alginate, Polysulfide, Polyether
 Monomer
A chemical compound capable of reacting to form polymer
Monomer. Monomer+Monomer  Mer-Mar-Mer-Mer
 Polymerization
Chemical reaction in which monorner of low molecular weight are converted into chains of polymers with a high
molecular weight
A molecule made up of many (poly) parts (mers).
'mer' ending represents the simplest repeating chemical structure from which polymer is composed

Classification
Based on thermal behavior, 2 types:
1. Thermoplastic Polymer
2. Thermosetting Polymer
A third group is "Elastomers"

Thermoplastic Polymer Thermosetting Polymers

Polymeric material made of linear and/or branched Polymeric material that becomes permanently hard above
chains that softens when heated above glass the temperature at which it begins to polymerize and that
transition temperature (Tg), at which molecular does not soften again on reheating to the same temperature
motion begins to force the chains apart. • On heating, undergo chemical
 Resin can be shaped and molded on reaction
heating • Usually cross-linked at this
 Upon cooling, they again harden stage
 Reversible materials, can be reheated to • Insoluble
reshape them if required • Superior abrasion resistance
 Cycle can be carried out and dimensional stability
repeatedly
compared to thermoplastic
 Soluble in organic solvents
polymers
Elastomers

Elastomers:
Elastomers readily undergo deformation, and exhibit extensive reversible elongation under small applied stress, i.e. they
exhibit elasticity
Eg. Elastomeric Impression materials
Elastomers are
 Group of rubbery materials
 Either chemically or physically cross linked
 Easily stretched and rapidly recover original shape after removal of stress
 Exist above glass transition temperature

Glass transition temperature

"Temperature at which polymer properties change from glass like to rubber like"
"At which molecular motion begins to force the chains apart"
Glass Transition Temperature
1. Above Tg
Rubber like material i.e. soft, flexible
2. Below Tg
Glass like i.e. brittle, transparent

Polymer heated to its Tg, weak van der Waal force and hydrogen bonding making polar bonds, break up
 Polymer chain can move freely relative to each other
 Inc, mobility effects physical properties
Strength and elastic modulus decrease at Tg
Thermal expansion increases

Why use Polymers?

1. They can be manufactured in a wide range of compositions
2. Their properties con be controlled by composition and processing
3. They can also be easily molded into both simple and complex shapes due to the flexibility exhibited
by the material

Types of copolymers
Other classification includes:
Homopolymer 1. Random copolymer
Only one type of repeating unit No sequential order exists
Copolymer ABBABABAAABABBB
with two or more types of mer unit 2. Block Copolymer
Identical monomer units in long sequences
Amorphous and Crystalline Polymer AAAAABBBBBAAAAABBBBB
Amorphous 3. Graft or Branched copolymer
Chains are randomly coiled and entangled in One type of mer units attached as graft on
very disordered manner backbone of second type of mer unit
Crystalline AAAAAAAAAAA
Chains align themselves to form highly II
ordered crystalline structure BBB
What are the features of polymers that determine their properties?
For dental applications polymeric materials should be mechanically strong and physically stable,
easily manipulated, excellent esthetics, chemically stable, biological compatibility and
reasonable costcan be achieved based on the following features
These properties

Fundamental Nature of Polymers/features

Consists of very large molecules
 Described as macromolecules (any chemical compound possessing molecular weight in excess of 5000 is
macromolecule) Capable of limitless configurations and conformations
Fundamental features are;
 Chain length, Extent of chain branching. Cross-linking, Organization of chains
1 .Chain length:
Longer the polymer chain the greater the number of entanglements, held together by van der waal forces, making it
more difficult to distort it. (Following the analogy of a plate of spaghetti)

 This gives rise to properties like rigidity, strength, and increase in melting point due to increase in chain length,
deformation and recovery and chain slippage. Longer the chain, more slowly polymer dissolves, reduces
solvation

Higher is the glass transition temperature

Example: a polymer with Tg 60 would be rigid at rtp in the mouth but on taking a hot drink at 70’C might become soft

2.Molecular weight
 An average value of molecular weight is used because number of repeating units vary from one molecule to
another, because polymerization is a random process and termination of chain formation may vary
 Number average (Mn) based on average number of mer repeating units in a chain or weight average (Mw) based
on molecular weight of average chain
 Number average molecular weight of denture polymers ranges from 8000 to 39000
 Weight average molecular weight as high as 600,000 (denture teeth with cross-linked resin have even higher)
 As molecular weight increases the Tg (glass transition temp) increases
The reduction of average molecular weight of a polymer is due to:
 Use of low molecular weight chains
 Residual monomer (unreacted) has a pronounced effect on the molecular weight (only 0.9% of residual
monomer in a polymer with an Mn of 22,400 if completely cured will reduce the molecular weight to 7,300

3.Degree of Polymerization
Total number of mers in a polymer molecule
Higher is the molecular weight of polymer, higher is the degree of polymerization
Depends on, temperature, method of activation (heat or chemical) and level of purity
4. Chain branching and crosslinking;
As chain branching increases, the physical entanglements increase, and these are reversible (TEMPERORY)
Where as;
Cross linking is formation of chemical bonds and requires more energy for reversal, at least 2 reactive sites are required
for crosslinking, this dramatically increases molecular weight. (PERMANENT)
Polymer backbones which contain phenyl backbones are more rigid than those containing carbon-carbon bonds.
EXAMPLE: Curing of polysulfide impression material or formation of calcium alginate from sodium alginate
This increases rigidity and gives resistance to solvents and water sorption , crazing and surface stresses and Tg of low
molecular weight polymers and has little effect on strength. Cross linking prevents chain separation, so retards
dissolution
Three basic types of
A cross-linked structure is formed by copolymerization (Improves properties) structures
There are 3 different types of copolymers 1. Linear
 Random (no sequence) 2. Branched
 Block (a relatively long sequence is followed called a block) 3. Cross-linked
 Graft or branched (one type grafted onto the backbone of another to give a branched look)

5. Molecular organization;
 Amorphous (disordered or random pattern of chains)
 Crystalline (chains align in highly ordered pattern)
Polymer crystallinity usually increases rigidity, strength hardness and melting temp but reduces ductility, swelling and
solubility .

Factors that reduce crystallinity include:

1. Copolymer formation
2. Chain branching
3. Random arrangement of side groups
4. Plasticizers
7.Plasticizers
 Often added in polymers to reduce the softening temperature
 Plasticizer cause a hard and stiff resin to become flexible and soft at room
temperature
 Neutralize secondary bonds or intermolecular forces that otherwise prevent molecules from slipping past one
another when stressed
 Also reduce strength and hardness
Plasticizing of a Resin

 Resin is copolymerized with a suitable comonomer

 Plasticizing agent becomes part of polymer (acts as internal plasticizer)
 Eg:Butyl methacrylate added to methyl methacrylate before polymerization
Increase intermolecular spacing

Liquids can penetrate between the randomly oriented chains of polymers, pushing the molecules further apart. As a
result force of attraction between molecules weakens
This gives rise to soft and flexible material
Properties of Polymers
Plastic Flow
 Irreversible strain behavior
 Chain slide past over one another and relocate leading to permanent deformation
Elastic Recovery
 Randomly aligned chains become aligned under stress and then recoil, like spring to return to original position
 Polymers show both plastic flow and elastic recovery called 'viscoelasticity'
Solvation Properties of Polymers
 Tend to absorb solvents and swell, rather than dissolve
 Longer the chain, more slowly polymer dissolves
 Cross linking prevents chain separation, so retards dissolution
 Small amount of swelling effects fit of prosthesis
 Absorbed molecules (eg. water) spread polymeric chains apart and slip between chains called Plasticization

Property Feature of polymer that gives rise to that property

Mechanical properties (deformation and Chain length and molecular weight

recovery ), chain slippage
Rheometric properties Chain length, crosslinking, temperature and force application
Solvation and dissolution Polydispersity (Mw:Mn), crystallinity, chain branching,
crosslinking, addition of plasticizer, chain length
Thermal properties and Tg (glass transition Molecular weight and molecular structure, chain length,
temperature) crosslinking, type of bond and strength of bond, chain
Hence giving 2 types (thermosetting and entanglements
thermoplastic

Polymerization
Monomers may be joined via one of two types of reactions
1. Addition Polymerization
2. Step-growth or Condensation Polymerization

Addition Polymerization
 Monomers are activated one at a time and add together in sequence to form a growing chain
 Starts from active center, adding one monomer at a time to rapidly form a chain
 Occurs in unsaturated molecules with double bonds

No by-product formation
No change in composition

Free Radical Addition Polymerization

Three distinct stages in free radical addition polymerization reaction
1. Initiation
(Activation and initiation together called induction stage)
2. Propagation
3. Termination
1. Activation
Three methods of activation in dental polymer
1. Heat Activation (mostly in denture base materials)
 Free radical released by benzoyl peroxide which is activated by heat
2. Chemical Activation(Self cured resin) (chemical reaction b/w initiator and activator
 Benzoyl peroxide (initiator) (forms free radicals)
 Tertiary Amine (Activator)
3. Light Activation(composite resin)
 Visible Light photons (Activator)
 Camphoroquinone and Organic amine (Dimethyl aminoethylmethacrylate) (Initiator)

Initiation
Initiated by a free radical (R*)
Free radical is generated by activation of free radical producing molecules
Activated by
 Heat
 Visible light or ultraviolet light
 Chemicals

Free radical having unpaired electron, bonds with double bond of monomer molecule, leaving other electron of double
bond free, free radicals react with C=C and reaction continues
R' + H2C=CH2= RH2C-Ch2
Most common initiator used is benzoyl peroxide
Activated between 50 to 100°C to release radicals per benzoyl peroxide molecule

Propagation
 A new free radical center is formed at free radical monomer complex
 Approaches another monomer to form dimer which again becomes free radical
 Polymerization process continues through propagation of the reactive center
 Exothermic reaction(Considerable heat is evolved)
 Growth of polymer chain ceases after destruction of reactive center by termination reaction

Termination
 When supply of monomer is exhausted
 By direct coupling of two free radical chain ends OR
 By exchange of hydrogen atom from one growing chain to another
 Reaction of growing chain with molecules of initiator, impurity or solvent can lead to termination

Inhibition of Addition Polymerization

 Monomer supply is not always exhausted, so impurity often inhibit reactions
 Impurity can react with activated initiator or with an activated growing chain to prevent growth
• E.g. Hydroquinone (a common inhibitor)
 Often added to prevent unwanted polymerization during storage of a monomer
Oxygen as Inhibitor

 Oxygen reacts rapidly with free radicals, inhibits polymerization

 Degree of polymerization decreased if conducted in open air as compared to an oxygen-deficient environment
  During restoring cavity, matrix materials covered with a matrix strip
(Helps in shaping the resin & as barrier to prevent contact with oxygen during curing)

Condensation Polymerization
 Involves two molecules reacting together to form a third large molecule
 With formation of a by-product (water, alcohol, ammonia)
 A linear chain formed by stepwise intermolecular condensation or addition of reactive groups in which all
monomer are activated simultaneously

Physical changes during polymerization

PHASE CHANGES: TEMPERATRUE CHANGES: DIMENSIONAL CHANGES:

 Monomers are usually liquid,  Polymerisation reactions are  Polymerisation
gases or pastes exothermic in most cases, hence, shrinkage/contraction
 Before polymerisation - low heat is liberated off after the completion of
viscosity  This could be hazardous in the case the reaction
 During polymerisation - of production of large scale  Could be decreased by
viscosity increases industrial polymers mixing with glass
 On completion of the process,  Suspension in water aids in dropping powders, preformed
the polymer hardens and the temperature polymer powders, using
acquires a solid state  Suspension also halts polymerisation more pressure during the
and the relatively fluid polymer can process etc
be moulded at this stage

DENTURE BASE POLYMERS

Introduction
Complete Denture
 A removable dental prosthesis that replaces the
entire dentition and associated structures of
maxilla and mandible
 Consists of artificial teeth attached with a
denture base
Denture Bases
 Denture base rests on the soft tissues and does
not include artificial teeth
 Derive its support through contact with the underlying oral tissues, teeth or implants
Denture Base Materials
 Metal and its alloys
 Acrylic Resins
=>Most widely used material for construction of dentures

Requirements of Denture Base Polymers

Physical Properties
1. Appearance of natural oral soft tissues
2. Dimensionally stable (shape should not change overtime )
May occur due to:
 Relief of internal stresses
 thermal softening
 Continued polymerization
 Water sorption
3. Radiopaque (accidents like car crash and denture is inhaled, X-ray done to fin possible route of treatment)
4. Absence of taste and odor
5. Colour stability
6. Low Density & low specific gravity (Denture as light as possible) esp upper denture

Thermal Requirements
1. high value of thermal conductivity
To protect oral mucosa and maintain normal stimulus to hot and cold, as if it fails to detect a very hot drink it may burn
the throat
2. Softening temperature or Glass transition temperature nigh enough to be affected by oral temperature (Oral fluids
and foods)
Patient take hot drink up to 70°C and sometimes clean denture in very hot or boiling water

Mechanical Requirements
1. High modulus of elasticity (rigid)
2. High elastic limit (May not plastically deform during mastication)
3. Sufficient Flexural strength ( to resist fracture due to flexing of upper denture in the midline)
4. High fatigue limit (fracture occurs due to fatigue mechanism in which flexural stresses develop overtime leading to
formation of small cracks and eventually fracture)
5. High Impact strength (Accidental dropping on hard surface)
6. High abrasion resistance ( as it may wear away due to cleaners or food items)
7. High craze resistance
8. High creep resistance

Chemical requirements
 Chemical stability, should be inert (processed or unprocessed denture)
 Low solubility and sorption of oral fluids (as this may affect mechanical properties of denture and make it
unhygienic)
Biological Requirements
1. Non toxic and non irritant
2. Impermeable to oral fluids (as bacteria or fungi may grow)
Other requirements
1. Adhesion to plastics, metals and porcelain
2. Ease of fabrication and repair
3. Moderate Cost

History of Denture Base Materials

 Prior to 1940, vulcanite was widely used denture bass polymer
  Others include, nitrocellulose, phenol formaldehyde, vinyl plastic and porcelain wars used
 Poly (methyl methacrylate) polymers introduced in 1937
 Other polymers developed since that time are, vinyl acrylic, polystyrene epoxy, nylon, vinyl styrene,
polycarbonate, polyvinyl acetate ethylene, hydrophilic polyacrylate, silicones, rubber reinforced acrylics
butadiene-reinforced acrylics

Acrylic Resins
 Since 1940, most of the denture bases have been fabricated using poly (methyl methacrylate) polymer
 Chosen based availability, dimensional stability, handling characteristics, color and compatibility with oral tissues
 Usually in powder (small beads of prepolymerized PMMA) and liquid (nonpolymerized methyl methacrylate)
system

ACRYLIC RESINS
Derivative of ethylene C2H4 and contain a vinyl (-C=C--) group in their structural formula
Two acrylic resin series are of dental interest
 One derived from acrylic acid CH2=CHCOOH
 Other from Methacrylic acid CH2=C(CH)COOH

Typical composition of poly (methyl methacrylate) denture bases (type 1 and 2 heat and self cured)

Powder phase Liquid phase

Polymer (methyl Monomer (methyl
methacrylate ) beads methacrylate)
Benzoyl peroxide Tertiary amine
(initiator) o.5% (activator) N,N dimethyl
para toluidine (ONLY
IN SELF CURING
MATERIALS)
Pigments like organic Cross linking agents and
dyes (salts of cadmium plasticizer (ethylene-
and iron) glycol dimethacrylate)
Colouring additives Inhibitors
with nylon or acrylic (hydroquinone)
fibres (to mimic blood prolongs shelf life
vessels and capillaries
Opacifiers (Zn/Tit
oxide)

Properties of monomer and polymer beads used in powder liquid system

Methyl Methacrylate (monomer in liquid)
 Clear, colorless low viscosity liquid
 Boiling point is 100.33°C
 Excellent organic solvent and has high vapor pressure
 Highly susceptible to free radical addition polymerization reaction, can occur by heat or light (especially
ultraviolet radiation) Stabilizers added to increase shell life
 Strong irritant of tissues, avoid contact with skin. Toxic if inhaled
Poly (methylmethacrylate)
 Molecular weight = 100
• Transparent stable and hard resin
Poly (Methylmethacrylate) (polymer beads in powder) • Knoop hardness 20
• Tensile Strength 60 MPa
• Specific gravity 1.19 g/cm'
• Modulus of Elasticity: 2.4Gpa
  Chemically stable to heat and softens at 125°C
 Between 125°C-200°C, depolymerization occurs
 At 450"C, material depolymerizes into monomer
 Does not discolor in ultraviolet light
 Tendency to absorb woter (imbibition)
 Has no vapour pressure

Heat Activated Denture Base Resins

 Used for fabrication of all denture bases
 Initially supplied as thermoplastic sheet which was heated for molding
 Now used in Powder and Liquid form, mixed together to form dough or plastic mass
 Activated by thermal energy provided
Water bath or Microwave oven

Detail explanation of Composition of Powder

 Prepolymerized spheres of Poly (methylmethacrylate)
Sometimes modified with small amounts of ethyl, butyl, or other alkyl methacrylates to enhance Impact strength
 Benzoyl peroxide as Initiator (0.5 to 1.5%)
 Pigments to obtain tissue like shades (natural appearance)
Salts of cadmium (cadmium sulfide "yellow", cadmium selenide or ferric oxide (brown) or organic dyes
 Locked into polymer beads during commercial polymerisation or mechanically mixed with polymer beads after
polymerisation
 Opacifiers ( to obtain translucency of oral mucosa)
 Zinc or titanium dioxide
 Dyed synthetic fibers made from nylon or acrylic to simulate small capillaries of oral mucosa)

Detail explanation of Composition of Liquid of Heat Activated Acrylic Resin)

1. Non-polymerized Methylmethacrylate
2. Inhibitor: Hydroquinone
Prevents undesirable polymerization and setting of liquid on storage
Liquid supplied in dark bottles to avoid polymerization by ultraviolet light
 Crosslinking agent Glycol Dimethacrylate
Structurally similar to methylmethacrylate but contains two double bonds in each molecule
Incorporated in to growing polymer chain to unite two chains
Decreases solubility, water sorption and increases resistance to surface crazing
 Plasticizer sometimes added for softer, more resilient resin
Low molecular weight ester like Dibutyl Phthalte

Powder composition for Autopolymerized Acrylic Resin is same as that of heat cured
Liquid Composition of Autopolymerized Acrylic Resin
1. Non-polymerized Methylmethacrylate
2. Activator: Tertiary Amine (Activator)
• N,N-Dimethyl-para-toluidine
• N,N-hydroxyethyl-para-toluidine
3. Inhibitor: Hydroquinone
4. Cross linking agent: Glycol Dimethacrylate
Compression Molding Technique
Heat cured denture base resins are shaped via compression molding
Before mold preparation, steps include:-
1. Impression Making
2. Cast generation
3. Record base fabrication
4. Articulator mounting
5 Teeth Arrangement
6 Wax contouring

Mold Preparation
The completed teeth arranged on occlusal rim on the and base is sealed to the master cast
Removed from dental articulator
Flasking (flask is a metal container)
Thin layer of separator is coated on master cast to prevent adhesion of dental stone during flasking
Lower half of flask filled with dental stone master cast (model) is placed onto it
Upper half of flask positioned on top and is filled with freshly mixed dental stone to completely cover all surfaces of
tooth arrangement and denture base
Upon setting of dental stone separating media is added
Deflasking
Denture flask embedded in boiling water for 7 min
The segments of flasks separated and discarded
Record base and wax is removed
Teeth will remain embedded in upper segment in dental stone and lower segment holds the master cast embedded in
dental stone
Mold cavity (still in flask) cleaned with mild detergent solution and rinsed with boiling water
Application of Separating Medium
Next step in denture base fabrication
- Application of appropriate separating medium on the walls of mold cavity (which is still within the flask)
- Prevents direct adhesion between mold surface and denture base resin/acrylic base
Separating Medium
Failure to place separating medium leads to two problems
1. Water diffusion from mold surface into denture base resin affects polymerization rate and physical properties of
resulting denture base
2. Portion of dental stone may become fused to denture base due to free monomer
Steps of applying Separating Medium
Dispensed in a container and applied with fine brush on all mold stone surface except on artificial teeth and allowed to
dry(Should not be applied on teeth)
May interfere with chemical bonding between acrylic denture teeth and denture base resins
Water-soluble alginate solution
2% sodium alginate in water with small amount of glycerin, alcohol, sodium phosphate and preservatives
Produce thin insoluble calcium alginate films
Protect direct contact of denture base and standing dental stone Separating Media Types
 Tin foil (time and labour-intensive)
 Cellulose lacquers
 Solutions containing alginate
compounds (commonly used)
 Soaps
 Starches
Proportioning (Polymer-Monomer Ratio)
It is important as it determines the workability of the mix as well as the dimensional changes (shrinkage) on setting
A polymer to monomer ratio of 3:1 is used
Allows adequate wetting of powder
How to avoid polymerization shrinkage as when two methylmethacrlate molecules react, formation of a new bond
between them leads to 21% shrinkage!!
1. To compensate for shrinkage of methyl methmethacrylate farming polymer, pre-
polymerized material is added in powder
2. Using 3:1 ratio, volumetric shrinkage reduced to approx. 5-7 % and linear shrinkage to
0.5%
>>Too high powder:liquid ratio the mix will become dry and not flow under pressure, and as
there is little liquid or less monomer so all polymer beads (powder) will not be able to bind
together giving rise to porosities (granular porosity)

Mixing (Polymer-monomer interaction)

Polymer monomer mixed with stainless steel spatula in proper proportions
Resultant mass passes through five distinct phases
1. Sandy
2. Stringy
3. Dough-like
4. Rubbery or Elastic
5. Still
Sandy Stage
 Immediately after mixing, material of sandy consistency is produced
 Little or no interaction occurs at molecular level
 Polymer beads remain unaltered
 Consistency of mixture is course or grainy
Stringy Stage
• Later mixture enters stringy stage
• Monomer attacks the surface of individual polymer beads
• Some polymers chains are dispersed in liquid monomer, which uncoil and increase the viscosity
• Stage is characterized by 'stringiness' or 'stickiness'
Doughlike Stage
 On molecular level, increased number of polymer chains enter solution
 Sea of monomer and dissolved polymer is formed, viscosity is further increased
 Mass behaves as pliable dough
 No longer tacky or does not adhere to surfaces of mixing vessel or spatula
In latter phases of this stage
 Physical and chemical characteristics are ideal for compression molding
 Material is inserted into mold cavity during dough-like stage
Dough-forming time
 Time taken by resin mixture to reach dough-like stage is Dough forming time
 ANSI/ADA Spec 12 requires that this consistency be achieved in less than 40 min from start of mixing
 Most resins in clinical use reach doughlike consistency in less than 10 min
Working Time: the time a material remains at dough stage and is moldable is working time
 Should be at least 5 min
  Can be increased by refrigeration, but moisture contamination should be avoided so should be placed in an
airtight container

Rubbery or Elastic Stage

 Monomer is dissipated by further penetration into polymer beads and by evaporation
 Mass rebounds when compressed or stretched

Stiff Stage
 Upon standing for a long time, mixture becomes stiff
 Evaporation of rest of the monomer
 Appears very dry
 Resistant to mechanical deformation
Packing
 Placement and adaptation of denture base resin within mold cavity
 Mold cavity should be properly filled at the time of polymerization
 Avoid over-packing
 Too much material leads to excessive thickness and results in mal-positioning
 Under-packing causes porosity
STEPS OF PACKING
 Resin removed from mixing container and rolled form
 Bent into horseshoe shape and placed over the past teeth
 Polyethylene (plastic) sheet is placed over resin and flask reassembled
 Placed under press and pressure applied incrementally
 Importance of pressure application:
 Dough flows into every part of the mould
 Effective reduction in polymerization shrinkage as excess dough is used
 Prevents formation of raised bite
 Excess resin will flow through mold space, called flash
 Using gently rounded instrument, flash is removed, avoid chipping stone surface
 After placing a new polyethylene sheet, flask assembly is again closed
 Process repeated until all flash is removed
 Definitive closure performed without sheet and placed in flask carrier which maintains pressure
Packing too early results in porosity
Packing at rubbery to stiff stage, material will be too viscous to flow under press
Delayed packing also result in loss of detail in denture and movement or teeth fracture
Polymer should not be manipulated with bare hands as monomer is solvent of body oils, will pick the dirt from hands,
giving non-esthetic dentures
 May also enter the bloodstream
 Avoid breathing the monomer

Injection Molding Technique (another type of technique)

1. Specially designed flask is used
2. One half of flask filled with dental stone and master cast placed into the stone
3. Sprues( channel through which metal or plastic is poured into a mould.) are attached with wax denture base
4. Remaining portion of flask positioned and dental stone poured
5. After wax elimination, Flask is reassembled
6. Flask placed into carrier to maintain pressure on assembly during resin introduction and processing
7. mixture in dough stage injected into mold using high pressure injection cylinder at room temperature.
8. Flask placed in water bath for polymerization of denture base resin maintaining the pressure
9. As material polymerizes, additional resin injected which offsets shrinkage
10. .Although more technique sensitive, produce clinical accuracy compared to compression molding technique
11. even though teeth do not move hence clinical accuracy but curing shrinkage is more as powder:liquid ratio is lower
because viscosity of resin mixture should be lower for injection technique (palatal fit is compromised)

CURING
Heat Activation
Curing temperature maintained close to 74°C as benzoyl peroxide decomposes above 65°C
 Minimum porosity occurs between 71 to 74°C & highest at 100°C
 Reaction is exothermic
 Resin and stone are poor thermal conductors, so heat cannot be dissipated
 Boiling point of monomer is 100.8°C
 If heated above this, un-reacted monomer may boil producing voids in dough called gaseous porosity

Curing Cycle/polymerization cycle
Should be well controlled to avoid effect of uncontrolled temperature rise
Curing via water bath
Different techniques for curing cycles
1. Processing denture base in constant temperature water bath (74°C) for 8 hrs
2. Processing in 74°C water bath for 8 hours, then increasing to 100’C for 1 hr
 After completion of curing cycle, cool denture flask slowly to room temperature (for 30 min)
 Immersed in cool tap water for 15 min
 Denture base deflasked, polished and prepared for delivery
 Denture should be kept in cold water till its placed in the oral cavity to minimize dimensional changes
Rapid cooling causes wreckage due to increased stresses due to difference in thermal contraction of resin and
investing stone

Polymerization Via Microwave Energy

 Specially formulated resin and no metallic flask used
 Conventional microwave oven used to supply thermal energy
 Advantage is the speed with which polymerization occurs
 Poly methylmethacrylate can be polymerized using this method as the methylmethacrylate is asymmetric

Chemically Activated Denture Base Reins

 Also called cold curing, selfcuring or auto-polymerizing resins
 Chemical activation carried out at room temperature through addition of tertiary amine in liquid
 Dimethyl-para-toluidine
 Tertiary amine causes decomposition of benzoyl peroxide

Chemically activated Vs Heat Activated Denture Base Resins

 Difference is how benzoyl peroxide is decomposed.
  Degree of polymerization achieved with chemically activated resin is not as complete as achieved with heat
activated resins
 Greater amount of un-reacted monomer in chemically cured denture base, creating two problems
1. Acts as plasticizer, so decreases flexural/transverse strength
2. Potential tissue irritant that compromises biocompatibility
 Chemically cured resins display less shrinkage than heat activated counterparts (Greater dimensional stability)
 Colour stability of chemically cured resin is inferior to that of heat activated resins. Due to presence of tertiary
amine,which are susceptible to oxidation and can thus change colour

Technical Consideration
 Chemically activated denture base molded through compression molding
 Mold preparation and resin packing same as that of heat cured material
 Working time is shorter as following mixing the powder and liquid, material starts to polymerize and proceed
more rapidly to different stages.
 Average time to reach packing consistency is 5 min in chemically activated material compared to
heat activated which takes 15 min
 To increase working time by decreasing rate of polymerization
 Decrease temperature of resin mass
 Refrigerating liquid and mixing vessel
Processing Considerations
 Following final closure, pressure must be maintained throughout polymerization process
 Initial hardening occurs in 30 min of flask closure but polymerization continues even after that
 To ensure complete polymerization, pressure should be maintained for 3 hours
 May display 3 to 5 % residual monomer compared to heat activated resin which display 0.2 to 0.5% as
polymerization of chemically activated resins is comparatively less
 Linear shrinkage with chemically activated acrylic resin is about 0.3% comapred with 0.5% for heat activated
resin.

Light Activated Denture Base Resins

● Single component denture base resin composite

● A mixture of:
1. Urethane Dimethacrylate (similar to that present in resin composite)
2. Microfine Silica As filler
3. High molecular weight acrylic resin monomer
4.Acrylic resin beads as organic filler
5.Camphorquinone as activator
6. Visible light as initiator

Processing
 Cannot be flasked in usual manner because dental stone does not allow light passage
Sheet and rope form supplied in light proof pouches to prevent polymerization
 Teeth are arranged and denture base sculpted using light activated resin
 Denture base placed into light chamber and polymerize
PROPERTIES OF DENTURE BASE ACRYLICS
1. Polymerization Shrinkage
2. Glass Transition Temperature
3. Porosity
4.Water absorption
5. Solubility
6. Processing Stresses
7.Crazing
1. Polymerization Shrinkage
>Polymerization of methyl methacrylate to poly (methyl methacrylate]
- Resulting In volumetric shrinkage of 21 %
● (new carbon-carbon bonds formed when molecule of methylmethacrylate are chemically bonded, so net
decrease in space occupied by the components)
>In heat activated resin with suggested powder to liquid ratio
- One third mass is prepolymerized resin
- Only 7 % volumetric shrinkage
>If manipulated properly, Volumetric shrinkage distributed to all surface evenly
Does not ellect adaptation of denture base
>Linear shrinkage effects denture base adaptation and cuspal Interdigitation
>Linear shrinkage caused by thermal contraction
>Heat activated resin brought to room temp, undergoes linear shrinkage
- Initially soft, so under flask pressure, contract at same rate as that of contraction rate of dental stone, but as
temperature goes below Tg of PMMA (105 C), becomes rigid and contract at different rate exhibiting linear shrinkage
>Chemically activated resins display better adaptation than heat activated
- Negligible thermal shrinkage

2. Porosity
Presence of surface or subsurface voids compromise the physical, aesthetic and hygienic properties of denture base
1. Gaseous Porosity
2. Contraction Porosity
3. Granular Porosity
READ TEMP CHANGES PG 480
1. Gaseous Porosity
 During polymerization, temperature is raised to 70'C and the reaction is exothermic
(Temperature of dough increases rapidly, & reaches above the boiling point of monomer)
 Dental stone is poor thermal conductor so heat is not dissipated
 Monomer evaporates leaving porous structure
 Mostly in thick sections near the center of investment mass
 Thin areas of denture base at periphery have less porosity, due to proximity to metal flask.

2. Contraction Porosity
 Due to contraction of monomer during polymerization
 Inadequate mixing of powder and liquid, some regions may contain more monomer
 May shrink more during polymerization producing voids
 Avoided by using proper polymer-monomer ratio & well controlled mixing procedure
 3. Granular Porosity
 High powder:liq ratio
 Evaporation of monomer with failure of polymer particles to unite
 Evaporation during mixing
 Evaporation after mixing until material reaches dough-like stage, if no lid is placed on mixing container
 Absorption of monomer into plaster during packing of dough
 Can be prevented by coating all plaster surfaces with separating medium before packing

POROSITY: Air inclusion incorporated during mixing and pouring (especially in fluid resins)
Sizable voids in resultant denture bases
Careful mixing spruing and venting can avoid this

3. Water Absorption
 PMMA exhibits water sorption value of 0.69 mg/cm?
 Water absorbed by diffusion, occupies place between polymer chains leading to
1 Sight expansion of polymerized mass
2. interfere entanglement between chains, so acts as plasticizer
 Advantage of expansion
(Offsets the thermal shrinkage in denture bases)
 ANSI/ADA Spec. 12 regarding the Testing and Acceptance for Water Absorption of denture base resins
 Disk of material with measured dimensions formed, dried and weighed (recorded as baseline value)
 Disk soaked in water for 7 days, again weighed & value compared with baseline value.
 According to spec., weight gain should not be more than 0.8 mg/cm2

4. Processing Stresses
 During shrinkage of monomer, compression on mold walls and soft resin inhibit the shrinkage
 Polymer chains remain stretched and sustain tensile stresses
Thermal shrinkage also produces internal stresses (Coefficient of thermal expansion of resin is ten times greater than
gypsum mold material)
 Improper mixing and handling, poorly controlled heating and cooling produce stresses
 Due to relaxation of these stresses, distortion may occur

5. Crazing
 Stress relaxation produce small surface flaws or microcracks called 'crazing'
 Elect the physical and aesthetic properties of denture
 Micro-cracks oriented randomly produced by mechanical separation of polymer chains
 Predispose denture resin to fracture
 Produce whitish appearance in a tinted resin
 in transparent resin, impart hazy or foggy appearance
CAUSES
 Patients frequently removes his denture and allow it to dry out, constant cycle of water absorbing following by dry
out may produce tensile stresses
- Instruct the patient to keep denture moist all the times
 Use of porcelain teeth cause crazing of tecth in region around tooth neck due to difference in coefficient of thermal
expansion
 May occur due to partial dissolution of a solvent e.g. attack by a solvent like ethyl alcohol
How to Avoid Crazing?

 More cross-linked denture base resins

 Improved acrylic resin teeth

6. Mechanical Properties
Strength determined by composition of resin, processing technique, thickness of denture base and conditions in oral
environment
Degree of polymerization also determines strength
Increase degree of polymerization, increased strength
- Chemically activated display low degree of polymerization, so low strength compared to heat cured resins
Strength
Compared to alloys like Co-Cr and stainless steel, acrylic resins are
 Soft, weak and flexible materials
 Brittle on impact
#Vickers hardness number indicate that acrylic polymers are soft, predisposes to wear caused by abrasive foodstuff and
dentifrices
#Subjected to bending forces so flexural stress required to cause fracture depends on the square of the thickness of the
denture (however makes the denture bulky and reduces thermal conductivity)
#ill-fitting denture may fail may fail due to fatigue

Material Modulus of elasticity Tensile strength Hardness

Acrylic resin 2.5 GPa 85 MPa 20VHN

Thermal Properties
Acrylic resins are good thermal insulators
Thermal conductivity is 100 to 1000 times less than metals
 A disadvantage as oral soft tissues are denied normal thermal stimuli, help to maintain mucosa in healthy
condition
 Patients lose response protective reflex response to hot and cold stimuli
Glass Transition Temperature
 Varies from one product to another depending upon the molecular weight and residual monomer
 By approaching this temperature, value of elastic modulus decreases and creep potential increases (patients
soak dentures in boiling water)
 Chemically activated PMMA Light activated PMMA

Adv Disadv Adv Disadv

Dimensionally accurate High residual monomer Simple processing High cost
content tech
Processing is less time High creep rate Short processing Decreased elastic
consuming as direct reaction time modulus
Reduced stiffness No Low flexural
Low impact strength methylmethacrylate strength
monomer
Colour instability
Low polymerization Inferior bond to resin
High solubility shrinkage denture

Adv Disadv
Good biocompatibility Low impact and
flexural strength
Low density Short fatigue life
Good esthetics Radiolucent
Insoluble in oral fluids
Chemical bond with resin teeth
Easy to fabricate
Good dimensional strength