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dental materials 27 (2011) 1024–1030
available at www.sciencedirect.com
journal homepage: www.intl.elsevierhealth.com/journals/dema
Effect of surface pre-treatments on the zirconia
ceramic–resin cement microtensile bond strength
Alessio Casuccia, Francesca Monticellib, Cecilia Goraccia, Claudia Mazzitellia,
Amerigo Cantoroa, Federica Papacchinia, Marco Ferraria,∗
aDepartment of Fixed Prosthodontics and Dental Materials, University of Siena, Siena, Italy
bDepartment of Surgery, Faculty of Health and Sport Sciences, University of Zaragoza, Huesca, Spain
article info
Article history:
Received 9 June 2010
Received in revised form
22 April 2011
Accepted 4 July 2011
Keywords:
Zirconia ceramic
Surface treatment
Bond strength
Resin cement
abstract
Objective. To evaluate the influence of different surface treatments on the microtensile bond
strength of resin cement to zirconia ceramic.
Materials and methods. Twelve cylinder-shaped (∅12×5.25 mm high) blocks of a commer-
cial zirconium-oxide ceramic (Cercon®Zirconia, DENTSPLY) were randomly divided into 4
groups (n= 3), based on the surface treatment to be performed: (1) airborne particle abrasion
with 125 mAl
2O3particles (S); (2) selective infiltration etching (SIE); (3) experimental hot
etching solution applied for 30 min (ST) and (4) no treatment (C). Paradigm MZ100 blocks (3M
ESPE) were cut into twelve cylinders of 4mm in thickness. Composite cylinders were bonded
to conditioned ceramics using a resin cement (Calibra®, DENTSPLY), in combination with the
proprietary adhesive system. After 24h bonded specimens were cut into microtensile sticks
and loaded in tension until failure. Bond strength data were analyzed with Kruskall–Wallis
and Dunn’s Multiple Range test for multiple comparisons (p<0.05). Failure mode distribution
was recorded and the interfacial morphology of debonded specimens was analyzed using a
scanning electron microscope (SEM).
Results. Bond strength values achieved after SIE and ST treatment were significantly higher
than after S treatment and without any treatment (p<0.05). Premature failures were mostly
recorded in the S group.
Significance. Conditioning the high-strength ceramic surface with SIE and ST treatments
yielded higher bond strengths of the resin cement than when zirconia ceramic was treated
with airborne particle abrasion or left untreated.
© 2011 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.
1. Introduction
The use of partially stabilized zirconium dioxide ceramics
to fabricate metal-free esthetic restorations has increased
in recent years, thanks to their excellent physical prop-
erties and optimal biocompatibility [1–6]. Several studies
∗Corresponding author at: Department of Fixed Prosthodontics and Dental Materials, University of Siena, Policlinico “Le Scotte”, Viale
Bracci 1, 53100 Siena, Italy. Tel.: +39 0577233131; fax: +39 0577233117.
E-mail addresses: md3972@mclink.it,RCFD96@mclink.it,ferrarimar@unisi.it (M. Ferrari).
reported that zirconia-based ceramics may achieve bet-
ter mechanical resistance than feldspathic, leucite, and
lithium disilicate ceramics, especially when restoring poste-
rior teeth [7–13]. Clinically, chipping of veneering porcelains
and loss of retention are the most frequently reported
complications of zirconia-based ceramics [14]. Particularly,
poor retention may be ascribed to incorrect tooth prepara-
0109-5641/$ – see front matter © 2011 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.dental.2011.07.002
dental materials 27 (2011) 1024–1030 1025
tion and inadequate luting technique or cement selection
[15,16].
Although zirconia restorations can be cemented with zinc
phosphate or modified glass-ionomer cements [17], it has been
reported that resin-based luting agents are the most appro-
priate materials for the purposes of marginal seal, retention,
and fracture resistance [18]. Resin cements containing 10-MDP
(10-methacryloyloxydecyl dihydrogen phosphate) have been
considered as the materials of choice, since the phosphate
ester monomers are capable of a chemical interaction with
the hydroxyl groups of the ZrO2ceramic [18,19].
Previous studies have investigated different chemo-
mechanical surface treatments aimed at optimizing the
cement/zirconia bonding mechanism [20–23]. The rationale
of these conditioning processes lies in increasing the sur-
face area available for bonding to obtain strong and durable
restorations [24–26]. Sandblasting has been widely applied for
increasing ceramics surface roughness and thus the surface
area available for bonding. Up to date, the combination of
sandblasting and 10-MDP monomer based resin is the recom-
mended method of bonding to zirconia frameworks [27–30].
However, the outcome of this procedure may be affected
by variables such as particle size and application distance.
Particularly, excessive particle size and reduced application
distance may induce crack initiation, possibly reducing the
ceramic long-term mechanical properties [31–34].
Novel surface treatments have been proposed in order
to improve zirconia/resin cement bonds, such as the selec-
tive infiltration etching (SIE). This treatment is based on the
application of a low viscosity melting glass on the surface of
zirconia, that create abraded and porous surfaces improving
bond strength [35].
More recently, an experimental hot chemical etching solu-
tion (ST), composed by HCl and Fe2Cl3in methanol, previously
used for conditioning metal and/or alloys has been applied on
zirconia ceramics with the result of improving their average
surface roughness [36–38]. However, it has not yet been veri-
fied whether such increase in superficial roughness promotes
the adhesion of the luting agent.
Therefore, the aim of this study was to evaluate the influ-
ence of different surface treatments on the bond strength
between a commercially available partially-stabilized zirco-
nia ceramic and a resin cement. The tested null hypothesis
was that there were no statistically significant differences
in the microtensile bond strengths measured at the zir-
conia ceramic–resin cement interface following different
pre-treatments of the zirconia ceramic surface.
2. Materials and methods
Twelve cylinder-shaped (12mm diameter, 5.25 mm height)
Cercon®zirconia sintered ceramic blocks (DETREY DENTSPLY
Ceramco, York, USA) were used for the study. Specimens were
polished with SiC abrasive papers (grit # 600, 1000, 1200 and
2000). Final polishing was carried out on nylon cloths using 1-
and 0.50 m grit diamond pastes. Specimens were sonicated
in deionized water for 5 min and randomly assigned to four
equally sized experimental groups, according to the surface
treatment performed on zirconia:
(1) Selective infiltration etching procedure. Specimens were
coated with a thin layer of an infiltrating agent contain-
ing low temperature melting glass and additives (SiO2
(65 wt.%); Na2O (15 wt.%); Al2O3(8 wt.%); Li2O (3 wt.%); B2O3
(4 wt.%); CaF2(5 wt.%)). They were heated up to 750◦C for
1 min using a computer-programmed electrical induction
furnace (Austromat 3001; Dekema Dental-Keramikofen,
Freilassing, Germany), cooled reaching 650◦C for 1 min,
heated again up to 750 ◦C for 20 min (increasing T intervals
60 ◦C/min), and finally cooled at room temperature. Rem-
nants of the infiltrating agent were dissolved immersing
ceramic discs in an ultrasonic bath with 5% hydrofluoric
acid solution for 30 min (SIE) [31].
(2) Experimental etching solution. A hot acidic solution contain-
ing HCl and Fe2Cl3in methanol was heated up to 100◦C.
The zirconia specimens were immersed in the solution for
30 min (ST) [36,37].
(3) Sandblasting with 125mAl
2O3particles for 10 s at
0.4–0.7 MPa from a distance of 20mm (S).
(4) No pretreatment (C).
Conditioned specimens were rinsed with tap water for 1min,
ultrasonically cleaned in a deionized water bath for 30 min and
gently air-dried.
Resin composite blocks (Paradigm MZ100, 3M ESPE, size
14; batch # 20060213) were cut by means of a water-cooled
diamond saw (Isomet 1000, Buelher, Lake Bluff, IL) into 12
cylinders of 4 mm in height.
The intaglio surface of each composite block was ground
with 180-grit SiC paper, cleaned with ethanol and gently air-
dried.
A dual-cure resin cement (CalibraTM DeTrey DENTSPLY;
batch # 080910) was used in combination with the proprietary
adhesive (XP Bond, DENTSPLY, batch # 0810003096) for luting
the composite disc to the conditioned ceramic surface. The
resin composite surface was etched with 37% phosphoric for
15 s, washed thoroughly for 1 min under tap water. Then a thin
layer of adhesive (XP bond Adhesive) was applied on zirconia
and composite surfaces, it was dried with a gentle airflow and
polymerized for 20 s. Zirconia and composite blocks were luted
using a resin luting material (Calibra) that was applied on zir-
conia surface; a seating pressure of 1 kg was maintained over
the specimens during the first 5 min of cement autocure.
Then, light irradiation (Vip, Bisco, Schaumburg, Illinois,
USA; Output: 500 mW/cm2) was performed for 40 s on each
side of the block to ensure optimal polymerization. Bonded
specimens were stored in a laboratory oven at 37 ◦C and 100%
relative humidity for 24h.
2.1. Microtensile bond strength test
Ceramic–composite bonded specimens were cut vertically into
2 mm-thick slabs with a slow-speed diamond saw (Isomet).
Each slab was serially sectioned into 2.0×2.0mm sticks. From
every ceramic–composite bonded specimen a number of sticks
variable between 16 and 9 was obtained.
Each stick was glued with cianoacrylate (Super Attack gel
Henkel Consumer Adhesives, Avon, Ohio, USA) to the free-
sliding components of a Girardeli’s jig, and loaded in tension
1026 dental materials 27 (2011) 1024–1030
with a universal testing machine (Triax digital 50, Controls,
Milan, Italy) at a cross-head speed of 0.5 mm/min until failure.
Failure modes were evaluated under a stereomicroscope
(Nikon Instrument Group, Melville, NY) at 40×magnifica-
tion and classified as adhesive (between composite and luting
agent or between ceramic and luting agent), cohesive (within
luting agent, composite or ceramic), mixed (adhesive and
cohesive failures occurred simultaneously). As the objective of
the study was to assess the adhesive potential of the cement
to the zirconia substrate, it was decided that adhesive fail-
ures at the cement–composite interface, as well as cohesive
fractures within ceramic or composite should not be consid-
ered in statistical calculations. Also microtensile sticks that
had failed prior to testing were excluded from statistical cal-
culations. The number of microtensile sticks that were tested
in each group is reported in Table 1.
2.2. SEM evaluation
Four fractured sticks were randomly selected from each exper-
imental group and prepared for scanning electron microscope
(SEM) analysis. Each sample was cleaned with 96% ethanol,
mounted on metallic stubs, gold-sputtered (Polaron Range SC
7620, Quorum Technology, Newhaven, UK), and viewed under
the SEM (JSM-6060LV, Jeol, Tokyo, Japan) at different magnifi-
cations, in order to evaluate the fracture pattern.
3. Statistical analysis
As the distribution of microtensile bond strength data was
not normal according to the Kolmogorov–Smirnov test, the
Kruskall–Wallis Analysis of Variance was applied, followed by
the Dunn’s Multiple Range test for multiple comparisons.
The distributions of failures patterns were compared
among the groups using the chi-square test.
In all the statistical analyses the level of significance was
set at ˛= 0.05.
4. Results
4.1. Microtensile bond strength test
Mean bond strength values and standard deviations (SD) of
the tested groups are summarized in Table 2.
The Kruskall–Wallis ANOVA revealed the existence of sig-
nificant between-group differences (p<0.001). According to
the multiple comparisons test, selective infiltration etching
produced a statistically significant increase in the cement
bond strength in comparison with untreated and sandblasted
specimens (p< 0.05). Also the specimens that were treated
with the hot etching solution measured higher cement bond
strengths than those recorded in the ‘sandblasting’ and the
‘no pretreatment group’(p<0.05). However, the difference was
statistically significant only with the ‘no pretreatment’ group
(p< 0.05).
As reported in Table 3 pretest failures were recorded with
similar percentages (5–7%) in the different groups; all of them
occurred at the interface between zirconia and resin cement.
Howeversignificant differences emerged in the distribution
of failure patterns.
Untreated and sandblasted specimens most frequently
failed adhesively at the zirconia–cement interface, while the
majority of specimens treated with SIE and ST exhibited mixed
failures.
4.2. SEM analysis
Representative SEM images of fractured beams are reported
in Fig. 1. S group specimens mainly failed adhesively at the
ceramic–cement interface (Fig. 1A). Although surface irreg-
ularities were evident, no resin cement remnants could be
detected on the zirconia surface after load. In SIE and ST
groups mixed failures were prevalent. Resin cement remnants
retained over a roughened zirconia substrate were seen in SEM
images of specimens from SIE and ST groups (Fig. 1B and C,
respectively). Untreated zirconia presented a smooth surface
with only few scratches and cement residuals (Fig. 1D).
5. Discussion
Although zirconium dioxide ceramics are able to withstand
relatively high fracture loads showing optimum strength, their
clinical success also depends on the establishment of a reliable
bond with the luting agent [39,5,40].
According to the achieved results, a significant improve-
ment in zirconia ceramic–resin cement interfacial strength
was recorded after SIE and ST treatments. Thus, the null
hypothesis has to be rejected.
Although there is not enough clinical evidence to support
a specific cementation protocol when dealing with zirconia
restorations [41], the use of resin cements in combination
with preliminary zirconia surface treatments is highly recom-
mended [42].
Ultramorphologic evaluation performed combining SEM
and AFM analysis revealed that different retentive surfaces
and changes in topography may be produced on zirconia
depending on the selected surface treatment [36,37]. These
treatments have been proposed to enhance retention, hence
providing microporosities where the luting agent can pene-
trate and establish a stronger micro-mechanical interlocking
[22].
The present study confirmed that differences in surface
pattern after substrate conditioning may affect the retention
of high-strength core ceramics. In particular, SIE and ST treat-
ments resulted in significantly higher cement–ceramic bond
strength.
In the present study a conventional bis-GMA-based resin
cement (Calibra) was chosen in order to avoid the chemical
affinity between MDP-based resin cement and the zirconia
ceramic, assessing the real effectiveness of the surface treat-
ments. Although some recent in vitro studies support the use
of Calibra for luting zirconia-based ceramics, the clinical long-
term outcome of this procedure is still to be assessed [45].
Untreated zirconium dioxide ceramic is a relatively inert
substrate with low surface energy and wettability. The high
percentage of adhesive failures and the low bond strength val-
ues recorded in the untreated zirconia group confirmed that
dental materials 27 (2011) 1024–1030 1027
Table1–Materials used in this study.
Materials Manufacturers Main components Batch
Composite blocks paradigm MZ100 3M ESPE 85 wt.% zirconia-silica ceramic particles.
The polymer matrix consists of bisGMA
and TEGDMA.
20060213
Resin luting agent CalibraTM DeTrey
DENTSPLY
Base. Barium boron
fluoroalumino silicate
glass; bis-phenol A
diglycidylmethacrylate;
polymerizable
dimethacrylate resin;
hydrophobic amorphous
fumed silica; titanium
dioxide;
dl-camphoroquinone.
Catalyst. Barium boron
fluoroalumino silicate
glass; bis-phenol A
diglycidylmethacrylate;
polymerizable
dimethacrylate resin;
hydrophobic amorphous
fumed silica; titanium
dioxide; benzoyl peroxide.
080910
Resin adhesive XP bond DENTSPLY Carboxylic acid modified dimethacrylate
(TCB resin); phosphoric acid modified
acrylate resin (PENTA); Urethane
dimethacrylate (UDMA); triethyleneglycol
dimethacrylate (TEGDMA);
2-hydroxyethylmethacrylate (HEMA);
butylated benzenediol (stabilizer);
ethyl-4-dimethylaminobenzoate;
camphorquinone; Functionalized
amorphous silica; t-butanol
0810003096
Groups NMean S.D. Median 25–75% Significance (p< 0.05)
Selective infiltration etching (SIE) 39 23.4 9.6 27.2 13.1–31.2 A
Hot etching solution (ST) 33 22.3 7.8 23.4 14.3–27.8 AB
Sandblasting (S) 27 17.3 8.9 20.1 8.4–24.7 BC
No treatment (C) 27 11.2 4.2 10.9 8.5–14.5 C
Table 2 – Descriptive statistics of microtensile bond strength data in MPa. In the ‘Significance’ column different letters
label statistically significant differences according to the post-hoc test.
Groups NMean S.D. Median 25–75% Significance (p< 0.05)
Selective infiltration etching (SIE) 39 23.4 9.6 27.2 13.1–31.2 A
Hot etching solution (ST) 33 22.3 7.8 23.4 14.3–27.8 AB
Sandblasting (S) 27 17.3 8.9 20.1 8.4–24.7 BC
No treatment (C) 27 11.2 4.2 10.9 8.5–14.5 C
Table 3 – Distribution of failure patterns in the experimental groups. Groups that had statistically similar failure modes
are labeled with the same symbol (p> 0.05).
Groups Adhesive between
ceramic and cement
Cohesive within cement Mixed Pre-test
Selective infiltration technique (SIE)#Count 7 4 28 7
% 15.2% 8.7% 60.9% 15.2%
Hot etching solution (ST)#Count 8 4 21 7
% 20.0% 10.0% 52.5% 17.5%
Sandblasting (S)§Count 25 0 2 7
% 73.5% 0% 5.9% 20.6%
No treatment (C)§Count 21 0 6 5
% 65.6% 0% 18.8% 15.6%
The simbols “#” and “§” reported differencies between groups at chi-square test.
1028 dental materials 27 (2011) 1024–1030
Fig. 1 – Representative SEM images of the interfacial fracture patterns observed in the different experimental groups (250×,
bar 100 m). (A) Sandblasting, (B) selective infiltration etching; (C) experimental hot etching solution applied for 30 min and
(D) no treatment. Sandblasting resulted in a slightly roughened zirconia surface and was not effective in creating
microretentive spaces. No residues of adhesive and resin cement were detectable on the zirconia surface (A). SIE and ST
treated zirconia surfaces exhibited retained cement remnants after testing (B and C). Untreated zirconia showed a smooth
surface with few scratches probably related to milling procedures (D).
no interaction occurred between Calibra and the zirconia sub-
strate [44]. The absence of adhesive functional monomers in
the cement composition may explain lower chemical bonding
values comparing to MDP monomer based resin [45,46].
On the contrary, differences in surface pattern
after substrate conditioning may influence the bond
strength to the partially stabilized zirconium dioxide
ceramic.
Airborne-particle abrasion of zirconia surface is one of
the most-investigated methods, provides good bond strength
to zirconia when combined with phosphate ester monomer
[40,47,48]. In recent literature it was reported that some vari-
ables such as grain particles size and pressure of application
during sandblasting have an important role on the bonding
capability of resin cements to zirconia substrate [49].Upto
date no consensus is still available regarding the grains size
that may guarantee durable bond strength. Several studies
reported an improvement in zirconia roughness after sand-
blasting with 50–110–125 mAl
2O3particles and encouraging
bond strength values [29,43,50–52]. It was also reported that
smaller particles (30–50 m) may enhance resin cement adhe-
sion [49,53,32].
The relatively low bond strength values achieved on zir-
conia after sandblasting and the remarkable percentage of
adhesive (Fig. 1A) and premature failures revealed that the
treatment did not result in the formation of enough under-
cuts to improve the bond strength. This finding is in agreement
with the results of the study by Oyagüe [43].
A controversial aspect regarding sandblasting procedures
are the effects on mechanical properties of zirconia. It was
reported that sandblasting induce tetragonal to monoclinic (T
to M) phase transformation on zirconia surface that increase
the flexural strength [33,54]. Some authors reported that parti-
cle abrasion of zirconia results in the creation of sharp cracks
and structural defects that render the zirconia framework sus-
ceptible to radial cracking during function [40,55].
Beside the grain size particles, pressure application of
sandblasting was recently evaluated for determining its
effects on zirconia surface. As previously reported for grain
size recent literature suggest different protocols for sand-
blasting. However it was reported that reducing sandblasting
pressure may decrease its detrimental effects on mechani-
cal properties [56]. Thus the relatively high pressure applied
during sandblasting in the present study that potentially
dental materials 27 (2011) 1024–1030 1029
can enhance surface roughness [36,37], did not reveal an
improvement in bond strength. Further mechanical test may
investigate its effect on mechanical properties.
In the present study a modified version of the original SIE
conditioning technique proposed by Aboushelib was used [35].
This procedure is based on the application on the zirconia
surface of an infiltrating agent composed of inorganic oxides.
During the procedure the agent is heated at 750 ◦C and cooled.
Ultimately the infiltration agent remnants are dissolved in a
5% hydrofluoric solution, leaving the zirconia surface condi-
tioned.
Discrepancies with the findings of a previous investigation
may be related to the use of a modified infiltration glass with
lower silica and higher potassium contents. Varying the glass
percentage in weight may have influenced the melting tem-
perature and, consequently, its effectiveness in infiltrating the
zirconia surface [35].
The ST treatment has been recently proposed as a novel
technique to improve zirconia surface retention [36,37]. The
hot etching solution may determine a selective chemical etch-
ing of zirconia, creating microretentions and enlarging the
grain boundaries through the preferential removal of the less-
arranged, high-energy peripherical atoms [57].
Once the resin composite infiltrates the 3D inter-grain
spaces, it may become structurally integrated with the surface
and higher forces would be necessary to debond it. The sig-
nificantly higher cement–ceramic bond strengths measured
in this study following ST treatment of zirconia confirm this
hypothesis.
It should be pointed out that in the present investigation
it was chosen to lute the ceramic blocks onto resin composite
blocks, rather than on teeth for the purpose of standardiza-
tion. It was indeed considered that the dental substrate might
have introduced in the microtensile test a greater source of
variability than a manufactured material such as the compos-
ite blocks [41]. Moreover the chemical affinity due to the same
composition, resin luting agent and composite (Table 1)may
guarantee higher bond strength than to zirconia surface, also
without the application of primers or silanes.
Further in vitro and in vivo studies should be performed to
evaluate the effectiveness of the tested surface treatments
in combination with MDP-based resin luting agents. Such
procedure would complement the benefit of the increased
micromechanical retention produced by zirconia surface
treatment with the contribution of the chemical interaction
mediated by MDP monomers.
6. Conclusions
Within the limitations of this study, it can be concluded
that treating zirconia surfaces with chemical procedures such
as SIE and ST is beneficial for improving the ceramic–resin
cement interfacial strength.
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