RESIN AKRILIK 2012

Polymer
Heat Activated Resin Chemically activated Resin Light Activated Resin Microwave Activated Resin Nylon base Resin

POLYMER

Polymer : chemical compound consisting of large organic molecules formed by the union of many repeating smaller monomers unit
Polymerization : chemical reaction in which monomer of low molecular weight are converted into chain of polymers with a high MW

Classification of Resin
Thermoplastic

- refers to resin that can be repeatedly softened and moulded under heat and pressure

Thermoset

- refers to resin that can be moulded only once, they set when heated and cannot softened by reheating

Application of resin in Dentistry

To restore Replace tooth structure & missing

Dentures (base, liner, artifial teeth) Cavity-filling material (composites) Sealant Impression material Cement resin carboxylate

Requirement of dental resin

Be tasteless, odorless, non toxic, non irritant Be esthetic, the color should be permanent Be dimensionally stable Have enough strength, resilience, abrasion resistance Be insoluble and impermeable to oral fluid Have a low specific gravity (light in weight) Tolerate temp. well above without undue softening or distorsion Be easy fabricated and repair Have good thermal conductivity Be radio-opaque

Uses of Dental Resin

1. Denture base 2. Artificial teeth 3. Filling materials 4. Bone substitute 5. Mouth protector

6. etc

Application in Medicine

Ortopedic Soft tissue

- cardiovascular - benang bedah

Dental Polymer
Polymer chemical compound consisting of large

organic molecules formed by the union of many repeating smaller monomer units (mers) Is capable of limitless configuration & conformations Most polymer molecules can be described as macromolecules ( > 5000 molecular weight) The traditional polymer can consist of inorganic polymer - silicon dioxide : ceramic resin composite

Structure of polymers
Linear

Branched

Cross-linked

Cross-linked

 Copolymer : structure that have only 2 or more type repeating unit - random copolymer AABBBBABBAAAAAA etc - Block copolymer AAABBBBBAAABBBBB etc -graft / branched AAAAAAA B B B

Molecular Organization
Amorphous structure

- disordered pattern
Crystalline structure

- highly ordered

Factors that prevent crystallinity:

Copolymerization decrease the ability Long branched polymer inhibit chain

Random arrangement of substituent.. Large side groups that polymer chain separated
Plasticizer .. Tend to separate the chains

Physical properties of polymer:

Plastic deformation

- is irreversible, new permanent shape Elastic deformation - is reversible, completely recovere Viscoelastic deformation - combination of elastic & plastic strain, but recovery of only elastic stran Plastic flow -irreversible strain with slide & permanent deformation Elastic recovery - reversible strain, return to their original location

Characteristic of polymer:
The longer chain, the more slowly polymer dissolves Polymer tend to absorb a solvent: swell, soften Cross-linked prevent complete chain separation and retard dissolution Highly cross-linked polymer can not dissolved Elastomers swell more than plastics A small amount of swelling can have undesirable on fit of prostheses Absorbed molecules (water) spread polymer chains apart and facilitate slip between chains

Properties of denture base resin

Hardness Transferse Elastic KHN, MPa Strength modulus (MPa) (GPa) Concentional 170 80-95 3.8 Self cure 160 84 1.6 Rapid cure 150-170 79-86 1.3-1.6 High impact 140 78-95 2.4-2.5 Light cure 175 80-110 2.1-3.1 Resin Impact strength (J/m2) 15-17 15 12-15 24-31 13

Chemistry of Polymerization
Step-growth polymerization

(Condensation polymerization) Addition polymerization - induction - propagation - chain transfer - termination

STEP-GROWTH POLYMERIZATION
(CONDENSATON POLYMERIZION)
Is preferred /called as step-Growth polymeriza- tion than condenzation polymerization (because has broadened meaning) A linear chain of repeating mer units is obtained by stepwise intermolecular condensastion or addition of the reactive groups which bifunctional or trifuncfinal monomer are all simultaneously activated The primary compounds react, often with the formation of by product (water, alcohol, halogen

acid, ammonia) or without side product

Addition Polymerization
Induction

- Activation . generates a free radicals - Initiation .. Electron attack to double bond to form an electron pair and a covalent bond ( freeradical monomer complex as new radical)

 Propagation

- dimers new radical with monomer to form polymer and continued

Chain transfer

 Termination

- direct coupling if two free radical chain end or exchange of H+ from one growing chain another

ACRYLIC RESIN (POLYMETHYL METHACRYLATE)

The majority of denture base have been fabricated

using poly methyl methacrylate resins Is a colorless and transparent solid Its color and optical properties stable under normal intraoral condition Its physical properties have proven adequate for dental application Is supplied as powder and liquid system The powder contains prepolymerized resin in the form of small bead The liquid contain nonpolymerized resin

Type of Denture base Resin

Heat activated denture base resin

- Heat-cured - Microwave-cured Chemically activated denture base resin (cold-cured, self-cured) Light activated denture base resin

HEAT ACTIVATED DENTURE BASE ACRYLIC RESIN

Available as :
Powder & liquid Gels- sheet Cakes

Commercial names:

Stellon, Lucitone, Trevelon

Composition:
Liquid

- Methyl methacrylate : plasticizes the polymer - Dibutyl phthalate : plasticizer - Glycol dimethacrylate : cross-link agent - hydroquinone : inhibitor setting Powder - Polymethyl methacrylate & copolymer - benzoyl peroxide : initiator - Zinc oxide / titanium oxide : opacifier - dibuthyl phthalate : plasticizer - dye

Polymerization reaction :
Heat external

Powder

+ liquid (monomer)

Polymer

+ heat (exothermal)

Properties of Denture Resins

Methyl Methacrylate Monomer
Is clear, transparent, volatile, sweetish odor Physical :

- melting point - Boiling point - Density - Heat of polymerization Volume shrinkage

- 48oC 100oC 0.945 g/ml 12.9 Kcal/mol 21%

Polymethyl methacrylate
Completely polymerized resin is tasteless & odorless A high amount of porosity resulting an unpleasant taste and odor Esthetics, clear transparent, can be pigmented easily, compatible with dyed synthetic fillers Density : 1.19 g/cm3 Compressive strength : 75 MPa Self cured resin have lower Tensile strength : 52 MPa Hardness : 18-20 KHN (HC), 16-18 KHN (SC) (easily scratched and abraded)

 Modulus elasticity : sufficient stiffness (2400 MPa) Dimensional stability is good, the processing shrinkage

is balanced by the expansion due to water sorption (reversible) Water sorption : 0.6 mg/cm3 and expand Is virtually insoluble in water and oral fluids (soluble in: ketone, ester, aromatic & chlorinates hydrocarbon; alcohol causes crazing) Thermal properties Thermal conductivity : poor Coefficient of thermal expansion is high Color stability : good Residual monomer: 26.2% (before start curing), 6,6% ( 1 hour), 0.29% (at 100oC) Self life : the best (P/L), lower (gel)

Processing Errors
Porosity (internal & external) - internal porosity is in the form voids or bubles cause is due to the vaporization of monomer - external porosity ; causes by lack of homogenity and lack of adequate pressure Crazing - is formation of surface crack (microscopic

/macroscopic) hazy or foggy - cause fractire - causes by mechanical stress, attack by solvent, incorporation of water

Strength of Polymers depend on :

1. Molecular weight 2. Degree of polymerization

3. Chain structural
4. Thermal properties

- thermoplastic - thermo setting 5. Plasticizer

Monomer-Polymer Interaction
Stage 1 : The polymer gradually settles into the

monomer to form a incoherent mass, mixture may be coarse or grainy (sandy phase) Stage 2 : The monomer attack the polymer, the layer polymer penetrated sloughs off and is dispersed in the monomer. Its characterized by stringiness and adhesive (stringy phase, sticky phase) Stage 3 : the mass becomes more saturated with polymer in solution, it becomes smooth and dough like, it does not adhere to the wall of the mixing jar (dough phase/gel phase), it is packed into the mold Stage 4 : the mass becomes more cohesive and rubberlike, it can not be molded (rubbery phase) Stage 5: stiff phase, very dry & resistant to mechanical deformation

HEAT ACTIVATED RESIN

Heat activated denture base resin are shape By compression molding technique

Compression molding technique

Articulator mounting
Tooth arrangement & wax contouring Flasking & deflasking

Selection & application separating medium

Packing Pressure Curing

Flasking

Wax elimination

Placement of alginate-base separatingmedium

ofSelection alginate-base separatingmedium of & application separating medium alginate-base separatingmedium of Involves the application of an approproate alginate-base separatingmedium separating medium onto the wall of mold cavity Failure to place may be lead to - water permitted to diffuse into the denture base resin and affect the polymerization rate, optical aand physical - dissolved polymer (free monomer ) produce compromises inthe physical and esthetic properties Currently, the popular agent is CMS (cold mold seal) a water-soluble alginate solution (formed a calcium alginate)

Packing of Dentures Base

The placement and adaptation of denture base within mold cavity The processes the most critical steps in denture base fabrication

The mold cavity be properly filled at the times of polymerization

Overpacking (excessive thickness) causes

malposition of prosthodontic teeth, too underpacking (little material) causes porosity

 The resin removed from its mixing container and

rolled into a ropelike form and bent into a horseshoe shape and

place into the portion that house the prosthetic teeth

Placed over the resin a polyethylene sheet Flask is reassembled and pressure Transferred to a flask carrier

a horseshoe shape

Proof pressure Excess material is removed

Polymerimarization Cycle
At slight above 70oC, the benzoyl perixide becomes free radical increased rate of polymerization and exothermis heat
The first technique

constant waterbath 74oC - 8 hours / longer The second technique constant waterbath 74oC - 8 hours, 100oC- 1 hour The third technique constant waterbath 74oC - 2 hours, 100oC- 1 hour

 After processing (polymerized)

Removed from waterbath and bench cooled for

30 minutes
Immersed in cooled tap water (15 minutes)

Deflasking Finishing & Polishing

Finishing & Polishing Denture Base Resin

C ontour with tungten carbide burs and sand paper

Use a rubber point to remove the scratches

Apply pumice with rag wheel, felt wheel,nbristle brush or propy cup

Apply tripoli or mixture of chalk and alcohol with rag wheel

CHEMICALLY ACTIVATED RESIN

The application of thermal energy leads to decomposition of benzoyl peroxide and produce

free radical Chemical activator (in liquid) : tertier amine (dimethyl para toluidine) Degree of polymerization is not as complete Unreacted monomer created major difficulties: - acts as plasticizer - serves potential irritant Slightly less shrinkage, color stability is inferior

 Initial hardening will occur within 30 minute of final flask closured To ensure sufficient polymerization should be held under for minimum of 3 hour Exhibits 3 -5% of residual monomer Failure to achieve a high degree of polymerization will predispose

- dimensional instability - lead soft tissue irritation

Comparison of heat and self cure resins

Heat Cure Resin
Heat is necessary Porosity of material is less Higher MW Lower residual monomer content Material is strong Shows less distortion Less initial deformation Less creep and quicker recovery Color stability is good Difficult to deflask Increased rate monomer diffusion at higher temperature Self Cure Resin Heat is not necessary Porosity of material is greater Lower MW Higher residual monomer content Material is not strong Shows greater distortion More initial deformation Greater creep and quicker recovery Color stability is poor Easy to deflask -

LIGHT ACTIVATED RESIN

Material as composite having a matrix of urethane dimethacrylate, microfine silica, acrylic resin monomer high MW (beads as filler organic) Visible light is the activator and camphorquinone serves initiator Opaque investing media prevent the passage of light Instead, teeth are arranged and denture base is molded on an accurate cast is exposed to a high intensity visible light source for appropraite period Following polymerization is removed from cast, finished and polished

Microwave Activated Resin

Composition

- Powder (similar with heat cured) - Liquid : triethylene glycol dimethacrylate or tetraethylene glycol dimethacrylate Used non metallic flask (high impact composite plastic) Heat from magnetron, at 2450MHz wave length Residual monomer is lower than conventional Processing time is greatly speeded up & less porosity Fit the denture is comparable or superior

Kuvet untuk plimerisasi gel.mikro

NYLON BASED THERMOPLASTIC

VALPLAST

55

Properties of Nylon based thermoplastic

Retention flexes into a retentive position below

the undercut Comfort thin, lightweight, and flexible Aesthetics pink shades that allow your patient's natural tissue tone to appear through the material Strength clinically unbreakable, more durable than acrylic, and won't absorb stains or odors Ease no tooth or tissue preparation is required, so you can offer patients a conservative and less painful solution

 Biocompatibility Patient with resin acrylic allergic Used to partial and full denture Untuk pasien yang tidak menghendaki fixed denture atau implan Trauma karena GT sering patah

Characteristic Nylon Base Resin

1. Mechanical strength 2. Abrasion resistance 3. Toughness 4. Low coefficient of friction 5. Absorbs water 6. Absorbs some liquid

cukup

Flexite Plus (Polyamide Nylon)

Comparable with Valplast, more flexible and color stable Unbreakable Biocompatibility Can added and repaired in non flexible areas

with rapid set and adhesive Can be relined and added mayor areas by reinjecting and using repair liquid adhesive Design are mostly tissue supported Requires less precision in the design and blockout of undercut
US Dental Depot

Mould preparation for Valplast: (Ali, Rahdaa, 2011)

The same as in heat cured mould preparation With wax sprue were prepared (6-8 mm) Wax elimination was performed using boiling water Injecting the polymer - preheated inside an oven set at 65oC - started with heating cylinder inserted into the slot at present inside the electrical furnace - furnace was allowed heating was 287oC removed -valplast cartridge, metal disc, solid metal cylinder inserted into the heating cylinder cylinder and left inside the furnace for to allow the granules inside the cartridge to melt - give pressure according the leaflet

Critical of Denture Base Resin

Polymerization shrinkage Porosity Water absorpsion Solubility Crazing Creep Growth of microorganism

Polymerization shrinkage :
The density of the mass changes volumetric shrinkage of resin acrylic 21%, but by the polymerization mass approximately 7% The high vol shrinkage can be used to produce clinically satisfactory denture base
Must consider the effect of linear shrinkage,

causes upon denture base adaptation and cuspal interdigitation

Porosity :
To develop in thicker portion of denture base, result from vaporation of unreacted monomer

and low MW Result from: - low MW vaporation - rapid tempearture elevation - inadequate pressure or insufficient in mold - associated with fluid resin appear to be caused by air inclusion incorporated

 High water absorption Decrease strength Decrease esthetica (discoloration) Poor hygyene halitosis Growth of microorganism : biofilm, candidiasis

Light micrographs of yeast cells attached to bacteria adherent on PMMA

(Busscher & Evans. Oral Biofilm and Plaque Control. 1998. pg.182)

SEM images of biofilm formation on PMMA

( Ramage et al. Biofilm formation.J Clin Micro, 2001: 39 (9): 3234-40 )

Candidiasis

Water Absorption :
Is facilitate by the polarity and mechanism by diffusion Water penetrate the PMMA and occupy position between polymer chain causes:

- a slight expansionof the polymer mass - interfere with the entanglement of polymer chain and act as plasticizer Affect the physically, mechanically and dimensional properties

Crazing :
Is incidenced by small linear cracking that appear hazy or foggy

Is predispose a denture resin to fracture

Solvent-induced crazing from prolonged contact with ethyl alcohol

Tensile stress most responsible for crazing and is producedby mechanical separation of individual polymer chains

Rebasing Denture Base

Rebasing involves replacement of the entire denture

base The cast and denture are mounted in a device designed to maintain the correct vertical and horizontal relationship The teeth are repositioned in their respective indices The denture base is waxed to desired form Following elimination of the wax and resin introduced into the mold cavity The prothesis consist of new denture base in conjuction with teeth from previous denture

Relining denture base

Relining involves replacement of the tissue surface of an exciting denture The tissue surface is cleaned to enhance bonding the excisting resin and the reline material An appropriate resin is introduced and shaped using a compression molding technique A low polymerization temp is desirable to minimize distorsion of the remaining denture

Chemically activated resin is chosen

Rebasing / Relining

Reparation of Denture Base

The fracture prosthesis must realign and lute component together using an adherent wax or

modeling plastic The fracture surface are trimmed to provide sufficient space for repair material Are preffered chemically activated resin (polymerized at room temp) A small amount of monomer is painted onto prepared surface of the denture to facilitate bonding of the repair material

Repairs