Dental Applications | Poly(Methyl Methacrylate) | Polymers

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Introduction
The dental industry has taken great advantage of polymer science to design materials. Materials used in the oral cavity or external prostheses have very specific requirements, ie, these materials must have physical, chemical, biological, and aesthetic requirements, not always fulfilled by currently available materials. A host of requirements must often be met, including adequate strength, resilience, wear or abrasion resistance, dimensional stability for both fabrication and use, translucency or transparency to provide a match of the natural tissue replaced, good color stability, resistance to the oral environment, show tissue tolerance and low toxicity, and exhibit ease of fabrication into a needed dental device. Since few resins fulfill all the mentioned requirements, the search for improved dental materials has been limited to a few classes of polymeric materials. The various types of monomers and polymers used in dentistry are discussed, along with brief attention given to new areas of promise for preparing better materials. The largest volume of polymeric materials used in dentistry is in prosthetic applications. Polymeric materials are also important in operative dentistry, being used to produce composite resins, dental cements, adhesives, cavity liners, and as a protective sealant for pits and fissures. Elastomers are employed as impression materials. Resilient prosthetic devices are often fabricated to restore external softtissue defects. Mouth protectors are fabricated to prevent injury to teeth, as well as prevent head and neck injuries. Other polymer applications include fabricating patterns for metal castings and partial denture frameworks, impression trays, orthodontic and periodontal devices, space maintainers, bite plates, cleft palate obdurators, and oral implants. Polymeric materials may also be used to fabricate an artificial tongue, when disease results in its loss.
Encyclopedia of Polymer Science and Technology. Copyright John Wiley & Sons, Inc. All rights reserved.

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The discovery of vulcanized rubber in 1839 gave rise to the first polymeric dentures, followed by celluloid dentures about 1870, and subsequent use of vinyl chloride copolymers, phenol–formaldehyde resins, and polystyrene. Acrylic-based resins gained rapid acceptance after 1937, and are being greatly used today. Their main disadvantages are related to shrinkage because of the free-radical polymerization of methyl methacrylate, poor abrasion resistance, and fracture toughness. Other polymers, such as epoxy resins, polystyrene, polyesters, polycarbonates, polysulfones, vinyls, silicones, polysulfides, and polyethers, have been explored or used to some degree. The various dental polymers discussed in this article include impression materials, dentures and denture liners, artificial teeth, crown and bridge materials, mouth protectors, maxillofacial materials, restoratives (consisting of glass polyalkenoates or glass-ionomers and composites), adhesives, and sealants. Specifications and standards for dental materials are also briefly mentioned in the text.

Impression/Duplicating Materials
Impressions must accurately show the dimensions, surface detail, and relationship of teeth and soft oral tissues. Materials used to accomplish this task include rigid gels of the reversible hydrogen-bonding type, irreversible alginate hydrocolloids, and elastomers such as silicones, polysulfides, and polyethers. Duplicates of original casts, used to fabricate partial or complete dentures, are made from duplicating materials. Agar (Reversible Hydrocolloids). Agar, a galactose sulfate or mucopolysaccharide (sulfonic acid ester of a galactan complex), is a long-chain polymer having a molecular weight of about 150,000. The material forms a colloid with water, with the solutions being liquid at ≥70◦ C and setting to a gel at 30–50◦ C. Strong hydrogen bonding causes the molecule to form a helical structure, which uncoils on heating. On cooling, the gel forms and reproduces the shape of the oral tissues. These materials can be used several times, but prolonged heating causes degradation. While agar is the main constituent, it is by no means the main constitutent by weight. For example, a typical formulation consists of about 85.5% water, 12.5% agar, 1.7% potassium sulfate, 0.1% alkyl benzoate, and trace amount of pigments. Fillers, such as zinc oxide and a hard wax or clay, are often used to modify the formulations. Borax or calcium metaborate may be used to control the pH, increase viscosity, toughness, and resiliency. These materials were developed to make accurate impressions, even of undercut areas. The agar used in duplicating uses has a composition similar to the agar impression material, but with a higher water content. ANSI/ADA Specifications No. 11 (1997) applies to agar-based impression materials. Alginates (Irreversible Hydrocolloids). The reactive component in these materials is the sodium or potassium salt of anhydro-o-D-mannuronic acid (alginic acid), isolated from brown seaweed (algae). A typical formulation consists of about 18% sodium or potassium alginate, 14% calcium sulfate dihydrate, 2% sodium phosphate, 10% potassium sulfate, 56% diatomaceous earth filler, and 4% sodium silicofluoride. When mixed with controlled amounts of water, the soluble

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hydrocolloid is converted to insoluble calcium alginate, ie, and an acid–base reaction leads to matrix cross-linking. In the sol–gel conversion, calcium cations form salt-bridges with the carboxylate anions, forming ionic cross-linking. The material can only be used once. The addition of sodium tripolyphosphate or tetrasodium pyrophosphate retards rapid precipitation of gel. Addition of a fluorosilicate completes the precipitation of the insoluble alginate, after adequate working time has elapsed. Besides diatomaceous earth filler, zinc oxide may be used to improve strength and yield a material with a smooth, nontacky surface. Alginates, used most frequently to make impressions, are inexpensive, easy to manipulate, and comfortable for the patient. But, alginates deteriorate rapidly on storage at ≥50◦ C and once set they must be kept in 100% relative humidity to prevent shrinkage. In addition, they are the least accurate of the impression materials. Both reversible and irreversible hydrocolloids have been used at the same time in a laminating technique. ANSI/ADA Specification No. 18 (1992) sets the requirements for fast and slow setting alginate impression materials. Synthetic Elastomers. Synthetic elastomers, such as polysulfides, silicone, and polyethers, exhibit much better dimensional stability than the hydrocolloids. They are mainly used in crown and bridge applications or for impressions of dentate patients. These polymers are used at a temperature above their glasstransition temperature (T g ). The viscosity of the materials used is influenced by both the working temperature above T g and the length of the polymer chains, as well as by fillers and other additives. The formulated materials are liquids or pastes at room temperature, which transform into a solid by covalent bonding between the long-chain molecules. The process of forming chemical bonds creates a three-dimensional organic matrix. The chemistry of the impression materials is described separately, followed by a brief comparison of their properties. ANSI/ADA Specification No. 19 (1982) sets requirements for the elastomeric-type impression materials. Polysulfides. The starting materials have molecular weights of about 2000–4000 and can be formulated to yield a wide range of physical and chemical properties. In the two-component (paste) system, the base material is a viscous polysulfide liquid prepolymer having terminal and pendant mercaptan (SH) groups, such as a Thiokol LP-2 rubber, commonly called thiols (see Fig. 1). Titanium dioxide (TiO2 ), calcium sulfate, calcium carbonate, silica, or alumina is used as fillers, to extend, reinforce, or harden the product. Dibutyl phthalate, tricresyl phosphate, or tributyl citrate is added as modifiers or diluents to improve mixing and flow properties. The paste may also contain sulfur and oleic or stearic acid, which act as a retarder to control the set. The SH groups are oxidized by lead dioxide or copper hydroxide supplied as a separate part of the formulation. When the accelerator (oxidizer) is added to the base (polysulfide) paste an exothermic reaction occurs, bringing about a 3–5◦ C rise in temperature, depending on the

Fig. 1. Polysulfide oligomer.

Two types of silicones are used in impression materials: addition (Fig. with the two having different end groups and different curing mechanisms. as no products are released during curing. necessitating storage in a dry environment. Polyether impression material reaction. The reactive oligomer used is a polyether having cyclic imine (ethyleneimine) residues. 2 Fig. Polyethers. and a glycol ether plasticizer as one paste. The elastic recovery and reproduction of detail are excellent. . 3) and condensation (hydrosilylation) (Fig. amount of sulfur used.1%) over several hours. a silicate filler. Addition silicone structure/reaction. The two-part formulation contains the imine functionalized polyether. Addition siloxanes are a two-paste system. The exothermic reaction is accompanied by a rapid increase of molecular weight and elimination of water. Mixing is moderately easy and dimensional changes in air are low (<0. with one paste Fig. silicate filler. These impression materials were developed in Germany in the 1960s. 3. caused by formation of the chain-extending and cross-linking S S bonds. they may not provide accurate reproduction of oral structures. 2. which undergo ring opening and subsequent crosslinking via a cationic initiator. and the cationic initiator (such as an alkylester of benzene sulfonic acid). making them more difficult to remove from the mouth. These materials have a much higher modulus of elasticity than silicones or polysulfides. Dimensional stability in water is poor. Adding a polyester diluent or thinner controls the rheological properties and working time. as shown in Figure 2.174 DENTAL APPLICATIONS Vol. and a plasticizer as the second paste (1). 4). Besides being sticky and having a disagreeable odor. In undercut areas. Polyether impression materials tear readily and have an equilibrium water sorption of about 14%. polysulfides [R(SH)x ] are difficult to mix and exhibit relatively poor elastic recovery when stressed. When properly used they exhibit good tear resistance and acceptable stability. Silicones. Both are based on using poly(dimethylsiloxane).

producing high tensile strength materials having good elastic properties. These systems may be used in a wide range of impression techniques. and addition silicones show angles of 49. viscous liquids of structure (Fig. since they lack the required stability. such as tetraethyl orthosilicate (TEOS). upon cooling from mouth temperature (37◦ C) to room temperature. and 98. should be avoided if they are to be disinfected. 4. Mixing the pastes gives a cross-linked elastomer. polysulfide. 3) and reinforcing filler and the other paste consisting of the hydrogen-terminated silanol oligomer. having 5–10 µm particle size. such as stannous octoate or dibutyltin dilaurate (2). are added to prepare a paste which is cross-linked with an alkyl silicate containing 50% ethoxy groups.1◦ . provided low viscosity formulations are used.3◦ .20% for the polysulfides. which eliminates ethyl alcohol. Organic tin activators. The contraction or shrinkage of condensation silicones. they will not properly wet out the surface of the tooth with saliva present. they tear at relatively low extension. ie. Impression Materials Merits. containing a low molecular weight silicone having terminal vinyl groups (Fig. The chief uses of silicone impression materials are for crown and fixed partial dentures. meaning impressions are not generally accepted by dental laboratories unless they are disinfected. and chloroplatinic acid catalyst. along with permanent-set values of about 1% at 40% strain. Elastomeric impression materials reproduce surface details very accurately. But.Vol.2◦ . addition silicones. This shrinkage is essentially caused by release of alcohol generated . filler. No volatiles are given off during polymerization—a definite advantage—compared to the condensation type. A guide for disinfecting impression materials may be found in the ADA Council on Dental Materials.35%. indicating that polyethers work best where saliva cannot be excluded. Since these materials are generally hydrophobic. influencing working and setting times. Equipment and Instruments (COMEI. respectively. or polyethers. Colloidal silica or micronized metal oxides. Communicable diseases have caused concern in handling of impression materials. 1988 and 1992). Condensation silicones are dimensionally less stable than polysulfides. However. 82. compared to 0. They are relatively easy to mix. 2 DENTAL APPLICATIONS 175 Fig. because of inadequate mixing and possibly some hydrolysis of TEOS. Contact angle studies of water on the elastomeric impression surfaces for polyether. The setting behavior of addition silicones and polyethers is the most consistent. are used at the 1–2% level. Reversible and irreversible hydrocolloids. as well as polyether impressions. is ca 0. disinfection must be accomplished without distorting the impression. The setting process for polysulfides is highly susceptible to temperature and humidity. Condensation silicone structure/reaction. 4). The condensation-type silicone impression materials are based on hydroxylterminated poly(dimethylsiloxane). Condensation silicones may also show erratic setting.

Polymerization shrinkage for the elastomers is of the order PE = AS < PS < CS. porcelain. and polysulfones. have good thermal conductivity. and metals. show resistance to oral fluids. have an absence of odor or taste. condensation silicones are cleaner to handle than polysulfides (3).176 DENTAL APPLICATIONS Vol. It happens that compression-molded. A cross-linking monomer. Dimethacrylate monomers/reactive diluents. followed by the addition of the acrylic resin. phenol– formaldehyde. polystyrene. To achieve needed comfort. and AS = CS = 200 ppm/◦ C. cross-linked acrylic dentures are as dimensionally stable and useful as the dentures made with special resins (4). a wax pattern is used. Tear strength would be approximated as follows: PS ≫ PE > AS and CS. dentures must be custom-made. in which the artificial teeth are embedded. The permanent set or resistance to deformation on removal would be as follows: PS > PE > CS > AS. The wax pattern is inserted in a plaster or dental stone in a split mold flask. cellulose nitrate. the MMA becomes poly(methyl methacrylate) (PMMA). and the polyether (PE) elastomeric impressions. addition silicone (AS). an ideal denture material would have high strength. Elastomer Thermal and Mechanical Properties. Denture wearers demand an accurate fit and natural appearance. be fracture resistant. TEGDMA (R = CH2 CH2 OCH2 CH2 OCH2 CH2 ). be resistant to bacterial growth. show good retention to other polymers. However. DEGDMA (R = CH2 CH2 OCH2 CH2 ). ie. with PE = 320. rubber or vulcanite. The materials may thermally contract on removal from the oral cavity. Significant challenges remain to produce the ideal denture material. using methyl methacrylate (MMA) monomer. After removal of the wax. but acrylics have become the materials of choice. such as ethylene glycol (Fig. polycarbonates. condensation silicone (CS). EGDMA (R = CH2 CH2 ). be easy to repair. Acrylic denture materials are made by free-radical (addition) polymerization. Comparing stiffness of the polysulfide (PS). PS = 270. The resins are available in either heat. and be inexpensive to make. usually an aqueous alginate solution. To form the customized denture. Denture Resins/Prosthetic Materials A variety of polymeric materials have been studied or used for preparing dentures. 5.or cold-cured formulations. the surface of the resulting mold cavity is painted with a separating medium. The separating medium aids in removal of the cured acrylic from the mold. Besides being easy to fabricate. including epoxy resins. hardness. The fit is very important. and toughness. have low density. since chewing efficiency of artificial dentures is substantially lower than that of natural teeth. vinyl acrylics. the ranking would be as follows: PS < CS < AS < PE. In the process. be radiopaque. have good storage life. stiffness. . 5) Fig. easy to clean. good dimensional stability. 2 during the condensation reaction.

are packed with pressure into the mold. proportional to the square root of the initiator concentration.3–0. normally consisting of about two to three parts of PMMA and one part of monomer by volume. which is subsequently blended with a polymer containing 2% BPO. ◦ C) for BPO at 72◦ C is 10 h (5). The MMA is normally inhibited with the methyl ether of hydroquinone (MEHQ) or butylated hydroxytoluene (BHT). 0. Visible light-cured versions have also become available. Heat-Cured Methacrylate Formulations. as well as the particle size of the PMMA powder. The dimethacrylates are covalently bonded at various points along the PMMA chains. and polished. DEGDMA). Techniques for preparing the molding are very similar to the procedure described for heat-cured dentures. The rise in temperature depends on the mass of material and the powder/liquid (P/L) ratio used. Traces of poly(acrylic acid) or soluble starch suspension agents may remain in the polymer. such as N.5–1%). is a simple modification of the heatcured formulations. 5). Autopolymerizing Resins. These resins consist of granular PMMA powder blended with liquid MMA. After cooling. along with a cross-linker (Fig. and acrylicor nylon-type reinforcing fibers.N-dimethylaminophenethanol (6). the denture is separated from the embedding material. dibutyl phthalate plasticizer. 5. The residual initiator content of the polymer beads may be at the level to obviate the need of further BPO to be added to the mix. initiated by a suitable redox (oxidizer–reducer) combination. along with a cross-linking monomer. the freshly mixed monomer–polymer blends are more limited in use because of the handling characteristics of the formulations. titanium/zinc oxide pigments and opacifiers. are added at about the 0. The rate and degree of polymerization depends on both the type and concentration of initiator (BPO) and activator (amine). trimmed. Small amounts of other acrylic monomers. forming a cross-linked matrix. and 1–5% of a cross-linking agent may be employed. The polymeric granules may also have methyl acrylate in the backbone or be plasticized by ethyl or butyl methacrylate or ethyl acrylate to increase solubility in the monomer syrup.8% level to the monomer. The powder component is mostly granules of PMMA. The liquid component contains the inhibited MMA. 2 DENTAL APPLICATIONS 177 or diethylene glycol dimethacrylate (Fig.Vol. Post-curing is usually done at 100◦ C for 60 min so as to produce a more fully cured denture with low porosity.Ndihydroxyethyl-p-toluidine or p-N. as shown in Figure 5 (EGDMA or DEGDMA). Room temperature (RT) curing. Particle size and molecular weight distribution of the PMMA controls the solubility of the polymer and the working consistency of the mixture. with the chemistry akin to that of composite restoratives. the polymerization is slightly delayed upon mixing. having the properly positioned teeth. The blends. Most dentures are fabricated from the heat-cured formulations with the polymerization rate increasing directly with temperature. is included with the MMA mixture to improve the mechanical properties. along with benzoyl peroxide initiator (BPO. The customary curing cycle of the fully mixed powder/liquid blend is about 90 min at 65◦ C. In this procedure. Since polymerization occurs from inner to . Red fibrous materials and beads of varying translucency are added in small amounts prior to curing so as to simulate the appearance fo natural oral-tissue. plasticizers. The half-life temperature (t1/2 . the monomer–polymer dough forms a rigid plastic. preventing wetting of the beads by the monomer. After mixing and heating. ie. In such formulations tertiary aromatic amines.

This procedure for preparing dentures is inferior to heat. may be added to the formulation to mask color shift. First. MMA is not used in the urethane dimethacrylate (Fig. Materials generated by using amines in the curing have poorer color stability upon aging. Room-temperature cured materials usually contains about 3–5% free monomer. since monomer evaporation is limited. The larger the amounts of free monomer present in the final product. Production of high dimensional accuracy is one of the main advantages of RT-cured resins. the cured materials have properties as good or better as the denture materials made by the methods described earlier. Polymerization shrinkage is a problem for this type of system. The cured dentures are usually not very porous. This technique requires great attention to detail in order to produce clinically acceptable prostheses. great care needs to be taken to use the correct P/L ratios. 8) cross-linked IPN matrix. the greater the propensity for warpage to occur. compared with only 0. . This technique shows good potential for expanded use. With the exception of brittleness. Thus. Chemically Cured Resins. However. Dentures cured at RT have better dimensional accuracy (8. Thus. possibly causing posterior teeth to be displaced in the resilient mold and out of the desired occlusal pattern (11). Visible Light-cured Resins.178 DENTAL APPLICATIONS Vol. The mixture is usually poured through sprues into a hydrocolloid-based mold. However. the formulation makes use of the camphorquinone–tert-amine initiator system. Employing high intensity visible (blue) light to bring about free-radical polymerization (curing) of the denture resins holds great promise (13). The denture flask is therefore held under pressure for several hours so as to ensure complete curing. The bulk of the polymerization takes place within 30–45 min. the materials produced have more in common with a composite restorative material than with the commonly used denture-based resins. this method of curing is not as efficient as the heat-cured process. filled with colloidal silica and acrylic polymer beads. but may continue for hours.2–0. since the product produced has less cross-linking density and a lower T g than the heat-cured materials. A photopolymerizable formulation in this case could consist of a urethane dimethacrylate–acrylic polymer combination. eventually creating distortion in the denture. it is an excellent technique for denture duplication. 2 outer portions of the mass. The matrix produced is a highly cross-linked acrylic.5% found in heat-cured materials. Differences between thermal expansion of the denture resin and the plaster mold may result in undesired dimensional changes when the mold is subjected to a wide temperature range during processing.9) than heat-cured dentures. a ultraviolet absorber (7). with polymerization conducted under pressure for about 30 min at RT (10). resulting from lower curing temperature leading to reduction of stresses in the matrix. both are clinically acceptable. reinforced with a microfine silica filler. Blue dye. The latter factors also make these RT-cured materials more susceptible to creep.and cold-cured acrylics. having an interpenetrating polymer network (IPN)-type structure. The pour and cure acrylic resins are blends of high molecular weight polymer powder mixed with monomer and other additives to achieve a pourable viscosity. Mixing/Working Properties. For denture resins certain aspects are important to note. temperatures within the bulk portion of the casting are higher than those at the surface. Akin to composite restoratives. Methods have been developed to improve the latter. Low Viscosity. by increasing the bond of acrylics to denture teeth (12).

Polymerization shrinkage and escape of volatiles can generate porosity. there is a considerable variation in mechanical properties. presence of alcohol.3–0. PMMA is highly biocompatible. Cross-linking helps reduce craze formation.5% across the posterior aspect. In all systems. with about the same elastic modulus as heat-cured materials. facilitating removal of voids and helping to cut down on curing contraction. but may also cause some denture distortion. compared to heat-cured dentures at ca 100◦ C. 2 DENTAL APPLICATIONS 179 usually about 2. Dimensional and Mechanical Properties.4% is clinically insignificant.0 vol%. depending on composition. which on the basis of volumetric shrinkage should be about 1. Control of porosity and prevention of processing stress are also two areas of concern. Even though the denture is placed on soft tissues. cold-cured dentures should have a better fit. Thus. ca 60◦ C.20–0. Too much powder will result in underwetting of the beads. crazing. with very few patients showing any type of allergic reaction. Thus. leading to production of a weak structure. As shown in Table 1. partially compensates for the shrinkage.Vol. Dimensional changes also give rise to internal stress. rather than porcelain teeth.0/1. and differential contraction due to the type of teeth used. about 1–2 wt%. Concerning shrinkage. Water sorption. which might elevate to the point of causing monomer vaporization and creating porosity. cutting shrinkage to about 5–8%. since the tissue on which the . The observed change is probably due to thermal contraction. processing technique.5–2.6:1. volume reduction of about 20% for the monomer is minimized by using polymer (PMMA) powder. free monomer. A brief summary of the denture materials’ properties is shown in Table 1. it is very important to pack the viscous mix in the mold in sufficient quantity to create pressure. Linear shrinkage is about 0. caused by temperature changes. Because of the latter. since the processing temperature is considerably lower. too much monomer will produce excessive shrinkage. and distortion of the denture. helping to reduce strain. Linear shrinkage of 0. and not to actual polymerization shrinkage. A separating medium must be used to prevent adhesion of the resin to the mold surface.0%. Room-temperature cured resins have lower strength and stiffness. The resin becomes very rigid once the temperature of the reaction descends below the T g of the material. and environment factors. Cold-cured formulations may be a problem. Post-curing of the denture helps lower free monomer content. Conversely. Adverse reactions are usually caused by leachable monomers. temperatures of cure should be controlled to avoid gaseous porosity and pressure maintained to eliminate contraction porosity. there is still great need for the denture to have dimensional stability. Polymerization shrinkage of the monomer–polymer dough is about 6–7%. but is actually in the range of about 0. It is very important that this contraction is not translated into the high linear-type contraction. since they tend to have more residual. which if allowed to relax may lead to warpage. eliminates differential shrinkage. Biocompatability. All ingredients must be thoroughly mixed to achieve the best results.5%. polishing. The use of acrylic teeth. The denture must fit as accurately as possible to promote retention of the denture to the mucosa. polymerization generates an exotherm. at which point the curing contraction will have essentially been completed. From this point onwards thermal contraction contributes to dimensional changes of the denture material. under normal denture processing.0 wt% or 1. Craze development is another problem that may develop in dentures as a result of strain relief.

While commercial denture materials are reasonably strong and show good flexibility.3 × 103 7–10 3150 41–55 14–20 71 × 10 − 6 130–170 6–7 0. convert MPa to psi. and may collect debris and imbibe bacteria at the surface. Kevlar.17) for visualization of aspirated or swallowed denture fragments. ANSI/ADA specifications or requirements for radiopaque materials for denture-based polymers have been described (18). MPab Knoop hardness (KHN) Coefficient of linear thermal expansion per ◦ C Heat-distortion temp. impact and transverse strength.8 × 103 1–2 1050 41–55 15–23 81 × 10 − 6 160–195 6–7 0. denture rests adjusts to such changes (14. % Impact strength. This is accomplished with additives such as barium sulfate. research is still needed to develop improved materials. tensile strength. and polyethylene) reinforcement have been found to significantly improve many of the aforementioned properties (19). 12 sets the requirements for denture-based Resins. Fillers reduce the thermal expansion of the dentures. d Linear shrinkage of commercial dentures is ca. 24 h. multiply by 0. which promotes higher water sorption. The chemistry used is based on the well-known MMA polymerization . Yet. It has been clearly shown that radiopaque materials are needed (16. Polymeric Teeth for Dentures. lowering dimensional stability.97%..4 taken from Ref.3–0. % a Partially b To b Poly(methyl methacrylate) 76 48–62 83–117 3. at least in the United States are produced from acrylics or vinyl acrylic resins. 0. N·mc Transverse strength. tend to stain. barium or bismuth glasses.15). pointed toward reducing the need for denture repair (21). providing higher impact strength. MPab Elongation. % Water sorption. etc. ANSI/ADA Specification No. c To convert N·m to ft·lbf. 12–0.180 DENTAL APPLICATIONS Vol. However. Seeking to improve such things as fracture toughness. carbon.07–0.74. About 60% of all preformed artificial teeth used in dentures. barium fluoride. multiply by 145. Glass fiber reinforced composite resins have also been introduced as a replacement for metal framework in crown and bridges or fixed partial dentures as per recent clinical studies (20). MPab Flexural strength. improved fracture resistance and fatigue strength are still sought. Acrylic resin denture teeth were introduced in the late 1930s. MPab Elastic modulus. and halogenated organic compounds. Some cross-linked resins contain 2hydroxyethyl methacrylate (HEMA). 2 Table 1. ◦ C Polymerization shrinkaged . they are difficult to polish. The physical properties of the materials are significantly affected by large quantities of these additives.4 Vinyl acrylics 70–76 51–60 69–110 2. 14. Physical Properties of Denture-Based Materialsa Property Compressive strength MPa Tensile strength. various types of fiber (glass.

and residual initiator. Furthermore. blanching. Mechanical retention serves. and bond to the denture base. elastic modulus of 2700 MPa (3.2bis-p(2 -hydroxy-3 -methacryloxypropoxy)-phenylpropane (BisGMA)-based resin have also been explored (23). Other additives/modifiers are also used to achieve a more natural appearance. using an RT. acrylic teeth have less resistance to creep.9×105 in. higher water sorption. greater fracture toughness. and the fabrication of layered teeth with an exterior made up of a 2.3 MPa. urethane dimethacrylate (Fig. Compared to porcelain teeth. 15. ANSI/ADA Specification No. etc. and ultimate tensile strength of 105. However.or cold-cured denture resins. with compressive strength of 76 MPa (11. found in earlier acrylic teeth. a combination of mechanical and chemical bonding is used to retain the teeth (22). PEMA powder. 8) resin. has been overcome by better methods of fabrication. To meet this need a hard relining material can be employed.000 psi). fracturing. elastic limit of 55 MPa (8000 psi). Repairs are achieved with little to no dimensional change. 13 (1999) sets the requirements for cold-cured repair resins. molecular weight. However. All formulations employ pigments to provide a natural appearance. There are three groups of these materials: hard and soft liners and tissue conditioners. improved formulations. 2 DENTAL APPLICATIONS 181 technology. Poor wear. Polycarbonates and polyslfones have also been explored for producing molded teeth. or by sending the denture to a laboratory to be repaired with a heat-cured acrylic resin. containing the plasticizer di-n-butyl phthalate or poly(ethyl methacrylate). have physical properties which are lower than those of metal alloys used for dentures and those of human enamel or dentin.5 and 10. highly cross-linked IPNs.or cold-cured acrylic resin at the dentist’s office. Compositions containing very finely dispersed spheres of pyrogenic silica as reinforcing fillers. − 2 ). since they can reduce the thickness of the denture base and allow diffusion of monomer or solvent into the base. respectively. abrasion resistance. For example. The molding technique for preparing the teeth must be highly controlled. The use of PEMA and BMA works best where . Plastic teeth are covered by ANSI/ADA Specification No. The BPO–amine redox initiator system is used for curing. The cold-cured formulations are basically of two types: a two part PMMA powder blended with MMA monomer. Further. the low modulus of elasticity in plastic teeth reduces the clicking sound often exhibited by denture wearers. A study of plastic teeth opposite plastic teeth or opposite smooth porcelain teeth has been published (24). with respect to particle size. blended with liquid butyl methacrylate (BMA) monomer. Denture Liner Materials. the mix flow properties and curing cycle must be highly controlled. and use of higher cross-linking density. porcelain teeth display better dimensional stability and increased wear resistance. In contrast. respectively. and good abrasion resistance. Acrylic teeth. the strength of the repaired denture may be substantially less than the original prosthesis (25). Soft liners weaken the strength of the heat-cured resins. to anchor the teeth in the chemically activated denture-based resins. crazing. to some degree. dentin and enamel have an ultimate compressive strength of 297 and 384 MPa. better resistance to thermal shock.Vol. It is often necessary to refit the denture because of the changes in the denture-bearing tissue. Fractured dentures are readily repaired with materials similar to the RT. Denture Repair Resins. Knoop hardness (KHN) range of 18–20 kg/mm2 .

182 DENTAL APPLICATIONS Vol. PEMA at 65◦ C. They are all useful for producing soft liners. A variety of materials have a T g low enough to be useful as soft liners. such as ethyl alcohol or ethyl acetate. such as dibutyl phthalate. and can readily support bacterial growth. Materials currently available are usually plasticized acrylics. At present. and a polymerizable monomer. including silicones and acrylics. PMMA is also useful when plasticized to obtain the required T g . starting with PMMA at 105◦ C. Also. acrylic monomers are available which produce polymers with a wide range of T g . soft liners may be used to reduce tissue inflammation caused by worn out or ill-fitting dentures. not impair denture function. 2 the patients may be sensitive to PMMA or MMA. HEMA-based resins may soften and swell excessively due to water sorption. rapidly promoting diffusion of the plasticizer into the polymer. But. Tissue conditioners are soft materials applied temporarily to the denture fitting surface. which cures in the presence of moisture or heat. which may create dimensional problems. monomers and a liquid or solvent. yielding a plasticized gel. However. In terms of softness. even though the denture fits well. allowing better distribution of stress. The alcohol swells the PEMA beads. In addition. be relatively resistant to oral fluids.32). provide a good cushioning effect. Silicone liners are similar in composition to the previously described elastomeric impression materials. and poly(n-butyl methacrylate) (PBMA) at 20◦ C. and be easily cleaned. Alcohol and plasticizer are . Soft liners were developed to eliminate the use of MMA directly against soft tissue. a material awaits discovery for fulfilling all of these requirements. the material must not be too soft or flow to the extent that it will be displaced from between the denture and the mucosa. Polyphosphazine fluoroelastomers have been formulated and cured with peroxides (26). Systems for the relining application may be either a one-component system. allow recovery from deformation. All formulations contain fairly high molecular weight acrylate or methacrylate polymers or copolymers. n-butyl. The materials adhere well to denture-based resins. The soft liners are generally supplied as powder-liquid kits or ready-to-use sheets. They exhibit viscous flow under pressure. The soft liner is more comfortable and provides a means of absorbing masticatory forces via the highly resilient material placed between the denture and the soft oral tissue. there are patients who are not able to tolerate a hard relining surface. derived from ethyl. etc. n-propyl. showing that systems may be found to eliminate some of the deficiencies found in currently available liners. forming a very soft cushion between the hard denture and the soft tissue. Fortunately. not support bacterial growth. the use of PEMA and BMA creates a liner with a lower T g . a plasticizer. However. The liners must show good adhesion to the denture. which are produced by condensation polymerization. More hydrophilic liners have been formulated by using HEMA or other copolymers (28). or a two-component system. These materials may consist of PEMA powder mixed with a solvent (such as ethyl alcohol) and a plazticizer (such as n-butyl phthalate and n-butyl glycolate) (31. These products alleviate discomfort from softtissue injury or inflammation. leading to undersirable functional changes. containing base and catalyst. The T g of the material is set to ≤47◦ C. Polymers with a T g slightly above the mouth temperature exhibit a rubbery behavior in the oral cavity. Tissue Conditioners. Both types generally have poor adhesion to the denture surface. they have poor elasticity and harden upon aging because of the loss of the plasticizer (27–30). have good wetability.

which may cause the material to become too rigid. stop teeth drifting. along with deforming more under bruxism. while waiting for the permanent prosthesis to be delivered. etc. vinyl plastisols. feel like real skin. However. can be formulated with colorants to provide a superior latex. poorer abrasion. liquid rubber latex. These materials have some utility in maxillofacial prostheses.37). they may cause an allergic reaction. compared to earlier materials. the materials are heat or light cured. Crown and Bridge Temporary Resins. until the patients supporting tissues return to normal state. Mouth Protectors. made up of small vinyl particles dispersed in a plasticizer. as well as silica. and can be readily matched to the color of the tooth structure. The materials should be biocompatible. in contrast to dimensionally stable and comfortable. They maintain the correct biting relationship. Over the counter protectors usually fit poorly. or polyurethane materials. than normal dental composites. or even an ethyleneimine-terminated monomer (33). may be formulated into materials for facial prostheses (38–41). and protect the prepared tooth against fracture. translucent. and cleaning solutions. The acrylic facings have poor adhesion to the metals. vinyl acrylics. After placing on the metallic substrates of the prostheses. including latexes. Polymers used for this application include acrylics. and polyurethanes. Polymeric materials are also used for fixing veneers on crown and bridges. polyurethane. They are heated to generate the . poly(vinyl acetate-co-ethylene). They have less mechanical strength. along with colorants. Guards may be produced from natural rubber. and sufficiently resilient to prevent tearing. being retained only by curing the monomers into mechanical undercuts designed into the metal substrate. MMA. they exhibit good flow. Used for interim tooth coverage. These materials are easy to fabricate. The widespread growth of contact sports has accelerated the use of mouth guards (34. Customized guards are often fabricated from poly(vinyl acetate-co-ethylene) blanks. and low curing shrinkage. Maxillofacial Prosthetic Materials A large number of polymers.Vol. In addition. It should be possible to modify the formulation to match skin color. and methyl methacrylamide. low exotherm. silicone elastomers (heat or RT vulcanized). composed of monomers and polymerization initiator. stable to heat. light. a recent terpolymer derived from n-butyl acrylate. customized mouth protectors. These materials do not have the strength and color stability to be very useful for this application. soft acrylic dough.35). Latexes. No material meets all these requirements. easy to fabricate. The liner must be replaced every few days to retain properties. 2 DENTAL APPLICATIONS 183 slowly leached out from the applied gel. The formulations are viscous liquids. easy to clean. However. less color stability. these materials are not as strong as other acrylics. Vinyl Plastisols.or quartz-microfilled composites. restoratives with polymeric veneers are less frequently used. and dimethacrylates. and laminated thermoplastic (36. The formulations are supplied as a two-component paste. Materials used in this area are usually based on methyl or ethyl methacrylates and BisGMA-acrylics mixtures (20). With the advent of porcelain fused to metal crowns and bridges. poly(vinyl chloride).

deform. The molded material is cured under pressure at 180◦ C/30 min. The material softens at about 60–65◦ C and melts in the vicinity of 100◦ C. preventing ingression of oral fluids into the canal. These materials have some only recently been used to produce maxillofacial prostheses. Heat-vulcanized formulations are supplied as a semisolid or putty-like material. Even though the fabricated prosthesis has a natural feel and appearance. Other materials used for endodontically treated. 6. and 14% wax plasticizer. 59–75% zinc oxide filler. 6). One natural material used is guttapercha (Fig. 1–17% heavy metal salts. a rubber obtained from the Taban tree. Colorants and other additives are also used in the formulations. desired materials. calcium hydroxide resin based formulations. a cis and trans form. A typical formulation used in a root canal has about 19–22% gutta-percha.and heat-vulcanized materials may be used. which requires the addition of colorants. This is the most recent material used in maxillofacial applications. These rubbers are hardened by vulcanization. accounting for the lack of interest in this technique. achieved by blending and heating with a few percent of sulfur. placed in a suitable mold. which causes cross-linking. Fabrication requires accurate proportioning of the components. fractured teeth are based on zinc oxide-eugenol. Silicones. Gutta-percha structure. having two possible conformations. The isocyanate and polyol are blended.184 DENTAL APPLICATIONS Vol. ie. polyvinyl resin. This material has been used in endodontics for over a hundred years. Polyurethanes. Other Uses Patterns for gold-inlay castings can be prepared from acrylics.3-butadiene (isoprene). Root-Canal Sealants A variety of materials have been used to hermetically seal the root canal. The heat-cured materials exhibit better strength and color stability than the RT-cured materials. Rubbers are polymers of 2-methyl1. 2 Fig. and allowed to cure at room temperature. and glass-ionomers formulations. and condense the material into the prepared root-canal space. Some dental laboratories use epoxy die . Both the RT. Castings made this way are not superior to castings produced from a wax pattern. with the trans form being gutta-percha. the final product is still relatively unstable. epoxy resin. providing a temperature range to soften. The loss of plasticizer and lack of stability decreases the use of these materials.

and more acceptable biocompatibility (44. well known today as BisGMA (45. combined with inorganic reinforcing fillers and suitable polymerization initiators.48). Bowen (47. Compared with the PMMA–MMA doughs. Autopolymerizing resin formulations are used to make custom impression trays. better esthetics. with much of the early work done at the National Bureau of Standards. the BisGMA monomer may also be produced by reaction of bisphenol A with 2 mol of glycidyl methacrylate. 7). 7) has two chiral carbon atoms (denoted by an asterisk) with the dimethacrylate diastereomers helping to make the BisGMA mixture a viscous syrup. the BisGMA-based formulations. an inorganic filler modified with a coupling agent. Dental Composite Restoratives.48) made the discovery that the diepoxide derived from bisphenol A and epichlorohydrin could be treated with methacrylic acid to form a unique hybrid monomer. and a suitable polymerization initiator system. 2 DENTAL APPLICATIONS 185 materials for fabrication of casts. BisGMA (Fig. as well as the need to have a new monomer which would be both free-radical polymerizable with less shrinkage in composites. reduced water sorption.45). is made up of free-radical polymerizable monomers. BisGMA. PMMA or other thermoplastics are used to prepare occlusal night guards. BisGMA structure(s). .Vol. Many studies have focused on improving these materials. were excellent matrix resins for a variety of composites. Alternatively. based on bisphenol A. made available composite fillings with lower polymerization shrinkage. and bite plates. thermosetting dimethacrylate. the polymer industry had previously shown that epoxy resins. with such resins containing substantial quantities of fillers to increase the rigidity of the materials. improved mechanical properties. However. Resins used to formulate dental composites/restoratives were initially derived from the free-radical polymerization of doughs made from PMMA beads blended with MMA monomer (42–46). epoxies exhibited poor ambient polymerization characteristics under conditions useful in the oral cavity. Restorative Materials Filling Materials. The formulation used to produce the organic matrix. Knowing the latter. splints. or alternatively formulated with Fig. Earlier. launched a new era for development of composites used in dentistry. The synthetic path to the bulky. or continuous phase. a more attractive coefficient of thermal expansion.47. A good review of dental composite resins has been published (49). by addition of cross-linking monomers and reinforcing fillers (45). temporary space maintainers. The monomer mostly used in the formulations for both anterior and posterior resins is BisGMA (Fig. 7. Other areas of dentistry make extensive use of polymers in retainers. Polymeric restoratives have three major components: an organic resin matrix.

a powder–liquid. are particularly useful for visible lightcuring (VLC) (53. compared to the VLC formulations. Although BisGMA is widely used in commercial dental composites. 8). using photoinitiators or photoinitiator–photosensitizer combinations with only the visible light range (400–500 nm) allowed for curing. such as camphorquinone (CQ). other types of dimethacrylates have also been studied or developed for use as alternatives to BisGMA (55–76). eg. owing to air inhibition. but are more lightly filled or possibly unfilled.N-dimethylaminoethyl methacrylate (DMAEMA) (52). When using VLC systems to fill deep cavities. But. Various polymerization initiators or activator–initiator combinations are known to be useful to achieve curing. Inhibitors are required to prevent polymerization during storage. VLC resins provide the dentist a significant control over the restorative hardening process. a urethane dimethacrylate monomer (Fig. properly mixed redox formulations polymerize much more uniformly. With light activation.54).N-dihydroxyethoxy-p-toluidine system. Further. glass or various ceramics. especially in areas of great bulk. Redox initiation systems may consist of such things as BPO/tert-amines. or a paste–paste formulation. A commonly used combination for redox use is the BPO/N. Monomers structures in urethane dimethacrylate mixture. Monomers or Matrix Phase. with diethylene glycol and triethylene glycol dimethacrylates (Fig. such as N. A prepolymerized resin containing pyrogenic silica may also be used to reduce polymerization shrinkage. a paste–liquid. Because of the high viscosity of BisGMA. A variety of fillers may be used to make up the reinforcing phase. which initiates the polymerization. Polymerization. the porosity and surface tackiness. Composites used in dentistry can come in various forms. are lower in the VLC-cured materials compared with that of the redox formulations. a variety of dimethacrylates have been found to be useful as reactive diluents or polymerizable modifiers to provide suitable viscosities for high filler loading. a uniform paste.186 DENTAL APPLICATIONS Vol. and BPO/tert-amine with synergistic promoters.or two-part formulation. 5) being good examples. 2 Fig. a layering technique must be used to ensure adequate polymerization. ie. peroxides with ascorbic acid or derivatives. hydroperoxides-thioureas. with silanization affording the coupling mechanism. Fillers may consist of silanized quartz. Methacrylate-based restoratives are free radical not radicals polymerized by redox systems or photochemically by visible light. a one. CQ and DMAEMA form an “exciplex” with the “exciplex” subsequently producing a DMAEMA-based radical. with a tertiary amine. The combination of α-diketones. 8. Studies on the kinetics and the nature of the network . polythiols (4.50–52). Sealants used in dentistry have similar compositions.

a blend of a BisGMA-based resin and a solid spiroorthocarbonate (SOC). ie. Elimination of polymerization shrinkage has been under study for some time (74. The viscosity of this formulation was comparable to that of BisGMA. PFMA (70–73. Some of these have been prepared from nonhydroxylated homologues of BisGMA. 8). gained great acceptance in Europe. 2 DENTAL APPLICATIONS 187 formation in the dimethacrylate polymerizations have been given significant attention (77–83). expanding polymerizations. seeking to improve such things as dimensional stability. using a “soft start” stage. along with solubility in a variety of diluent monomers.97). which also polymerizes by a free-radical. In one case. to date. A variety of fluorine-containing monomers and polymers have been prepared and examined to produce hydrophobic dental composites with low water sorption. with an example being the monomer derived from the reaction of HEMA with a branched aliphatic diisocyanate (Fig. and sol–gel technology (121) has started to be examined for preparing improved . with the types of monomers used and the degree of carbon–carbon double bond conversion achieved determining the T g obtained (49).65). In contrast. reduced margin leakage. More recently. the polymerization shrinkage and strength deficiencies were not improved. Also. having low viscosity. creep resistance. wear resistance (66. inorganic–organic hybrid monomers (117–120). Following the latter study.Vol. combined with a diluent monomer (64.1. The goal is to formulate a better alternative to the commonly used amalgam. hyperbranched polymers (115.75). such as 1. which enhances toughness. a multimethacrylate prepared from esterification of a low molecular weight styrene–allyl alcohol copolymer was shown useful in reducing shrinkage or polymerization contraction stress in BisGMA/TEGDMA neat resin blends (96. fracture toughness. There is growing interest in varying the polymerization stages. showing some promise to improve the performance properties of an ethoxylated bisphenol A dimethacrylate (BisEMA)-based composite (99–101). having lower viscosity (66). The focus has mainly been on SOC and SOC-type monomers with epoxy resins (102– 113). ring-opening mechanism. the possible use of liquid crystalline monomers (114). Resins have also been designed to utilize multifunctional methacrylate prepolymers. high contact angles. focused on eliminating or reducing the shrinkage as well as improving the physical and mechanical properties of composites. and resistance to surface staining (67–73).84– 95). Incorporating urethane residues in the matrix.98). derived from the chain-extending reaction of BisGMA with a diisocyanate. was cured to give thermosets with very low volume shrinkage (75). One such formulation consisted of 75 wt% octafluoro-1.5-trihydropentyl methacrylate and 25 wt% of a nonhydroxylated homologue of BisGMA (66–68). But. The dimethacrylate derivative of a fluorinated triethylene glycol. In the early work. the volatility of the nonbulky fluorinated-monomer component was a problem.6-hexamethylene diisocyanate. as a way to improve the resin properties. Many experimental dimethacrylates have been explored for reduction of shrinkage and water sorption in composites. was recently examined as a reactive diluent. ie. a great variety of compositions have been designed for ring opening. This concept has not. a stronger hydrophobic composite was prepared from a low surface-energy matrix resin consisting mainly of a highly fluorinated multifunctional methacrylate prepolymer. produced marketable dental restoratives.116).

3 1. the in situ generation of a nanocomposite. Microfilled composites generally have inferior properties compared to conventional or the more recent hybrid restoratives. vol% Thermal conductivityd.0 20–40 0.03 5. Physical Properties of Resin Restoratives Unfilled PMMA 55–78 15 14–28 1. 2 composites. Physical Properties. with Table 2. organic prepolymenized composite particles are also useful as a dispersed phase. wt% Compressive strength.2–5. micro-filled. multiply by 145. Fillers serve to increase hardness and compressive strength.0–20. A breakdown at the interface. The use of multimethacrylate substituted hyperbranched polymers looks to be a particular attractive path to explore for generating composites with significantly lower shrinkage.50–0. it is critical for the resin matrix and filler to have a strong interfacial bond. where the inorganic component is truly distributed at the molecular level in the cured composite. 1–5. 0. In addition to quartz. to 0. 10 − 6 ◦ C Water sorption. will not allow the stresses developed to be effectively distributed throughout the material.000. followed by load application. many types of reinforcing fillers have been studied or used in dental composites. finely divided. respectively. Vigorous efforts have been focused on maximizing filler volume or obtaining highly loaded composites. MPab Modulus of elasticity. b To convert MPa to psi. fused or colloidal silica. in order for the composites to have acceptable mechanical properties. c To convert GPa to psi. Traditional. Filler technology has brought many improvements to currently used composites.0–1.188 DENTAL APPLICATIONS Vol.8 6. since low viscosity. may satisfy the great need for preparing restoratives with both low shrinkage and significantly improved wear resistance.4 Microfilled composite 33–51 225–350 5–30 30–55 3.2–6. GPac Linear coefficient of thermal expansion.0 Property Inorganic contenta . is 0. high molecular weight entities can be formulated into the monomer–polymer mixture.04–0.3 92 1.70–2. Table 2 shows some physical properties of unfilled (neat) resins and filled composites.e W/(m·K) a The volume (weight) of the filled systems varies from about 30 to 77% (50–85%). Also.4. mg/cm2 Polymerization shrinkage. and hybrid composites have fillers ranging in size. which exhibit much better stress-bearing capability. But.0 µm. incorporated into the formulation at the surface of the filler.0 50–70 0.5–4.70 1.2–8. multiply by 145. respectively. MPab Knoop hardness (KHN) Tensile strength.20 1. Reinforcement Phases. and significantly reduce shrinkage of the restoratives. from 8–12. d Thermal conductivity of enamel and dentin. . This is especially true for microfilled and hybrid composites (122–124). small particle filled.3–8.9–2. Bonding is achieved by the use of coupling agents.87 and 0.4 Conventional and filled hybrid composite 70–80 250–400 50–60 50–90 8. and other inorganic fillers.0 2.94–2.59 W/(m·K).6–1. After introduction of quartz filler in the late 1950s. e Composite restoratives are good insulators.

maleic. Alginates. A series of acid– base reactions brings about hardening or setting of the cements. acid-base reactions of dimer and trimer acids with various basic powders may be used (140).000– 50. ionically cross-linked. ie. and other alkenoic acids (ie. 2 DENTAL APPLICATIONS 189 the exception of polishability. Cements based on glass ionomers adhere well to enamel but only weakly to dentin. 1–5. The higher volume ratio of polymer to inorganic filler. previously described under Impression Materials. optionally. with the polymer having an average molecular weight of 30. which evolved from the zinc phosphate cements. were subsequently used to make shelf stable aqueous solutions with lower viscosity. to 0. But. hybrids (blends) have a combination of colloidal and fine particles as filler. The properties of various cements are given in Table 2. Dental Cements. Zinc oxide was the basic powder component. small quantities of silica. along with fillers and other additives. itaconic.4. various co.Vol. at approximately 60–65 vol% with the fillers ranging in size from 8–12. with ionic-type cross-linking achieved by the ionized carboxylate groups forming a complex (saltbridge) with the divalent metal cations. 96 (1994). They may be of the VLC type and/or chemically cured type. having about 30–50% solids. which may result in reducing recurrent decay. which have an opaque appearance due to the high concentration of zinc oxide.04–0. calcium hydroxide. were the first ionic polymers to be employed in dental applications. 27. Several articles present the chemistry associated with GIs (136–139). Polymeric matrices used in formulating cements are similar to those used in methacrylate-based composites and sealants. to make the formulated adhesive useful in the oral cavity. Requirements for dental composites are covered by ANSI/ADA Specification No.000. By definition. Polyalkenoate cements. The acid component was an aqueous solution of poly(acrylic acid). enabling them to be used as bases under permanent fillings and to cement prefabricated restorations and orthodontic appliances. of the microfilled resins leads to lower modulus of elasticity. Copolymers of acrylic and other alkenoic acids. and other salts. with such systems displaying excellent hydrophobic and energy-absorbing properties. low filler content. BisGMA or some other dimethacrylate is blended with monomers such as MMA. Chain-extending. 0. producing a highly. The water-based cements are covered by ANSI/ADA Specification No. hydrophilic matrix. less resistance to indentation. A family of nonaqueous polycarboxylate cements may also be formulated. itaconic acid and maleic acid) are used in aqueous solutions for formulating polyelectrolyte-based cements. Cements of this type. Free powder embedded in the stiff polymeric hydrogel or matrix acts as a normal reinforcing agent. providing a cement with better properties. greater thermal dimensional changes.0 µm. eg. polyelectrolytes derived from poly(acrylic acid). and aconitic acids. stannous fluoride. . adhere well to tooth structure and base metals. They may also contain additives such as inorganic fluoride salts. These materials are also known as glass polyalkenoates or more commonly glassionomers (GIs) (125–135). and higher water sorption. were formulated with an organic polyacid and subsequently called zinc polyacrylate cements (127).6–1. Polyelectrolyte-Based Restoratives. Other types of additives are incorporated into the formulations to improve certain properties. with smaller amounts of magnesium or tin oxide and.and terpolymers of acrylic acid. Glass Polyalkenoate Cements.

190 DENTAL APPLICATIONS Vol. More translucent glass polyalkenoate. Glassionomer cements may be used as a cosmetic filling materials and for the repair of cervical erosions because of good adhesion and semitranslucent nature.2–50.2–5. with poly(vinyl phosphonic acid) being an example (141. a polyelectrolyte network matrix is formed by ionic chain extension and cross-linking reactions involving leachable multivalent cations and the organophosphoric acid groups. vol% Thermal conductivity. W/(m·K) a To b To convert MPa to psi. GPab Linear coefficient of thermal expansion. multiply by 145.or polyelectrolyte-based cements (GI) were developed by using similar aqueous solutions of polyacids.2 127–350 28–63 7. mg/cm2 Polymerization shrinkage. providing a possible path to improved. binding carboxylate groups in ionic cross-links (salt-bridges). Acrylic acid copolymers were recently modified with N-acryloyl.000. as shown by statistically designed experiments.3 10.150). and ion-leachable calcium fluoro aluminosilicate type glass powders (126.94–2. The matrix in this conventional-type GI is formed by acid-base reactions involving the di.8 Property Inorganic content. Experimental cements have also been described for taking advantage of the reaction of an aqueous solution of phytic acid and myoinositol hexakisphosphate with zinc oxide or alumino-silicate glass powders (143). The study showed that an 8:1:1 (AA:IA:MGA) .3–8. In such a formulation.0 46–70 0.4 Microfilled composite 33. wt% Compressive strength.2–5. 2 Table 3.1–16. In the area of mechanical strength.142). The AA IA MGA copolymer having an 8:1:1 monomers ratio looked particularly attractive to use in formulating conventional GIs. poly(acrylic acid-co-maleic acid).9 221–330 28–56 3.5–13.2–8.74 1. Other polyelectrolytes have also been explored as polymeric acids for formulating GIs. producing a stiff hydrogel into which partially reacted glass particles are embedded (136–138). 10 − 6 ◦ C Water sorption. etc. convert GPa to psi.2 25–40 0.0 2.or Nmethacryl-oylamino acids.9–5. such as poly(acrylic acid).135). such as N-methacryloyl-glutamic acid (MGA). The copolymers studied had the carboxylic acid groups tethered at various distance off the copolymer backbone.3 92 2. with the acid groups having a range of pK a or dissociation constants (149.(Ca2+ ) and trivalent (A13+ ) cations. similar to the zinc polycarboxylate cements. multiply by 145. poly(acrylic acid-co-itaconic acid). The vinyl phosphonic acid polymer formulations were too acidic to allow suitable working and setting times (142).128. Physical Properties of Resin Restoratives Unfilled PMMA 55–76 14–28 2. conventional GIs (144–148).20 1. MPaa Modulus of elasticity. exhibit good adhesion properties.8 6. Glass-ionomers. MPaa Tensile strength.4–80. approaching the dental silicate cements in compressive strength and modulus of elasticity (Table 3).4 Conventional and filled hybrid composite 70.13–0.03 5. GI-based cements are superior to zinc phosphate and zinc polycarboxylate.

156–158). These formulations consist of an organic and an inorganic phase. basic or reactive glass particles. were determined by statistical design of experiments. have better adhesion to tooth structure. The VLC GIs are less technique sensitive. These hybrid-type formulations. now commonly called compomers (160–166). redox. improve fracture toughness. The physico-mechanical properties of GIs. bringing about further hardening due to formation of some ionic-type cross-linking. compomers offer the advantages of both GI and composites in one material. the optimum monomer ratios and molecular weights. These are water-soluble polylectrolytes having both pendant carboxylic acid groups and free-radical polymerizable moieties. and salt-bridge reaction in the same formulation appears to work best (157. are mixed. the GI formulations used in the United States are either the free-radical. which are more composite-like. or a combination of VLC and redox initiation types (128. All in all. Clearly. VLC Glass-Ionomers. with one being an aqueous solution of the polyelectrolyte (acidic polymer). placed in the cavity. A combined VLC. The term polyacid modified composite more readily describes the chemistry of compomers. On exposure to light. has been explored for modification of poly(acrylic acid-co-itaconic acid). VLC. cure in shorter time. and reactive monomers and the second the basic glass powder consisting of calcium fluoro-aluminosilicate.150). leading to recommendations that these materials could be used in Class V and Classes I and II restorations in primary teeth.161) work.158). free-radical polymerization occurs to give the cured resins. initiators. with the inorganic phase having some level of fluoride-containing. and exposed to visible light. Starting from the first resin modified cements (160. to give good mechanical properties. 1-vinyl-2pyrrolidinone. For these copolymers. compomers were first introduced to the market in 1995. redox initiated. This type of modification was also shown to enhance the adhesion of the GI to tooth structure. and . To some degree. are more plastic in nature. such as methacrylate residues. Presently. and reduce microleakage better than the conventional GI formulations (159). The two-component formulations. 2 DENTAL APPLICATIONS 191 copolymer gave the highest compressive strength (148). may be finished at the time of placement. Raman spectroscopy studies showed that tethering the acid groups various distances off the copolymer backbone influences the level of salt-bridge formation (149). Hardening occurs in two ways: formation of a free-radically cross-linked organic matrix and salt-bridge formation. new polyelectrolytes can be prepared for formulating improved GIs. are also referred to as resin modified glass-ionomers (RMGIs) (138. The copolymers with pendant amino acid residues have also been developed for preparing VLC formulations (146. Formulations containing NVP residues were also developed for VLC applications.136–139). the RMGI modifications made the GI family of restoratives significantly stronger than the conventional GIs. The monomer N-vinylpyrrolidinone (NVP). The organic phase also contains carboxylic acid functionalized monomers and initiators.Vol. All the improvements were attributed to greater availability of the carboxylic acid groups to ionize and form salt-bridges. Water diffusion also facilitates the release of fluoride ions to the tooth structure. Glass-ionomers have evolved along with composite resin technology to produce a new family of materials for restoratives. compomers. and enhance fluoride release. Compomers. Water sorption of the cured organic matrix facilitates an acid-base reaction. providing a path to new polyelectrolytes for formulating GIs (151–155).

where the sealants used for this purpose are called preventive dental sealants (PDS). From a material science perspective. A brief history and state-of-the-art ion enamel and dentin bonding was published in 1995 (178). and other methacrylates are very popular as monomers for resin sealants. here we call these adhesive materials the restorative dental sealants. Sealants are vital for promotion of adhesion. Preventive dental sealants. Pit and Fissure Sealants. Clearly. respectively. with polymerization shrinkage in the range of 2. and also to seal microspaces between the tooth and restorative materials. BisGMA. are classified into pit and fissure sealants and smooth surface sealants. They provide dental pulp protection and protection from secondary caries formation. These materials are used to seal high caries-susceptible pits and fissures of the deciduous and permanent molars. used to seal the susceptible areas of teeth. Recent advancements in synthetic chemistry and polymer science of dental sealants are now briefly reviewed or discussed. Pit and fissure sealants are covered under the American Dental Association (ADA) Acceptance Program. having a viscosity low enough to penetrate easily into narrow pits and fissures. along with other monomers. Resin sealants consist of a free-radical polymerizable monomer mixture. pit and fissure sealants can be further classified into resin sealants and GI cements. as well as their resistance to wear.0%. The reported coefficient of thermal expansion for coronal tooth structure is about 11 ppm/◦ C. Dental caries that occur around restorations are called secondary caries. Most dental sealants are resinous materials derived from free-radical polymerizable monomers. including those designed for various clinical uses. which significantly reduces caries formation (169–177).192 DENTAL APPLICATIONS Vol. with many people having one or more applications of a sealant. Preventive dental sealants are usually placed onto molar teeth of young children who are at high risk for caries development. but GI dental cements (discussed earlier) also have some use as sealants. directed toward prolonging the lifetime service of natural teeth. enabling these materials to adhere firmly both to prepared cavity walls and to other restoratives. The compressive strength and diametral tensile strength for compomers is in the range 280–460 MPa and 52–62 MPa. Sealants A variety of sealants have been explored or developed (168). Sealing with resinous materials or GIs is part of modern preventive technology. research on compomers suggests that there are still others ways to be discovered for improving the handling characteristics and compensating for polymerization shrinkage in the design of dental restoratives.and VLC-type GIs. urethane dimethacrylate. 2 composite restoratives have recently been compared (167).0–3. with this and other efforts showing that the mechanical properties of compomers. and the coefficient of thermal expansion (ppm/◦ C) being in the range 12–41. to lower . Sealing the microspaces with adhesive resinous materials is effective in controlling secondary caries. capable of being cured to a hard and durable sealing material. are significantly better than both conventional.

189). to provide the required tooth bonding to the nonadhesive resin (179–181). Uses of this type of hydrogel (184) vary with the dental treatment. not yet totally reached. where low viscosity pastes. are applied to the enamel pit or fissure area prior to application of the sealant. Fluoride ion released from these compositions helps prevent caries formation. and thin-film formation are required. Shear bond strengths of composite restoratives on enamel. or other acidic solutions. 2 DENTAL APPLICATIONS 193 mixture viscosity to enhance penetration ability. The highly active. improving the acid resistance of surrounding dental enamel (186). which fosters better penetration of the sealant into the fissure and results in stronger adhesion between the sealant and the tooth surface (182). However. Glass-ionomer cements. and intrinsic compositional variation (187). Glass-ionomer cements fail to meet these requirements because of insufficient physical properties. such as phosphoric acid. with two-component. which is critical to achieve good bonding. photopolymerizable sealants can be cured very rapidly (<60s) by exposure to visible light.or two-component formulations. substantial progress has been made to facilitate minimal invasive restorative therapy. citric acid. are used. Instead. characterize the cements for pit and fissure sealing. This so-called acid etching changes the enamel surface to a microrugged structure. is influenced by dentinal conditions (moist or dry) and by the type of solution used (188. One-component. etched with 30– 40% phosphoric acid solutions are typically in the range of 18–25 MPa (182). or acrylic acid copolymers with maleic and itaconic acids (6). First. and physical damage to susceptible teeth. which is interesting to note. anerobically cured cyanoacrylate monomers have also been evaluated for sealant applications (179). These sealants may be one. reinforced with ultrafine silica particles. is to have a simplified application . The cement paste cures within a short time through the salt-bridge formation between poly(acrylic acid) (185). it was discovered that resin penetration into the acid etched (conditioned) dentin. good physical properties. Etchants. staining. chemical stability. and Ca2+ and Al3+ cations leaching out from the glass powder. producing bond strengths of 2–4 MPa. fluid-filled tubules. and therefore strong adhesion to enamel and dentin. bonding to dentin is a much tougher challenge because of its organic constituents. There is great correlation of the bond strength received with the permeability and dentin penetration depth (189– 191).Vol. by design of new bonding techniques/agents. highly cross-linked resin sealants. Polymerization of the sealants is initiated chemically with BPO/amine or sulfinate (redox combinations) or visible (blue) light irradiation. which exhibit fast setting. Smooth surface sealants are used to prevent bacteria. The elusive goal. Poly(acrylic acid) undergoes ionic interaction with calcium ions on the enamel surface. good wear resistance. Acidic monomers have been developed for use in the sealant formulations to further enhance the penetration and adhesion. are widely used as sealants. where the chemistry was described earlier in the text. self-curing sealants taking significantly longer time to harden or cure after mixing (183). In this process a glass powder and an aqueous polymer solution are mixed in given proportions and packed into pits and fissures without prior acid etching of the tooth surfaces. In comparison. where the formulation contains CQ as the photosensitizer. biological stability. Cured sealants are directly exposed to the oral conditions.

the evolutionary development of surfaceactive comonomers with both hydrophilic and hydrophobic moieties. For specific information on some of the most recent. Panavia 21 (Kuraray Co. which consists of PMMA powder and MMA monomer. and Optibond Solo (Kerr Sybron). Japan) is an adhesive cement. Examples of two amalgam bonding agents illustrate the latter. Single Bond (3M Dental Products). The amalgam has no chemical interaction with the cavity wall. o-sulfobenzimide accelerator. characterized by the use of 10-methacryloyloxydecyl dihydrogen phosphate (MDP). Japan). Prime Bond (Dentsply/DeTrey). Dental amalgams are mixed and condensed into molar teeth cavities. which remains uncured before application. Thermo. Other formulation additives may be tert-butyl hydroperoxide initiator. also played a very important role in the design of improved dentin bonding systems (202–206). hardened by the amalgamation process. as part of the primer system..6 MPa without acid etching. Apart from using simple acid etching. However curing occurs within 2 min between a glass plate and the amalgam. This sealant is composed of only one liquid. but cures quickly once applied to amalgam. see literature on Excite (Ivoclar AG or Vivident).and load-cycling studies are essential for determining or predicting the dentin-restoration bond longevity (196. TBB-O is activated by the water on the surface of adherents and promotes graft polymerization of MMA onto collagen in dentin.195). Composite resin polymerization shrinkage is the main reason for marginal gaps and stress at interfaces. leading to microleakage (192. has made a very significant impact on improving bonding to dentin (198–201).207.0 MPa and bonds amalgam–dentin by about 2. Because of tert-butyl hydroperoxide and o-sulfobenzimide. One commonly used adhesive resin cement is Amalgambond (Sun Medical Co. When placed between two glass plates at 25◦ C. Chemical composition of this sealant or bonding agent may be as follows: a monomer such as diethylene glycol dimethacrylate (Fig. brief discussion. This cement consists of a primer and a composite paste. Dental Restorative Sealants. The primer is a monomer solution containing MDP. promoting strong adhesion (201. These adhesives are of two types: adhesive resin cements and bonding agents originally developed for composite restorations. Amalgam Restorative Sealants. it takes more than 10 min to cure. polymerization occurs anaerobically when it is cut off from air and it contacts the copper in the amalgam. and irregular microspaces are produced along the interface between them. The work on self-etching primers.194 DENTAL APPLICATIONS Vol. This sealant achieves amalgam–enamel bonding by about 1. commercial enamel and dentin bonding systems.197). 2 method for a dentin bonding system which will produce a very durable bond with total elimination of future microleakage (192–194).. which develops strong adhesion to enamel and dentin. One Step (BISCO). containing 4-methacryloxyethyl trimellitate anhydride (4-META) and tributylborane oxide (TBB-O) as a catalyst. Amalgam sealant and amalgam bonding agents are used to seal the microspace and control the incidence of secondary caries around the amalgam restoration. and hydroquinone inhibitor. to improve the understanding of what it takes to bond well to dentin. The MEP (207) monomer is used to enhance penetration of the sealant into micro spaces and achieve adhesion to both arnalgam and tooth surface. 5) or a comonomer such as methacryloxyethyl phthalate (MEP). The .208).

Liquid monomers. . Systems used in this case consist essentially of dimethacrylate mononers. as discussed in the section on Composite Resins. Surface conditioning before applying adhesives effectively increases the surface bonding area and enhances the strength of the bonding agent. The sealants used for restorations (called bonding agents) are applied onto the cavity walls prior to the placement of composites and bond the two substances tightly.Vol. homologues of BisGMA. with polymerization/curing caused by the catalyst BPO/textamine/sulfinate. 37 to enamel. application of acidic monomers is common for getting reliable adhesion. ceramics. Combining the etching and bonding agents reduces the number of steps and gives higher bonding strength to the dentin. and silanated inorganic fillers. Most current enamel bonding systems employ phosphoric acid in various concentrations and viscosities as an etchant (169. Composite Restoration Sealants. Dental Adhesives (For Alloys and Ceramics) Various materials such as polymers. alloys. adhesion to composite restorations. The enamel is commonly etched with an aqueous solution of phosphoric acid or other acids. HEMA.170). It is vitally important for these materials to be bonded securely to the tooth surface. 2 DENTAL APPLICATIONS 195 cement paste is a mixture of polymerizable monomers. 15 to amalgam. The well-known Gluma adhesive system is made up of water. Pretreatment of cavity walls with bonding agents is a must for composite restorations.209. Bonding Agent Chemistry. such as MMA. Composite bonding agents are a mixture of polymerizable monomers or a solution of monomers in volatile solvents. and glutaraldehyde (211). (4) application of the bonding agent and visible light irradiation. Recent dental adhesive techniques are based on chemo-mechanical bonding between the adhesive and adherend. in MPa. using a lightcured bonding agent and a light-cured composite is as follows: (1) cavity preparation. and composites are used to restore or replace tooth structure. which cures through free-radical polymerization on the cavity walls or between cavity walls and composite restorations. and ethylene glycol dimethacrylate. urethane dimethacrylate. of 20 to dentin. When the teeth cavity walls are wet. (5) composite restoration filling and visible light irradiation. A typical procedure for restoration with composites. and inorganic filler. Panavia has a shearbond strength. physical properties of the cured polymers.210). (2) washing and air drying. including MDP. HEMA (207. Strong adhesion to tooth substances and amalgam is achieved. Monomer composition is selected for a balance of hydrophilicity and hydrophobicity. even when using a water-free adhesive primer (189). other erythritol methacrylates. Polymerization catalysts used are similar to those for pit and fissure sealants. Lack of bonding between the materials and tooth will induce secondary dental caries or restoration detachments. and so on. exhibit strong adhesion to dry teeth. curing time. Researchers have improved this procedure by using acidic monomer in the bonding agent as the acid for etching. such as BisGMA. and (6) finishing and polishing. and 47 to Ni–Cr alloy. (3) acid etching of the cavity wall.

are the most common way to prepare the alloy surface. Silane couplers are also used for surface modification of filler particles included in dental composites (214).10-decanediol. 1. and phosphoric acid groups. that is why methacrylate-based polymer materials are used in dentistry. The original MMA–TBB resin without 4-META is a transparent.216) is achieved by various inorganic and metal compounds incorporated into the formulations. 4-(3methacryloyloxypropoxy carbonyl) phthalic anhydride (MPRPA). a hydrophobic intermediate spacer. such as carboxylic acid monomers. The phosphoric acid derivative. silica coating. aluminum. Etching with an aqueous solution of hydrofluoric acid roughens the ceramic surface. such as 4-methacryloxyethyl trimellitate anhydride (4-META). The MMA-based adhesive system. A primer containing 0. such as air-abrading with 50–200 µm alumina. monomer liquid. Mechanical methods. The functional monomer usually consists of a polymerizable methacrylate or vinyl group. Functional groups effective for bonding base metal alloys are the acid anhydride. Other types of surface modification include electroplating.000. and ion-coating. prepared by condensing hydroxyalkyl methacrylates and trimellitic anhydride acid chloride.5% 6-(4-vinylbenzyln-propyl)amino-1. Acid anhydride or acidic monomers. ferric chloride. Monomers used are MMA or bifunctional methacrylate monomers. carboxylic acid. the primers for chemical bonding also contain functional monomers. and/or a tri-n-butylborane derivative (TBB) (212. functional (polymerizable) monomers are added to the primer or liquid part of the adhesive.4-dithol (VBATDT) in acetone is used to bond noble metal alloys. The dental ceramic surface is primed with silane couplers activated in acids. The initiator is partially oxidized TBB (TBB-O). Bonding to enamel and base metal alloys is improved by addition of 4-META monomers to the liquid part. and powder. Because the composition of dental adhesives is based on methacrylate monomers. while noble metals include gold (Au). Initiation systems are BPO–t amine or TBB (201). Base metals include cobalt–chromium (Co–Cr). These very useful. The ceramic surface is treated with a . and 4-(4methacryloyloxybutoxycarbonyl) phthalic anhydride (MBPA). are very important coupling agents. nickel–chromium (Ni–Cr). adherend surface is treated with a primer for chemical bonding. MDP is synthesized from methacrylic acid. Thiol derivatives are used to prime noble metal alloys. Dental ceramics consist mainly of metal oxides of silicon. potassium.196 DENTAL APPLICATIONS Vol.5-triazine-2. Electrolytic etching creates micro-mechanical retention on the alloy surface. One prerequisite for dental adhesives is an ability to cure in the mouth. and sodium.213). with a number-average molecular weight of about 100. has three components: initiator.3. After surface preparation. 4-methacryloxyethyl trimellate (4-MET). and titanium (Ti) alloys. the restorative material is bonded to the tooth structure with auto-polymerizing adhesive resin. The powder is finely pulverized PMMA. The needed optical opacity (215. The roughened. Mercaptan (SH) groups on the VBATDT monomer bond to noble metals and copper on the alloy surface. and palladium (Pd) alloys. 4-META/MMA–TBB resin formulation. 2 Casting alloys in dentistry are categorized into base metals and noble metals. and a functional group capable of bonding to the adherend surface. silver (Ag). and phosphorus oxychloride. unfilled resin. The monomer liquid contains 5% 4-META in MMA.

Shepard. Symp. and W. H. 51. Res. 67. G. Paffenbarger. L. Paffenbarger. Resin-bonded fixed partial denture or resin-bonded ceramic restoration methods are often employed. Mageli and J. 2. BIBLIOGRAPHY “Dental Applications” in EPST 1st ed. Instruments and Equipment. pp. Am. while 4-META is suitable for Ni–Cr alloy and titanium. J. Dent. 357 (1983). Clarke. C. and H. M. 70. Dentsply International. Paffenbarger. Ill. 4. 4. Braden. while the other liquid contains 5% 4-META (or 4-MET) in MMA or 0. Antonucci.Vol. 6. Sweeney. J. 727–739. Sweeney. North Am. Dent. 4. Argentar. Polysciences. For Ni–Cr alloys. 83. The γ -MPTS is activated by mixing with 4-META (or 4-MET) or ferric chloride to silanate the dental ceramic surface. Am. 561 (1968). Am. J. 413 (1960). W. Am. 5. The monomer VBATDT is effective for bonding Ag–Pd alloy. Rupp. 1st ed.. 19. Dent. Dent. Clin. P. B. Dig. Assoc. R. J. and W. L. 1016 (1966). 2. 2 DENTAL APPLICATIONS 197 two-part liquid primer before applying 4-META resin. Sweeney. 1. Halpern and W. 57. Ser. and R. Halpern. New York. Soc. by G. 1. J.. Dentist’s Desk Reference: Materials. 460 (1971). Bowen. J. Assoc. Causton. 61. W. Chem. Pamphlet 3542C. 698–719. Paffenbarger. Encyclopedia of Polymer Science and Technology. T. 1983. 3 (1984). G. Suppl. M. G. Prosthet. Dent. G. D. J. 889 (1972). E. 12. p.5% ferric chloride in ethanol. M. Paffenbarger. Polysciences. R. C. C. Res. L. Chandler. B. Dent. J. Woelfel. 1968.D. . N. 40 (1963). Mater. Woelfel. C. 14. 45. Advis. Karo. 1981. by B. Pa.. L. the chromium content influences bond durability. 67 (1971). Vol. pp. and R. 211. and G. Biomed. E. J. Braden and J. American Dental Association. “Dental Applications” in EPST 2nd ed. One liquid contains 4% γ methacryloxypropyl trimethoxysilane (γ -MPTS). Adhesive resins are also used for bonding orthodontic brackets. Vol. Powell. S. J. 345 (1958). Chicago. pp. p. Brauer and H. amalgam restoratives. Inc. 601 (1971).. reducing the amount of healthy tooth reduction needed in clinical treatment. W. 7. T. 11. Dent Assoc. a Division of John Wiley & Sons. 10. The use of MMA polymer (PMMA)-coated titanium oxide (217) makes 4-META/MMA–TBB-O resin optically opaque. B. Mowery and co-workers. 9. B. Vol. Woelfel. Dentsply TRIAD Denture System. National Bureau of Standards.. Winkler. National Bureau of Standards. Interscience Publishers. 77. H. Dent. R. Shear bond or tensile tests determine the dental adhesive bond strength. and many other metal and ceramic materials.. Woelfel. Ortman. Res. 13. Dent. Dent. M. J. Assoc. 205–230. M. 97. G. 245 (1971).. 15. J. O. Dent. 1170 (1965). Brauer and J. and W. Ferric chloride combined with a silane coupler significantly improves the bond strength of 4-META/MMA–TBB-O resin joined to dental porcelain. Inc. C. by B. 8. J. 15. Am. Ceramic restoratives are often bonded directly to the tooth surface with adhesive resins. 9. Elliott. C. Assoc. T. Inc. York. L. Am. Vol. Bowen. B.. with thermocycling in water effectively evaluating the bond durability. 16. 9. 3. Kolczynski.

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