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Restorative Dentistry

A brief history and current status of metal-and ceramic surface-conditioning concepts for resin bonding in dentistry

Mutlu Özcan, DDS*/Peter Pfeiffer, Prof Dr**/Ibrahitn Nergiz, Dr***

The bond strength of resin to metal or ceramic .\urfaces has been increased with the introduction of vari- ous surface-conditioning techniques. The principles of currently used conditioning methods and clinical trials with these methods are summarized. The advances in surface-conditioning methods have increased bonding to a high level: however, interpretation of the literature review itidicates that chemical honding by means of recently introduced techniques provides better results than does mechanical bonding. (Quintessence Int 1998:29:713-724)

Key words: ceramic surface conditioning, metal surface conditioning, resin bonding

Clinical relevance

Chemical bonding appears to give better results in different clinical applications, such as resin veneers, resin-bonded prostheses, and veneered clasps, than do other conditioning methods.

A lthough satisfactory bonding between porcelain and metal is achieved with current dental practices,

during the last decade many attempts have been made to create and develop techniques for bonding composite materials and dental metals. This has led to the develop- ment of various surface-condition ing techniques. With the advent of adhesive dentistry, competition in developing techniques and adhesive materials with in- creased bonding strength has emerged between dental scientists and manufacturers. Therefore, the intent of this article is to review the published literature on the advantages and disadvantages of the most commonly used surtace-conditioning concepts, concentrating on their brief history and their applications with different dental materials, as well as to provide an overview of clinical results obtained.

* Research Assistant, Deparlment of Prosthodonlics. School of Oral and Demal Medicine. University of Cologne, Cologne, Germany.

'^Professor, Department of Prosthodontics. School of Oral and Denial Medicine, University of Cologtic, Cologne, Germany. '»'Assistant Professor, Department Prosthoiionlics, School of Oral and Dental Medicine, university of Coiogne, Cologne, Germany, Reprint requests: Prof Dr P. Pfeiffer, Department of Prosthodontics. School of Oral and Dentai Medicine, Utiiversily of Cologne, Kerpener Strasse 32. 50931 Coiogne, Germany, E-maii: peter.pfei ffer@uni-koeln.de

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Surface-conditioning methods

Mechanical bonding

In 1989, Hansson' reported that in clinical practice, either a direct or an indirect technique could be used for the construction of resin-bonded prostheses. The direct technique was first described in 1973, by both Ibsen-' and Portnoy,-' as a simple method in which an acrylic resin denture tooth or the patient's own tooth was bonded, using a resin composite material, to the etched enamel of the abutment tooth without metal reinforcement. In the same year, Rochette-'^ presented an alternative method, an indirect technique, in which a perforated cast-metal splint was bonded to the enamel with poly(methyl methacrylate) resin. On the basis of these investigations, mechanical bonding gained importance.

Macromechanical bonding

Macromechanical bonding is one of the oldest methods used to retain metal restorations, allowing the cement to lock into the metal. This method involved a perforated design, which had the disadvantage of exposing the resin to saliva, causing piaque retention, and subjecting the resin to wear and crack propagation.*" The simple, old technique of using mechanical beads had the main disadvantage that considerable thickness was added to the restoration. The network retainer system, first intro- dticed by Shen' in 1984, was composed of prefabricated mesh casting patterns to provide undercuts in the re- tainer surface. This also had the disadvantage of requir- ing considerable metal thickness.

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From available information, it is clear that mechani-

cal retention has the following disadvantages : unreliable

bonding values, gap formation, and microleakage result- ing from differences in thermal coefficients of expan- sion, Furtbermore, mechanical retention requires a thickness of materials that might result in overcontour- ing of the restoration, which is inconsistent with the conservative approach.*

Micromechanical bonding

Mi crome chani cal bonding systems involveii sandblast-

ing, which improved the retention between the metal and resin by cleaning oxides or any greasy materials from metal surfaces. Sandblasting created very fine roughness and ihus increased the bonding surface area, enhancing mechanical and chemical bonding between some resins and metals.* However, bond strengths obtained from sandblasting were insufficient. Long-term durable bond- ing was obtained with resin composites (Panavia Ex, Ktiraray) that contained phosphate monomer,

¡Electrochemical etching

Electroetched retainers were developed in 1982 by Lividitis and Thompson^ at the University of Maryland, Fine irregularities in the surface of base alloys were formed to increase the bond strength, ehminating resin exposure. Furthermore, metal could be made thinner to avoid overcontouring and massive tooth reduction. Electrolytic etching is the most widely used procedure to create increased mechanical retention to metal surfaces, but only some nickel-chromium and cobait-chrotnium alloys have been successfully etched,''*'Electrochemical etching has tbe di.sadvantages of difficulty in creating a properly etched surface and not working well witb pre- cious alloys. It is also technique sensitive, requires expensive equipment, and is time consuming. Electrochemical etching of the metal framework cer- tainly improves the longevity of tesin-bonded restora- tions; however, to circumvent its limitations, numerous alternatives have been proposed in recent years.

Electrolytic tin plating

Most debondings in resin-bunded prostheses resuit from failure at the resin-metal interface,"-'^ It was therefore necessary to improve the retention between the resin lut- ing cement and the metal sutface of the prosthesis. The tin-plating technique consists of coating the rnetal sur- face electrolytically, at 6 V, with a thin layer of tin oxide. The layer is placed on the freshly sandblasted metal sur- face, which acts as the cathode, with a felt-tipped anode

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moistened with a solution of opaque resin and tin. The surface is then oxidized and air dried, A second coating of tin is applied at 9 V, and the sttrface is oxidized, washed with water, and dried, A special opaque resin is then applied before the resin veneer is built up. Electrolytic tin plating is required particularly for precious metal alloys because only base metal alloys can be etched,'•• Other studies noted that tin oxides form crystals on the surface of the alloy, making it easy for the resin to penetrate and produce micromechanical and chemical retention,'^"'

Chemical etching

The use of an acid-based gel is an alternative to etching the alloy retainer electrolytically. This alternative was originated by Lividitis" in 1986, Although new chetni- cal-etching systems have been claimed to provide better retention than either electrolytic etching or perforated prostheses when used with some metals,'* these chemi- cal etchants produce a shallower etching pattem than is found on electrolytically etched metal.'' This technique has the advantage of being very simple to use chaiiside; furthermore, the restoration can be re-etched in case of failure, without the need for sophisticated laboratory procedures.

Chemical bonding

SR Spectra Link. SR Spectra Link (Ivoclar) creates a physicochemical bond between the resin and the metal without silane coating (Table 1), The adhesive resin is a light-cured bonding medium based on metliacrylic acid, which has a metal-active, a resin-active, and a water- repellent component. Because SR Spectra Link contains a fluorinated alkyl methacryiate, it greatly reduces the susceptibility of the bonding system to hydrolysis, Tbe metal-active part of Spectra Link reacts with metal oxides and thus provides tbe necessary conditiotts for an optimum bond. The Spectra Activator prepares the polymerized surface of the Spectra Link for chemi- cal bonding with tbe specially developed light-curing Spectra Opaquer, Polymerization takes place in the Spectramat iu 5 minutes. This is followed by the appli- cation of the resin-activator component. Spectra Activator, The framework is coated with Spectra Opaquer and polymerized twice to make sure that all the surfaces are irradiated. The surface treatment is completed by tbe use of tbe desired Spectrasit color. This method can also be used to provide a high-quality bond between the metal and denture base material, Silicoater Classical. Silicoater (Heraeus-Kulzer) was developed at Jena University by Tiller et al-" in 1984

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{Table 2), The method was initially developed for bond- ing veneer resins to metal. Mechanical retention, such as beads or wires, was not required, aud tnicroleakage between the veneer and metal was eliminated. The pro- cedure originates from the need for an intermediate layer containing silicon dioxide (SiO^), because this provides sufficient bonding of the resin via a silane bonding agent that does not ahsorb water. The surfaces of precious alloys are sandblasted first with 25O-(tm aluminum oxide for 15 seconds at 0,4 MPa, The sandblasted surfaces are coated with Siliclean solution (Heraeus-Kulzer), After washing, the metal is dried for 2 minutes at room temperature in air. This tech- nique consists of heating SiO^ with a flame (Siliflam, Heraeus-Kul/er) in a specially designed apparatus. The flame should be adjusted to provide enough deposition of SiO^ molecules on the metal surface, Siliflam is ap- plied for 5 minutes (air-propane ratio of 20:1; air, ap- proximately l.iO L/h, propane, 6,5 L/h), After the speci- men is dried for 4 minute s in air, a silane layer (a mixture of Silicoup A and B, Heraeus-Kulzer) is applied. Silica coating leads to initial bond strengths 25% higher than those to etched metal-' and can be used to bond either composite or acrylic resin to any metal surface. The technique has the disadvantage of being expen- sive, and the internal resin interface caunot be altered during try-in,' The other shortcomings of the system are the nneven distribution of the flame over the restoration aod chemically unstable silica layers. Assuming a usual delay of 2 to 7 days between laboratory fabrication and clinical cementation, this layer requires protection dur- ing transportation. This problem can be overcome by coating the inner surface of the retainers with a thick layer of opaque base paste or a bonding agent (without its catalyst) from a resin composite luting cement, Silicoater MD. The Siiicoater MD (metai-dotted) (Heraeus-Kulzer) is the new version of the 14-year-old Silicoater Classical technique. The new technique requires a special oven tbat burns a chrome-endowing silica layer onto the surface (Table 3), The difference between the techniques is that in the new method the metal surface is coated with SiO^ as a liquid and is fired at highly controlled and carefully regulated temperatures. The surfaces of precious alloys are sandblasted first with 250-|jm aluminum oxide for 15 seconds at 0,4 MPa. The sandblasted surfaces are coated with Siliclean solution. After it is washed, the metal should air dry for 2 minutes at room temperature. Finally, the surface is treated with Sililink (Heraeus-Kulzer) and positioned in the Silicoater MD oven, and the Sililink is activated for 8 minutes. The framework is then allowed to cool for 5

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minutes at room temperature. Following this, the surface is conditioned with Siliseal (Heraeus-Kulzer) bonding agent and dried at room temperature for 4 minutes. This system has the advantage of avoiding flame- adjustment problems, ie, eiiminating the human factor. The principle of this technique is based ou a property of chromium, whieh forms waterproof bonds with sili- cates. These bonds are obtained as a result of the com- plicated chemistry of chromium bonding at tempera- tures higher than 250"C, Similar waterproof bonds can also be formed with certain alloy components, such as copper, other metals, and their oxides,----'' Kevloc AC. Kevloc AC (Heraeus-Kulzer) is a rela- tively new system, introduced in 1995, that offers a com- bination of chemieiti and mechanical bonding. It has presented promising results in resin veneer alloy bond- ing, inlays, onlays, and implant-supported restorations as well as removable prostheses (Table 4},'^ The Kevloc method was designed to bond resin lay- ers to the surface of dental alloys. The temperature needed for the activation of the bonding layers is gener- ated by contact heat transfer and heat radiation in the activation chamber of tbe Kevloc AC apparatus. In this system, the surfaces of the alloys are sand- blasted with fresh llO-pm aluminum oxide at 0,2 MPa. The sandhlasted surface is cleaned with a clean bmsh, and the loose particles are removed. Kevloc-Primer (Heraeus-Kulzer) is applied with a clean brush in one direction and dried at room temperature for 1 to 2 min- utes. Then, Kevloc Bond (Heraeus-Kulzer) is applied with a brush. After it is dry, the framework is placed in the chamber of Kevloc AC, to be activated for 8 min- utes. Then the specimen is cooled at room temperature for 5 minutes. The specimen is then positioned in the activating chamber. After the metal has cooled, which takes about 4 minutes, Dentacolor Opaquer (Heraeus- Kulzer) or Artglass Opaquer (Heraeus-Kulzer) is applied in thin layers and polymerized for 90 seconds in the Dentacolor XS (Heraeus-Kulzer),

Siloc. The surfaces are first sandhlasted with 250- pm aluminum oxide and dried with water-free and oil- free air at 0,3 MPa (Tahle 5), Siloc-Pre (Heraeus- Kulzer) is applied with a brush and dried at room temperature for 2 minutes. The specimen is placed in the Siloc apparatus (Heraeus-Kulzer), and program 2 is selected. Later, the framework is cooled at room tem- perature for 4 minutes. The activated surface is coated with Siloc-Bond (Heraeus-Kulzer) and dried in the air for 5 minutes. Following this, Dentacolor Opaquer is applied and light polymerized in the Dentacolor XS unit for 90 seconds.

Rocaiec. The Rocatec system (BSPE) introduced in 1989, presented a new kind of acrylic resin-metal bond-

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TABLE 1

SR Spectra Link process

t

Application ot

Solvent evaporated after 30 seconds

retention beads

2

Sandbiasting

Aluminum oxide, 50 to 250 |jm. steam cleaning, drying with oil-tree compressed air

3

Coating

Spectra Link: Polymerization in Spectramat for 5 minutes

4

Surface activation

Spectra Activator (resin-reactive component)

5

Coating

Spectra Opaquer: Polymerization in Spectramat and coating witfi Spectrasit Cclor

TABLE 3

Silicoater IVID process

1. Aluminum oxide, 250 |jm; pressure: 2 0.4 MPa; time: approximately 15 seconds

2. Siliclean; Ait drying

Sandblasting

Rinsing

3. Brushing a thin iayer ot Sililink; sample positioning in the middle of the apparatus; 2 minutes of cooiing down

4. Coating with Siliseal; drying for 2 minutes

5. Dentacolor Opaquer; Polymerization in Dentaooior XS for 90 seconds

Conditioning

Siianization

Coating

TABLE 5

Süoc process

1. Aiuminum oxide, 250 pm; drying with oil-free air at 0.3 MPa

2. Siloc; Applied and dried for 2 minutes

Sandblasting

Conditioning

3. In Siloc apparatus: cooling down fcr 4 minutes

4. Siloc-Bond: Applied and dried for 5 minutes

5. Poiymerization

Activation

Bonding

Dentacoior Opaquer: Poiymerization in the iight unit Dentacoior XS for 90 seconds

ing system (Table 6). The principle is a tribochemical application of a silica layer by means of sandblasting. First, surface conditioning takes place in the Rocatector Delta (ESPE) with Rocatec Pre, llO-pm aluminum oxide (ESPE), at a pressure of 0.25 MPa. Then the sam- ples are blasted with 1 lO-pm aluminum oxide modified with silicic acid, Rocatec Plus (ESPE), in the Rocatector Delta at 0.25 MPa at a distance uf 1 cm from the metal surface for 13 sec/cm-. The theoretic calculated speed of the Rocatec Plus particles hitting the alloy surface is 200 m/s, producing spot heating up to !,000°C. This spot heating, together

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TABLE 2

Silicoater Classica! process

1, Sandbiasting

Aiuminum oxide, 250 [jm; pressure: > 0.4 MPa:

1. Hinsing

time: approximately 15 seconds Silioiean: Air drying

3. Positioning in the Silicoater apparatus

Mounting

4. Silitlam' Approximately 5 minutes; tiame proportion ol air-propane 20:1 (air application 130 L7h; propane 6.5 L/h for approximateiy

Conditioning

4

minutes; cooling down in air)

5. Silicoup A and B: Drying for apprcximateiy 4 minutes

Siianization

6. Dentaooior Opaquer; 90-second poiymerizatioo in Dentaooior XS apparatus

Coating

TABLE 4

Kevloc AC process

Sandblasting

1. Aluminum oxide, 110 [jm. pressure: 0.2 MPa

Coating

2. Kevloo-Primer; Appiied and dried for 1 to 2 minutes

3. Kevloc Bond in Kevloc AC for

Aotivation

8

minutes; cooling down tor 5 minutes

4. Dentacoior Opaquer or Artglass in thin layers, in Dentacolcr XS for 90 seconds

Polymerization

TABLE 6

Rocatec process

1. Sandblasting

Rcoatec Pre in Rocatector; pressure; 0.25 MPa

2. Conditioning

Rocatec Plus in Rocatector; pressure; 0 25 MPa;

_ time; approximately 13 sec/cm' a

3. ESPE-Sil; Drying time, 5 minutes ^

distance: 1 cm trom the surface;

Siianization

Coating

4. VisioGem or Slnfcny Opaquer

with the hlasting pressure, results in the embedding of silica particles on the metal surface, rendering the metal surface chemically more reactive to resin via silane. ESPE-Sil silane agent (ESPE) is applied before the sur- face is coated with the opaquer and dried at room tem- perature for 5 minutes. The particular advantages of the process are the bpeed and accuracy of coating, the fact that the adhesive layer can be checked visually, and the fact that thermal stressing of the framework is avoided. This is especially useful in repairs hecause remaining acrylic resin does not have to be removed."

Volume 29, Number 11, 1998

Care should be taken to sandhlast the metal surface at an angle of 90 degrees and not to touch the treated surface during any steps of the preparation. The Rocatec system uses the mechanical energy of silica-covered aluminutn grains as these are hlasted onto the metal sur- face. The silane coupling agent adheres to the surface when the mechanical energy is transformed to thermal energy, providing a chemical hond between the silica layer and the resin cement. Gugg en berger-'' deñned the Rocatec procedure as a novel acrylic resin-metal bond- ing system and concluded that shear/compression and tensile tests revealed bonding strength values obtained with the Rocatec system to be greater than those obtained with mechanical bead retention, even after thennocycling and storage in water for 1 year.

Adhesive chemical bonding

Recently, chemical adhesive systems have become very popular in bonding resin to metal. The greatest advan-

tage of these systems is that they are very easy to apply

require laboratory processes . Sandblasting

renders the metal surface fresh and clean of any metal oxides or any greasy materials and makes the surface chemically more reactive to resin by increasing the metal surface, Bxamples of these adhesive systems are Panavia Ex and Panavia 21 adhesive resin cements (Knraray). In both laboratory and clinical research, Panavia Ex is one of the most popular metal adhesive cements. Bonding to the sandblasted nonprecious alloys is highly satisfactory with good physical properties.*

and do not

Comparison of conditioning systems

Metal conditioning

Numerous studies over the years have assessed the sur- face conditioning of alloy surfaces. Crcugers et aV were among the pioneers of such studies. They compared the bond strength of silica coating in combination with MicroponI (Kulzer), sandblasting with Panavia Ex, elec- troplating with Panavia Ex, and etching in combination with Clearfil to nickel-chromium and cob alt-chromium alloys. The mean tensile bond strengths of silica-coated and sandblasted specimens were significantly higher than those of both electrolytically tin-plated specimens and etched specimens. There was an overall effect of luetal alloy on the bond strength but no significant dif- ferences between both alloy types for etched specimens. In a subsequent study, Luthy et al" investigated fac- tors influencing metal-resin bond strength to filled com- posites. Apparently, bond strength was greater to silica- coated metal than to sandblasted and electroetched

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specimens. In a similar study, statistically significant differences in bond strengths were observed between precious and nonprecious alloys. It was observed that silica coating produced higher shear bond strengths than either electroetching or chemical etching.-" On the other hand, the bond strength created by the Rocatee system, independent of the alloy used, proved the reliability of chemical bonding over sandblasting alone and treatment with silane.-^

Caeg et aP^ and Ishijima et aP" demonstrated that the silica treatment process always provided better results than that of electroetching in palladium-, cobalt- chromium-, and nickel-chromium-based alloys. In the last decade, a number of studies were focused on comparison of Silicoater Classical, Silicoater MD, and Rocatec systems. Silicoater MD provided a notably lower degree of bond strength to nonprecious alloys, whereas Silicoater Classical and Rocatec systems showed superior bonding to all types of alloys, espe- cially to pure titanium.^'"" It has been possible to create a chemical bond resembling the metalloceramic bond between dental alloys and resin composites. Ruyter et al'-' attributed a 17% to 47% reduction in bond strength in two palladium and three gold-based alloys coated with silica to water diffusion through the interfacial layer; the moisture attacked the SiO layer between the metal and the composite. The process of sandblasting makes the surface rough, which is essential for building up and locking in the silica oxides; this could explain the differences in the bonding values among various alloys. This study was one of the first explaining the importance of the silica-coating mechanism.

The effect of water storage on bonds obtained with Silicoater Classical, Silicoater MD, Rocatec system, and Panavia Ex to different types of alloys was ad- dressed by Beldner et al,^^ who concluded that the bond strength developed with both the Rocatec system and Panavia Ex to cobalt-chromium alloys remained the same, without significant change. The values related to Silicoater MD dropped by a value of 30%, while those obtained with the Silicoater Classical system increased slightly from the results obtained before water soaking.

When nickel-chromium-beryllium alloys were treated with silica and then silanated (Silicoater MD and Rocatec), cohesive failure of the opaqtiers between the composite veneering materials and the porcelain fusing alloys was ohserved in both experimental groups.^^ The analysis of pre sandblasting, which is rec- ommended as pretreatment to thermal silica coating or as part of a tribochemical silica-coating process, and the influence of particle size on the loss of substance revealed that volume loss, surface morphology, and compositional changes are greater in noble alloys

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(gold-silver-copper) than in base alloys (nickel- chromium and cobalt-chromium); however, these dif- ferences did not seem to be critical for the fit of the restorations.-" Embedded alumina particles were also found in all alloys after sandblasting, and alumina con- tent was increased by 14 to 37 wt% as measured by en- ergy-dispersive K-ray spectroscopy. Also following tri- bochemical silica coating, a layer of small silica

particles remained on the surface, increasing the silica

content to between 12 and 20 wt%."

However, in another study,"* slightly higher loss of substance was observed with palladium alloys, and par- ticle sizes smaller than 30 p m caused dust production and obstruction of the nozzle during sandblasting. Therefore, it was recommended that the thin metal mar- gins be blasted only with silicated corundum with a par- ticle size of 30 |im before bonding. Unnecessary sand- blasting of the restorations should be avoided because it is likely to damage the margins of the restorations.

The bond strengths of two adhesives (Microfill pon- tic, Kulzer; Nimetic-grip. ESPE) and two metal pre- treatment methods (Silicoater MD and Rocatec) were assessed by Stark and Holste"' for bonded fixed partial dentures. The test procedure was carried out in accor- dance with German Industrial Standards (DIN 532S3; DIN 8200), which ensure high reproducibility in sand- blasting and bonding pairs of metallic specimens. Although few differences were detected between the adhesives, the Rocatec method showed significantly lower strength values than Silicoater MD. The same outcome was reported in a comparative study of the bonding of high-gold and nonprecious alloy treated with these systems and adapted with Microfill pontic to the enamel of extracted human teeth. The two methods of veneering increased the composite strength and the nonprecious alloy yielded the highest values for shear strength. The shear resistance of the Silicoater MD system was found to be higher than that of the Rocatec system.'* The results of these two studies contradicted the findings of previous studies. Nevertheless, both methods can be used for bonded fixed partial dentures because the bond strengths they provide are adequate. In summary, studies related to surface conditioning with current methods revealed that silica coating of the alloy is an important advance in adhesive bonding of resin composites to metal because it reduces the impor- tance of the alloy composition and its oxide formation to the bonding mechanism.

Ceramic conditioning

A new glass-infiltrated alumina ceramic (In-Ceram, Vita Zahnfabrik) has shown greater ñexural strength than

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other ceramic or glass materials. Because of its high strength, this ceramic has been suggested as a core ma- terial for resin-bonded fixed partial den tu re s,"*"-^' This clinical application requires a stable resin bond to the ceramic and is advantageous for other clinical applica- tions, such as inlays or artificial crowns. Etching silica- based ceramics with hydrofluoric acid or ammonium bi- fluoride creates a sufficient resin bond that is enhanced with a silane coating of the etched ceramics. However, neither etching with these solutions, nor adding silane, resulted in an adequate resin bond to the alumina-based In-Ceram ceramic.'"—'" Although In-Ceram ceramic can be etched with boil- ing sulfuric acid, all of the etched samples were found to have debonded after 150 days of storage in isotonic artificial saliva solution because of a weakened bond to the superficial alumina particles as a result of etch- ¡i^g .16,49 Therefore, the development of alternative meth- ods of bonding to In-Ceram was needed. In following studies, it was noted that the use of resin composites that contained phosphate monomer, in combination with sandblasting or silica coating, increased the bond strength to In-Ceram.-"*"^''"-'" After sandblasting or silica coating of In-Ceram, the tensile bond strength of the modified bis-GMA resin Panavia Ex {Kuraray) showed no significant changes within the first 30 days, but there was a pronounced decrease after 150 days of storage and thermocyciing. Silica coating In-Ceram with the Roeatec system resulted in a better bond strength to the conventional resin. Micro- fill pontic. than did use of .silane only.''^ In vitro shear strength of the resin bond was found to be higher to glass-infiltrated aluminum oxide ceramic material treated with Sihcoater or Rocatec systems than to nonprecious metal alloys. With this method, the small marginal gap and film thickness of the luting cement was decreased.^' Most notably. Kern et ai," using alignment appara- tus, bonded resin composite filled in Plexiglas tubes to disk-shaped metal, core ceramic, glass-ceramic, and enamel .specimens. Specimen surfaces were conditioned cither by sandblasting and etching or the Silicoater MD procedure. After storage, statistically significant differ- ences were recorded in bond strength between the test materials. The group treated with Silicoater MD gave the best bonding results at the end of 150 days" water storage and thermal cycling. Gobel et al'' studied the effect of surfaee conditioning on different dental ceramic materials—glass ceramics (Bioverit, Schott; Vita-Miirk2, Vita Zahnfabrik; Cerec, Vita Zahnfabrik), sintered ceramics (Vita Omega, Vita Zahnfabrik), and aluminum oxide ceramics (In- Ceram)—in shear bond strength tests of the ceramic- cotnposite bond. Among the conditioning methods, silica

Volume 29, Number 11, 1998

coating with Silicoater Classical, Silicoater MD, aud Rocatec, as well as Siloc, Kevloc, and Spectra Link, pro- vided better results tban did sandblasting, grinding, or etching with phosphoric acid. Wben glass-infiltrated, cyhndrical alumina ceramic In-Ceram specimens were bonded to phosphoric acid-etched human enamel, the results of the shear tests indicated that durable bond be- tween enamel and In-Ceram was more likely to be ob- laiued witb Rocatec than with Silicoater MD or Panavia.-"

Mode affaiiure

Altemative adhesive methods for bonding to In-Ceram exhibited different bond failure modes in scanning elec- tron microscopic studies,^-" The reason for the adhesive failure and low bonding in tbe presence of loose silica panicles on the silica-coated alloy surface was studied.^' It was suggested that ultrasonic cleaning instead of sim- ple bench tapping, as recommended by the manufac- turer, should be performed to increase the bond strength. Scanning electron microscopy and chemical analysis demonstrated adhesive failure patterns on tbe treated surface. With the Rocatec tribochemical silica-coating system, failures occurred witbin the silica layer itself. When thermal silica coating witb Silicoater MD was used, only cobesive failures within the resin layer were found. On tbe otber band, sandblasting showed different failure modes,^'

Effect of water storage and tbermocycling on bond strength

Several authors conducted research concentrated on the effect of water storage and thermocycling to simulate the aggressive oral environment under laboratory condi- tions-' and found no significant differences between fresh silica-coated nonprecious alloys and those stored in water at 37''C for I week, except for sandblasted specimens bonded witb Panavia Ex, where bonding val- ues were increased, A sbort-term storage study was per- formed by Laufer et al," and tbey concluded that ce- mentation significantly increased the bond strength for both etched and silica-coated specimens after 30 min- utes to 3 days of water immersion. An increase in bond strength of silica-coated, nickel-chromium alloy speci- mens after 30 days of water immersion was reported by Guggenberger,^^ No statistically significant decline was found in the adhesive strength of the Rocatec system from baseline to long term; tbe initial bonding results were obtained after 20 hours of water storage at 36''C plus 6 hours of thermocycling, repeated 180 times be- tween 15°C and 70°C, and long-term values were calcu-

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Ozean et al

lated after 1 year of water storage and 900 repetitions of thermocycling between I5''C and 70°C, Another study in the arena of water storage, by Peutzfeldt et al,-" found that immersing the samples in boiling water for 55 minutes and then storing them at 22°C for 5 minutes, repeated four times before tensile bond testing, did not change the bond strength values of silica-coated Wirobond alloy (cobalt-chromium) (Bego), whereas it did cause a statistically significant decline in the bond strength of gold-based and palla- dium-based alloys. Testing of nonsilicated specimens also resulted in significantly lower bond strengths. This decrease was related to the difference,'; in coefficient of expansions, which pre.sumably sped up the diffusion of water between tbe resin cetnent and the metal,

Pfeiffer" studied the bond strength of Panavia Ex and Orthomite (J, Morita) to nickel-chromium and pal I ad iurn-silver alloys after 3 days aud 150 days of water storage at 37°C. He noted that tbe initially high bond strength values of nonprecious alloys bonded with Panavia Ex remained unchanged. The palladium- silver alloys, in contrast, had initial bonding values lower than those of the other alloys, and tbese values were further reduced by 33% after 150 days' water storage. Kern et aF^ compared five different resin bonding systems to cobalt-chromium alloys, Tbese were stored in artificial saliva for 150 days at 37°C and every sec- ond day were subjected to 1,000 thermocycles in a tem- perature range of 5°C to 55°C for a total of 75,000 cy- cles. Specimens were tested after 24 bours, 10 days. 30 days, 90 days, and 150 days. The results indicated that in contrast to the micromechanical bonding systems, mechanical-chemical ones (Rocatec system) showed no significant change in the tensile bond strength during this observation period. The ,system was recommended as suitable for cobalt-chromium alloy used in resin- bonded restorations,

Tbe effect of short-, medium-, and long-term water storage and thermocycling on the bonding durability and failure bebavior of Rocatec and Silicoater systems used witb gold-silver- and palladium-silver-based al- loys was studied, Silicoater produced better results after 20 hours of water storage. Three hundred sixty thermal cycles between 15''C and 70°C for 12 weeks resulted in a significant drop of the bond strength and an adhesive mode of failure and without significant change in adhesive failure after storage of the samples. On the otber hand, 1,080 thermal cycles for 22 weeks reduced the bond value between 38% and 69% in the group treated with Silicoater, which exhibited adhe- sive failure. They attributed this drop in bond values to the effects of thermocycling. which facilitated water

719

attack of the SiO^-composite bonding. The Rocatec system recorded the lowest drop in bond values, rang- ing from 8% to 15%," Ishijima et aP" evaluated the effect of I week of water storage, 500 cycles, and 1,500 thermai cycles on the hond strength produced with the Silicoater system, Panavia Ex, and Superbond used with different precious and nonprecious alloys. They found that increasing the thermal stress led to the diminution of the bond strengths of all systems. Smith et al" compared bond strength and durability of the Silicoating, electroetching, and Panavia Ex sys- tems bonded to nickel-chromium alloy. After short- term (2,672 cycles) and long-term (10,584 cyeles) ex- posure, silica aud silane-treated specimens demonstrated the greatest decrease in bond strength (39%), whether it was under aqueous or thermocycled conditions. The second highest value was obtained from electroetched specimens, while Panavia Ex speci- mens had the least decrease in bond strength. The Silicoating technique resulted in a significant reduction in hond strength with respect to time with or without

the bond was decreased in the case of gold alloys,^'* Pfeiffer^^i reported that regardless of the resin type, the Silicoater MD system produced high initial bond strengths, which deteriorated after thermoeycling and long-term water storage. The Rocaiec system, in com- bination with Nimetie-grip, provided lower but clini- cally acceptable, stable bonding even after thermocy- cling and water storage. When tensile bond strength was tested, the tribo- chemical silica-coating procedure with Rocatec was found to be suitable for cobait-chromium alloys in resin-bonded restorations after 18,750 thermocycles,^^ Hansson and Moberg''' evaluated three different meth- ods of increasing the bond strength of resin to metal. The original Silicoater technique, Silicoater MD, and the Rocatec systems were tested. The results proved that with each system, the retention of resin to the gold specimens decreased after thermocycling but retention to the coba h-chromium alloy and titanium was not af- fected. The original Silicoater technique produced higher hond strengths than its new version, Silicoater MD,

thermocycling, which could indicate that there is a high initial attachment of resin to metal but that this effect

Clinical studies

may deteriorate over time in a water environment. The bond quality achieved with Rocatec, Silicoater MD,

Resin veneers

and SR Spectra Link systems and different types of precious and nonprecious alloys was tested after the specimens were subjected to 10,000 thermocycles. The results demonstrated that the Silicoater MD system produced the lowest bond values to the nonprecious al- loys, while the Rocatec system achieved superior bond strength to all types of alloys,^" The bond strength of Panavia Ex. Cover up (Parkell), and silica-coated stainless steel and the effect of ther- mocycling on the bond values were evaluated in another study, Panavia Ex and Cover up produced bond strengths superior to that produced by the Silicoater sys- tem. Interestingly, thermocycling was found to have no signiflcant effect on the hond values,^^ In a similar study, the effect of storage conditions (24 hours of water storage and 1,000 thermocycles) on the hond strength of eight different bonding systems, in- cluding Rocatec. Panavia Ex and Silicoater, to a nickel- chromium alloy was tested, Thermocycliug was found to have no effect on the Rocatec system but resulted in a decreased bond strength for Panavia Ex and Silieoater MD; the reduced values were close to the critical clini- cal values,**" More recently, it was found that the retention of resin to cobalt-chromium and titanium alloys treated with the Rocatec system was not affected by immersion of the samples in boiling water for 25 minutes, while

Musil and Hàselbarth,''" after applying the Silicoater technique for resin veneers, carried out a follow-up study from 1984 to 1988 on 13,133 Den taco lor-coated prosthetic applications. They ob.served only a 2,7% inci- dence of fracture failure, WÖstman'^^ observed fracture failures of the facings in 54 patients with 157 veneers (Silicoater/Dentacolor). Between the period of 6 and 18 months, in the silica- coated group, fractures were found in only 4 of 157 ve- neers ohserved, Bruhn et al"'' earned out a 3-year fol- low-up study comparing the Silicoater/Dentacolor technique to other methods in 304 crowns. Surface con- ditioning with Silicoater gave clinically acceptable re- sults esthetically, although there were some small color differences that could be attributed to insufficient poly- merization. Over this period of time, a defect rate of 4% was observed, Heidi'*' followed up on 4,893 crowns (Silicoater/ Dentacolor), observing a fracture rate of 2,3% for gold- based alloys, van der Veen^** compared the Silicoater system clinically and experimentally with other systems and, after thermocycling, obtained the highest bond val- ues with the Silicoater system. Clinically he evaluated 40 flxed partial dentures. At the end of 2 years, 10% debonding was observed. The importance of a thin opa- quer layer was also emphasized,^^

720

Volume 29, Number 11, 1998

Resin-bonded

prostheses

Kerschhaum'''' evaluated 1,453 resin-honded prostheses

and found die

with the Silicoater system, 65% less with acid-etching, and 15% less with net technique than with sandhlasting over 4 years. The results suggested that resin-bonded prostheses can successfully survive if meticulous atten- tion is given to the procedures outlined. The survival of posterior resin-honded prostheses was achieved follow- ing a common protocol.'" A meta-analysis of posterior resin-bonded fixed par- tial dentures treated with electrolytic etching and Clearfil F2 (Covex); sandblasting with 50-nm alu- minum oxide, and Panavia Ex: and silicate coating and Microfill pontic was carried out after 2.5 years," The results of this clinical trial revealed that silicate coating was the most suitable of the tested adhesive systems. After complete polymerization, Panavia Ex was also found to be acceptable in combination with cobalt- chromium, nickel-chromium, Wiron 77 (Bego), or Wiron 99 (Bego). A combination of silica coating and Clearfil F2 was thought to he an interesting alternative for clitiical use. Verzijden et al'- evaluated 201 posterior resin- honded tlxed partial dentures and found no significant dilïerences among Clearfil with etching, Panavia Ex with sandblasting, and Microfill pontic C with silicate coating or among the different preparation forms. Three years of clinical experience in 47 patients with 120 resin-honded restorations placed after Rocatec application demonstrated few failures.^' Of the 13 failures, 11 fractured between the metal and the VisioGem (ESPE) opaque layer. The other two small fractures were observed at the acrylic resin and were difficult to see. The rest of the restorations U"eated with Rocatec exhibited no color changes and were resistant to abrasion. Boening" evaluated 46 resin-honded prostheses for 45 months. The metal surfaces were tribochemically coated with silica, and the abutments were etched wilh 35% phosphoric acid for 60 seconds. Ten failures resuit- itig from bond failures and porcelain fractures were ob- served. Humidity control was also stressed as a very im- portant factor for long-term success in resin-bonded prostheses.

probability of dehonding to he 75 % less

Veneered clasps

Despite its unesthetic appearance, resin coating report- edly made partial denture clasps look better. Schott'^ reported that, as a result of silica coating, long-term bonding of the composite and the metal was possible without the use of retention pearls and undercuts. U.se

Quintessence International

of Dentacoior opaquer following SiO^ conditioning with Silicoater and siianization imparted tooth color to the partial denture clasps.

In some studies, the Rocatec/Visiogem system has

been used for veneering clasps, which has the advantage of having no thermal or mechanical effect on the denture and opaquer, instead bonding the metal surface through the kinetic energy of Rocatec Plus.'"" However, the liter- ature reviews in these studies revealed no long-term clin- ical results, although t!ie esthetic advantages are obvious.

Discussion

Cuncnt research efforts in modern surface conditioning have been reviewed in this article. A iiumher of tech- niques that mechanically facilitate alloy-resin honding for adhesive prosthodontics have heen discussed. Although clinical studies proved the weakest link to be hetween the resin and the metal, resin-bonded pros- theses have shown that Panavia Ex, which is an adhe- sive his-GMA resin composite, also exhibits very pre- dictahle results.'- Tin plating is a surface treatment recommended for improving the strength and durability of the bond between adhesive resins and the metal. With electrochemical etching, on the other hand, it is difficuh to create a properly etched surface, and the technique does not work well with precious alloys. The method is also technique sensitive, requires expensive equipment, and is time consuming.

A frequently mentioned criticism of etching non-

precious alloys is the complexity and technique sensi- tivity of the treatment. In this regard, Sihcoater is also complex and technique sensitive.

Rocatec treatment is simpler than tin plating. Roca- tec was developed to pemiit chemical honding hetween resin veneers and the metal framework in fixed partial dentures, hut the simplicity of the technique makes it a potentially useful surface treatment in adhesive prosth- odontics. Rocatec, Silicoater. and tin plating surely im- prove bond strength compared to sandblasting.

The influence of prolonged thermal cycling and water storage seems to affect the hond strength of resin to alloy that has heen treated with trihochemical and thermal silica-coating procedures. Important variables, such as storage media, thermocychng, or medical fa- tigue, are likely to affect the hond strength of the com- binations tested and will ultimately influence the devel- opment of more reliable systems in the future. Although the interim clinical results are encouraging, only long- term clinical studies will determine whether chemical adhesion to metal surfaces resists not only masticatory forces but also diffusion of water and temperature varia- tions in the oral cavity.

721

Ozean et al

According to their manufacturers, most of the new chemical bonding systems require sandblasting of the metals prior to honding to achieve a high bond strength. Sandblasting the restorations has the potential to remove significant amounts of material and could af- fect the cUnical adaptation of the prosthesis. Thus, the material loss resulting from these procedures is impor- tant to the clinical fit of restorations. Therefore, knowl- edge of the surface characteristics of different alloys after these surface treatments is needed to improve the understanding of the bonding mechanism and the fail- ure modes involved. Sandblasting with alumina not only resulted in micromechanical roughening of the surface but also left alumina particles embedded in the surface. The role of this alumina in honding for these systems is not known. Unfortunately, there are no data available to indicate whether the adhesive failures reported appear within, at, or outside the silica layer, which necessitates further research. The encouraging results obtained from the application of silica coating indicate that it could be tried in other types of porcelain. In light of the previous disadvantages of mechanical retention, it was necessary to develop an alternative gap-free system that consistently chemically bonds resin to any metal and allows the use of a large variety of metal alloys. Panavia Ex and Panavia 21 have demon- strated good bond results in many studies, whereas the

bond strengths oh tai ne d from sandblasting

with conventional bis-GMA adhesive are poor. Recent advances in surface-conditioning methods have increased bond strength values greatly; however, the interpretation of the literature review indicates the necessity to focus more on an understanding of why hond values achieved with the Silicoater and Rocatec systems are different or similar, because the mecha- nisms of these methods are not the same.

and bonding

Summary

Data examined in this review indicated that chemical surface conditioning by silica coating with the newly in- troduced methods gives better results than the mechan- ical retention used in current clinical practice. It is ap- parent that further research is necessary and that the bonding of resin-bonded prostheses should continue to be investigated both in vivo and in vitro utilizing the latest surface-conditioning methods.

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Dtsch

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76, Wichmann M. Die verblendete Modellgussklammer.

77,

mimm

Answers to Ql 8/98 Questions

=

^

i»r^^

1.

D

5.

B

9,

D

13. C

 

2.

A

6,

D

10.

B

14. D

3.

D

7,

C

11.

A

15. D

4.

A

8,

D

12,

B

16. A

724

Voiume 29, Number 11