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Journal of Oral Science, Vol. 53, No. 1, 109-116, 2011 Original

Bonding and wear characteristics of a tri-n-butylborane initiated adhesive resin filled with pre-polymerized composite particles
Koji Naito
Division of Applied Oral Sciences, Nihon University Graduate School of Dentistry, Tokyo, Japan
(Received 8 January and accepted 14 February 2011)

Abstract: This study evaluated the wear characteristics and bonding to silver-palladium-coppergold (Ag-Pd-Cu-Au) alloy of an acrylic resin that was filled with pre-polymerized composite particles and initiated with tri-n-butylborane (TBB) derivative (Bondfill). Three methyl methacrylate (MMA)-based resins (Bondfill, Super-Bond, and Multi-Bond II) and a microfilled composite restorative material (Metafil C) were assessed. Disk specimens were cast from the alloy and were air-abraded with alumina. The disks were bonded with nine bonding systems selected from two priming and three luting agents. Shear bond s t r e n g t h s w e r e m e a s u r e d b e fo r e a n d a f t e r thermocycling. Bond strength varied from 2.2 MPa to 28.2 MPa. Three systems based on thione primers (Metaltite and V-Primer) and TBB-initiated resins (Bondfill and Super-Bond) had the highest bond strength after thermocycling (15.9-20.4 MPa). The toothbrush-dentifrice abrasion test showed that the Metafil C material was the most wear-resistant, followed by Bondfill and Super-Bond. In conclusion, Bondfill resin is an alternative to Super-Bond resin for luting metallic restorations and for restoring tooth defects. However, care is required in selecting appropriate clinical cases. (J Oral Sci 53, 109-116, 2011)

Keywords: Ag-Pd-Cu-Au alloy; bonding; thione; toothbrush; tri-n-butylborane; wear.

Introduction
During the most recent decade, the use of adhesives in bonding restorations has increased substantially. This trend is due to the development of adhesive functional monomers that are compatible with tooth structure, casting alloys, and ceramic materials. Currently available adhesives contain functional monomers designed for intraoral applications. Among these, acidic monomers are used for bonding tooth structure (1,2), whereas thiol or thione monomers are used for priming noble metal alloys (3-5). An adhesive resin initiated with tri-n-butylborane (TBB) derivative, in combination with thiol or thione primer, has been used for bonding between tooth structure and noble metal alloy (6,7), between indirect composite material and noble metal alloy (4,8-10), and for metal-to-metal bonding (11-14). In addition, TBB resin has been used in direct restoration (15,16). Tooth wear, attrition, and formation of wedge-shaped defects gradually progress due to occlusal contact, mastication, grinding, tooth brushing, and other factors. It would likely be beneficial for both tooth structure and dental material if interface integrity and wear resistance were equivalent, particularly within the molar occlusal plane. One problem associated with TBB-initiated adhesive resin has been insufficient wear resistance (15,16), which results from the fact that TBB resin contains no inorganic fillers, except for opaque or radiopaque components, and consists mainly of thermoplastic acrylic resin matrix. Recently, a modified TBB resin was developed for both luting and restorative agents, and, unlike the original TBB

Correspondence to Dr. Koji Naito, c/o Professor Hideo Matsumura, Department of Fixed Prosthodontics, Nihon University School of Dentistry 1-8-13 Kanda-Surugadai, Chiyodaku, Tokyo 101-8310, Japan Tel: +81-3-3219-8145 Fax: +81-3-3219-8351 E-mail: matsumura@dent.nihon-u.ac.jp

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resin, it contains pre-polymerized filler particles. Although the manufacturer claims that the bonding characteristics and wear resistance of the filled TBB resin have improved, there is no published information on the properties of this new material. The purpose of the present study was to evaluate the bonding and wear characteristics of TBBinitiated adhesive resin filled with pre-polymerized composite particles. The working hypothesis was that bonding to casting alloy and the wear resistance of a TBBinitiated resin are improved by incorporating prepolymerized composite filler into the powder composition.

Materials and Methods

Shear bond test
A silver-palladium-copper-gold (Ag-Pd-Cu-Au) alloy (Castwell M.C.12, GC Corp., Tokyo, Japan) was selected as the adherend material. Two priming agents Metaltite (Tokuyama Dental Corp., Tokyo, Japan) and V-Primer (Sun Medical Co., Ltd., Moriyama, Japan) were assessed as bonding promoter. Two single-liquid primers containing the adhesive functional monomer 6-methacryloyloxyhexyl 2-thiouracil-5-carboxylate (MTU-6) or 6-(4-vinylbenzyl-

n-propyl) amino-1,3,5-triazine-2,4-dithione (VTD) were used (Table 1). Three auto-polymerizing methyl methacrylate (MMA)-based acrylic resins (Super-Bond C&B Opaque Ivory and Bondfill, Sun Medical Co., Ltd.: Multi-Bond II, Tokuyama Dental Corp.) were used as luting materials. Both the Super-Bond and Bondfill resins comprise three components: TBB derivative, monomer liquid, and powder. They differ in that the latter contains pre-polymerized composite filler particles. The MultiBond II resin is a powder-liquid composition. The liquid contains borate compound and MTU-6. Information on the materials is summarized in Table 1. The Ag-Pd-Cu-Au alloy was cast in a cristobalite mold (Cristoquick 20, GC Corp.) using a high-frequency induction heating machine (Argoncaster-C, Shofu Inc., Kyoto, Japan). A total of 162 disk specimens (10 mm in diameter; 2.5 mm in thickness) were prepared from the alloy and divided into nine sets of 18 disks. All disks were wetground with 800-grit silicon carbide abrasive paper (WetorDry Tri-M-ite, 3M Corp., St. Paul, MN, USA). The alloy surfaces were subsequently air-abraded with alumina (50-70 m; Hi-Aluminas, Shofu Inc.) by means

Table 1 Materials assessed

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of an airborne-particle abrader (Jet Blast II, J. Morita Corp., Suita, Japan) for 10 s at an air pressure of 0.6 MPa. The distance of the abrader orifice from the disk surface was approximately 10 mm. After air-abrasion, a piece of double-coated tape with a circular hole, 5 mm in diameter, was positioned on the metal specimen to define the bond area. The disks, except for those included in unprimed groups, were primed with one of the two priming agents. An SUS 303 stainless steel ring (6 mm in inside diameter by 2 mm deep with a 1-mmthick wall) was placed around the opening area. A brushdip technique was used to fill the ring with one of the three MMA-based acrylic resins. Thirty minutes after preparation, the specimens were stored in 37C water for 24 h. This state was defined as 0 thermocycles. One half of the specimens (nine sets of nine specimens) were tested at 0 thermocycles. The remaining specimens (nine sets of nine specimens) were subsequently thermocycled between 5C cold water and 55C hot water for 20,000 cycles with 60 s dwell time per bath (Thermal Shock Tester TTS-1 LM, Thomas Kagaku Co., Ltd., Tokyo, Japan). Each specimen was placed in a steel mold and seated in a shear-testing jig. Shear bond strengths were then determined with a mechanical testing machine (Type 5567, Instron Corp., Canton, MA, USA) at a crosshead speed of 0.5 mm/min.

Japan) with nylon filaments (Tynex, Dupont Japan, Tokyo, Japan) was fixed in the toothbrush holder of the machine and moved back and forth on the specimen at 140 strokes per minute. A consistent load of 3.4 N was applied to the top of the toothbrush holder with a steel weight. The specimens were abraded with a total of 20,000 reciprocal strokes. The toothbrush and slurry were replaced for the testing of each specimen. Seven specimens were tested for each material. After the testing, specimens were removed from the machine, ultrasonically cleaned in distilled water for 10 min, and gently air-dried. The vertical loss of each specimen was determined with a confocal scanning laser microscope (1LM21W, Lasertec Corp., Yokohama, Japan) equipped with a He-Ne (wavelength: 633 nm) laser light source. The resolution performance of the microscope was approximately 0.03 m. The distance from the original specimen surface to the deepest abraded point was defined as wear depth. The method for measuring wear depth is illustrated in Fig. 2.

Scanning electron microscopic observation

After surface preparation, debonding, and wear testing, typical specimens were mounted on stubs, dried in a vacuum desiccator for 24 h, and sputtered with osmium (HPC-1S, Vacuum Device Inc., Mito, Japan) for 30 s. The specimens were then observed with a scanning electron microscope (S-4300, Hitachi High-Technologies Corp., Tokyo, Japan) operated at 15 kV.

Toothbrush-dentifrice abrasion test

Twenty-eight cuboid specimens (Fig. 1) were prepared from four resin-based materials: three MMA resins (SuperBond Polymer Brush-Dip Clear and Bondfill, Sun Medical Co., Ltd.; Multi-Bond II, Tokuyama Dental Corp.) and a direct composite restorative material (Metafil C, Sun Medical Co., Ltd.). The MMA resins were packed into a stainless steel mold (16.0 2.0 2.0 mm) with brush-dip technique and covered with a piece of glass plate (1.3 mm thickness, Micro Slide Glass, Matsunami Glass, Osaka, Japan). The Metafil C composite was packed into the mold, covered with the glass plate, and light-exposed for 120 s. Thirty minutes after polymerization, the top surface of each specimen was wet-ground with a series of silicon carbide papers (#800-2000, WetorDry Tri-M-ite). All specimens were stored in distilled water at 37C for 24 h. Each specimen was fixed in a specimen holder attached to a toothbrush abrasion testing machine (K236, Tokyo-Giken Co., Ltd., Tokyo, Japan). A dentifrice containing abrasives of conventional silica (Crest Tartar Protection Regular Paste, RDA-Value 136, Procter & Gamble Co., Cincinnati, OH, USA) was used as an abrasive slurry with a paste-to-water ratio of 1:1. The vessel of the machine was loaded with 150 g of slurry. A toothbrush (Bee King, Bee Brand Medico Dental Co., Ltd., Osaka,

Statistical analysis
Statistical analyses were performed with the statistical software package SPSS version 19.0 (IBM Corp., Somers, NY, USA). For the two tests, medians, interquartile ranges, means, and standard deviations were calculated. The values

Fig. 1 A representative photograph of a cuboid specimen and metal jig before wear testing.

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for shear bond strength and wear depth were primarily analyzed by the Levene test for evaluation of equality of variance. When the results of the Levene test did not demonstrate homoscedasticity in all categories, the results were analyzed by the Kruskal-Wallis test (IBM SPSS 19.0). Based on the results of Kruskal-Wallis test, the nonparametric multiple comparison Steel-Dwass test was used to compare differences among the nine adhesive systems for each thermocycling condition and among the four dental materials for wear depth (Kyplot 5.0, KyensLab Inc., Tokyo, Japan). The difference between prethermocycling and post-thermocycling bond strengths was analyzed with the Mann-Whitney U test. A P value less than 0.05 was considered to be statistically significant in all analyses.

Results
On the Levene test, the results of shear bond strength

testing were not homoscedastic for several groups, and the results of the nine adhesive systems were thus analyzed by the Kruskal-Wallis test and multiple comparison SteelDwass test. The vertical columns in Table 2 show the bond strengths of the nine adhesive systems before and after thermocycling. Mean pre-thermocycling bond strength varied from 10.9 MPa to 28.2 MPa, and the values were categorized as a through e. Before thermocycling, Metaltite/Bondfill had the highest bond strength (category a) and V-Primer/Multi-Bond II had the lowest bond strength. After thermocycling, mean bond strength varied from 2.2 MPa to 20.2 MPa and was classified into four categories (f-i). After thermocycling, the three systems with Metaltite/Super-Bond had the highest bond strength (category f), and the three groups with the two unprimed systems had the lowest bond strength (category i). The Mann-Whitney U test revealed that the reduction in bond strength after thermocycling was significant in all nine

Fig. 2 Specimen design and location of laser microscope scanner during evaluation of specimen wear depth.

Table 2 Shear bond strength of nine adhesive systems to Ag-Pd-Cu-Au alloy (MPa), n = 9

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systems (P < 0.05 for all comparisons). The greatest decrease in bond strength was for unprimed Bondfill

(89.4%), while Metaltite/Super-Bond had the lowest decrease (22.0%). Figure 3 shows the roughened relief pattern after surface air-abrasion of the casting alloy with alumina. Figures 4a-4d show the debonded alloy surfaces. Although these specimens were thermocycled, remnant resin material was detected in the groups with high bond strengths (Figs. 4a and 4b; bond strength categories f and g). Table 3 shows the results of wear testing. After

Table 3 Vertical loss after toothbrush-dentifrice abrasion (m), n = 7

Fig. 3 Scanning electron micrograph of a cast Ag-PdCu-Au alloy disk air-abraded with alumina. Original magnification, 500.

Fig. 4 Scanning electron micrographs of the debonded surface of thermocycled Ag-Pd-Cu-Au specimens. The specimens were originally bonded with (a) Metaltite primer and Super-Bond (categories f and g), (b) V-Primer and Bondfill (category g), (c) Metaltite and Multi-Bond II (category h), and (d) Bondfill (category i). Original magnification, 500.

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toothbrush-dentifrice abrasion, the greatest wear was observed in the Multi-Bond II (category l) specimens, followed by the Bondfill and Super-Bond (category k) specimens. The Metafil C composite was the most wearresistant material among the four materials assessed (category j). Figures 5a-5d show scanning electron micrographs of abraded material surfaces. Parallel ruts caused by use of the toothbrush-dentifrice were visible in three acrylic materials (Figs. 5a-5c). The splintered filler particles in the Bondfill resin appeared to be more wearresistant than the resin matrix (Fig. 5b). In contrast, detachment of spherical particles (probably polymethyl methacrylate) from the abraded surface was observed on the Multi-Bond II surface (Fig. 5c). The surface of the Metafil C composite was smooth and wear-resistant under conditions of abrasion (Fig. 5d).

Discussion
This study evaluated bonding to noble metal alloy and wear resistance of a modified TBB resin. Evaluation of the bond strength of nine adhesive systems revealed the characteristics of priming agents and luting agents, as

well as their combined performance. Comparison of postthermocycling bond strength is especially useful in evaluating the bonding durability of adhesive systems. Regarding the two priming agents, Metaltite was superior to V-Primer when combined with Bondfill (categories f and g) and Multi-Bond II (categories h and i). These results are in partial agreement with those of a previous study that evaluated combinations of thione primers and acrylic resins (17). The superiority of Metaltite may be due to the difference in monomer structure between MTU-6 in Metaltite and VTD in V-Primer. Specifically, MTU-6 is a thione-methacrylate that is soluble in ethanol and methacrylic monomers, whereas VTD is a vinyl-thione that is insoluble in most alcohols and methacrylates. Perhaps these differences had a negative effect on co-polymerization of VTD and methacrylic monomers, particularly in a peroxide-tertiary amine redox initiation system. The difference in bond strength between Super-Bond and Bondfill resins was not significant when the alloy was primed with Metaltite (category f) or V-Primer (category g), possible because the composition of these resins is almost identical. The present results also suggest that

Fig. 5 Scanning electron micrographs of the worn surface of (a) Super-Bond, (b) Bondfill, (c) Multi-Bond II, and (d) Metafil C specimens. Original magnification 500.

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incorporation of pre-polymerized fillers does not affect the bonding performance of Super-Bond resin. In addition, the bonding durability of Multi-Bond II to Ag-Pd-Cu-Au alloy was inferior to that of Super-Bond and Bondfill (categories f and g; categories h and i), which is probably due to the difference in initiation systems, i.e., TBB and peroxide-amine redox initiators (17). Wear testing revealed the surface characteristics of the four materials. As shown in Fig. 5c, detachment of polymer particles was frequently observed in Multi-Bond resin after wear testing. In the current methodology, wear was defined as the depth of the worn surface, and detachment of the macro-filler considerably increased the wear depth of the specimen. This is the principal reason why the wear resistance of Multi-Bond II resin was inferior to that of other resins. Testing revealed that the wear resistance of Super-Bond and Bondfill resins was comparable. As shown in Figs. 5a and 5b, pre-polymerized filler appeared to be more wear-resistant than the surrounding resin matrix. However, in the present study, wear was defined as the distance from the material surface to the deepest point. As the result, the wear resistance of the Super-Bond and Bondfill resins was equivalent. Moreover, when surface roughness values were calculated, the surface of filled resin was rougher than that of unfilled resin. As compared with the three acrylic resins, the Metafil C composite material had a smoother surface and lower wear value, findings which are clearly due to the properties of the thermosetting matrix and to increased loading of prepolymerized fillers composed of sub-micron and nano-sized silicon oxides. The working hypothesis, that the incorporation of prepolymerized composite filler into the powder composition improves bonding to casting alloy and wear resistance of TBB-initiated resin, was rejected under the experimental conditions of the present study. However, incorporation of a small amount of pre-polymerized fillers did not negatively affect the wear resistance of TBB-based Super-Bond resin or its ability to bond to Ag-Pd-Cu-Au alloy. Also, the properties of the two TBB-based resins were superior to those of conventional acrylic resin. In conclusion, the present results suggest that both types of TBB resin can be used for luting metallic restorations to tooth structure and for direct restorations.

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Acknowledgments
This work was supported in part by Special Research Grant for the Development of Distinctive Education from the Promotion and Mutual Aid Corporation for Private School of Japan (2009 and 2010).

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