Journal of Oral Rehabilitation 2007 34; 622630

Bonding of resin composites to etchable ceramic surfaces an insight review of the chemical aspects on surface conditioning
J. P. MATINLINNA*, & P. K. VALLITTU

*Nordic Institute of Dental Materials NIOM, Haslum, Norway and

Department of Prosthetic Dentistry and Biomaterials Science, Institute of Dentistry, University of Turku, Turku, Finland

The longevity of silane promoted adhesion of the surface conditioned etchable ceramic materials is a continuous and costly concern in dentistry. Moreover, it poses a functional and aesthetic dilemma both for the dentist and the patient. Several methods for surface conditioning exist, however some of them are not any more widely in clinical use. Tribochemical silica-coating combined with silane application, compared in vitro and in vivo to some other silanization protocols, is according to the literature a clinically proved, relevant adhesion promotion method to enhance bonding of resin
SUMMARY

composites to etchable ceramics. The repair of fractured ceramic with tribochemical silica-coating and followed by a silane application is, according to the literature a relevant adhesion promotion method in prosthetic dentistry. Silica-coating is followed by a silane coupling agent application. The bonding is adequate for clinical use according to the literature study. KEYWORDS: silica-coating, silanization, surface conditioning, dental ceramics, silanes, acid etching Accepted for publication 8 August 2005

Introduction
Dental materials and adhesive interfaces are subject to stress in the hostile conditions of the mouth: masticatory forces, temperature changes, saliva and pH changes. In general, conditioning of dental material surfaces is the treatment by which the critical surface energy will be increased. Two approaches are possible in dentistry: pure chemical and physico-chemical conditioning. Often etchants, such as hydrouoric acid (HF), that is washed off the surface, are considered as conditioner (1, 2). The use of a particular surface priming technique may also introduce micromechanical features into the substrate, e.g. acid etching of dental enamel and acid etching of soluble ceramics. Silane coupling agents, hybrid inorganicorganic compounds bond dissimilar materials, organic and inorganic, together. Unfortunately, the terms conditioner and primer are not always used consistently, and sometimes silanes are, perhaps, erroneously called with these terms (3). Indications of silanization for ceramics are:

bonding of indirectly made restorations with resin cements and repair of fractured ceramic structures. Ceramic fractures are costly and serious problems in dentistry and they pose a functional and aesthetic dilemma which has created a demand for practical repair systems (4). This is why this review aims at presenting chemical background and clinical experience of the silane-aided bonding in etchable ceramic systems. This review is based on a literature survey in which the PubMed data base and other silane literature sources have been utilized (Table 1). The purpose of this article is to review articles the authors perceive as being able to address the above concerns.

Surface conditioning
The establishment of reliable and durable chemical bonds between dental ceramic and resin composite is of high importance. This is because of the extensive use of resin composites resin-bonded restorations and
doi: 10.1111/j.1365-2842.2005.01569.x

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Table 1. Amount and type of references (total 75) cited in this review in selected time intervals

623

Type of literature Materials in dentistry Non-dental materials science Total

19621974 4 2 6

19751984 7 1 8

19851994 14 3 17

19952006 36 8 44

porcelain repair system kits. In general, ceramic onlays and inlays, laminate veneers and crowns are luted with resin composites (5). Fractured ceramic restorations can be repaired with various methods and materials that have been introduced (6, 7). With the introduction of silane coupling agents, a durable solution to ceramic repair became possible, as we can conclude below. The concept of critical surface energy (tension) is highly signicant. When the surface tension of a liquid is less than the critical surface energy of a particular surface, i.e. spontaneous spreading of the liquid will occur (2). The critical surface energy is dependent on roughness and chemical composition of the substrate. Obviously, a high critical surface energy is desired to promote wetting by a wide range of liquids (8). In many cases, the surface may contain low-energy contaminants, such as oil, grease, and proteins, which have to be removed prior to the bonding protocol in dentistry. The bond between ceramic surface and resin composite can be created via (i) micro-mechanical bonding by grit-blasting or acid etching with HF and (ii) silane coupling agent (2). For a successful bonding (luting) cement some requirements are: (i) adequate micromechanical retention, when clinical adhesion is negligible, (ii) adequate wetting of the substrate by the bonding agent and (iii) resistance to fatigue, stress, erosion, and stress relief (911). Surface conditioning methods in conjunction with silanization of ceramic repair have been investigated and evaluated, with the conclusion highlighting the importance of the meticulous conditioning procedure and the role of the silane coupling agent (4, 911). A clinical review on silanization systems for attaching resin composite to porcelain has been published (12).

structurally covalently bonded SiO4- tetrahedra. Addition of certain metal oxides, e.g. NaO2, CaO, MgO, B2O3 change the glass transition temperature and melting point dramatically (13, 14). Recently numerous new dental ceramic materials have been introduced, like high-aluminium trioxide (alumina) ceramics, leucitereinforced feldspathic ceramics, castable glass-ceramics, and novel machining and CAD/CAM ceramic systems. It must be emphasized that modern non-etchable ceramics (zirconia and alumina), because of their structures, create many problems in obtaining strong and durable bonds with dental tissues. They are not discussed in this context but in other reviews (10, 15, 16). In earlier days the bonding between gold alloys and porcelain was based on the roughening of the contact surfaces and the hot temperature leading to mechanical retention (17). Later, a technique for the ceramic part, baked on gold framework matrix and then resin bonded to the silane coupling agent treated (silanized) ceramic, was introduced (18). In clinical conditions, the dentist should be aware of which ceramics the fractured crown has been manufactured. An experienced eye may recognize the ceramic type at once, otherwise the patient records must be checked.

Chemistry of silane coupling agents

Silanes function as mediators and promote adhesion between inorganic and organic matrices through dual reactivity. In general, silanes used for surface pretreatment in order to promote adhesion are usually organofunctional trialkoxy silanes, silane esters, of the general formula R-Y-SiX3, where R is a non-hydrolysable organic group, Y a linker (usually a propylene link) and X a hydrolysable group. These silane coupling agents are bifunctional, i.e. they have a dual reactivity: the non-hydrolysable functional group with a carbon carbon double bond can polymerize with resin composite monomers containing double bonds. The hydrolyzable alkoxy groups (e.g. methoxy -O-CH3, ethoxy O-CH2CH3) react with a hydroxyl group rich

Dental ceramics
Many of the dental ceramics are based on silicon dioxide (silica, SiO2) that has different crystalline or amorphous forms, depending on the temperature. Silica has a very high melting point that is due to the

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ceramic surface. Usually for intraoral repair or for the commonly washed off etchable ceramic surfaces after chemical etching, the exposed ceramic surface is hydrated from the surface adsorbed water. A major problem in chair-side silanization is to remove the excess surface adsorbed water. Several methods have been developed for this task, like intensive dry and warm air or application of volatile drying agents prior to silanization or washing off the ceramic conditioner (acid) with a pre-activated silane with no intermediate water rinsing stage. Alkoxy groups are intermediates in the formation of silanol groups ( Si-OH) for bonding to suitable inorganic surfaces. As alkoxy groups, methoxy groups are preferred because of the lower evaporation point of methanol, produced during silane hydrolysis and condensation reactions (19). It must be remembered that wetting of the surface is regarded as an important pre-condition for adhesive bonding. The low viscosity of silane solution would assist wetting, and once in close contact with the silica-coated substrate, van der Waals forces would be operative (21). During the drying and reaction period silanes form a branched thin siloxane lm (20100 nm) on the conditioned, or silica-coated, surface. The siloxane lm thickness is mainly determined by the concentration of the silane solutions, not the reaction time with the substrate surface. The curing time and temperature also have an effect. If the siloxane lm is too thick, it may lead to cohesive failure, while a too thin lm may lead to incomplete coverage of the ceramic surface by the thin silane layer, and insufcient contact between the silanized ceramic substrate and the resin composite matrix (23, 27, 28).

Silanization
It is generally accepted that hydrophobic silanes must rst be hydrolysed (activated), and then they selfsustained condense and deposit onto the inorganic substrate (2023). With an acidic catalyst in an alcohol water solution the labile alkoxy groups, -O-R, react with water to form reactive, hydrophilic, acidic silanol groups, Si-OH (24). Water is needed for the silanol conversion (hydrolysis), and silanes are soluble in alcohols. Simplied, this can be presented:  Si O Rsolution H2 O ! Si OHsolution R OH 1 The silanols are adsorbed, deposited and polymerized on the substrate surface, then hydrogen bonds and covalent Si-O-Si bonds form during this process, called silanization (25).  Si OHinterface  Si OHsolution !  Si O Si siloxane film H2 O 2

Commercial pre-activated silanes

Silane coupling agents have been extensively utilized in the development of porcelain repair systems, resin composites and resin-bonded restorations. The most applied silane in dentistry is 3-methacryloxypropyltrimethoxysilane (MPS). It is usually pre-hydrolysed (preactivated) and diluted in ethanolwater solution, ca. 12%, pH 45 adjusted with acetic acid. A low concentration is guarantees a relatively long shelf-life, such as 23 years, for the silane solution. MPS is used to optimize and promote the adhesion between metalto-composite, ceramic-to-composite and compositeto-composite. There are also two-bottle systems available for immediate hydrolysis in the clinical conditions, which contain adhesive or dimethacrylate monomers (3). The choice of MPS is obviously based on the compability of the functional methacrylate group with the dimetacrylates used in the composites. MPS molecules also tend to orientate parallel to the silica surfaces. As the MPS concentration increases, orientation of the MPS molecules become more randomized. This behaviour may be crucial in the present day understanding of silanization of ceramic surfaces and the amount of silane needed for the bond optimization (29).

When deposited on an inorganic surface, silanol oligomers react with each other, forming branched hydrophobic siloxane bonds, -Si-O-Si-. With a surface of silica containing typically reversibly attached hydroxyl groups, OH, they form siloxane bonds. Silanes are deposited in thin lms: as a result of silanization, a hydrophobic and branched three-dimensional siloxane lm will be formed. Free water molecules, ions and gases (O2, N2, CO2) can appear and remain in the lm (20, 26).

Acid etching of ceramic substrates

Silanes can also be viewed as materials to increase the surface energy of an etched ceramic so that a

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hydrophobic resin composite can more easily penetrate into it. The ceramic restorative materials, typically (i) leucite reinforced, (ii) glass-inltrated alumina and (iii) lithium disilicate, are etched with 5% or 95% HF gel that is often HF in a coloured gel matrix. Etching generates a micromechanically retentive surface, but also promotes hydroxyl group formation on the ceramic surface (11, 14). The etching takes place when the matrix contains silica or silicates. First, a volatile silicon tetrauoride (tetrauorosilane) is formed (30): 2HF2 l SiO2 s ! SiF4 l 2H2 Ol 3 apparatus consists of a carousel on which the sandblasted (pre-treated) casting passes through a special ame. The coating solution is injected into the ame and this results in a pyrochemical silica-coating, approximately 011 lm thick. The silane in question is tetraethoxysilane, TEOS. The main chemical reaction presented as simplied is: SiO CH2 CH3 4 g in propane flame !! SiO2 s xCO2 g yH2 Og 6 Treatment time and distance can vary. The temperature is 150200 C when the highly reactive silane fragments, of type Si(OH)x-C (where x 1, 2, 3), reach the metal surface, condense on it and the surface becomes embedded. When the silica-coated surface has cooled down to room temperature, it is then silanized with a silane coupling agent. The silica layer prior to silanization is about 5080 nm thick. After the silane drying and reaction time (about 5 min) an opaquer (a dimethacrylate containing pigments) is light-cured and then the veneering resin composite is built on. This treatment is recommended because of the enhanced bond strengths for composite inlays prior to cementation (3638). The Silicoater MD and Siloc systems are based on a colloidal silica and chromiumtrioxide application at high temperature, 320 C (39). These methods described above are not anymore widely in use. A novel pyrochemical version, meant also for ceramics, is a compact hand-piece for extra-oral use, PyroSil Pen which employs the same physico-chemical principle as Silicoater (16, 40). As a pre-treatment before Silicoater technique, a careful sand-blasting of feldspathic ceramics and high-alumina is recommended. Clinical experience of this new method has not yet been reported.

625

Silicon tetrauoride forms with the HF a soluble complex ion, hexauorosilicate: HF2 l SiF4 l ! SiF6 2 aq 2H 4

It can further react with the protons to form tetrauorosilicic acid that can be rinsed off with water: SiF6 2 aq 2H aq ! H2 SiF6 l 5

The chemical composition of an etched ceramic surface is now prone to silane-aided bonding. Application of MPS has been concluded to enable the bonding of porcelain teeth to acrylic resin in denture bases and to improve the adaptation of resin to etched ceramic and reduce voids (31, 32). It has been proposed that silanes could also be used to attach resin to porcelain without HF etching. Although the initial bond strength may be high, it has been shown that it deteriorates over time. The deterioration of the bond may be associated with the formation of a multimolecular layer of silane, which is less stable than a monolayer of the deposited silane (5, 20). Thus it has been concluded that ceramic materials that can be etched should be etched prior to resin bonding (3335).

Pyrochemical silica-coating systems

Pyrochemical and thermal silica-coating systems, Silicoater Classical, Silicoater MD and Siloc*, have been used in dental laboratories for over 20 years. The substrates are typically base metal alloy (Co-Cr) or noble alloy (Au-Ag-In-Pd) bridges but the silica-coating system can be used also with ceramics. The Silicoater

Grit-blasting
Abrasion and roughening with bur is obviously nonconsistent and arbitrary. A suitable treatment with many industrial applications on numerous material surfaces is grit-blasting. Grit-blasting cleans any greasy substances from ceramic surfaces and creates micromechanical bonding. In dental laboratories the

*Heraeus-Kulzer, Wehrheim, Germany.

Bredent, Senden, Germany.

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procedure can be carried out by using alumina particles (e.g. with 110 lm diameter) in pressurized air (with e.g. Korox sand), typical working parameters being the perpendicular distance of the nozzle from the surface of 10 mm, with an air pressure of 380 kPa, and application time of 1015 s (41). It must be noted that if alumina particles get embedded to the substrate they provide hydrolytically unstable Al-O-Si bonds that are weaker than Si-O-Si bonds (25). It can be concluded in this context that the terms air-borne particle abrasion, grit-blasting, roughening, sand-blasting, silica-coating, all appear in literature, often used as synonymes. The reader should be careful as this variety in terms might lead to misinterpretation and misunderstanding of research methods and results. crucial ingredient in creating long-term bonds of resinto-ceramic has been suggested (41, 45). There exist several commercial micro-roughening, activating and cleaning hand-piece systems. For intraoral silica-coating applications, the following can be mentioned: CoJet and Rocatector, Dento-Prep, and Microetcher**. Silica-coated ceramic is silanized by brushing two to three drops of pre-activated silane on the substrate. The silane is then gently air-dried before a dimethacrylate based veneering resin composite application (44, 46, 47). It must be emphasized that the shear bond between a conditioned surface without silanization would be ca. 65% less than the silanized (38, 39, 48).

Insight in ceramic restorations and repairs: experience

As introduced above, etchable glass ceramics used in dentistry are heterogeneous materials that contain high fusing ller in a low fusing glass matrix. The lower fusing glass matrix is more soluble in acids, which allows for micromechanical porosities to occur when the matrix is dissolved and leaves the roughness of the ller. It has been shown that fracture is the main reason for ceramic restoration failure, in particular for all-ceramic in-lays and crowns. Modern reinforced ceramic materials have shown better durability compared with red ceramics (49). As new non-silane type repair agents, methacryloxyethyltrimellitic anhydride, 4-META, and tributylboraneoxide, BB-O, have been introduced. They are, however, even more techniqueand operator-sensitive substances than silanes as has been reported and are discussed elsewhere (50). Some dentists prefer porcelain dentures to resinbased teeth. Porcelain teeth have been bonded to acrylic denture base resin using a silane solution as the coupling agent (31). However, silanization has suffered from difculties caused by the instability of the silane solutions used to prepare the ceramic surface: silane solutions may autopolymerize (51). Evaluation of silanes establishing bonds to metal or to ceramics has suggested that silanes had not bonded to the metal surface as they did with the ceramic (52). Three commercial silane based porcelain to resin bonding agents have been evaluated. The use of these porcelain
Rnvig, Daugaard, Denmark. **Danville Engineering, San Ramon, CA, USA.

Tribochemical silica-coating system

Increasing of the surface energy of a ceramic surface can take place by coating it with suitable, high-energy coating. A tribochemical silica-coating, performed by Rocatec System, is based on silica-coated alumina particles, and is designed for conditioning the ceramic substrate surface, including non-etchable alumina and zirconia, extra-orally. The method increases the bond strength effectively due to the increase in silica content of the substrate surface which provides a chemical basis for silanes to enhance resin bonding, as described above. Silica-coating with Rocatec is used in dental laboratories (4244). As the rst step a coating procedure, the ceramic surface is blasted with the air-borne particles that are silica-coated alumina particles, accelerated by compressed air. The particles hit the surface and create locally high temperatures (up to 1200 C) caused by the transfer of kinetic energy of the particles. The fresh SiO2 layer penetrates and is embedded onto the ceramic surface. An immediate silane application forms covalent bonding between the silica-coated ceramic layer and resin composite. The silica-coating method also provides micromechanical retention for the resin. For an effective bond of resin to feldspathic porcelain, metals, and composites, the use of silane in combination with a surface conditioning is typically required. For enhanced clinical success, the use of silane coupling agent as a

BEGO, Bremen, Germany. 3M ESPE, Seefeld, Germany.

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repair systems has been suggested mainly as only a temporary clinical procedure (53). However, promising results for the use of silane in the repair of porcelainfused-to-metal, PFM, restorations have been presented (54). In some subsequent studies silane coupling agents have been found to improve the bond of monomers of the dental resin composite to ceramic substrate by about 25% (55). The ndings of the study have clearly supported the idea of using silanes to improve the strength and the quality of the bond. But it has also been emphasized that the siloxane bond system is sensitive to moisture in the interface between the resin and the ceramic matrices (56). A further development step has been presented in a study where intra-oral fractured porcelain facings have been repaired successfully. The bonding system consisted of MPS, iron(III) chloride (FeCl3) and an adhesive opaque resin (57). Three out of four commercially available organosilanes meant for bonding resin composite to porcelain have shown equally acceptable shear bond strength values in the tests that were performed. All dry specimens have shown, however, higher bond strengths than the specimens stored in water in all products (58). In another study, four silane products, when imposed for thermal stressing thermocycling, have shown different results for bond strengths, when specimens were exposed to thermal stress (59). Grit-blasting of all-ceramic feldspathic porcelain restorations has been advised to be avoided as it has yielded a 36-fold loss of material compared with alumina ceramics. A rapid increase in the amount of water absorbed by the composite material has been observed, causing hydrolysis and degradation of the siloxane lm. Ageing methods, water storage and thermocycling have been described as detrimental for the siloxane-ceramic bond. It has also been reported that silanized interfaces appear to be unstable in humid conditions and the siloxane bonds have been found to deteriorate under atmospheric moisture. As the resin composites are permeable to water, the bond between silane and resin composite has been expected to deteriorate by hydrolysis over time. It has been concluded that in humid conditions this might lead to stress and crack growth (60). An in vitro study has been carried out on the effect of contamination on etched and silanized porcelain surfaces and the shear bond strength of dual-cured resin composite luting cement onto them. It has been concluded that in clinical work the contamination caused by saliva and latex gloves did not signicantly affect the shear bond strength. However, die stone contamination had reduced the bond strength and cleaning had not restored it. Cleaning the surfaces with acetone has signicantly reduced the shear bond strength under experimental conditions (61). Two studies have conrmed that the use of silane increased the bond strength of resin composite to hydrogen uoride etched porcelain (62). On the contrary, the use of a uoroalkylethyl silane in dental ceramics has been found to reduce stress-corrosion at the bonding interface (63). This idea has been supported with long term water storage test results (64). Etching a feldspathic porcelain with HF followed by priming with a commercial two-bottle silane has yielded the most durable shear bond strength (33 MPa) when the porcelain was bonded with a 4-META and MMA-based resin. The primer system contained MPS and 4-META (65). Roughening the ceramic surface with alumina particles prior to cementation has provided higher shear bond strengths for high-alumina dental ceramics. The values have increased signicantly after silica-coating that was followed by silanization (66). In a comparison of resin bond strength to commercial alumina ceramic, the results have suggested that a stable bonding of a commercial Bis-GMA (Bis-phenol-A-diglycidyldimethacrylate) based resin composite was achieved, e.g. using alumina particle blasting followed by priming the surface with an alloy primer or an MPS type silane (67). It has been concluded that although silane coupling agents are capable of forming bonds with both inorganic and organic surfaces, silane itself has not been found to help bonding on ceramic surfaces. Therefore, its use in combination with silica-coating has been recommended. The bonding strength of the non-silanized samples decreases after water storage for 30 days. The data has shown that when only silane has been applied on the ceramic surfaces, the bond strength does not improve because of insufcient mechanical retention (68). Efforts to enhance the adhesion promotion property of silane have been made by means of incorporating a catalyst and an initiator in the system. The results have spoken for a stronger bonding between the ceramic blocks with a dual-cured luting agent (69). The effects of etching, sand-blasting and silane primer have been compared in bonding dual-cured resin cement to glass ceramics. Accordingly, silane combined with an acidic primer has increased the micro-shear bonds

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signicantly, apparently due to increased extent of hydrolysis. Glazed ceramic surfaces have proved to be ineffective for adhesion to resin composites with silanes, because of the lack of micromechanical retention (70). Heat treatment for silanized substrates has proved to contribute to the bond strength when a resin composite was light-cured to porcelain. The test set-up included three commercial silane systems and an experimental, laboratory-made one (71). Bonding inlays and the resin luting cement has proved to be most effective when the inlay surface was grit-blasted and silanized (72). Silicacoating followed by silanization with MPS solution has demonstrated, in general, high in vivo and in vitro results compared with without silanization (35). Other research results have suggested that porcelain to resin composite bonding with a brief hydrogen uoride etching + silanization would result in better bonding than with silane + acrylic bonding primer, or the latter alone (73). This observation has been supported by further studies (65). An extensive comparison of repair options in combination with silanes has lately been reviewed, and the use of silane coupling agent has been emphasized (4). Different ceramic surface treatments have been evaluated on the microtensile bond strength of composite that was bonded to hot-pressed lithium disilicate ceramics. Acid-etching combined with MPS silanization has been found to promote the maximum strength, and gritblasting only without silanization yielded poor results (74). A study to survey improvement of the resin to a silica based ceramic bond, with the aid of silane, has not suggested the need for hydrogen uoride acid etching for the ceramics when appropriate silane concentration was used; even the siloxane bond was inert against boiling water (5). Very recently it has been reported that a laboratory-made MPS solution was effective for coupling to porcelain surfaces over a 1-year period in storage (75). Clinically it is important to realize that pre-activated silanes can autopolymerize during a long storage time: silane turns to milky looking and useless. This is why the expiration date is important to follow. 2 Silanes can also be used to attach resin to porcelain without HF etching. Although the initial bond strength may be high, it deteriorates over time. 3 Glazed ceramic materials that can be etched should be etched and silanized prior to resin bonding. Nonetchable ceramics should be silica-coated tribochemically and then silanized before a composite resin luting cement application. 4 The research activities have been so far concentrated and restricted mainly on one methacrylated silane, MPS. The large silane family with silanes with other functional groups than methacrylate, might offer also other silanes for clinical use (7677).

Acknowledgments
The study was funded by the Nordic Institute of Dental Materials (NIOM, Oslo, Norway) and the Finnish National Technology Agency (Tekes, Helsinki, Finland). The study is part of the NIOM Biomaterials Network cooperation and Bio- and Nanopolymers Research Group activity of the Centre of Excellence of the Academy of Finland. Mr Jack Wright (London, UK) is acknowledged for the proofreading.

References
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Conclusions
The following general conclusions of the literature study can be presented: 1 The function of silanes is based on chemical bonding of resin composites to ceramics and improving surface wettability for micromechanical retention.

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Correspondence: Jukka P. Matinlinna, Nordic Institute of Dental Materials NIOM, Haslum, Norway. E-mail: jumatin@utu.

2007 The Authors. Journal compilation 2007 Blackwell Publishing Ltd