DENTAL COMPOSITES One of the basic requirements of aesthetics in dentistry is to restore anterior teeth and any extraorally conspicuous aspects of posterior teeth with a material that has the same color, shade and all visual perceptions as that of the adjacent tooth structure while keeping them unchanged in function Since the birth of dentistry there has been a continuous attempt to formulate a material and technique with such aesthetic requirements.besides having the expected biocompatibility to behave in the oral environment INTRODUCTION Silicate cement was the first transcluscent direct filing material to be introduced in 1871. • Used extensively to restore carious lesions in anteriors • But use diminished because of solubility problems, discoloration, loss of contour, surface crazing, and lack of adequate mechanical properties Acrylics were developed in Germany in 1930s. • They were low molecular weight polymers and lacked the reinforcement provided by the filler particles. • The early clinical failures of acrylics were related to high polymerization shrinkage, high coefficient of thermal expansion and lack of abrasion resistance resulting in marginal leakage, pulp injury, recurrent caries, color changes and excessive wear. • Thus the Poly Methyl Methacrylate based resins were not so successful In an effort to improve the physical properties of unfilled resins Ray C. Bowen introduced a polymeric dental restorative material reinforced with silica particles in 1962. This became the basis for restorations and are termed as COMPOSITES. They are often termed as Dental Composites, Composite Restorative Materials, Filled Resins,Composites resins,Resin composites, Resin Based Composites, Filled Composites COMPOSITE REFINEMENTS Reviewing the last 50 years. Dentin-Bonded Unbonded Composites Composites 3c, 2c, 1c Dentin Bonding System Acid-Etching and Enamel Bonding 1950 1960 Original Development 1970 1980 1990 PACKABLES MIDIFILL Composites MIDIFILL Composites Midi-HYBRID Composites 2010 NanoHYBRID COMPOSITE FLOWABLES MICROFILL Composites MACROFILL Self-Cured Composites 2000 CONTROLLED SHRINKAGE Prototypes Mini-HYBRID Composites SELF-CURED UV-CURED VLC-CURED [QTH, PAC, Laser, LED] DEFINITION OF COMPOSITE Phases and Interfaces INTERFACE INTERFACE Enamel Surface Unfinished Composite Surface INTERFACE Finished Composite Surface INTERFACE Etched Enamel Rods INTERFACE Voids at Margins Silicate Reinforcing Filler COMPOSITE Crosslinked Resin Matrix 50 v/o filler = 75 w/o filler DEFINITION COMPOSITES are defined as a compound of two or more distinctly different materials with properties that are superior or intermediate to those of individual constituents. DENTAL COMPOSITES are highly cross linked polymeric materials reinforced by dispersion of glass, crystalline or resin filler particles and/or short fibres bound to matrix by silane coupling agents Examples of natural composites are tooth enamel and dentin.In enamel, enamelin represents the organic matrix whereas in dentin the matrix consists of collagen both of which having filler as hydroxyapatite crystals. COMPOSITION Composites involve a dispersed phase of filler particles distributed with a continuous phase (Matrix phase) Composites consist of • Organic phase (continuous phase) – resin matrix • Inorganic phase (dispersed phase) – filler particles • Interfacial phase coupling agent Organic Phase • 1) 2) 3) 4) 5) It consists of : Monomers Activator Initiator system Inhibitors UV light absorbers Pigments and Opacifiers Monomers • They are either aromatic or aliphatic diacrylates • Bisphenol A-Glycidyl methacrylate (Bis-GMA), Urethane dimethacrylate (UDMA),Triethylene glycol dimethacrylate (TEGDMA) are most commonly used in dental composites • In high molecular monomers particularly BisGMA is extremely viscous at room temperatures. • The use of diluent monomers is essential to attain high filler levels and to produce a paste of clinically usable consistencies which are mostly low molecular wt less viscous TEGDMA Monomers • Binds filler particles together • Provides “workability” • Typical monomers – Bisphenol A glycidyl methacrylate (Bis-GMA) O CH2=C-C-O-CH2CH-CH2O CH3 OH CH3 -C- O OCH2CHCH2O-C-C=CH2 CH3 OH CH3 – Urethane dimethacrylate (UEDMA) O O CH3 CH3 O O CH2=C-C-O-CH2CH2-O-C-NHCH2CH2CHCH2-C-CH2-NH-C- OCH2CH2O-C-C=CH2 CH3 CH3 CH3 – Triethylene glycol dimethacrylate (TEGMA) O O CH2=C-C-O-CH2CH2-OCH2CH2 OCH2CH2O-C-C=CH2 CH3 CH3 • Unfortunately TEGDMA or other such low molecular wt substances increase polymerization shrinkage a factor that limits the amount of low molecular wt dimethacrylates used in composites • Polymerization converts an aggregate of freely flowing molecules to rigid assembly of cross linked polymer chains ie.those held by Van der waal’s forces get bound by covalent bonds. • This in turn leads to volumetric shrinkage creating unrelieved stresses in resin after it has gelled leading to micro leakage but Bis GMA and UDMA have 5 times molecular wt methacrylate so density of methacrylate double bonds is 1/5th as high in these monomers so less polymerization shrinkage. Activator Initiator system • Methyl methacrylates and dimethacrylates polymerize by the addition polymerization mechanism initiated by free radicals generated by chemical activation or by external energy activation (light or heat) • Basically there are three types of systems described o Chemically activated resins: Supplied in the form of two pastes which contains Benzoyl peroxide as initiator and a tertiary amine activator ( N- N dimethyl –p- tolueidine. • When two pastes are spatulated the amine reacts with the benzoyl peroxide to form free radicals and addition polymerization is initiated • Mainly used for restorations and build ups that are not readily cured with light source o Light activated resins : The first light activated system used UV light to initiate free radicals now replaced by visible light activating systems • Available as a single paste containing a photoinititor molecule and an amine activator which on exposure to light of correct wave length (approx 468 nm) react to form free radicals that initiate addition polymerization • Commonly used photoinitiator is camphoropuinone at level of 0.2 wt % and Amine accelerator is 0.15 wt % dimethylaminoethyl methacrylate o Dual cure resins : Contains initiators and accelerators that light activation followed by self curing Inhibitors • To minimize or prevent the spontaneous polymerization of monomers, inhibitors are added to the resin system. • These inhibitors have a strong reactive potential with free radicals • A typical inhibitor is butylated hydroxytoluine in a concentration of 0.001wt % • They extend the storage life times of all resins and ensure sufficient working times Pigments and UV Absorbers • Pigments – metal oxides • provide shading and opacity • titanium and aluminum oxides • UV absorbers – prevent discoloration – acts like a “sunscreen” • Benzophenone Optical Modifiers • Composites must have visual coloration and translucency that can simulate tooth structure. • Shading is achieved by adding different pigments • These consist of different metal oxides that are added in minute quantities • Titanium oxide and aluminium oxide in minute amounts ( 0.001 wt % - 0.007 wt % ) are effective opacifiers • Eg.Cl IV incisal area translucency of unmodified composite may allow too much light to pas thru restoration so less light reflected back so restoration appears too dark • Darker shades and greater opacifiers decrease depth of light curing ability which requires either increased exposure time or taking a thin layer during curing ] Color stabilizers (UV light absorbers) • Decomposition of tertiary amine activator occurs by the natural UV light , creating discoloration. • So UV light absorbers are added to minimize color changes by oxidation Inorganic Phase • Incorporation of filler particles into resin matrix significantly improves the properties of the matrix material. • Fillers are important as they Reduce polymerization shrinkage Decrease water sorption and coefficient of thermal expansion Improve compressive strength, tensile strength and modulus of elasticity Improves abrasion resistance • Filler particles are most commonly produced by grinding or miling quartz or glasses to produce particles ranging in size from 0.1 – 100 um • Silica particles of colloidal size approx 0.004 um are referred collectively as microfiller ar obtained by pyrolytic or precipitation process in which SiCl4 is burnt in an O2 – H2 atmosphere producing SiO2 macromolecules • A distribution of filler particle sizes is important to incorporate maximum amount filler into resin matrix as if they are of uniform sizes there is space between the particles • Inorganic filler particles generally account for between 30 – 70 vol % or 50 – 80 wt % of the composites • The amount of filler incorporated into the resin matrix generally is affected by the relative filler surface area • The surface area of colloidal particles is 50 – 400 m2/gm which increases the viscocity so they contain only 20 – 59 vol % colloidal silica as inorganic filer component and rest is pulverized precured resin organic filler particles with size 5 – 20 um size • To ensure acceptable esthetics, translucency of filer must be similar to that of tooth structure and resin ie glasses and quartz used for fillers have refractive indices of approx 1.5 which enough to achieve sufficient translucency • The radiopacity of filer material is provided by a number of glasses and ceramics that contain heavy metals like Barium, Storntium, Zirconium Coupling Agent • Chemical bond – filler particle - resin matrix • transfers stresses • Organosilane (bifunctional molecule) – siloxane end bonds to hydroxyl groups on filler – methacrylate end polymerizes with resin CH2 Bis-GMA OH CH3-C-C-O-CH2-CH2-CH2-Si-OH Bonds with resin O Silane OH Bonds with filler Phillip’s Science of Dental Materials 2003 Interfacial phase • It is important the filler particles are well bonded to resin matrix to allow transfer of stresses from more flexible polymer matrix to stiffer filler particles • The bond between the two phases of composites is provided by a coupling agent • Organosilanes such as r- methacryloxypropyltrimethoxy silanes are used most commonly. • In hydrolyzed state the silanol groups of organosilanes bind with silanols on the filler surface by the formation of siloxane bond ( Si–O– Si) • The methacrylate group of organosilane forms covalent bonds with the resin when it is polymerized thus completing the coupling process CLASSIFICATION • Composites are generally classified with respect to the components, amounts properties of filler particles or matrix phase or by handling properties • There are many classification schemes given in many ways According to filler particle size : • Category Megafill Macrofill Midifill Minifill Microfill Nanofill Hybrid Particle size 0.5-2 um 10-100 um 1-10 um 0.1 – 1 um 0.01-0.1 um 0.005-0.01 um Mixed particle size range Midi -filler 2 um (beachball) Mini -filler 0.6 um (canteloupe) Microfiller .04 um (marble) Nanofiller .02 um (pea) Relative Particle Sizes (not to scale) Phillip’s classification based on mean particle size • Category Conventional/Traditional Small particle filled Microfilled Hybrid Average particle size 8-12 um 1-5 um 0.004-0.4 um 0.6-1.0 um Traditional (Macrofilled) • Developed in the 1970s • Crystalline quartz – produced by grinding or milling – large - 8 to 12 microns • Difficult to polish – large particles prone to pluck • Poor wear resistance • Fracture resistant • Suitable for Class 3, 4 and 5 Microfills • Better esthetics and polishability • Tiny particles – 0.04 micron colloidal silica – increases viscosity • To increase filler loading – – – – filler added to resin heat cured ground to large particles remixed with more resin and filler Ground polymer with colloidal silica (50 u) Polymer matrix with colloidal silica Microfills • Lower filler content – inferior properties • increased fracture potential • lacks coupling agent • lacks radiopacity • Linear clinical wear pattern • Suitable for Class 3, 5 – exceptions with reinforced microfills • Class 1 or 2 Small Particle • 1 - 5 micron heavy-metal glasses • Fracture resistant • Polishable to semi-gloss • Suitable for Class 1 to 5 • Example: Prisma-Fil Silane-coated silica or glass (1-5 u) Polymer matrix Hybrids • Popular as “all-purpose” – AKA universal hybrid, microhybrids, microfilled hybrids • 0.6 to 1 micron average particle size – distribution of particle sizes Silane-coated silica or glass • maximizes filler loading – microfills added • improve handling • reduce stickiness Polymer matrix with colloidal silica Hybrids • Strong • Good esthetics – polishable • Suitable – Class 1 to 5 • Multiple available Table of Properties Property Traditional Microfilled Small Particle Hybrid Compressive strength (MPa) 250-300 250-300 350-400 300-350 Tensile strength (MPa) 50-65 30-50 75-90 70-90 Elastic Modulus (GPa) 8-15 3-6 15-20 7-12 Coefficient of Thermal Expansion (10-6/ºC) 25-35 50-60 19-26 30-40 Knoop Hardness 55 5-30 50-60 50-60 Phillip’s Science of Dental Materials 2003 FILLER PARTICLES Schematic Examples MEGAFILL Different Filler Particle Sizes MACROFILL MIDIFILL Not Shown HYBRID (MIDIFILL) MINIFILL MICROFILL NANOFILL Not Shown HYBRID (MINIFILL) Mixtures Of Filler Sizes Heterogeneous MIDIFILL Mixtures Of Pre-Cured Pieces of Composite Heterogeneous MINIFILL Heterogeneous MICROFILL HOW DO YOU MAKE FILLERS? Not Shown Not Shown • Crushing, Grinding, Sieving • Vapor Phase Condensation • Sol-Gel Precipitation Marzouk’s classification based on their chronological development First generation composites : Consists of macroceramic reinforcing phases in an appropriate resin matrix Has highest mechanical properties in lab testing, highest propertion of destructive wear clinically due to dislodging of the large ceramic particles Second generation composites : With colloidal and microceramic phases in a continuous resin phase Best surface of all composite resins Wear resistance is better than that of first generations due to dimension proximity of dispersed filler particles to dispersion matrix macromolecules and difficulty of engaging these minute ceramic particles in abrading element Third generation composites : Is a hybrid composite in which there is a combination of macro and microceramics as reinforcers in a ration of 75:25 in a suitable continuous phase resin The properties are somewhat of a compromise between the first and second generation ones Fourth generation composites : Hybrid cmposites but instead of macroceramic fillers these contain heat cured irregularly shaped highly reinforced composite macroparticles with a reinforcing phase of micro ceramics Fifth generation composites : They are hybried system in which the continuous resin phase is reinforced with microceramics and macro spherical highly reinforced heat cured composite particles The spherical shape of the macro composite particles will improve their wettebility and their chemical bonding to the continuous phase of the final composite They are of hybrid types in which the continuous phase is reinforced with a combination of microceramics and agglomerates of sintered microceramics Exhibit highest percentage of reinforcing particles and best mechanical properties ADA Classifation • ADA Type I Restorative : Are typical of the older, unfilled restoratives which are allowed to posses tensile strength as low as 3480 psi and water sorption as high as 1.7 mg/cm2 • ADA Type II Restorative : Are more modern highly filled composites having tensile strength of 4390 psi or higher and a maximum water sorption 0.7 mg/cm2 According to filler composition • Homogenous : If the composites simply consists of filler and uncured matrix material it is classified as homogenous • Heterogeneous : If the composites consists of precured composite or other unusual filler it is called heterogenous Precured particles are generated by grinding cured composites to 1-20 um sized powder They become chemically bonded to new material and can be finely finished If it includes novel filler modifications in addition to conventional filers then it is called modified such as fiber modified homogeneous minifill According to matrix composition • Bis phenol A Glycidyl methacrylate based • Urethane dimethacrylate based According to polymerization method • Self cured / chemically cured / cold cured : Cold curing is initiated by mixing two pastes one of which contains BPO as initiator and other a tertiary amine activator (N-N-dimethylp-toluidine) Amine accelerator contributed todiscoloration after 3-5 years Air bubbles may be incorporated during mixing leading to oxygen inhibition during polymerization • UV light curing : UV light is used to generate free radicals.Presents some safety problems and were replaced with visible light curing systems • Visible light curing : Supplied in a single paste contained in a syringe Free radical system contains an initiator camphoroquinone and an amine activator exposure to light of correct wavelength (468 nm) produces excited state of photoinitiator and initiate addition polymerization They provide increased working time and exhibit greater color stability and less internal porosity If composite thickness exceeds 1.5-2mm thickness then light intensity can be inadequate to produce complete curing especially with darker shades of composites • The distance of light from resin should be 1 mm or less at 90 degree angle Various light curing units used are : Quartz/tungsten/halogen light curing system Plasma arc curing system Argon laser curing system Light emission diodes • Factors that affect the efficeincy of visible light curing unit : Distance from light tip 1mm or less is ideal Dirty light tip can decrease wavelength below level resulting in insufficient curing Age of bulb where light tips are used more bulbs should be changed every 6 months or more Optical translucency of material :How well the material allows the passage of light through outer surface to greatest depth of material Refractive index has to do with the scatter of light within material morel scatter enhances polymerization laterally but inhibits depth of cure Microfill : small numerous particles scatter more light Hybrid : Larger fewer particles scatter less light Monomer system: High mol wt monomers have greater degree of polymerization • Dual curing : In order to overcome the problem of curing light cured composite in inaccessible area dual cured are used esp interproximal areas This combines self curing and visible light curing components in the same material The self curing component rate is slow and is designed to cure only those portions not adequately light cured • Staged curing : By filtering light from the curing unit during an initial curing it is possible to produce soft partially cured material that can be easily finished Afterwards the filter is removed and composite curing is completed with full spectrum visible light According to viscosity • Flowable composites : These are low viscosity materials that possess particle size distribution similar to hybrid composite but reduced filler content They have inferior mechanical properties as compared to standard hybrid composite Viscosity allows them to be dispensed by as syringe for easy handling Recommended for cervical lesion , pediatric restorations and other small low stress bearing restorations • Packable composites : They were developed to produce handling characterstics similar to amalgam. Primarily used for class I and II restorations Have low polymerization shrinkage and low wear rate According to the technique used • Direct composites : The tooth is prepared ,etched, bonding adhesive applied and composite material is directly inserted in to the mouth • Indirect composites : In order to overcome the disadvantages of direct adhesive such as technique sensitivity, anatomic form, polymerization shrinkage and inter proximal contacts the indirect composite resin were introduced EVOLUTION OF CLASSIFICATIONS • Composites generally are classified with respect to the components, amounts, properties of their filler or matrix phases or by their handling properties • Almost all important properties are improved by using higher filler levels except the problem that as filer content is increased fluidity decreases • Also highly filled compositions typically contain large filler particles but this composition results in a rougher finished surface • The degree of filler addition is represented in terms of the weight percent or volume percent of filler and since silica fillers are 3 times as dense as acrylic monomer 75 wt % filler is equivalent to 50 vol %. • Filler particles for the earliest composites averaged 10 to 20 um with many of larger particles as many as 50 um. • With evolution of formulations towards better finishing characteristics and greater resistance to wear, smaller and smaller filler particles were used • Since the early fillers were relatively large they were known as macrofill materials. • After early macrofill composites next generation had fillers that were 8 t0 10 um in average size (midifillers) and were originally designated fine particle sized composites to imply improved finishing characteristics which soon replaced silicates and direct filing resins and soon became known as traditional or conventional composites • The next step in evolution was to utilize 0.02-0.04 um diameter particles to produce microfill composites • They were also called fine finishing composites but smaller filler size produced high viscosities in uncured mixes of BISGMA and TEGDMA which required the addition of greater amounts of monomer diluents, along with a reduced overall filler content to maintain workable consistencies • To circumvent the viscosity problem two strategies were developed. To blend precured microfill composite with uncured material particles of which are generated by grinding cured composites to a 1-20 um sized powder which in turn become chemically bonded to the new material provide islands with better properties and can be finely finished(heterogeneous microfills To sinter small filler particles into large but porous filler particles impregnate them with monomer and add new particl to microfill composite.Within the local region the materal is highly filled and yet capable of being polished • Although vast preponderance of fillers in composites fever reinforced system are gaining interest due to the fibers having excellent strength in primary fiber direction but difficult to pack the fiber or orient their direction. • Small additions of fibers to regular fillers are effective in improving properties with a limiting factor to use fibers with dimensions greater than 1 um for carcinogenicity concerns for submicron fibers as asbestos.currently used of diameters 5-10 um and lengths 20-40 um. • Single crystals generally have symmetric shapes behaving like fibers with an advantage that they are much stronger than non crystalline or poly crystalline fibers.Best eg of crystal modified composite is SiC single crystals but they are colored so cant be used for esthetics but can be used where strength is required • With advances in control of filler sizes and to improve the handling characteristics introduction of two types: Flowable : low viscosity materials that possess particle sizes and size distributions similar to hybrids but with reduced filler content allowing increased amount of resin to decrease viscosity..Further classified as with low filler content used as pit and fissure sealents and for small anterior restorations and those with high filler content used for Cl I to V conservative restorations. Packable (condensable) : To produce handling similar to amalgam primarily for Cl I and II restorations.Composition similar to traditional hybrids except less sticky and higher viscosity than latter. • In addition to inorganic or composite fillers it is possible to add crystalline polymer fillers to supplement the traditional fillers.They being stronger than amorphous polymer material • Two basic forms of silical fillers used in dental compositions : Colloidal silica : precipitated from a liquid solution as amorphous silica Pyrogenic silica : Precipitated from a gaseous phase as amorphous particles • For posterior composites also possible to place one or two large glass inserts (0.5-2mm particles) into composites at points of occlusal contact or high wear called inserts(megafillers).They have demonstrated improved wear resistance to contact area wear but do not totally eliminate contact free area (CFA) wear • After it was realized that highly filled microfills were difficult to use composites were made with mixtures of particles in the microfiller range to 2 to 5 um size allowing high filler levels and permitted good finishing called hybrid composites .Currently the principal particle size for newer materials is in 0.1-1 um range called minihybrids • New composites nano fillers particle size 0.005-0.01 um which is below the wavelength range for visible light(0.02-2 um).Since these particles do not interact with visible light they do not produce scattering or significant absorption. • Non silicate based composites can be used for nano fillers because they are effectively invisible.They do not agglomerate in chains like silica filers and are so small they fit between several polymer chains allowing very high filler loading and still workable consistencies NANOCOMPOSITES What is all this “nano” stuff all about? 70% Midi-Hybrid 30% Mini-Hybrid Nano-Hybrid MegaFiller MacroFiller MidiFiller MiniFiller MicroFiller NanoFiller 100 10 1 mm 0.1 0.01 10-4 10-5 10-6 10-7 10-8 0.001 0.0001 METERS 100 10-1 10-2 10-3 1m 1 dm 1 cm 1 mm 1 mm Dentinal Tubule Width IPS Target Bacteria for Wear Resistance Standard Dentistry Reference 10-9 10-10 1 nm 1Å Atomic Dimensions CURING OF RESIN BASED COMPOSITES • Chemical Activation: Initial method of curing initiated by mixing two pastes just before use. During mixing it is impossible to avoid incorporating air into the mix thereby forming pores that weaken the structure and trap oxygen which inhibits polymerization during curing Also with chemical activation the operator has no control over the working time after the two components have been mixed So both insertion and contouring must be completed quickly once the resin components are mixed Light activation • Light activation is the currently used technique to cure the resin based composites so it has to be discussed at a stretch: • Advantages : Mixing not required so less porosity and staining and greater strength An alliphatic amine as an activator so greater color stability Command polymerization on exp to blue light controls W.T • Disadvantages : Limited depth of cure ie 2mm or less Poor access in posterior and interproximal areas Variable exposure times with diff shades,longer exp times for darker shades increases opacity Sensitivity to room illumination forming a crust or skin IR band-pass filter UV band-pass filter INTENSITY INTRAPULPAL HEAT, GINGIVAL IRRITATION UV Visible CQ WAVELENGTH (nm) • • • • • • Power Supply Cycle Timer (Circuit Board) Bulb / Reflector Filter Fan Fiber-Optic Train IR • • • • • Curing Lamps Curing lamps are hand held devices that contain the light source equipped with a short rigid light guide madeof fused optical fibers At present the most widely used light source is a quartz bulb with a tungsten filament in a halogen environment similar to those used in automobile head lights Precisely power supply heats the tungsten filament in the bulb the output of which depends on voltage control and operational characteristics Within the unit the light is collected by reflecting it from a silverized parabolic mirror behind the bulb towards the path down the fiberoptic chain to tip So imp to keep the mirror surface clean as it heats during operation and cools in between condenses vapors from mercury,bonding system solvents or moisture in operatory • So it should be cleaned with alcohol swabs or with methyl ethyl ketone • Of the light produced only 0.5 % is useful for curing most of it being converted to heat at some point of time so to minimize heat two band pass filters UV and infrared are placed in path of light just before fiber optic system which eliminate significant amount of unnecessary light and convert it to heat within the unit for which a fan is placed to dissipate the unwanted heat • Light passed through fiber optic bundle is emitted from the tip some of which is lost through the fiber optic system.Also high intensity is observed from the center of the bundle.So tip should be free of cured resin and if necessary cleaned with rubber wheel on slow speed • Curing light output is monitored directly with a built in radiometer or by trial curing of composite. • Most modern units have a radiometer as part of it which measures the no of photons per unit of area per unit of time but does not discriminate the light energy that is matched toinitiator.Generally QTH lamps have an output of 400 to 800 mW/cm2 and should not fall below 300 mW/cm2 • Shifting from a standard 11mm diameter tip to a small 3mm tip increases the light output 8- fold.This increases the chance that heat produced will raise the temperature of the restoration and surrounding dentin to dangerous levels.Increase more then 5 to 8oC causes cell death • Ideally tip should be adjacent to the surface being cured but this would cause tip to get contaminated by material being cured.The intensity of light striking the composite is inversely proportional to the distance from tip to composite surface .So ideal is tip within 2mm of the composite to be effective which may not be possible due to anatomy or distance into prep extensions create geometric interference • Distances of 5-6 mm are also encountered in fact distances beyond 6mm for QTH lamps output may be less than one third at tip so to permit closer approximation of the light to composite Light transmitting wedges for interproximal curing and light focusing tips for access to proximal boxes • Smaller tips are very useful but may require more light curing cycles to cover the same amount of cured area • Filler particles tend to scatter light and darker colorants absorb the light so no more than 1.5-2 mm increments be light cured at a time.Smaller particles in range of 0.1-1um interfere most with the light and maximize scattering. • The intensity of the tip output generally falls off from the center to edges producing a bullet shaped curing pattern which may produce inadequate curing in regions as proximal box line angles of Cl II restorations • Most light curing requires a minimum of 20 secs for adequate curing under optimal conditions of access.To guarantee adequate curing has occurred it has become common to post cure for 20 to 60 secs (curing again after completion of the recommended curing procedure which may improve surface layer properties like wear resistance • Typical curing cycles of 20 secs are laborious and interests in much shorter ones is strong • Lamps with increased intensities opening the possibility of reduced exposure times and greater depth of cure • But light absorption and scattering in composites reduces the power density and degree of conversion (DC) exponentially with depth of penetration • DC is measure of percentage of carbon-carbon double bonds that have been converted to single bonds to form a polymeric resin The higher the DC better the strength, wear resistance, and many other properties.A DC of 50-60 % for BIS-GMA implies that 50-60 % of the methacrylate groups have polymerized. This does not imply that 40-50 % monomer molecules are left in resin because of one of the two methacrylate groups per dimethacrylate could still have reacted and could be covalently bonded to polymer forming a pendant group however conversion is controlled by many factors Total DC within resins does not differ between chemically activated and light activated having same monomer formulations. Conversion values of 50-70% are achieved at room temperature for both types DC is related to intensity of light and duration of exposure decreasing considerably with depth A curing light may only produce a 55 % degree of cure at 1mm into composite and even less at greater depths The boundary between between somewhat cured and uncured material is called the depth of cure and is of 5mm for light Vita shades (A2 or A3)of material in which tip is close to composite but in cases of poor access or darker shades it is less and so materials placed and cured in increments of 1.5-2mm and for darkest increments of 1mm. Light is also absorbed and scattered as it passes through tooth structure especially dentin causing incomplete curing in critical areas as proximal boxes so while attempting to cure through tooth structure exposure time should be increased by a factor of 2 to 3 • High intensity curing involves combination of increased light output and a narrowed wavelength range for output using more discriminating band pass filters or other means • This goes well if initiator is coincident with the wavelength range of the light source • Heat is an important problem with this system.They do not produce the same type of polymer network during curing • Rapid polymerization produces more stresses and weakens the bonding system layer against tooth structure As at beginning only some monomer is consumed and system is still a viscous liquid but as it progresses net volume decreases and as long as it is liquid it deforms but as DC reaches 10-20% the network creates a gel and beyond this gel point shrinkage creates strain on network and attachment area to bonding system, the stresses being relieved afterwards but are deleterious at the time of curing because of effects on restoration marginal walls • Light curing influences the initiation process(of the 4 steps :activation,initiation, propagation,termination) • Increased light intensity increases the amount of effective activation and subsequent number chains started. • However there is a practical point at which it is no longer useful to encourage activaiton • The stages in polymerization occur quickly already. • Activation and initiation occur in less than a second • Early propagation rates are extremely fast 100000 to 1000000 reactions per second. • So increased light intensity is useful only to push the degree of conversion to high levels deeper within a material • However amount of unreacted material is important as it may diffuse out of system • Current composites have two or more principal monomers and they do not coreact equally. • TEGDMA constitutes most of the unreacted monomer • Keeping this in view many things have been attempted in terms of technique and the armamentarium used for composite restorations One way to overcome limits of curing depth and other problems with light curing is to go for dual cure resins consisting of two light curable pastes one having BPO and other containing an aromatic tertiary amine.When they are mixed and exposed to light, light curing is promoted by amine/CQ combination and chemical curing by amine/BPO interaction esp in situation that does not allow sufficient light penetration eg cementation of bulky ceramic inlays Also extraoral heat or light can be used to promote a higher level of cure eg. A chemical or light cured composite can be used to produce an inlay on a tooth or die This can be cured directly within the tooth or on die and transferred to an oven where it receives additional heat or light curing • Reduction of residual stresses : In case of chemical cured resins internal pores act to relax residual stresses that build up during curing(pores enlarge during hardening and reduce the concentration of stresses at margins).Also slower curing rate of chemical activation allows a larger portion of shrinkage to be compensated by internal flow among the developing polymer chains before formation of extensive cross linking • But for the light cured resins two approaches: By altering the chemistry and/or composition of resin system which is more desirable and intensive research efforts are currently going to develop resins with low shrinkage and low TE Clinical techniques designed to offset the effects of polymerization shrinkage: Incremental build up and Cavity configuration: attempts to reduce the so called C-Factor which is related to cavity preparation geometry and is represented by ratio of bonded to non bonded surface areas. Residual polymerization stress increases directly with this ratio.During curing shrinkage leaves bonded cavity surfaces in a state of stress and nonbonded free surfaces(ie those that reproduce the original external tooth anatomy) relax some of the stress by contracting inward toward the bulk of material A layering technique in which the restoration is built up in increments curing one layer at a time effectively reduces polymerization stress by minimizing the C-factor ie thinner layers reduce bonded surface area and maximize nonbonded surface area thus minimizing the associated C-factor Thus incremental build up overcomes both limited depth of cure and residual stress concentration but adds to time and difficulty of placing a restoration Soft Start,Ramped curing and Delayed Curing: Another approach is an initial low rate of polymerization thereby extending the time available for stress relaxation before reaching the gel point which is accomplished by a soft start technique in which curing begins with low intensity and finishes with a high intensity allowing high initial level of stress relaxation during early stages and it ends at max intensity once gel point has reached This drives the curing reaction to the highest possible conversion only after much of the stress has been relieved Variations in this technique include ramping and delayed curing o Ramping means the intensity is gradually increased or ramped up during exposure.This ramping consists of either stepwise,linear or exponential modes. o Delayed curing means restoration is initially incompletely cured at low intensity and then the clinician sculpts and contours the resin to correct occlusion and later applies a second exposure for the final cure , the delay allowing substantial stress relaxation to take place.The longer the time available for relaxation lower the residual stress In addition to the normal QTH lamps other types with high intensity curing rate have been introduced with an intention to decrease the curing time : PAC lamps : uses a xenon gas that is ionized to produce a plasma.The high intensity white light is filtered to remove heat and to allow the blue light to be emitted Argon laser lamps : Have highest intensity and emit at a single wavelength. Lamps currently available emit light 490 nm Curing depths equivalent to that of a 500 mW/cm2 QTH lamp(2mm at 40 sec) have been demonstrated using an exposure time of 10 sec with PAC lamps and 5 sec with argon laser lamps PROPERTIES OF COMPOSITES • • • • PHYSICAL PROPERTIES THERMAL PROPERTIES MECHANICAL PROPERTIES CLINICAL PROPERTIES’ PHYSICAL PROPERTIES Working and Setting time : • For light cured composites initiation of polymerization is related specifically to application of light beam to material • About 75% of polymerization occurs during the first 10 mins while the curing reaction continues for a period of 24 hours.Remaining 25% of available carbon double bonds remain unreacted in the bulk • If surface is not protected from air by transparent matrix,polymerization is inhibited • Although restorations can be finished and are functional after 10 mins but optimum properties achieved 24 hours after reaction is initiated • Within 60-90secs after exposure to ambient light the surface looses its capability to flow readily against tooth structure POLYMERIZATION SHRINKAGE SHRINKAGE (%) 5 50% Filler 25% Bis-GMA 25% TEGDMA 65% Conversion 4 3 Porosity Formation 2 (Internal Contraction) 15-25% = Gellation Bond Stretching (External Contraction) 1 Flow 0 0 25 50 75 CONVERSION (%) 100 Polymerization Shrinkage : • Composites shrink during hardening referred to as polymerization shrinkage • It produces internal stresses and causes pulling away of the material from the cavity walls • Most composites only can be practically cured to levels of 55-60% degree of conversion of reactive monomer sites • In early stages,there are limited no of polymer chains and they are not well connected but with 20% conversion polymer network is sufficient to create a gel where the system changes from behaving like a liquid that can flow to a solid that has increasingly stronger mechanical properties • So during the first 20% the shrinkage is accommodated by fluid changes in dimension of system • But after the gel pointshrinkage produces both internal stresses within the network and stress along all the surfaces of system • Bounded surfaces of enamel and dentin may undergo some local stress which could reduce the strength of the recently forming bonding layer.Unbounded surfaces will distort,when possible,to accommodate the stresses • In early 80s when composites were less highly filled and bonding systems were not as reliable or strong it was possible that shrinkage stresses form composite curing actually dislocated the newly bonded surfaces and created marginal openings • The consequences of this process were first analyzed by Feilzer and others and described in terms of the ration (Configuration factor or C-factor) • C-factor: It is the ratio of bonded surfaces to the unbonded surfaces in the tooth preparation It ranges typically for dental restorations form 0.1 – 5.0 with higher values >1.5 indicating more likelihood of high interfacial stresses. Light cured composites develop higher stress than auto cured analogues further high with higher energy curing light Newer dentin bonding systems are designed thicker gto be stress relieving so typical wall stresses on during curing may actually be only 1-2 Mpa within acceptable range Stresses both within cured composite and along walls appear to be relived in few hours accelerated by water absorption Recently strong interest in oxirane & oxitane chemistry as a method of designing controlled shrinkage composites THERMAL PROPERTIES Linear coefficient of thermal expansion : • It is rate of dimensional change of material per unit change in temperature • The closer the LCTE of material to the LCTE of enamel,the less chance there is for creating voids or opening at the junction of the material and tooth • LCTE of Tooth structure is ppm / oC Unfilled resin is 72 ppm / oC Composites 28-45 ppm / oC • LCTE of composite is approx. 3 times that of tooth structure • During extreme intraoral temperature changes and times significant stresses are generated at the tooth restoration interface where the composites are micromechanically bonded • If the interfacial bond fails microleakage may produce unesthetic staining, pulpal sensitivity due to dentinal fluid flow, pulpal irritation due to diffusion of bacterial endotoxins and predisposition towards recurrent caries • Intraoral temperature changes of 20 to 30 oC that involve only 20-30 secs may be insufficient to produce significant temperature change in either tooth structure or composites • The more is the resin matrix higher is LCTE Water sorption : • It is the amount of water that a material absorbs over time per unit surface area or volume • Water absorption swells the polymer portion of the composite and chemically degrades matrix into monomer or other derivatives • Materials with higher filler content exhibit lower water sorption value.Those with fine particles have greater value than those with microfine particles Water solubility : • It is loss of weight per unit surface area or volume due to dissolution or disintegration of material in oral fluids over time at a give temperature • The value varies from 0.01-0.06mg/cm2 • Inadequately polymerized resin has greater solubility manifested clinically by color instability. MECHANICAL PROPERTIES Strength : • Compressive strength and tensile strength of composite is higher than silicate and ASPA • The flexural strength of various composites are similar Modulus of elasticity : • It is the stiffness of the material.A material having a higher modulus is rigid conversely that having lower value is more flexible. • The microfill composite with greater flexibility may perform better in Cl V restoration than a more rigid hybrid • Particularly true fo Cl V restorations with heavy occlusal forces where stresses concentration exists in cervical area Bond strength : • The bond strength of composites to etched enamel and dentin is typically between 20 and 30 Mpa • Composites can be bonded to existing composite restoration, ceramics and alloys when the surface is roughened and primed appropriately • Bond strength to treated surfaces are typically greater than 20 Mpa CLINICAL PROPERTIES Degree of conversion : • It is the measure of the percentage of consumed carbon carbon double bonds • It is related to both the intensity of light and duration of exposure • It decreases considerably with depth into a composite material • Most composites can practically be cured only to level of 55-65 % • The vast majority of current composite employ camphoroquinone as a photoinitiatior and it absorbs photons of light energy predominantly at 474 nm • Most light curing requires min of 20 secs for adequate curing and for complete curing post curing of 20-60 secs CHEMICAL PROPERTIES Curing Light 3. DEPTH-OF-CURE 0 mm 1 2 65% 3 4 45% 25% 1. DEGREE-OFCONVERSION 2. SHAPEOF-CURE Z100 FACTORS AFFECTING CURE Equipment + Procedural + Restorative Factors • • • • • • • • • Bulb frosting or degradation Light reflector degradation Optical filter degradation Fiber-optic bundle breakage Light-guide fracture Tip contamination by resin buildup Line voltage inconsistencies Sterilization problems Infection control barriers Procedural Factors • • • • • • Light tip direction Access to restoration DISTANCE from surface Size of tip Tip movement TIME of exposure Restoration Factors • • • • • Restoration thickness Cavity design Filler - amount and size Restoration shade Monomer ratios Curing Equipment Factors Check Fiber Optic Tips Clean Reflector Check Bulb and Reflector Wear resistance : • It refers to material’s ability to resist the surface loss as a result of abrasive contact with opposing tooth structure,restorative materials,food bolus or tooth picks • The wear of composite is affected by : Filler particle size,shape and content Location of restoration in dental arch Occlusal contact relationship • Types of wear Wear by food (Contact free area wear /CFA) Impact by tooth contact in centric(Occlusal cont. area wear) Sliding by tooth contact in function(Funct. cont. area wear) Rubbing by tooth contact interproximally Wear from tooth brush or dentifrices COMPOSITE WEAR 5 Wear Types: CFA = food bolus wear OCA = impact wear FCA = sliding wear PCA = sliding wear TBA = abrasive wear 1st Premolars 30% 40% 100% FOOD BOLUS 60% 2nd Premolars 1st Molars 2nd Molars • Theories of wear in CFA are : Microfracture theory : The filler particles are compressed into adjacent matrix during the occlusal loading and this creates a microfracture in weaker matrix with passage of time these microfractures become connected and surface layer of composite exfoliates Hydrolysis theory : It proposes that the silane bond between the resin matrix and filler particles is hydrolytically unstable and becomes debonded.The bond failures allow surface filler particles to be lost Chemical degradation theory : Material from food and salive are absorbed onto the matrix causing degradation and sloughing from the surface Protection theory : o Proposes that the weak matrix is eroded between the particles o Wear can basically occur due to improper case selection,inferior material used and insufficient operator’s skill o Large extensive posterior composites that have total occlusal contact are more prone to fail o Composite restorations that are relatively narrow in its preparation minimizes food bolus contact and provide sheltering for the restoration called Macroprotection theory o Filler particles are much harder than resin matrix thus sheltering the intervening matrix called Microprotection theory o Microfills are most wear resistant formulations WEAR (CFA, mm) Wilder AD, May KN, Bayne SC, Taylor DF, Leinfelder KF. 17-year clinical evaluation of UV-cured composite resins in posterior teeth. J Dent Res 1996; 75: 173, Abstr 2100. 300 MACRO PROTECTION R2 = 0.99 ENAMEL LATE WEAR 200 MIDDLE WEAR 100 MICRO PROTECTION 1 2 5 10 EARLY WEAR 20 TIME (years) SC Bayne Surface texture : • Restoration close to the gingival tissues requires surface smoothness for optimum gingival health • Size and composition of filler particles determines the smoothness of restoration • Midifill composites with larger particles show more surface roughness than microfill having smaller filer size particles Radio opacity : • Aesthetic restorative materials should be sufficiently radiopaque so that the radiolucent margin of recurrent caries around or under the restoration can be more easily detected • Most composites contain radiopaque filer such as Barium glass to make the material radiopaque Fluoride release : • Conventional composites lack fluoride releasing abilities • Fluoride releasing composites are available containing some filler particles with releasable fluoride, long tem fluoride release is quite low • Incorporation of inorganic fluoride has resulted in increased fluoride release but with creation of voids in matrix as the organic fluoride leaches out • Dispersion of leachable glass or soluble fluoride salts into polymer matrix water soluble diffusion of fluorides from the composite into local environment.Most of fluoride is during the setting reaction with a small long term fluoride release • Addition of organic F salts like Methacrylol fluoride – Methyl methacrylate acrylic amine –HF salt, t- butylamine ethyl methacrylate HF and recently terbutyl ammonium tetrafluoroborate CLINICAL CONSIDERATIONS Color matching Interfacial staining and secondary caries Wear Marginal integrity Fracture Post operative sensitivity Color matching : • Color matching not only depends on initial color match but also on relative changes that occur with time.Both restoration and tooth structure change color with age • Assessment is made with tooth properly hydrated.Temporarily drying the tooth structure makes it appear lighter and whiter in color because of dehydration of enamel • With time chemical changes in matrix polymer makes composite to appear more yellow which is accelerated by exposure to UV light,oxidation,and moisture. • Self cured ones under go more yellowing while newer visible light cured systems containing high filler contents and are modified with UV absorber and antioxidants making it more resistant to color change • However tooth structure undergoes a change in its appearance over time because of dentin darkening from aging.Aged tooth appears opaque and darker yellow.Dentin is more likely to change color more rapidly most rapidly during middle age (35 to 60 years) • Bleaching which is very popular complicates the process of trying to establish and maintain good color match of an anterior restoration .If bleaching occurs as a treatment of fixed duration restorative procedures should be postponed until after teeth have assumed a stable lighter shade (probably after 2 weeks).Bonding done 48 hrs after bleach • Also gradual transition in color and translucency between restoration and tooth structure.This goal is accomplished by beveling the enamel, which blends the color difference associated with margin over approx 0.5-1mm rather than making it abrupt Interfacial staining and secondary caries : • Marginal leakage leads to accumulation of subsurface interfacial staining that is difficult to remove and creates a marked boundary for the restorative appearance • Proper beveling and etching of enamel results in good resistance to interfacial staining. • As long as margins are well bonded and no marginal fractures occurs resistance to secondary caries should be good • Most secondary caries occurs along proximal or cervical margins where enamel is thin, less well oriented for bonding, difficult to access during the restorative procedure and potential subject to flexural stress as well.Rarely secondary caries are evident along margins on occlusal surfaces or non cervical aspects of other surfaces Wear : • The principal concern for posterior composites is that occlusal wear could occur at a high rate and continue over long periods of time, exposing underlying dentin and leading secondary caries or sensitivity • Evidence of composites actually wearing to point of exposing underlying dentin is only minimal and after many years of service worn restorations can be repaired simply by rebonding a new surface onto the old composite to replace a worn or discolored surface Marginal integrity : • It is very good under most circumstances.Clinical appearance is affected by the nature of margin.Butt joint margins emphasize composite wear more than beveled margins. • Butt joint margins of well bonded margins of well bonded restorations wear more slowly and create meniscus appearance against the enamel • However as beveled margins wear thinner edges of material are produced that are more prone to fracture Fracture : • Bulk fracture of posterior is rare • Microfill composites are more prone to fracture at occlusal contact areas Post operative sensitivity : • Causes of post operative sensitivity are : Operative trauma:Deep cavity preparation with excessive dry cutting at ultra high speed Previous insults:Cumulative effects of repeated episodes of pulpal irritation may often results in chronic to sub acute pulpal inflammation and final necrosis Undercure: of either composite material or protective base may result in skin effect a hard fully cured outer layer and a relatively soft under cured inner layer Hyper occlusion :If a high spot is left on composite restoration the tooth will become hypersensitive within a few days Polymerization contraction : May place the cusps under tension thereby disturbing fluid balance in dentinal tubules.Same shrinkage may draw the base away form the dentinal interface thus resulting in a contraction gap,microleakage and subsequent bacterial invasion causing post operative pain and sensitivity Indications of composites Aesthetic restorations of Class I,II,III,IV,V,VI cavities Foundation or core build ups Sealants and conservative composite restorations Aesthetic enhancement procedures Partial veneers Full veneers Tooth contour modifications Diastema closure Cement for indirect restorations temporary restorations Periodontal splinting Contradictions of composites In areas of heavy occlusal stresses Sites that cannot be isolated In patients who are allergic or sensitive to composite resin Advantages of composites • Aesthetic restoration • Conservation of tooth structure (as less extension,uniform depth not necessary,mechanical extension not required) • Less complex when preparing tooth • Insulative, low thermal conductivity • Used almost universally • Bonded to tooth structure resulting in good retention, low microleakage, minimal interfacial staining and increased of remaining tooth structure • Repairable Disadvantages of composites • Gap formation occurs on root surfaces due to forces of polymerization shrinkage of composite being greater than initial bond strength of material to dentin • More difficult, time consuming, costly than amalgam • Tooth treatment usually requires multiple steps • Insertion is more difficult • Establishment of proximal contacts,axial contours,embrasures,and occlusal contacts more difficult • More technique sensitive • Exhibits wear in areas of high occlusal stress or when all contacts are on compostie • High LCTE resulting in marginal percolation if improper bonding technique is used Extended applications for composites • • • • • • Anterior veneers Porcelain bonding Core build up Posterior restorations Orthodontics Pit and fissure sealants Anterior veneers : • Application of anterior cosmetic veneers to mask hypoplasia or discoloration has become an integral part of dentistry • Composites placed in a thin layer over etched enamel and sculpted to provide enhanced tooth form or esthetics • Lower viscosity composites for direct application against etched enamel have been developed which is diff to control • Those with filler content less than 20 wt% formulated with opacifiers added iv a variety of shades to block out stained enamel • Tinted composites with added color modifiers are also available in varied shades such as yellow,brown,blue,black and pink to provide characterization for an anterior veneer • These shade modifiers are all photoinitiated and although they require additional exposure to light, can be cured as they are applied to gain desired esthetic effect • By layering these composites either under or between applications of composites life like color characteristics can be developed • Labial veneers can also be made indirectly on a model with newer materials in which the degree of polymerization can be increased with higher energy light sources,vaccum chambers,and applied heat.Then the prefabricated veneer is luted to the etched enamel surface with a lower viscosity composite cement. • Weakest portion of the bonded interface is the bond between the precured composite veneer and freshly applied composite cement which may leak and require repair Porcelain bonding : • Porcelain bonding systems have been developed to lute indirect anterior veneers to etched enamel and also to place a composite restoration that replaces fractured porcelain • When broken porcelain is being repaired the interface must be roughened to increase surface texture and to create some mechanical locking • These lasted for short periods frequently as they were generally in full incisal function and those with least use had best prognosis • Porcelain veneers can be bonded to enamel with similar techniques and a low viscosity composite cement which is more successful as a larger surface area of porcelain is available and is generally roughened by a HF treatment during fabrication Core build ups : • Modifications have been made to alter the viscosity and the setting time of highly filled composites to formulate core materials that will closely adapt to pins and posts • They are usually chemically initiated so that they can be inserted with a syringe enclosed in a metal or celluloid crown form or matrix and cured in bulk.This is why these materials have slightly prolonged working time (approaching 2 mins) and a relatively quick snap set • Since they are highly filled composites they provide optimum resistance to deflection forces and shear stresses • Also highly colored or opaque materials so that there will be a visible interface at the composite-tooth junction during final cavity preparation Posterior restorations : • Indications: Primary indication is aesthetics Need for conservative preparations but not used for cuspal coverage or better not to use for restorations exceeding 1/3rd the buccolingual width of the tooth Use of composites to decrease thermal conduction • Many composite formulations for posterior applications like one is microfine filler sintered into macrosized particles to improve wear resistance while another has hydrophobic resin matrix to reduce water sorption with the hope that failure of silane coupling agent be reduced • The packable/condensable composites introduced in late 1990s derive from inclusion of elongated fibrous filler particles of about 100 um in length and/or textured surfaces • • • • • that tend to interlock and resist flow This causes the uncured resin to be stiff and resistant to slumping yet moldable under force of amalgam condensing instruments(pluggers). Rough surfaces and blends of fibrous and particulate filler produce a packable consistency and enable it to be used At present they have not yet proven to be an answer to the general need for highly wear resistant,easily placeable posterior resins with low curing shrinkage and a depth of cure greater than 2mm It is still uncertain in dental profession whether a 250 um loss of substance truly represents a clinically acceptable restoration that adequately supports occlusal function.Also the wear being greatest in occlusal functional contact Limited to Cl-I,II in premolars with minimal B-L extension • Indirect posterior composites: Indirect composites for fabrication of onlays are polymerized outside the oral cavity and luted to the tooth with a compatible resin cement which has been said to reduce the wear and leakage and overcome some limitations of resin composites Several different approaches for resin inlay construction: o Use of both direct and indirect fabrication methods o Application of light,heat,pressure,or a combination of these o Combined use of hybrid and microfilled composites Fabrication process for direct composite inlays requires application of a separating medium to the tooth(glycerin,agar sol) resin pattern is then formed,light cured and then removed.Rough inlay then exposed to light for more 4 to 6 mins or heat activated at 100oC for 7 mins after which the preparation is etched and the inlay is cemented in to place with a dual cure resin and then polished Composite systems are also available as indirect products.Indirect inlay resins require an impression and fabrication of inlay in lab,in addition to conventional light and heat curing,lab processing may employ heat 140oC and pressure 0.6Mpa ofr 10 mins.The potential advantage of these materials is somewhat higher degree of polymerization is achieved improving physical properties and wear resistance Polymerization shrinkage does not occur in prepared teeth and so induced stresses and bond failures are reduced which reduces the potential for leakage.Also repairable in mouth and not abrasive to opposing tooth structure like ceramics Orthodontics : • Lower viscosity filled composites are also being used for the cementation of orthodontic brackets to the facial surfaces of both anterior and posterior teeth. • Enamel is acid etched in the usual manner and each bracket is applied directly to the surface in the desired position • High modulus fine composites resist stress better than unfilled or microfine composites so most orthodontic composites are fine particle or hybrid composites Pit and fissure sealants : • Pit and fissure sealants were first proposed in 1960s which prevent tooth preparation and restoration techniques fro the elimination of caries prone pits and fissures on occlusal surfaces of teeth • Pits and fissures that are not self cleansing are caries prone • The objectives of these materials is to eliminate the geometry that harbors bacteria and to prevent nutrients reaching bacteria in base of pit and fissure • Since they have modest wear resistance,contact area wear and food abrasion may quickly wear it away from naturally self cleansing areas where it is not needed although key areas remain occluded • The principal feature of sealant is adequate retention • Sealant is applied only after gross debridement isolation and acid etching of surfaces.And can’t be applied so precisely that there is no excess extending onto self cleansing areas of occlusal surfaces. • So it is important the material is adjusted as needed following placement so that it does not interfere with normal occlusal contacts or disrupt occlusal paths,once removed from self cleansing areas rest blocks the non cleansing area • Classification and History: They can be self curing and visible light curing Early ones were based on methyl methacrylates or cyanoacrylates Most contemporary are unfilled or lightly filled and based on difunctional monomers such as used for matrix of composites Principal monomer of this system BIS-GMA is diluted with lower mol wt species like TEGDMA to reduce the viscosity with addition of colorants such as titanium dioxide • Composition,Structure and properties : Primary clinical property is flow into small access spaces:Penetration coefficient that is relative rate of flow in a standard sized orifice.Penetration is a function of capillary action and viscosity. If a site is well cleaned,etched,rinsed and dried than acrylic monomer can wet the surface reasonable well even if the opening is small it will draw the material by capillary action if the viscosity is low long enough. Complete penetration is not absolutely critical only if the neck region is occluded it is clinically acceptable Glass ionomers were explored for pit and fissure applications but lacked sufficient abrasion resistance ,were brittle and prone to fracture Traditional composites are not good sealants as they do not penetrate into pits and fissures readily due to high viscosity but instead useful in treating such caries Newer low viscosity versions composites,flowables have been used for this purpose had good wetting,sufficient flow,adequate abrasion resistance,god fracture resistance. Properties are like the resin matrix of composites.No evidence that water sorption,chemical degradation,or other events observed with composites detract from longevity of these materials However one controversy of BIS-GMA degrading into BPA which was found to be estrogenic although many flaws in the report as misidentification of TEGDMA as BPA Also measured levels of monomer released from sealents was unusually high but it was not noted that air inhibited superficial layer of resin had not been removed by wiping with cotton roll before sampling which is generally wiped away or lost during the first few chewing strokes and this is not the actual cured sealant material • Clinical considerations: Prevention of occlusal caries at defects depends simply on exclusion of bacteria or their nutrients Many say as long as pits and fissures remain completely sealed there is 100% prevention of caries at those sites. The ideal time to apply sealants is soon after occlusal surfaces erupt into the oral environment but with with partial eruption difficult to maintain isolation (cotton rolls/absorbent wedges) Sealants also have been applied to smooth surfaces to try to eliminate caries but are abraded by food and/or brushes Another important consideration is degree to which children and adolescents are susceptible to caries.The one who are at greater caries risk are the most benifitted.Older patients with decreased salivary flow are also good candidates Also used to repair or seal leaking or failing dental restorations It is now accepted that sealants provide outstanding service when done properly for very low costs.In societies committed to dental care this is a core strategy for early management of caries FINISHING AND POLISHING Original rough surface SURFACE ROUGHNESS = Ra Average up-and-down geometry = 20 mm COARSE finished Significant material removal New surface approximates abrasive size 2 mm 0.2 mm FINE finished Polished Fine grooves Smearing and burnishing to smoothen surface TWO CRITICAL FACTORS for Finishing and Polishing: (1) Abrasive size (2) Filler particle size FINISHING OF COMPOSITES • Optimum finishing and polishing of composite resins is very important step in completion of restoration as residual surface roughness can encourage bacterial growth leading to myriad of problems including secondary caries,gingival inflammation and surface staining • The best possible finish is produced by not polishing the surface at all at least for surfaces that have polymerized next to matrix strip.The smoothest surface on a restoration on a restoration can be obtained by curing the composite against a smooth matrix strip which minimizes porosities as well as the oxygen inhibited layer • Three important factors affecting finishing and polishing: Environment,Delayed vs Immediate finish,Type of material Environment refers to whether to perform in dry or wet field.Some suggest dry field on a slow speed for better visualization but it has been shown that the heat produced disturbs the marginal seal and that structural and chemical changes occur in restoration in dry field but some say dry polish has no effect on hardness or surface structure. o In a way it should be carried out in moderation in an environment in which the margins are clearly discernible and where minimal heat is generated.Water cooling during grinding and finishing should ensure standard quality Elapsed time has too an effect as some say delaying the finishing for up to 24 hrs because polymerization is incomplete at placement although manufacturers recommend that finishing be accomplished shortly after placement.But studies indicate not much of a diff in both o Thus for all practical purposes all composite restorations should be finished and polished shortly after placement during the same appointment although the finishing should be delayed for approximately 15 mins after curing Several systems can be used for this purpose.Use of a scalpel blade or any thin sharp edged instrument to remove flash on the proximal areas is recommended although very risky esp if trimming involves shearing in direction away from gingival margin which can lead to debonding and leakage.Trimming forces should be parallel or towards the gingival tissue o Coarse to ultrafine aluminium oxide discs produce the best surface and minimal trauma.Tungsten carbide burs or fine diamond tips used to adjust occlusal forces and blending o Other systems extrafine polishing pastes,silicone resin finishing devices,silicone carbide brushes and points o The most important step in finishing and polishing is application of a bonding agent or a surface sealer o It is been widely documented that finishing and possibly polishing is detrimental to composite surfaces in that it introduces microcracks and removes the most highly polymerized area of the restoration o Application of surface sealer or low viscosity resin with letter or no filler ensures that surface porosities are filled and microcracks are sealed which also decreases microleakage by improving the marginal seal of restorations REPAIR OF COMPOSITES • Composites may be repaired by placing new material over the old one • When a restoration has just been placed and polymerized it may still have an oxygen inhibited layer of resin on the surface.Additions of new composite can be made directly to this layer because this represents an excellent bonding substrate.A restoration that has just been cured and polished may still have more than 50 % of unreacted methacrylate groups to copolymerize with the newly added material • As it ages fewer unreacted methacrylate groups remain and greater cross linking decreases the ability of fresh monomer to penetrate in matrix.Strength of the bond between the original and new resin decreases with time elapsed between polymerization and addition of new resin • Also polishing exposes filler surfaces free from silane so the filler surface area does not chemically bond to the new composite layer. • Under the most ideal condition the addition of a silanate bonding agent to the surface before the addition of new composite,the strength of the repaired composite is less than half the strength of the original material Biocompatibility of composites • The chemical insult to pulp from composites is possible if components leach out or diffuse from the material and subsequently reach to pulp.Adequately polymerized composites are relatively biocompatible because they exhibit minimal solubility and unreacted species are leached in very small quantities • Inadequately cured material at the floor of a cavity can serve as a reservoir of diffusible components that can induce long term pulp inflammation esp for light activated materials ie too thick a layer cured for less of time leaving uncured or poorly cured material • Second concern is with shrinkage of composite during polymerization and subsequent marginal leakage • This leakage allows bacterial ingrowth and cause secondary caries or pulp reactions • Bisphenol A a precursor of bis-GMA has been shown to be a xenoestrogen or a synthetic compound found in the environment that mimics the effects of estrogen by having an affinity for estrogen receptors • BPA and other endocrine disrupting chemicals (EDC) have been shown to cause reproductive anomalies especially in developmental stages of fetal wildlife • Although unclear in humans testicular cancer, decreased sperm count,and hypospadias have been sen due to csp to EDCs • BPA has recently been shown to exhibit antiandrogenic activity which may prove to be detrimental in organ development and estrogenicity mainly related to BPA and BPA dimethaacrylate (in vitro applied to cancer cells) COMPOMERS • They are defined as poly acid modified resins • These materials are basically light cured, low fluoride releasing composite resins • The difference between composites and compomers is that compomer monomer contains acidic functional group that can participate in an acid base glass ionomer reaction following polymerization of the resin molecule • It consists of a paste of Ca, Al, F silicate glass fillers in dimethacrylate monomer with acrylic acid like molecules • They contain poly acid modified monomers with fluoride releasing silicate glasses and are formulated without water.Some compomers have monomers that provide F release • They are packaged as single paste formulations in compules and syringes • Setting primarily occurs by light cured polymerization but an acid-base reaction also occurs as the compomer absorbs water after placement and on contact with saliva.Water uptake important for F transfer • They require bonding agent to bond to tooth structure • Indications : Cervical restorations Class III restorations Minimal Class I and II restorations Deciduous teeth restorations Geriatric restorations Miscellaneous restorative repair CEROMERS • Term ceromer stands for ceramic optimized polymer. • It is an advanced composite that utilizes combinations of ceramic fillers to provide unique handling,wear and esthetic properties • Consists of a paste containing barium glass,spheriodal mixed oxide, Ytterbium trifluoride and silicone dioxide in demethacrylate monomers • They set by a polymerization of carbon carbon double bonds of methacrylate.They must be bonded to tooth • The properties of ceromers are similar to those of composites and they exhibit F release lower than glass ionomers or compomers ORMOCERS • It is an acronym for organically modified ceramics • This class of material represents a novel inorganic-organic copolymer in the formulations that allows for modifications of its mechanical parameters • This inorganic-organic copolymer are synthesized form multifunctional urethane and thioether methacrylate alkoxysilanes as sol-gel precursors • Alkoxysilyl group of the same permit the formulation of an inorganic Si-O-Si network by hydrolysis and polycondensation reactions • The methacrylate groups are available for photochemical polymerization.Filler particles are 1-1.5 um in size and filler content is 77% by wt and 61 vol%. SMART COMPOSITES • Class of composites was introduced as the product Ariston pHc in 1998.It is an ion releasing composite material. • It releases fluorine, hydroxyl and calcium ions as the pH drops in area immediately adjacent to the restorative material which is the result of active plaque which results in a corresponding increase in release or functional ions • They work based on newly developed alkaline glass filler which reduces secondary caries at margins of restoration produced by bacterial invasion.This results in reduced demineralization and a buffering of acid produced by caries forming micro orgs. • Paste contains Ba,Al,F silicate glass fillers(1 um) with ytterbium trifluoride,silicone dioxide and alkaline calcium silicate glass(1.6 um) in dimethacrylate monomers • Filler content 80 wt % or 60 vol% the use of an adhesive to tooth is not recommended • However the dentin should be sealed to reduce sensitivity • The F release is lower than conventional glass ionomers but more than that of compomers] COMPOSITES WITH EXPANDING MONOMERS • The primary cause of failures of resin based composites is secondary caries because of polymerization shrinkage of these restorations • Several approaches being pursued to reduce polymerization shrinkage • Composites containing expanding monomers such as spiroorthocarbonates were introduced in 1970s.It is believed that low shrinkage results from expansion of oxirane rings as it opens which partially offsets the shrinkage associated with the formation of covalent bonds as monomers are linked during polymerization • The difficulties with these materials has been in producing sufficient ring opening expansion to offset the polymerization contraction without reducing the extent of cure • Recently the system containing expanding monomers a diepoxide monomer and a polyol has reduced polymerization contraction stress compared to commercial Bis-GMA/TEGDMA composites • Various properties of epoxy polyol mixtures: Water sorption with these materials are slightly higher Cycolo polymerizable di and multifunctional oligomers synthesized through the reaction of acrylates and formaldehyde can produce resin with higher conversion and lower shrinkage than acrylates MONOMERS FOR ENHANCED DEPTH OF CURE • Use of monomer with high molecular weight such as multiethylene glycol dimethacrylates have added benefits of producing resins with enhanced cure • Esterified multimethacrylate oligomers of poly (isopropyllidenediphenol) have recently been synthesized and mixed with TEGDMA to produce resin with reduced polymerization shrinkage • One commercial composite contains multifunctional methacrylate monomers organically developed for the indirect resin composite Artglass • Addition of chain transfer agents such as propanal and diacetyl increases the degree of conversion and cross linking of Bis-GMA and UDMA resins from 80-90% to 98% FIBER REINFORCED RESINS • Fiber reinforced polymer resin has been available for many years • Silane treated glass fibers are commonly used as plasma treated polyethylene often in woven form • Unlike glass fibers polyethylene does not appreciably raise the stiffness of the material • They strengthen and toughen the composite for single and multiple unit restoration ANTICARIOGENIC MATERIALS • Imazate developed an antibacterial monomer MDPB(methacryloxydodecylpyridinium bromide) to be added to dental resin • This methacrylated monomercan polymerize assuring that the antibacterial portion of the molecule is permanently affixed to the resin matrix • Composite containing MDPB has been shown to inhibit growth of S.mutans and do not reduce the degree of cure and other properties • Recently an antibacterial material Halo was added at concentration upto 1 wt% to a commercial composites and showed antibacterial behaviour against S.mutans and A.viscosus that lasted for upto 10 weeks BIOACTIVE REMINERALISING COMPOSITES • Calcium phosphate has been used as a filler to make composites that serve as bioactive liner and bases to enhance remineralization • Though this composite provides sustained release of calcium and phosphate ions they have low strength and stability • Recently bioactive polymeric composites based on amorphous calcium phosphate but strengthened by hybridization of fillers with glass forming elements have been developed Surface coating of polymer • A thin clear polymeric material that could be coated onto the tooth to inhibit plaque formation and demineralization may be beneficial • These coatings are made form copolymer of acrylic acid and alkylmethacrylate such as isobutylmethacrylate and a polysiloxane • This copolymer is cross linked via pendant silane group using tetraethylorthosilicate FUTURE POLYMERS • Evidence of molecular addition that enhances cure and radiopacity (triphenylbismuth and other brominated monomers) • Memory polymers that could serve as inlay/onlay materials that expand or contract to fit the prepared tooth as a result of intraoral heating • Lining,coating and restorative material that are self adhesive to dentin • Cationic initiated curing reaction on basic surfaces • Biodegradable polymer scaffolds for carrying drugs, cells and growth factors to tissue sites to repair or close defects