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Effect of zirconium-oxide ceramic surface treatments on the bond

strength to adhesive resin


Saadet Saglam Atsu, DDS, PhD,a Mehmet A. Kilicarslan, DDS, PhD,b
H. Cenker Kucukesmen, DDS, PhD,c and P. Sema Aka, DDS, PhDd
Kirikkale University, Faculty of Dental Medicine, Kirikkale, Turkey; Ankara Dental Hospital, Turkey
Ministry of Health, Ankara, Turkey; Suleyman Demirel University, Faculty of Dental Medicine, Isparta,
Turkey; Ankara University, Faculty of Dental Medicine, Ankara, Turkey
Statement of problem. Surface treatment methods used for resin bonding to conventional silica-based dental
ceramics are not reliable for zirconium-oxide ceramics.
Purpose. The aim of this study was to compare the effects of airborne-particle abrasion, silanization, tribo-
chemical silica coating, and a combination of bonding/silane coupling agent surface treatment methods on
the bond strength of zirconium-oxide ceramic to a resin luting agent.
Material and methods. Sixty square-shaped (5 3 5 3 1.5 mm) zirconium-oxide ceramic (Cercon) specimens
and composite resin (Z-250) cylinders (3 3 3 mm) were prepared. The ceramic surfaces were airborne-particle
abraded with 125-mm aluminum-oxide (Al2O3) particles and then divided into 6 groups (n=10) that were sub-
sequently treated as follows: Group C, no treatment (control); Group SIL, silanized with a silane coupling agent
(Clearfil Porcelain Bond Activator); Group BSIL, application of the adhesive 10-methacryloyloxydecyl dihydrogen
phosphate monomer (MDP)–containing bonding/silane coupling agent mixture (Clearfil Liner Bond 2V/ Por-
celain Bond Activator); Group SC, silica coating using 30-mm Al2O3 particles modified by silica (CoJet System);
Group SCSIL, silica coating and silanization (CoJet System); and Group SCBSIL, silica coating and application
of an MDP–containing bonding/silane coupling agent mixture (Clearfil Liner Bond 2V/Porcelain Bond Acti-
vator). The composite resin cylinders were bonded to the treated ceramic surfaces using an adhesive phosphate
monomer–containing resin luting agent (Panavia F). After the specimens were stored in distilled water at 37°C
for 24 hours, their shear bonding strength was tested using a universal testing machine at a crosshead speed of
0.5 mm/min. Debonded specimen surfaces were examined with a stereomicroscope to assess the mode of fail-
ure, and the treated surfaces were observed by scanning electron microscopy. Bond strength data were analyzed
using 1-way analysis of variance and the Duncan test (a=.05).
Results. The bond strengths (mean 6 SD; MPa) in the groups were as follows: Group C, 15.7 6 2.9; Group
SIL, 16.5 6 3.4; Group BSIL, 18.8 6 2.8; Group SC, 21.6 6 3.6; Group SCSIL, 21.9 6 3.9; and Group
SCBSIL, 22.9 6 3.1. The bond strength was significantly higher in Group SCBSIL than in Groups C, SIL,
and BSIL (P,.001), but did not differ significantly from those in Groups SC and SCSIL. Failure modes
were primarily adhesive at the interface between zirconium and the resin luting agent in Groups C and SIL,
and primarily mixed and cohesive in Groups SC, SCSIL, and SCBSIL.
Conclusion. Tribochemical silica coating (CoJet System) and the application of an MDP–containing bond-
ing/silane coupling agent mixture increased the shear bond strength between zirconium-oxide ceramic and
resin luting agent (Panavia F). (J Prosthet Dent 2006;95:430-6.)

CLINICAL IMPLICATIONS
The results of this in vitro study recommend the application of a silica coating and a phosphate
monomer–containing bonding/silane coupling agent mixture to increase the adhesive resin
bond strength to an airborne-particle–abraded surface of the zirconium-oxide ceramic tested.

a
Assistant Professor, Department of Prosthodontics, Kirikkale Univer-
sity, Faculty of Dental Medicine.
T he popularity of all-ceramic dental restorations has
increased in recent years due to their superior esthetic
b
Associate Professor, Ankara Dental Hospital, Turkey Ministry of appearance and metal-free structure.1 Although all-
Health.
c ceramic restorations show adequate resistance to occlu-
Assistant Professor, Suleyman Demirel University, Faculty of Dental
Medicine.
sal force for a single crown or short-span fixed partial
d
Professor, Department of Prosthodontics, Ankara University, Faculty denture (FPD), their use is limited with long-span
of Dental Medicine. FPD treatment.2 Zirconium, a high-strength ceramic,

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ATSU ET AL THE JOURNAL OF PROSTHETIC DENTISTRY

was recently introduced for dental use as a core material followed by silanization. Those authors found that the
for conventional and resin-bonded FPDs and complete- best long-term results were obtained with airborne-
coverage crowns.2-4 The use of the zirconium-oxide particle abrasion and the application of the adhesive
all-ceramic material provides several advantages, includ- phosphate monomer 10-methacryloyloxydecyl dihydro-
ing a high flexural strength (.1000 MPa) and desirable gen phosphate (MDP). Blatz et al18 compared the bond
optical properties, such as shading adaptation to the strength of different bonding/silane coupling agents
basic shades and a reduction in the layer thickness (com- and resin luting agents to zirconium-oxide ceramics.
pared to conventional ceramics) of the veneer ceramic The authors revealed that the application of an MDP–
required to achieve the desired color.5,6 Along with containing bonding/silane coupling agent mixture to
the strength of the material, the cementation technique zirconium-oxide ceramic restorations abraded with air-
is also important to the clinical success of a restora- borne Al2O3 particles may yield a superior shear bond
tion.7,8 Due to their high fracture resistance, zirco- strength.18 Moreover, some authors reported that an
nium-oxide crowns and FPDs can be cemented using MDP–containing resin luting agent and an MDP–
conventional methods recommended by the manufac- containing bonding/silane coupling agent mixture
turers. However, resin bonding between a tooth and provided a strong resin bond to airborne-particle–
the restoration is advocated for improving the retention, abraded zirconium- and aluminum-oxide ceramic
marginal adaptation, and fracture resistance of restora- restorations.18-20
tions.7,8 Obtaining adhesion between a luting agent Nevertheless, little information is available on the
and a ceramic surface requires surface pretreatment.9,10 effect of silica coating followed by silanization and
Although hydrofluoric acid etching and the application different surface treatments on the bonding of zirco-
of a silane coupling agent to silica-based ceramics in- nium high-crystalline ceramics and resin luting agents.
creases the bond strength between all-ceramic restora- Therefore, the aim of this study was to test the hypothesis
tions and composite resins,9,11 these techniques do that applying a silica coating and an MDP–containing
not improve the bond strength of zirconium and alu- bonding/silane coupling agent mixture increases the
mina ceramics because their high crystalline content bond strength between zirconium-oxide ceramic and a
makes them resistant to acid etching.9,12,13 However, phosphate monomer–containing resin luting agent.
it has been shown that silica coating followed by silani-
zation can be used to improve the bond strength for
MATERIAL AND METHODS
silica-based, glass-infiltrated alumina and zirconium ce-
ramics.9,14-17 Silica coating and silanization of surfaces This study measured the shear bonding strength
can be achieved by several methods.10,12,15-17 The between a resin luting agent and zirconium-oxide
CoJet System (3M ESPE, Seefeld, Germany) creates a ceramic specimens treated with various surface condi-
tribochemical silica coating on a surface for clinical pro- tioning methods: airborne-particle abrasion, silanization,
cedures, such as the intraoral repair of fractured metal- tribochemical silica coating, and a combination of bond-
ceramic and all-ceramic restorations.10,15,17 Ozcan ing/silane coupling agent. Sixty square-shaped (5 3 5 3
et al9 showed that a silica coating followed by silaniza- 1.5 mm) zirconium-oxide ceramic specimens were fab-
tion may significantly increase the bond strength for ricated from ingots (Cercon; Degussa Dental, Hanau,
high-alumina and zirconium-oxide ceramics compared Germany) according to the manufacturer’s recommen-
to that of airborne-particle abrasion alone. dations. The specimens were airborne-particle abraded
Few studies have evaluated the effect of different sur- with 125-mm Al2O3 particles (Koraks, #201408;
face treatments on the bond strength of zirconium oxide BEGO, Bremen, Germany) applied perpendicular to
to a resin luting agent.9,12,13,15,16,18,19 Bottino et al15 the surface at 0.28 MPa for 15 seconds at a distance of
used the CoJet System to evaluate the effect of silica 10 mm, and then ultrasonically cleaned in 96% isopropyl
coating on zirconium-oxide ceramic bond strength to alcohol (Isopropyl alcohol; Sigma-Aldrich, St Louis,
resin and found that tribochemical silica coating systems Mo) for 3 minutes. The specimens were divided into
(consisting of 3 phases: airborne abrasion with alumi- 6 groups of 10 specimens each and treated as follows.
num oxide (Al2O3) particles, airborne abrasion with In Group C, no further treatment was applied to the
30-mm Al2O3 particles modified by silica, and silaniza- ceramic surfaces; this group served as a control. In
tion with a silane coupling agent) increased the tensile Group SIL, the ceramic surfaces were coated with a si-
bond strength between phosphate monomer–containing lane coupling agent (Clearfil Porcelain Bond Activator,
resin composite (Panavia F) and zirconium-oxide #00164B; Kuraray Medical Inc, Okayama, Japan) and
ceramic. However, Kern and Wegner19 found that ther- allowed to air dry for 5 minutes. In Group BSIL, bond-
mal cycling induced bonding failures between zirco- ing (Clearfil Liner Bond 2V Primer, #00130B-00127B;
nium ceramics and conventional Bis-GMA resin luting Kuraray) and silane coupling agent (Clearfil Porcelain
agents when the surface was treated with airborne- Bond Activator; Kuraray) were mixed according to the
particle abrasion, silane application, and silica coating manufacturer’s recommendations and the literature.18

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THE JOURNAL OF PROSTHETIC DENTISTRY ATSU ET AL

This mixture was applied and air-thinned for 3 seconds Table I. One-way ANOVA results
with air spray. In Group SC, the ceramic surfaces were
Sum of Mean
treated with 30-mm Al2O3 particles modified by silica Source df squares square F P
(CoJet System, #171456; 3M ESPE) using an air-
Between groups 5 460.57 92.11 8.31 ,.001
borne-particle–abrasion device (CoJet System; 3M
Within groups 54 598.23 11.08
ESPE) filled with 30-mm silicon-dioxide particles Total 59 1058.81
(CoJet Sand, #172562; 3M ESPE). The abrasive was ap-
plied perpendicular to the surface at 0.28 MPa for 15
seconds at a distance of 10 mm. In Group SCSIL, the ce-
ramic surfaces were treated as described for Group SC Table II. Group bond strength values (MPa) (n=10)
and then a silane coupling agent (ESPE-Sil; 3M ESPE) Groups Mean SD Minimum Maximum
was applied and allowed to air dry for 5 minutes. In c
C 15.7 2.9 11.9 19.3
group SCBSIL, after the ceramic surfaces were treated
SIL 16.5c 3.4 12.9 22.8
as described for Group SC, a bonding agent (Clearfil BSIL 18.8bc 2.8 15.1 22.8
Liner Bond 2V Primer; Kuraray) and a silane coupling SC 21.6ab 3.6 17.3 27.6
agent (Clearfil Porcelain Bond Activator; Kuraray) SCSIL 21.9ab 3.9 16.7 28.0
were mixed according to the manufacturer’s recommen- SCBSIL 22.9a 3.1 16.5 27.6
dations, and this mixture was applied to the treated Same superscripted letters indicate no significant difference (a=.05).
ceramic surfaces and air-thinned for 3 seconds with
air spray.
One additional specimen from each group was coated recommendations. The ceramic–resin luting agent–
with gold-palladium alloy using a sputter-coating tech- composite resin combination was placed under a load
nique (Hummer VII; Anatech Ltd, Alexandria, Va) of 750 g in a press (Articolo 719/00, #1L01; Carlo de
and examined by scanning electron microscopy (SEM) Giorgi, Milano, Italy),15,17,19 and excess composite
(JSM-5600 Scanning Microscope; JEOL Ltd, Tokyo, resin was removed with a brush. The resin luting agent
Japan) at 3400 magnification to observe the topo- was polymerized for 40 seconds on each side of the
graphic patterns. Moreover, SEM coupled with an bonding area, and then oxygen-blocking gel (Oxyguard
energy-dispersive spectroscopy (EDS) (EDS 2000; II, #00445A; Kuraray) was applied for 10 minutes be-
IXRF Systems Inc, Houston, Tex) was used for identi- fore removing the specimens from the press.15,17 The
fying and quantifying elemental composition of the specimens were washed with air-water spray and stored
specimen areas, which were as small as a few cubic micro- in distilled water at 37°C for 24 hours.
meters. The characteristic x-rays were produced when The shear bond strength was tested with a universal
the materials were bombarded with electrons in an testing machine (Lloyd-LRX; Lloyd Instruments,
electron beam instrument, such as an SEM. Spectra Fareham, UK) at a crosshead speed of 0.5 mm/min
were obtained using a silicon crystal doped with lithium using material testing software (Nexygen version 2.0;
[Si (Li)] EDS detector with a super-ultrathin window Lloyd Instruments). The bond strength (s) values
(Be), under 20-kV accelerating voltage, 100-mA beam (expressed in MPa) were calculated using the formula:
current, 100-second acquisition time, and 30% to
s ¼ L=A;
40% dead time. Quantitative analysis of the percent
weight concentration of the probed elements was where L is the load at failure (in N) and A is the adhesive
performed by nonstandard analysis and atomic number, area (in mm2) measured using a digital caliper
absorbance, fluorescence (ZAF) correction methods. (7117057; Mitutoyo, Tokyo, Japan). A 1-way analysis
Acrylic resin tubes, 3 mm in height and diameter of variance (ANOVA) and the Duncan test were used
(Mediset, #S 409707; Eczacibasi Baxter, Ayazaga, to assess the significance of differences in shear bond
Istanbul, Turkey), were filled with composite resin (Z- strength between groups (a=.05).
250, #3 MM; 3M ESPE) to fabricate composite resin Debonded specimen surfaces were examined by the
cylinders, which were light polymerized (Heliolux same observer with a stereomicroscope (Leica MZ 12;
DLX; Ivoclar Vivadent, Schaan, Liechtenstein) with a Leica Microsystems, Bensheim, Germany) at 340 mag-
polymerization light intensity of 500 mW/cm2 and nification to assess the mode of failure. Adhesive and/or
the light source positioned immediately above the spec- cohesive failure of bonding could occur in 3 locations:
imens for 40 seconds on each side, for a total of 120 (1) adhesive failure at the interface between the ceramic
seconds.18 After 2 minutes of light polymerization, the and resin luting agent or between the resin luting agent
composite resin cylinders were bonded to the zirco- and the composite resin interface; (2) cohesive failure
nium-oxide ceramic specimens with a resin luting within the ceramic, within the resin luting agent, or
agent containing a phosphate monomer (Panavia F, within the composite resin only; and (3) adhesive and
#41243; Kuraray) according to the manufacturer’s cohesive failure at the same site, or a mixed failure.21

432 VOLUME 95 NUMBER 6


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Fig. 1. A, SEM image (original magnification 3400) of zirconium-oxide ceramic surface airborne-particle abraded with 125-mm
Al2O3. B, SEM image (original magnification 3400) of zirconium-oxide ceramic surface treated as specimen in A, and then
subjected to high-speed surface impaction with 30-mm Al2O3 modified by silica. Note finer surface texture of image in B.

Fig. 2. A, B, SEM images (original magnification 3400) of zirconium-oxide ceramic surfaces prepared the same as specimens in
Figure 1, A and B, respectively, followed by silanization with silane agent to increase bond strength. Note difference in surface
texture between images, indicating that silane infiltrated both roughened structures (which are finer in B).

RESULTS (21.9 6 3.9 MPa), and Group SCBSIL (22.9 6 3.1


MPa). Also, the bond strengths did not differ signifi-
Table I presents the results of the 1-way ANOVA, cantly between Group C (15.7 6 2.9 MPa), Group
which revealed that the bond strengths differed signifi- SIL (16.5 6 3.4 MPa), and Group BSIL (18.8 6 2.8
cantly between groups (P,.001). The mean shear MPa).
bond strength values and SDs of the groups are listed Scanning electron microscopy images of the differ-
in Table II. The highest bond strength of 22.9 6 3.1 ently treated ceramic surfaces are shown in Figures 1,
MPa (mean 6 SD) was obtained with the silica coating 2, and 3. The topographic patterns differed between
and the application of the combination of bonding/ the specimens abraded with airborne Al2O3 particles
silane coupling agent (Group SCBSIL). For the silica (Groups C, SIL, and BSIL) and the silica-coated speci-
coating process, the bond strength differed significantly mens (Groups SC, SCSIL, and SCBSIL). Figure 4
between Groups C and SC, SIL and SCSIL, and BSIL shows the EDS analysis of zirconium, silicon, and alumi-
and SCBSIL. The bond strength values were signifi- num for Groups C and SC. The silicon content was
cantly higher for silica-coated specimens (Groups SC, higher for the silica-coated specimens than for those
SCSIL, and SCBSIL) than for Group C (15.7 6 2.9 specimens abraded with airborne Al2O3 particles.
MPa) and Group SIL (16.5 6 3.4 MPa) (P,.001) Failure modes were primarily adhesive in Group C,
specimens. The bond strength values did not differ with an average of 90% adhesive failures between the
significantly between the specimens treated with silica ceramic and resin luting agent, and 10% mixed failures.
coating: Group SC (21.6 6 3.6 MPa), Group SCSIL Group SIL specimens exhibited an average of 80%

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THE JOURNAL OF PROSTHETIC DENTISTRY ATSU ET AL

Fig. 3. A, B, SEM images (original magnification 3400) of zirconium-oxide ceramic surfaces prepared the same as specimens in
Figure 1, A and B, respectively, followed by MDP–containing bonding/silane coupling agent mixture. Note difference in surface
texture between images, indicating that mixture of bonding/silane agent infiltrated both roughened structures (which are finer in B).

Fig. 4. A, EDS analysis of zirconium-oxide ceramic surface abraded with Al2O3 particles. B, EDS analysis of zirconium-oxide
ceramic surface treated with 30-mm Al2O3 particles modified by silica. Note that silicon content is higher in silica-coated spec-
imen than in specimen abraded with Al2O3 particles.

adhesive failures between the ceramic and resin luting DISCUSSION


agent, 10% cohesive failures in the resin luting agent,
and 10% mixed failures. Group BSIL specimens showed Zirconium-oxide ceramics have been proven to resist
an average of 40% adhesive failures between the ceramic fracture loads and show optimum strength in vitro,2-4
and resin luting agent, 30% cohesive failures in the resin but their use also requires a reliable bond with the luting
luting agent, and 30% mixed failures. Group SC speci- agent. The hypothesis of this study was that the bonding
mens showed an average of 30% adhesive failures be- could be increased by the application of a silica coat-
tween the ceramic and resin luting agent, 20% cohesive ing and an MDP–containing bonding/silane coupling
failures in the resin luting agent, and 50% mixed failures. agent mixture. The results of this study confirm the hy-
Group SCBSIL specimens showed an average of 50% co- pothesis that silica coating increases the bond strength
hesive failures in the resin luting agent and 50% mixed between zirconium-oxide ceramic and a phosphate
failures. Group SCSIL specimens showed an average monomer–containing resin composite (Panavia F).
of 20% adhesive failures between the ceramic and resin The bond strength was found to be significantly higher
luting agent, 20% cohesive failures in the resin luting in Groups SC, SCSIL, and SCBSIL (treated with silica
agent, and 60% mixed failures. Pure ceramic and pure coating) than in Groups C, SIL, and BSIL, respectively,
composite resin cohesive failures were not observed. which indicates the silica coating system would improve

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the bonding of zirconium-oxide ceramic restorations. Groups C and SIL showed lower bond strengths and
Moreover, the results partially confirm the hypothesis adhesive type failures at the interface between zirconium
that the MDP–containing bonding/silane coupling and the resin luting agent, whereas the groups with
agent mixture increases the bond strength. Although higher bond strengths showed cohesive and mixed
the highest bond strength was obtained with the combi- type failures in the resin luting agent. In this study the
nation of silica coating and the bonding/silane coupling ceramic was cemented to composite resin cylinders,
agent (Group SCBSIL), no differences were found in rather than to natural tooth structures, because of the
the groups with a silica coating (Groups SC, SCSIL, uniform structure of the composite resin cylinders and
and SCBSIL) and those without (Groups C, SIL, and the microstructural variations in tooth structure (enamel
BSIL). These results may be attributable to silica coating or dentin) that could result in incorrect interpretation of
systems creating a fine rough surface that increases the the results.15 Furthermore, the purpose of the present
surface area and, thus, enhances the mechanical and study was to evaluate only the bond strength of resin
chemical bonding.9,10,14,16 These systems also produce luting agent to ceramic, while varying the treatment
a silica layer on the ceramic surface processed with high- applied to the ceramic surface. Thermal cycling and
speed surface impaction of alumina particles modified by long-term storage are the factors that can have effects
silica, forming a chemical bond between the ceramic on the durability of the resin bond strength to zirco-
surface and the silane agent.1,9,10,14-17 The silane agent nium, and they are important parameters to simulate
used for silanization also contributes to the bond oral conditions.2,9,18,19 In the present study, the effects
strength by promoting a chemical bond to resinous ma- of thermal cycling and long-term storage on the bond
terials via cross-linkages with methacrylate groups, and strength were not evaluated and may be considered lim-
also increases the substrate surface energy and improves itations of this study. In future studies, the effects of
the surface wettability to resin.1,11,14 The results from these parameters on the bond strength of zirconium-
the present study are consistent with those of Bottino oxide ceramic should be examined. Moreover, controlled
et al,15 who found that silica coating followed by silani- clinical trials are needed before clinical recommenda-
zation increased the bond strength of zirconium-oxide tions can be provided.
ceramic to an MDP–containing composite resin relative
to the use of airborne-particle abrasion with zirconium- CONCLUSION
oxide ceramic. In contrast, another study found that a Within the limitations of this study, the following
durable resin bond to zirconium-oxide ceramic was ob- conclusions were drawn:
tained after airborne-particle abrasion of the ceramic and
the use of a composite resin containing an adhesive 1. The bond strength was significantly higher in
phosphate monomer, while the zirconium-oxide Group SCBSIL (tribochemical silica coating and a
ceramic treated with silica coating and bonded with mixture of phosphate monomer–containing bond-
Bis-GMA resin luting composite failed.19 In the present ing/silane coupling agent) than in Group C (no
study, treatment with an MDP–containing bonding/ treatment), Group SIL (silanized with a silane cou-
silane coupling agent mixture slightly increased the bond pling agent), and Group BSIL (application of an
strength of zirconium ceramic when applied over sur- MDP–containing bonding/silane coupling agent
faces that had been airborne-particle abraded and coated mixture) (P,.001).
with silica. These results may be explained by the im- 2. The bond strength differed significantly between the
proved wettability of the rough zirconium surface due groups in which the silica coating process was applied
to the mixture of the bonding/silane agent and the pres- (between Groups C and SC, SIL and SCSIL, and
ence of chemical bonding. The results of this study are BSIL and SCBSIL) (P,.001), which indicates that
consistent with those of Blatz et al,18 who demonstrated the silica coating system improves the bonding of
that application of an MDP–containing bonding/silane zirconium-oxide ceramic restorations.
coupling agent mixture to zirconium-oxide ceramic 3. The bond strength was significantly lower for air-
restorations abraded with airborne Al2O3 particles can borne-Al2O3-particle abrasion (Group C) and silane
yield a superior shear bond strength. application after airborne-particle abrasion (Group
Mechanical testing of in vitro dental specimens allows SIL) than for the silica-coated zirconium-oxide ce-
the resin bonding to the ceramic to be evaluated so as to ramics (Groups SC, SCSIL, and SCBSIL) (P,.001).
identify potentially superior materials and methods be-
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