You are on page 1of 8

Vol 14, No 1, 2012 75

Comparison of Alternative Adhesive Cementation


Concepts for Zirconia Ceramic: Glaze Layer vs
Zirconia Primer
Cenk Cura
a
/Mutlu zcan
b
/Gl Isik
c
/Ahmet Saracoglu
c
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 (5C to 55C) and the other half was kept in the
dark for 24 h at 37C 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: 7582. Submitted for publication: 05.01.10; accepted for publication: 24.09.10.
doi: 10.3290/j.jad.a21493
T
he use of zirconia all-ceramic fixed dental pros-
theses (FDPs) provides tooth-colored restorations
with high flexural strength.
41
With the introduction
and advancements in adhesive promoters, adhesively
bonded restor ations can be considered an integral
part of minimally invasive dentistry. Not only the
strength of the restor ation but also the adhesion of
cements both to the dental tissues and to the particu-
lar restorative material is important for the long-term
clinical success of the restor ation.
3,8,39
This aspect
becomes even more important when retention of
FDPs does not rely on macromechanical principles,
a
Associate Professor, Department of Prosthodontics, Ege University, School
of Dentistry, Izmir, Turkey. Idea, experimental design, performed experi-
ments in partial fulfillment of degree.
b
Professor, University of Zrich, Dental Materials Unit, Center for Dental and Oral
Medicine, Clinic for Fixed and Removable Prosthodontics and Dental Materials
Science, Zrich, Switzerland. Idea, hypothesis, wrote and proofread manuscript,
performed test and statistical evaluation, contributed substantially to discussion.
c
PhD student, Department of Prosthodontics, Ege University, School of Den-
tistry, Izmir, Turkey. Performed experiments.
Correspondence: Prof. Dr. med. dent. Mutlu zcan, University of Zrich, Dental
Materials Unit, Center for Dental and Oral Medicine Clinic for Fixed and Remov-
able Prosthodontics and Dental Materials Science, Plattenstrasse 11, CH-8032,
Zrich, Switzerland. Tel: +41-44-63 45600, Fax: +41-44-63 44305. e-mail:
mutlu.ozcan@zzmk.uzh.ch
Cura et al
76 The Journal of Adhesive Dentistry
as in the case of resin-bonded FDPs or cantilever rest-
orations.
14
Although etching the cementation surface with
hydrofluor ic acid (HF) and subsequent silanization of the
glassy matrix ceramics is an effective method to achieve
durable adhesion of resin-based materials,
9,30,34
nei-
ther etching with these solutions nor adding silane cou-
pling agents resulted in adequate resin bond to high-
alumina
26,27,32,34
or zirconia ceramics,
23,34
since such
ceramics do not contain a silicon dioxide (silica) phase.
For this reason, in order to enhance the bond strength
of luting cements to oxide-based ceramics, a number of
surface conditioning methods have been suggested during
the last two decades.
3,4,34,40
While some of these meth-
ods micromechanically facilitate resin-ceramic bonding by
employing air-borne particle abrasion with alumina parti-
cles,
3,6,11,12,34,42
others are based on physicochemical ac-
tivation of the ceramic surfaces using silica-coated alumina
particles followed by silanization,
3,34,44
or chemical activa-
tion with cements containing functional monomers.
23,43

In addition to these methods, flame treatment/silane
deposition,
21
selective infiltration etching
1
of the surface,
and the use of cements containing the phosphate ester
monomer 10-methacryloyloxydecyl dihydrogen phosphate
(MDP) have been proposed.
43
Durable adhesion of bis-
GMA resin to zirconia ceramics was not achieved using
some of these methods,
24
and roughness created by air
abrasion was thought to be the main bonding mechanism
for MDP monomers.
1
The selective infiltration etching
technique and the use of MDP monomers have also been
combined with novel reactive silane monomers to yield
initial high bond strengths that decreased after thermo-
cycling.
2
Even though comparative studies exist showing
the advantages of various types of surface conditioning
methods on oxide-based ceramics,
5,34,42
there has been
no consensus in the dental literature regarding the best
surface conditioning method for optimum bond strength
depending on the luting cements and zirconia used.
14
Since concern exists about the possible damage in-
flicted by the air-abrasion methods,
45
some manufactur-
ers started to promote primers based on organophos-
phate/carboxylic acid monomers specifically for zirconia,
by means of which aggressive conditioning methods could
be eliminated. Unfortunately, only limited information is
available on their performance.
25
The hydrolytic stability
of such primers is often questionable.
14,28,36
Table 1 Product names, manufacturers, compositions and batch numbers of the materials used in this study
Product name Manufacturer Chemical composition Batch number
PMMA AutoPlast, Candulor; Altsttten,
Switzerland
Polymethylmethacrylate F42028
ICE ZirconZahn ZirkonZahn; Bruneck, South
Tirol, Italy
ZrO
2
(+HfO
2
) wt%: 90, Y
2
O
3
wt%: 4.95 to 5.26,
Al
2
O
3
wt%: 0.15 to 0.35
SiO
2
wt%: max. 0.02, Fe
2
O
3
wt%: max. 0.01, Na
2
O
wt%: max. 0.04
324
ICE Glaze Ceramic ZirkonZahn 60 to 70 wt% ceramic powder and pigments (not
available from the manufacturer)
30 to 40 wt% glycol
827
Ultradent
Porcelain Etch
Ultradent Products;
South Jordan, UT, USA
9.5% hydrofluoric acid 165092
Ultradent
EtchArrest
Ultradent Products Calcium carbonate and sodium bicarbonate P129
Monobond-S Ivoclar Vivadent; Schaan, Liech-
tenstein
Mixture of ethanol, water and silane 64-17-5
HelioBond Ivoclar Vivadent Mixture of bis-GMA, dimethacrylate, initiators and
stabilizers
1565-94-2
Metal/Zirconia Primer Ivoclar Vivadent Mixture of water and initiators, mixture of < 50%
phosphonic acid acrylate, < 50% hydroxyethyl
methacrylate (HEMA), < 4% methacrylate modified
polyacrylic acid and stabilizer
868-77-9
Variolink II Ivoclar Vivadent Paste of dimethacrylates, inorganic fillers, ytterbi-
umtrifluoride, initiators, stabilizers and pigments
878-9
Multilink Automix Ivoclar Vivadent Dimethacrylates, hydroxyethyl methacrylate
(HEMA), inorganic fillers, barium glass, ytterbium-
trifluoride, spheroid mixed oxide, initiators, stabiliz-
ers and pigments
868-77-7
Vol 14, No 1, 2012 77
Cura et al
It can be anticipated that a thin glaze layer that adheres
well to zirconia
27
could deliver durable adhesion similar to
glass ceramics when it is etched with hydrofluoric acid.
This could consequently be a solution to the problem of
bonding to zirconia. In principle, overglazing techniques
rely on fring thermally compatible, low-fusion glasses on
the outer surface of the glass ceramics.
15
Overglazing of
ceramics increases the strength of glassy matrix ceram-
ics, since they reduce the surface faws and yield higher
fexural strengths than the use of auto-glaze techniques
when tested in tension.
16
Although such strengthening
may not be of importance for zirconia with high flexural
strength, overglazing may have advantages in terms of
adhesion, since their silica content permits them to be
etched. Currently, only limited information is available on
the effect of application of a glaze layer on zirconia in order
to achieve improved adhesion of resin cements.
10,12,31
The objectives of this study were, therefore, to evaluate the
bond strengths of two resin cements and their corresponding
adhesive systems to unglazed and glazed zirconia, and to
assess the failure types. The tested hypotheses were that a)
application of a glaze layer would increase the bond strength
of the resin cements compared to the unglazed (control) group
and would give more reliable results than non-glazed groups,
and b) thermocycling would decrease the bond strength.
MATERIALS AND METHODS
The product names, manufacturers, chemical composi-
tions, and batch numbers of the materials used in this
study are listed in Table 1.
Specimen Preparation
Disk-shaped zirconia ceramic (ICE ZirkonZahn; Bruneck,
South Tirol, Italy) specimens (diameter: 8 mm; thick-
ness: 2 mm) (N = 80, n = 10 per group) were obtained
from the manufacturer. Following the manufacturers
instructions, they were sintered in a sintering oven
(ZirkonZahn) at 20-1500C using a rise time of 3 h and
kept at 1500C for 2 h. The specimens were randomly
divided into 2 groups. While half of the group received
one coat of glaze ceramic, the other half was left as re-
ceived. Feldspathic glazing ceramic powder (ICE Zirkon
Glaze, ZirkonZahn) mixed with stain liquid (ICE Stain
Liquid, ZirkonZahn) was applied in a thin coat using a
ceramic brush. The specimens were then placed in a
porcelain furnace (Vacumat 200 Vita Zahnfabrik; Bad
Sckingen, Germany). The heat treatment program
started at 400C with 6 min preheating. Then the tem-
perature was raised by 55C per minute under vacuum.
Specimens were kept at the final temperature of 820C
for one minute before cooling started.
Surface Conditioning Methods
The distribution of experimental groups based on the
surface conditioning, cement type, and aging conditions
is presented in Table 2.
Both glazed and unglazed specimens were finished
by wet grinding using 1200-grit silicone carbide abrasive
under water cooling (Struers; Rodvre, Denmark). All
specimens were then cleaned ultrasonically for 10 min
in ethanol (Bandelin Sonurex RK 102 Transistor, Bande-
lin Electronic; Berlin, Germany) and dried gently using
oil-free compressed air.
Table 2 Experimental groups based on the surface conditioning, cement type, and aging conditions
Groups Substrate Step 1 Step 2 Step 3 Step 4 Step 5
1 Zirconia Glaze HF (9.5%) +
neutralizing agent
Silane+ adhesive Variolink II Dry
2 Zirconia Glaze HF (9.5%)+
neutralizing agent
Silane+ adhesive Variolink II TC
3 Zirconia No glaze - Silane+ adhesive Variolink II Dry
4 Zirconia No glaze - Silane+ adhesive Variolink II TC
5 Zirconia Glaze HF (9.5%) +
neutralizing agent
Zirconia primer Multilink Au-
tomix
Dry
6 Zirconia Glaze HF (9.5%) +
neutralizing agent
Zirconia Primer Multilink
Automix
TC
7 Zirconia No glaze - Zirconia Primer Multilink
Automix
Dry
8 Zirconia No glaze - Zirconia Primer Multilink
Automix
TC
Cura et al
78 The Journal of Adhesive Dentistry
The glazed specimens were conditioned with 9.5% HF
acid gel (Ultradent; South Jordan, UT, USA) for 60 s and
rinsed with water for 90 s. They were then neutralized
with the diluted solution of neutralizing powder (CaCO
3
and Na
2
CO
3
), washed thoroughly for 20 s using water,
and air dried.
The glazed and non-glazed specimens were further di-
vided into two groups. Two resin cements, namely Vari-
olink II and Multilink Automix, were adhered onto the zirco-
nia surfaces with their corresponding adhesive systems.
Cementation Procedure with Variolink II
The HF-conditioned surfaces were coated with silane
coupling agent (Monobond-S, Ivoclar Vivadent) using a
brush, left to react for 60 s, and dried. Subsequently, a
thin layer of adhesive resin (Heliobond, Ivoclar Vivadent)
was applied with a microbrush, gently air thinned, and
photopolymerized from a distance of 2 mm for 10 s
using an LED photopolymerization unit (Elipar Freelight
2, 3M ESPE; Seefeld, Germany) at a light intensity of
1000 mW/cm
2
. Base and catalyst paste of Variolink II
were mixed at a 1:1 ratio on a mixing pad for 10 s. The
cement was then packed into polyethylene molds (inner
diameter: 4 mm, height: 4 mm) with a hand instru-
ment and photopolymerized for 40 s incrementally in
layers of not more than 2 mm. The irradiation distance
between the exit window and the resin surface was
maintained at 2 mm to obtain adequate polymerization.
After polymer ization, the polyethylene molds were gently
removed from the test specimens. An oxygen-inhibiting
gel was applied on the free surfaces. After 5 min, it was
washed away, rinsed, and dried.
Cementation Procedure with Multilink
One coat of zirconia primer (Metal/Zirconia Primer,
Ivoclar Vivadent) was applied with a microbrush, left to
react for 180 s, and dried with water- and oil-free air.
Multilink Automix was dispensed from the double-push
syringe and the two pastes were mixed at a 1:1 ratio
on the mixing pad. The cement was then packed into
the polyethylene molds (inner diameter: 4 mm, height:
4 mm) with a hand instrument and photopolymer-
ized for 40 s incrementally in layers of not more than
2 mm. The irradiation distance between the exit window
and the resin surface was maintained at 2 mm. After
polymer ization, the polyethylene molds were gently re-
moved from the test specimens. An oxygen-inhibiting
gel was applied on the free surfaces. After 5 min, it was
washed away, rinsed, and dried.
Half of the specimens in each cement group were ran-
domly subjected to 5000 thermocycles (5C to 55C,
dwell time: 30 s, transfer time from one bath to the other:
5 s) (Willytec; Grfelfing, Germany).
20
The other half was
kept in the dark for 24 h at 37C after bonding procedures
prior to testing.
Glaze Thickness Measurement
In a separate set of disk-shaped zirconia ceramic speci-
mens (diameter: 8 mm; thickness: 2 mm) (n = 10), the
glaze thickness was measured using the measurement
software (AnalySIS, Stereo Module ADDA Soft Imaging
Systems; Kyoto, Japan) function of the field-emission
scanning electron microscope (FE-SEM) (JSM 5200;
Kyoto, Japan) at 2500X magnification.
Testing Procedure and Failure Analysis
Specimens were mounted in the jig of the universal
testing machine (Autograph Model AG-50kNG; Shi-
madzu, Japan) and force was applied using a shear-
ing blade with a 45-degree inclination at the tip to the
ceramic/cement interface until failure occurred. The
load was applied to the adhesive interface as close as
possible to the surface of the substrate at a crosshead
speed of 1 mm/min, and the stress-strain curve was
analyzed with the software program.
SEM images were made at 25 Kv at a magnification
of 2000X to 2500X. The debonded ceramic/cement sur-
faces were first sputter coated with a 3-nm-thick layer of
gold (80%)/palladium (20%) prior to examination. After
evaluating all SEM images, the failure types were defined
as either adhesive with no composite left on the zirco-
nia (score 0) or as mixed where less than half of the
cement was left on the ceramic surface with no cohesive
failure of the substrate (score 1).
Statistical Analysis
Statistical analysis was performed using SPSS 11.0
software for Windows (SPSS; Chicago, IL, USA). Bond
strength data (MPa) were submitted to three-way analy-
sis of variance (3-way ANOVA) with the bond strength as
Table 3 The mean shear bond strength values (MPa)
(standard deviations) for the experimental groups
and distribution and frequency of failure types per ex-
perimental group analyzed after bond strength test
Group Bond strength Score 0 Score 1
1 9 1.3 0 10
2 7.4 1.7 0 10
3 2.4 0.6
B,C
10 0
4 1.7 1.4
B,C
10 0
5 4.9 1.1
B
2 8
6 3.7 0.6
B
4 6
7 10.9 1.7
A
10 0
8 8.2 1.9
A
10 0
Score 0, adhesive: no resin cement left on the substrate; score 1,
mixed: less than half of the cement left on the ceramic surface. The
same letters in the same column indicate no significant differences
(a = 0.05). For group descriptions, see Table 2.
Vol 14, No 1, 2012 79
Cura et al
the dependent variable and cement type with their cor-
responding adhesive systems (2 levels; silane-adhesive-
Variolink II vs zirconia primer-Multilink Automix), glazed,
non-glazed situation (2 levels), aging condition (2 levels;
dry vs thermocycling) as independent variables. Multiple
comparisons were made using Dunnett-T3 post-hoc
tests. P values less than 0.05 were considered to be
statistically significant in all tests.
RESULTS
Mean bond strength results and significant differences
between the experimental groups are presented in Table
3. 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). Inter-
action terms were also significant (p < 0.05) (Dunnett-
T3) (Fig 1). In the Variolink II group, glazing improved
the bond strength significantly compared to the non-
glazed group (p > 0.05), but in the Multilink Automix ce-
ment group, the glazed group showed significantly lower
bond strengths (p < 0.05). On the glazed zirconia, the
silane-adhesive-Variolink II combination did not differ sig-
nificantly from the zirconia primer-Multilink Automix com-
bination on the non-glazed zirconia (p > 0.05).
Thermocycling did not decrease the results in any
of the groups when compared to the non-aged groups
(p > 0.05).
Failure analysis revealed exclusively adhesive failures
(score 0: 40 out of 40) in the non-glazed groups, but pre-
dominantly mixed failures (score 1: 34 out of 40) in the
glazed groups (Table 3, Fig 2).
The thickness of the glaze layer varied between 6.9
and 8.9 m in all specimens. Representative SEM im-
ages of the etched glazed layer on zirconia are presented
in Fig 3.
DISCUSSION
Bonding to silica-free oxide ceramics requires other
methods than those that are traditionally used for silica-
based ceramics, such as HF acid etching and silaniza-
tion. Recommended methods often include the use of
silica coating and silanization,
7,32-34,42
or phosphate
monomer-containing MDP composite resins.
22,43
Both
methods require surface cleaning or surface activation
by air-borne particle abrasion prior to cementation that
not only requires additional equipment in the labora-
tory or chairside, but also may detrimentally affect the
fatigue properties of zirconia.
45
Although predictable
results may be found in the short term, long-term water
storage or thermocycling decreases the bond strengths
in both methods.
22,34
For these reasons, this study was
undertaken to examine the effect of the application of
an etchable, thin glaze layer on the bond strength of
two adhesive cements with their corresponding adhe-
sives.
S
h
e
a
r

B
o
n
d

S
t
r
e
n
g
t
h

(
M
P
a
)

Groups
Fig 1 Mean bond strength values
(MPa) for the experimental groups
before and after thermocycling.
Cura et al
80 The Journal of Adhesive Dentistry
MPS silanes are known to react with water to form
three silanol groups (SiOH) from the corresponding
methoxy groups (SiOCH
3
). The silanol groups then
react further to form a siloxane (SiOSiO) network
with the silica surface. Methacrylate end groups of the
silane molecules react with the methacrylate groups of
adhesive resins in a free-radical polymerization process.
Thus, the bonding process between silica-based ceramics
and the methacrylate-based resin cements is achieved
by the silane coupling agent.
34
As an alternative to MPS
silane, phosphonic acid a-methyl-substituted acrylates
have been introduced, in which the polymerizable acrylate
group is connected to the strong acidic phosphonic acid
group via a hydrolytically stable ether bond.
29
Phosphonic
acid acrylates show an enhanced hydrolytic stability and
can be used as an adhesive monomer in dentin adhe-
sives.
29
The use of such adhesive promoters could be
considered safer than air-abrasion methods.
In this study, the application of a glaze layer and sub-
sequent HF etching and silanization significantly improved
the bond strength as opposed to the non-glazed group in
the case of Variolink II cement. The application of zirconia
primer is a considerably simpler clinical procedure than
is glazing. In order to have a balanced design, zirconia
primer was also used on the glazed zirconia. In principle,
zirconia primer use is recommended for the metal and
zirconia surfaces in conjunction with any resin-based ce-
ment but not with glass-based ceramics. In groups 3 and
Fig 3a (above) Representative SEM image of the etched
glazed layer on zirconia (2500X).
Fig 3b (right) Note the highest level of glaze thickness
(7.1 m) indicated by the arrow (2500X).
Fig 2a Representative SEM image (25X) of adhesive (score 0)
failure.
Fig 2b Representative SEM image (25X) of mixed (score 1)
failure.
Vol 14, No 1, 2012 81
Cura et al
4, where non-glazed zirconia was treated with MPS silane,
almost no adhesion was obtained (1.7 to 2.4 MPa). It
is well known that MPS silane cannot react with oxide-
based ceramics due to the lack of glassy matrix. However,
manufacturers still recommend it for the purpose of bet-
ter surface wettability of the resins. Similarly, low bond
strengths were obtained in groups 5 and 6 (4.9 to 3.7
MPa), where glazed zirconia specimens were treated with
zirconia primer. This clearly confirms that phosphonates
react with metal oxides but not with the silica matrix. Even
though the glazed surfaces were roughened with the HF
acid gel, most probably the mechanical interlocking was
not sufficient to achieve durable bond results. Surface
topography and etching patterns of glazed ceramics after
HF acid gel application should be studied in future inves-
tigations. Low bond strengths reported earlier with the
etched and glazed materials could be attributed to the
unfavorable etching pattern.
10,12,31
Nevertheless, when
the groups in which the manufacturers instructions were
strictly followed Variolink II with MPS silane and Multi-
link Automix with zirconia primer are compared, no sig-
nificant differences were observed, indicating that glazing
was not necessary and zirconia primer alone delivered
comparable bond strength results.
The bond strength results should always be coupled with
the failure type analysis. Regardless of the cement type
in non-glazed groups, exclusively adhesive failures were
noted. In contrast, in the glazed groups, the incidence of
mixed failure types (where more than half of the cement
was left adhered on the ceramic surface) was more fre-
quent. This supports the hypothesis that the application
of a glaze layer gives more reliable results. Hence, the first
hypothesis could only be partially accepted. Since no cohe-
sive failures within the ceramic substrate were observed,
the durability of the adhesion could still be questioned.
According to the manufacturer of the material used in this
study, the coefficient of thermal expansion (CTE) for ICE Zir-
conia was 10 x 10
-6
K
-1
and that of ICE glaze 9.6 x 10
-6
K
-1
.
The mismatch between CTE values is of importance when
ceramic is fused to the bulk framework material. A large
discrepancy between the porcelain veneer and core materi-
als can cause residual stresses and result in chipping of the
veneer. In a recent study, no large chippings but delamina-
tion of the wash or glaze coating were seen in SEM images
after mechanical testing.
18
In principle, the presence of the
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
strengths were lower than those of the studies in which
resin cements were adhered to etched and silanized glassy
matrix ceramics.
34
Therefore, the lower bond strengths in
the glazed groups could be partially associated with the
wettability and adaptation of the glaze layer applied, which
certainly requires further investigation. With other glaze ma-
terials, however, the results may be different.
Since thermocycling did not decrease the bond
strengths in any of the groups, the second hypothesis
was rejected. In other studies, a significant decrease
was observed with MDP-containing cements, even after
5000
35
or 37,500 thermocycles.
25
Although there was
a trend towards decreased bond strength, the nonsig-
nificant decrease after thermocycling in this study could
be attributed to less thermal degradation of the dimeth-
acrylate-based cements studied. No decrease in bond
strength was noted when MPS silane was applied on
the hydrofluoric-acid-etched glass-matrix ceramics.
34
On
the other hand, bond strength results obtained from the
glazed group are similar to those reported in two recent
studies where experimental and conventional glaze mate-
rials were tested for the same purpose.
10,31
In this study,
the recommendation of the ISO standard was followed
that requires a minimum of 5000 thermal cycles.
20
In
these recent studies, the specimens were tested only
after 1 week of water storage.
10,31
However, in future
studies, hydrolytic resistance of the bonded specimens
needs to be tested after even longer aging periods.
In a similar study, MDP-containing zirconia primer was
reported to deliver high bond strengths with frequent
cohesive failures.
25
However, in that study, the zirconia
surfaces were initially air abraded, and the cement was
first photopolymerized with a dental curing unit, but sub-
sequently further polymerized in a xenon strobe polymeri-
zation unit for an additional 90 s. Both practices might
have contributed to better results. During cementation
procedures, the use of such a photopolymerization unit is
not practicable. Thus, the clinical use of this application
remains questionable. Moreover, that study did not docu-
ment whether the cohesive failures were in the substrate
or in the cement itself. In the current study, no cohesive
failures were found in the ceramic substrate. Neverthe-
less, the results of this study need to be verified using
microtensile tests.
The thickness of the glaze layer was measured to deter-
mine whether it interferes with the fit of the FDPs. It was
previously reported that the thickness of the glaze layer
is negligible, ranging between 0.02 and 0.04 mm.
13,15
The thickest areas of the glaze layer in this study varied
between 6.9 and 8.9 m in all specimens. Given that the
internal fit values of zirconia FDPs range between 30 and
50 m with recent CAD-CAM systems,
17
the thickness
may be considered not to interfere with the fit of the
restoration. However, the application of the glaze layer
should be standardized in future studies. Clinical studies
particularly on surface-retained FDPs should verify the
results obtained with the zirconia primers vs a glaze layer.
CONCLUSIONS
From this study, the following could be concluded:
1. The zirconia primer/Multilink Automix resin cement
combination does not necessitate glazing, as it
provided the same bond strength as the glazed and
silanized group of Variolink II.
2. After glazing, both cement groups showed more
mixed failures, but non-glazed groups demonstrated
exclusively adhesive failures.
3. Thermocycling did not decrease the bond strength in
any of the groups.
Cura et al
82 The Journal of Adhesive Dentistry
ACKNOWLEDGMENTS
The authors thank Ivoclar Vivadent, Schaan, Liechtenstein for pro-
viding the Multilink Automix and Metal/Zirconia Primer, and Zirkon-
Zahn GmbH, Bruneck, South Tirol, Italy for the zirconia specimens.
REFERENCES
1. Aboushelib MN, Kleverlaan CJ, Feilzer AJ. Selective infiltration-etching
technique for a strong and durable bond of resin cements to zirconia-
based materials. J Prosthet Dent 2007;98:379-388.
2. Aboushelib MN, Matinlinna JP, Salameh Z, Ounsi H. Innovations in bond-
ing to zirconia-based materials: Part I. Dent Mater 2008;24:1268-1272.
3. Atsu SS, Kilicarslan MA, Kucukesmen HC, Aka PS. Effect of zirconium-
oxide ceramic surface treatments on the bond strength to adhesive
resin. J Prosthet Dent 2006;95:430-436.
4. Bailey LF, Bennett RJ. DICOR surface treatments for enhanced bonding.
J Dent Res 1988;67:925-931.
5. Blatz MB, Sadan A, Kern M. Resin-ceramic bonding: a review of the
literature. J Prosthet Dent 2003;89:268-274.
6. Borges GA, Sophr AM, Goes MF, Sobrinho LC, Chan DCN. Effect of
etching and airborne particle abrasion on the microstructure of different
dental ceramics. J Prosthet Dent 2003;89:479-488.
7. Bottino MA, Valandro LF, Scotti R, Buso L. Effect of surface treat-
ments on the resin bond to zirconium-based ceramic. Int J Prosthodont
2005;18:60-65.
8. Burke FJ, Fleming GJ, Nathanson D, Marquis PM. Are adhesive tech-
nologies needed to support ceramics? An assessment of the current
evidence. J Adhes Dent 2002;4:7-22.
9. Calamia JR. Etched porcelain veneers: the current state of the art.
Quintessence Int 1985;1:5-12.
10. Cattell MJ, Chadwick TC, Knowles JC, Clarke RL. Development and test-
ing of glaze materials for application to the fit surface of dental ceramic
restorations. Dent Mater 2009;25:431-441.
11. Derand P, Derand T. Bond strength of luting cements to zirconium oxide
ceramics. Int J Prosthodont 2000;13:131-135.
12. Derand T, Molin M, Kvam K. Bond strength of composite luting cement
to zirconia ceramic surfaces. Dent Mater 2005;21:1158-1162.
13. Douglas HB Jr, Moon PC, Eshleman JR, Lutins ND. The occusal dimen-
sional change upon glazing porcelain. J Dent Res 1981;60:828-829.
14. Edelhoff D, zcan M. To what extent does the longevity of fixed dental
prostheses depend on the function of the cement? Clin Oral Implants
Res 2007;18:193-204.
15. Fairhurst CW, Lockwood PE, Dingle RD, Thompson WO. The effect of
glaze on porcelain strength. Dent Mater 1992;8:203-207.
16. Giordano R, Cima M, Prober R. The effect of surface fnish on the
fexural strength of feldspathic and aluminous dental ceramics. Int J
Prosthodont 1995;8:311-319.
17. Gonzalo E, Surez MJ, Serrano B, Lozano JF. A comparison of the mar-
ginal vertical discrepancies of zirconium and metal ceramic posterior
fixed dental prostheses before and after cementation. J Prosthet Dent
2009;102:378-384.
18. Hjerppe J, Frberg K, Lassila L, Vallittu P. The effect of heat treatment
and feldspathic glazing on some mechanical properties of zirconia. Sili-
con 2010;2:171-178.
19. Hobo S. Distorsion of occusal porcelain during glazing. J Prosthet Dent
1982;47:154-156. International Organization for Standardization. Polymer-
based, Crown and Bridge Materials, ISO 10477, Amendment 1; 1998.
20. Janda R, Roulet JF, Wulf M, Tiller HJ. A new adhesive technology for all-
ceramics. Dent Mater 2003;19:567-573.
21. Jensen ME, Sheth JJ, Tolliver D. Etched porcelain resin-bonded full
veneer crowns: in vitro fracture resistance. Compendium 1989;10:
336-338.
22. Kern M, Thompson VP. Bonding to glass infiltrated alumina ceramic:
adhesive methods and their durability. J Prosthet Dent 1995;73:
240-249.
23. Kern M, Wegner SM. Bonding to zirconia ceramic: adhesion methods
and their durability. Dent Mater 1998;14:64-71.
24. Lehmann F, Kern M. Durability of resin bonding to zirconia ceramic
using different primers. J Adhes Dent 2009;11:479-483.
25. Lu YC, Tseng H, Shih YH, Lee SY. Effects of surface treatments on
bond strength of glass-infiltrated ceramic. J Oral Rehabil 2001;28:
805-813.
26. Madani M, Chu FC, McDonald AV, Smales RJ. Effects of surface treat-
ments on shear bond strengths between a resin cement and an alu-
mina core. J Prosthet Dent 2000;83:644-647.
27. Magne P, Paranhos MPG, Burnett Jr LH. New zirconia primer improves
bond strength of resin-based cements. Dent Mater 2010;26:345-352.
28. Moszner N, Zeuner F, Pfeiffer S, Schurte I, Rheinberger V, Drache M.
Synthesis, radical polymerization and adhesive properties of hydro-
lytically stable phosphonic acid monomers. Macromol Mater Eng
2001;4:225-231.
29. Nicholls JI. Tensile bond to resin cements to porcelain veneers. J Pros-
thet Dent 1998;60:443-447.
30. Ntala P, Chen X, Niggli J, Cattell M. Development and testing of multi-
phase glazes for adhesive bonding to zirconia substrates. J Dent
2010;38:773-781.
31. zcan M, Alkumru HN, Gemalmaz D. The effect of surface treatment on
the shear bond strength of luting cement to a glass-infiltrated alumina
ceramic. Int J Prosthodont 2001;14:335-339.
32. zcan M. The use of chairside silica coating for different dental applica-
tions: a clinical report. J Prosthet Dent 2002;87:469-472.
33. zcan M, Vallittu PK. Effect of surface conditioning methods on the
bond strength of luting cement to ceramics. Dent Mater 2003;19:
725-731.
34. zcan M, Kerkdijk S, Valandro LF. Comparison of resin cement adhe-
sion to Y-TZP ceramic following manufacturers instructions of the ce-
ments only. Clin Oral Investig 2008;12:279-282.
35. Piascik JR, Swift EJ, Thompson JY, Grego S, Stoner BR. Surface
modification for enhanced silanation of zirconia ceramics. Dent Mater
2009;25:1116-1121.
36. Romero M, Rincon JM, Acosta A. Crystallisation of a zirconium-based glaze
for ceramic tile coatings. J European Ceram Soc 2003;23:1629-1635.
37. Rosenstiel SF, Gupta PK, Van der Sluys RA, Zimmermann MH.
Strength of a dental glass-ceramic after surface coating. Dent Mater
1993;9:274-279.
38. Rosenstiel SF, Land MF, Crispin BJ. Dental luting agents: a review of
the current literature. J Prosthet Dent 1998;80:280-301.
39. Sun R, Suansuwan N, Kilpatrick N, Swain M. Characterization of tribo-
chemically assisted bonding of composite resin to porcelain and metal.
J Dent 2000;28:441-445.
40. Tinschert J, Zwez D, Marx R, Anusavice KJ. Structural reliability of
alumina-, feldspar-, leucite-, mica- and zirconia-based ceramics. J Dent
2000;28:529-535.
41. Valandro LF, Della Bona A, Bottino MA, Neisser MP. The effect of
ceramic surface treatment on bonding to densely sintered alumina ce-
ramic. J Prosthet Dent 2005;93:253-259.
42. Wegner SM, Kern M. Long-term resin bond strength to zirconia ceramic.
J Adhes Dent 2000;2:139-147.
43. Xible AA, Tavarez RRJ, Araujo CRP, Bonachela WC. Effect of silica coat-
ing and silanization on flexural and composite-resin bond strengths of
zirconia posts: An in vitro study. J Prosthet Dent 2006;95:224-229.
44. Zhang Y, Lawn BR, Rekow ED, Thompson VP. Effect of sandblasting on
the long-term performance of dental ceramics. J Biomed Mater Res B
Appl Biomater 2004;71:381-386.
Clinical relevance: The silane (Monobond S)-adhe-
sive (Heliobond)-Variolink II resin cement combina-
tion benefitted from glazing the zirconia surface, but
the zirconia primer-Multilink Automix resin cement
combination alone delivered sufficient bond strength
to zirconia. Glazing may change the failure type.