Professional Documents
Culture Documents
Purpose: Zirconia-based ceramics offer strong restorations in dentistry, but the adhesive bond strength of resin
cements to such ceramics is not optimal. This study evaluated the bond strength of silane/adhesive/resin cement
and zirconia primer/resin cement combinations on non-glazed and glazed zirconia surfaces before and after aging.
Materials and Methods: Disk-shaped zirconia ceramic specimens (diameter: 8 mm; thickness: 2 mm) (N = 80,
n = 10 per group) were randomly divided into 2 groups. While half of the specimens received one coat of glaze
and were later finished by grinding, the other half was only ground using 1200-grit silicone carbide abrasives
under water. The glazed specimens were then conditioned with 9.5% HF acid gel for 60 s, rinsed with water for
90 s, and neutralized. The glazed and non-glazed specimens were further divided into two groups. Two resin ce-
ments, namely, Variolink II and Multilink Automix were adhered onto the zirconia surfaces with their correspond-
ing adhesive systems. In the Variolink II group, zirconia surfaces were silanized (Monobond-S), and adhesive
resin (Heliobond) was applied and photopolymerized. In the Multilink Automix group, one coat of Metal/Zirconia
Primer was applied with a microbrush, left to react for 180 s, and dried using oil-free air. Half of the specimens
in each cement group were subjected to 5000 thermocycles (5°C to 55ºC) and the other half was kept in the
dark for 24 h at 37°C prior to testing. Specimens were mounted in the jig of the universal testing machine,
and force was applied to the ceramic/cement interface until failure occurred (1 mm/min). After evaluating all
debonded specimens under SEM, the failure types were defined as either “adhesive” with no cement left on the
zirconia (score 0) or “mixed” with less than half of the cement left on the surface with no cohesive failure of the
substrate (score 1). Data were analyzed using three-way ANOVA and Dunnett-T3 post-hoc tests.
Results: Application of a glaze layer significantly improved the bond strength in the silane/adhesive/Variolink II
group (p < 0.05), but no significant effect was found in the zirconia primer/Multilink Automix group (p > 0.05)
(three-way ANOVA). Interaction terms were also significant (p < 0.05) (Dunnett-T3). Thermocycling did not de-
crease the results significantly in any of the groups (p > 0.05). Failure analysis revealed exclusively adhesive
failures (score 0: 40 out of 40) in the non-glazed groups, but predominantly mixed failures (score 1: 34 out of
40) in the glazed groups.
Conclusion: The silane (Monobond S)/adhesive (Heliobond)/Variolink II resin cement combination benefitted
from glazing the zirconia surface, but the zirconia primer/Multilink Automix resin cement combination alone also
provided sufficient bond strength to zirconia.
Keywords: adhesion, adhesive cement, glaze, surface conditioning, zirconia, zirconia primer.
J Adhes Dent 2012; 14: 75–82. Submitted for publication: 05.01.10; accepted for publication: 24.09.10.
doi: 10.3290/j.jad.a21493
Table 1 Product names, manufacturers, compositions and batch numbers of the materials used in this study
ICE ZirconZahn ZirkonZahn; Bruneck, South ZrO2 (+HfO2) wt%: 90, Y2O3 wt%: 4.95 to 5.26, 324
Tirol, Italy Al2O3 wt%: 0.15 to 0.35
SiO2 wt%: max. 0.02, Fe2O3 wt%: max. 0.01, Na2O
wt%: max. 0.04
ICE Glaze Ceramic ZirkonZahn 60 to 70 wt% ceramic powder and pigments (not 827
available from the manufacturer)
30 to 40 wt% glycol
Monobond-S Ivoclar Vivadent; Schaan, Liech- Mixture of ethanol, water and silane 64-17-5
tenstein
Metal/Zirconia Primer Ivoclar Vivadent Mixture of water and initiators, mixture of < 50% 868-77-9
phosphonic acid acrylate, < 50% hydroxyethyl
methacrylate (HEMA), < 4% methacrylate modified
polyacrylic acid and stabilizer
as in the case of resin-bonded FDPs or cantilever rest- monomer 10-methacryloyloxydecyl dihydrogen phosphate
orations.14 (MDP) have been proposed.43 Durable adhesion of bis-
Although etching the cementation surface with GMA resin to zirconia ceramics was not achieved using
hydrofluoric acid (HF) and subsequent silanization of the some of these methods,24 and roughness created by air
glassy matrix ceramics is an effective method to achieve abrasion was thought to be the main bonding mechanism
durable adhesion of resin-based materials,9,30,34 nei- for MDP monomers.1 The selective infiltration etching
ther etching with these solutions nor adding silane cou- technique and the use of MDP monomers have also been
pling agents resulted in adequate resin bond to high- combined with novel reactive silane monomers to yield
alumina26,27,32,34 or zirconia ceramics,23,34 since such initial high bond strengths that decreased after thermo-
ceramics do not contain a silicon dioxide (silica) phase. cycling.2 Even though comparative studies exist showing
For this reason, in order to enhance the bond strength the advantages of various types of surface conditioning
of luting cements to oxide-based ceramics, a number of methods on oxide-based ceramics,5,34,42 there has been
surface conditioning methods have been suggested during no consensus in the dental literature regarding the best
the last two decades.3,4,34,40 While some of these meth- surface conditioning method for optimum bond strength
ods micromechanically facilitate resin-ceramic bonding by depending on the luting cements and zirconia used.14
employing air-borne particle abrasion with alumina parti- Since concern exists about the possible damage in-
cles,3,6,11,12,34,42 others are based on physicochemical ac- flicted by the air-abrasion methods,45 some manufactur-
tivation of the ceramic surfaces using silica-coated alumina ers started to promote primers based on organophos-
particles followed by silanization,3,34,44 or chemical activa- phate/carboxylic acid monomers specifically for zirconia,
tion with cements containing functional monomers.23,43 by means of which aggressive conditioning methods could
In addition to these methods, flame treatment/silane be eliminated. Unfortunately, only limited information is
deposition,21 selective infiltration etching1 of the surface, available on their performance.25 The hydrolytic stability
and the use of cements containing the phosphate ester of such primers is often questionable.14,28,36
Table 2 Experimental groups based on the surface conditioning, cement type, and aging conditions
It can be anticipated that a thin glaze layer that adheres Specimen Preparation
well to zirconia27 could deliver durable adhesion similar to Disk-shaped zirconia ceramic (ICE ZirkonZahn; Bruneck,
glass ceramics when it is etched with hydrofluoric acid. South Tirol, Italy) specimens (diameter: 8 mm; thick-
This could consequently be a solution to the problem of ness: 2 mm) (N = 80, n = 10 per group) were obtained
bonding to zirconia. In principle, overglazing techniques from the manufacturer. Following the manufacturer’s
rely on firing thermally compatible, low-fusion glasses on instructions, they were sintered in a sintering oven
the outer surface of the glass ceramics.15 Overglazing of (ZirkonZahn) at 20-1500ºC using a rise time of 3 h and
ceramics increases the strength of glassy matrix ceram- kept at 1500ºC for 2 h. The specimens were randomly
ics, since they reduce the surface flaws and yield higher divided into 2 groups. While half of the group received
flexural strengths than the use of auto-glaze techniques one coat of glaze ceramic, the other half was left as re-
when tested in tension.16 Although such strengthening ceived. Feldspathic glazing ceramic powder (ICE Zirkon
may not be of importance for zirconia with high flexural Glaze, ZirkonZahn) mixed with stain liquid (ICE Stain
strength, overglazing may have advantages in terms of Liquid, ZirkonZahn) was applied in a thin coat using a
adhesion, since their silica content permits them to be ceramic brush. The specimens were then placed in a
etched. Currently, only limited information is available on porcelain furnace (Vacumat 200 Vita Zahnfabrik; Bad
the effect of application of a glaze layer on zirconia in order Säckingen, Germany). The heat treatment program
to achieve improved adhesion of resin cements.10,12,31 started at 400°C with 6 min preheating. Then the tem-
The objectives of this study were, therefore, to evaluate the perature was raised by 55°C per minute under vacuum.
bond strengths of two resin cements and their corresponding Specimens were kept at the final temperature of 820°C
adhesive systems to unglazed and glazed zirconia, and to for one minute before cooling started.
assess the failure types. The tested hypotheses were that a)
application of a glaze layer would increase the bond strength Surface Conditioning Methods
of the resin cements compared to the unglazed (control) group The distribution of experimental groups based on the
and would give more reliable results than non-glazed groups, surface conditioning, cement type, and aging conditions
and b) thermocycling would decrease the bond strength. is presented in Table 2.
Both glazed and unglazed specimens were finished
by wet grinding using 1200-grit silicone carbide abrasive
MATERIALS AND METHODS under water cooling (Struers; Rodøvre, Denmark). All
specimens were then cleaned ultrasonically for 10 min
The product names, manufacturers, chemical composi- in ethanol (Bandelin Sonurex RK 102 Transistor, Bande-
tions, and batch numbers of the materials used in this lin Electronic; Berlin, Germany) and dried gently using
study are listed in Table 1. oil-free compressed air.
Table 3 The mean shear bond strength values (MPa) gel was applied on the free surfaces. After 5 min, it was
(±standard deviations) for the experimental groups washed away, rinsed, and dried.
and distribution and frequency of failure types per ex-
perimental group analyzed after bond strength test Cementation Procedure with Multilink
One coat of zirconia primer (Metal/Zirconia Primer,
Group Bond strength Score 0 Score 1 Ivoclar Vivadent) was applied with a microbrush, left to
react for 180 s, and dried with water- and oil-free air.
1 9 ± 1.3ª 0 10 Multilink Automix was dispensed from the double-push
2 7.4 ± 1.7ª 0 10 syringe and the two pastes were mixed at a 1:1 ratio
on the mixing pad. The cement was then packed into
3 2.4 ± 0.6B,C 10 0 the polyethylene molds (inner diameter: 4 mm, height:
4 1.7 ± 1.4B,C 10 0
4 mm) with a hand instrument and photopolymer-
ized for 40 s incrementally in layers of not more than
5 4.9 ± 1.1B 2 8 2 mm. The irradiation distance between the exit window
and the resin surface was maintained at 2 mm. After
6 3.7 ± 0.6B 4 6
polymerization, the polyethylene molds were gently re-
7 10.9 ± 1.7A 10 0 moved from the test specimens. An oxygen-inhibiting
gel was applied on the free surfaces. After 5 min, it was
8 8.2 ± 1.9A 10 0
washed away, rinsed, and dried.
Score 0, adhesive: no resin cement left on the substrate; score 1, Half of the specimens in each cement group were ran-
mixed: less than half of the cement left on the ceramic surface. The domly subjected to 5000 thermocycles (5°C to 55ºC,
same letters in the same column indicate no significant differences
(a = 0.05). For group descriptions, see Table 2. dwell time: 30 s, transfer time from one bath to the other:
5 s) (Willytec; Gräfelfing, Germany).20 The other half was
kept in the dark for 24 h at 37°C after bonding procedures
prior to testing.
the dependent variable and cement type with their cor- Failure analysis revealed exclusively adhesive failures
responding adhesive systems (2 levels; silane-adhesive- (score 0: 40 out of 40) in the non-glazed groups, but pre-
Variolink II vs zirconia primer-Multilink Automix), glazed, dominantly mixed failures (score 1: 34 out of 40) in the
non-glazed situation (2 levels), aging condition (2 levels; glazed groups (Table 3, Fig 2).
dry vs thermocycling) as independent variables. Multiple The thickness of the glaze layer varied between 6.9
comparisons were made using Dunnett-T3 post-hoc and 8.9 μm in all specimens. Representative SEM im-
tests. P values less than 0.05 were considered to be ages of the etched glazed layer on zirconia are presented
statistically significant in all tests. in Fig 3.
RESULTS DISCUSSION
Mean bond strength results and significant differences Bonding to silica-free oxide ceramics requires other
between the experimental groups are presented in Table methods than those that are traditionally used for silica-
3. Application of a glaze layer significantly improved the based ceramics, such as HF acid etching and silaniza-
bond strength in the silane-adhesive-Variolink II group tion. Recommended methods often include the use of
(p < 0.05), but no significant effect was found in the silica coating and silanization,7,32-34,42 or phosphate
zirconia primer-Multilink Automix group (p > 0.05). Inter- monomer-containing MDP composite resins.22,43 Both
action terms were also significant (p < 0.05) (Dunnett- methods require surface cleaning or surface activation
T3) (Fig 1). In the Variolink II group, glazing improved by air-borne particle abrasion prior to cementation that
the bond strength significantly compared to the non- not only requires additional equipment in the labora-
glazed group (p > 0.05), but in the Multilink Automix ce- tory or chairside, but also may detrimentally affect the
ment group, the glazed group showed significantly lower fatigue properties of zirconia. 45 Although predictable
bond strengths (p < 0.05). On the glazed zirconia, the results may be found in the short term, long-term water
silane-adhesive-Variolink II combination did not differ sig- storage or thermocycling decreases the bond strengths
nificantly from the zirconia primer-Multilink Automix com- in both methods.22,34 For these reasons, this study was
bination on the non-glazed zirconia (p > 0.05). undertaken to examine the effect of the application of
Thermocycling did not decrease the results in any an etchable, thin glaze layer on the bond strength of
of the groups when compared to the non-aged groups two adhesive cements with their corresponding adhe-
(p > 0.05). sives.
Fig 2a Representative SEM image (25X) of adhesive (score 0) Fig 2b Representative SEM image (25X) of mixed (score 1)
failure. failure.
MPS silanes are known to react with water to form acid acrylates show an enhanced hydrolytic stability and
three silanol groups (–Si–OH) from the corresponding can be used as an adhesive monomer in dentin adhe-
methoxy groups (–Si–O–CH3). The silanol groups then sives.29 The use of such adhesive promoters could be
react further to form a siloxane (–Si–O–Si–O–) network considered safer than air-abrasion methods.
with the silica surface. Methacrylate end groups of the In this study, the application of a glaze layer and sub-
silane molecules react with the methacrylate groups of sequent HF etching and silanization significantly improved
adhesive resins in a free-radical polymerization process. the bond strength as opposed to the non-glazed group in
Thus, the bonding process between silica-based ceramics the case of Variolink II cement. The application of zirconia
and the methacrylate-based resin cements is achieved primer is a considerably simpler clinical procedure than
by the silane coupling agent.34 As an alternative to MPS is glazing. In order to have a balanced design, zirconia
silane, phosphonic acid a-methyl-substituted acrylates primer was also used on the glazed zirconia. In principle,
have been introduced, in which the polymerizable acrylate zirconia primer use is recommended for the metal and
group is connected to the strong acidic phosphonic acid zirconia surfaces in conjunction with any resin-based ce-
group via a hydrolytically stable ether bond.29 Phosphonic ment but not with glass-based ceramics. In groups 3 and
4, where non-glazed zirconia was treated with MPS silane, a trend towards decreased bond strength, the nonsig-
almost no adhesion was obtained (1.7 to 2.4 MPa). It nificant decrease after thermocycling in this study could
is well known that MPS silane cannot react with oxide- be attributed to less thermal degradation of the dimeth-
based ceramics due to the lack of glassy matrix. However, acrylate-based cements studied. No decrease in bond
manufacturers still recommend it for the purpose of bet- strength was noted when MPS silane was applied on
ter surface wettability of the resins. Similarly, low bond the hydrofluoric-acid-etched glass-matrix ceramics.34 On
strengths were obtained in groups 5 and 6 (4.9 to 3.7 the other hand, bond strength results obtained from the
MPa), where glazed zirconia specimens were treated with glazed group are similar to those reported in two recent
zirconia primer. This clearly confirms that phosphonates studies where experimental and conventional glaze mate-
react with metal oxides but not with the silica matrix. Even rials were tested for the same purpose.10,31 In this study,
though the glazed surfaces were roughened with the HF the recommendation of the ISO standard was followed
acid gel, most probably the mechanical interlocking was that requires a minimum of 5000 thermal cycles.20 In
not sufficient to achieve durable bond results. Surface these recent studies, the specimens were tested only
topography and etching patterns of glazed ceramics after after 1 week of water storage.10,31 However, in future
HF acid gel application should be studied in future inves- studies, hydrolytic resistance of the bonded specimens
tigations. Low bond strengths reported earlier with the needs to be tested after even longer aging periods.
etched and glazed materials could be attributed to the In a similar study, MDP-containing zirconia primer was
unfavorable etching pattern.10,12,31 Nevertheless, when reported to deliver high bond strengths with frequent
the groups in which the manufacturers’ instructions were cohesive failures.25 However, in that study, the zirconia
strictly followed – Variolink II with MPS silane and Multi- surfaces were initially air abraded, and the cement was
link Automix with zirconia primer – are compared, no sig- first photopolymerized with a dental curing unit, but sub-
nificant differences were observed, indicating that glazing sequently further polymerized in a xenon strobe polymeri-
was not necessary and zirconia primer alone delivered zation unit for an additional 90 s. Both practices might
comparable bond strength results. have contributed to better results. During cementation
The bond strength results should always be coupled with procedures, the use of such a photopolymerization unit is
the failure type analysis. Regardless of the cement type not practicable. Thus, the clinical use of this application
in non-glazed groups, exclusively adhesive failures were remains questionable. Moreover, that study did not docu-
noted. In contrast, in the glazed groups, the incidence of ment whether the cohesive failures were in the substrate
mixed failure types (where more than half of the cement or in the cement itself. In the current study, no cohesive
was left adhered on the ceramic surface) was more fre- failures were found in the ceramic substrate. Neverthe-
quent. This supports the hypothesis that the application less, the results of this study need to be verified using
of a glaze layer gives more reliable results. Hence, the first microtensile tests.
hypothesis could only be partially accepted. Since no cohe- The thickness of the glaze layer was measured to deter-
sive failures within the ceramic substrate were observed, mine whether it interferes with the fit of the FDPs. It was
the durability of the adhesion could still be questioned. previously reported that the thickness of the glaze layer
According to the manufacturer of the material used in this is negligible, ranging between 0.02 and 0.04 mm.13,15
study, the coefficient of thermal expansion (CTE) for ICE Zir- The thickest areas of the glaze layer in this study varied
conia was 10 x 10-6 K-1 and that of ICE glaze 9.6 x 10-6 K-1. between 6.9 and 8.9 μm in all specimens. Given that the
The mismatch between CTE values is of importance when internal fit values of zirconia FDPs range between 30 and
ceramic is fused to the bulk framework material. A large 50 μm with recent CAD-CAM systems,17 the thickness
discrepancy between the porcelain veneer and core materi- may be considered not to interfere with the fit of the
als can cause residual stresses and result in chipping of the restoration. However, the application of the glaze layer
veneer. In a recent study, no large chippings but delamina- should be standardized in future studies. Clinical studies
tion of the wash or glaze coating were seen in SEM images particularly on surface-retained FDPs should verify the
after mechanical testing.18 In principle, the presence of the results obtained with the zirconia primers vs a glaze layer.
glassy phase in ceramics favors better siloxane bonds, and
any silica available in the glassy matrix of the ceramic could
contribute to the bonding mechanism. However, the bond CONCLUSIONS
strengths were lower than those of the studies in which
resin cements were adhered to etched and silanized glassy From this study, the following could be concluded:
matrix ceramics.34 Therefore, the lower bond strengths in
the glazed groups could be partially associated with the 1. The zirconia primer/Multilink Automix resin cement
wettability and adaptation of the glaze layer applied, which combination does not necessitate glazing, as it
certainly requires further investigation. With other glaze ma- provided the same bond strength as the glazed and
terials, however, the results may be different. silanized group of Variolink II.
Since thermocycling did not decrease the bond 2. After glazing, both cement groups showed more
strengths in any of the groups, the second hypothesis mixed failures, but non-glazed groups demonstrated
was rejected. In other studies, a significant decrease exclusively adhesive failures.
was observed with MDP-containing cements, even after 3. Thermocycling did not decrease the bond strength in
500035 or 37,500 thermocycles.25 Although there was any of the groups.