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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
Dentures (base, liner, artifial teeth) Cavity-filling material (composites) Sealant Impression material Cement resin carboxylate
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
1. Denture base 2. Artificial teeth 3. Filling materials 4. Bone substitute 5. Mouth protector
6. etc
Application in Medicine
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
Random arrangement of substituent.. Large side groups that polymer chain separated
Plasticizer .. Tend to separate the chains
- 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
Chemistry of Polymerization
Step-growth polymerization
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
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
Chain transfer
Termination
- direct coupling if two free radical chain end or exchange of H+ from one growing chain another
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
- Heat-cured - Microwave-cured Chemically activated denture base resin (cold-cured, self-cured) Light activated denture base resin
Available as :
Powder & liquid Gels- sheet Cakes
Commercial names:
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)
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
3. Chain structural
4. Thermal properties
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 denture base resin are shape By compression molding technique
Articulator mounting
Tooth arrangement & wax contouring Flasking & deflasking
Flasking
Wax elimination
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)
rolled into a ropelike form and bent into a horseshoe shape and
a horseshoe shape
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
30 minutes
Immersed in cooled tap water (15 minutes)
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
- 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
55
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
1. Mechanical strength 2. Abrasion resistance 3. Toughness 4. Low coefficient of friction 5. Absorbs water 6. Absorbs some liquid
cukup
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
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
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,
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
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
Tensile stress most responsible for crazing and is producedby mechanical separation of individual polymer chains
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
Rebasing / Relining
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