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Abstract

To evaluate the influence of different surface treatments on the microtensile bond strength of resin cement to zirconia ceramic. Twelve cylinder-shaped (∅ 12×5.25 mm high) blocks of a commercial 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 μm Al₂O₃ particles (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). 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. 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.
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 750C for
1 min using a computer-programmed electrical induction
furnace (Austromat 3001; Dekema Dental-Keramikofen,
Freilassing, Germany), cooled reaching 650C 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 100C.
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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... Casucci et al. [56] further investigated SIE as a surface treatment for zirconia ceramics. After applying a glass-containing agent to the zirconia surface and heating it to approximately 750°C, the researchers found that SIE infiltrated the grain boundaries. ...
... Once the glass was removed with hydrofluoric acid, a microretentive, roughened surface remained, which is ideal for bonding with resin cements. Casuccia's study found that SIE-treated zirconia samples exhibited significantly higher MTBS compared to traditional treatments such as sandblasting, a result attributed to the nano-retentive porosities created during the process [56]. SEM analysis confirmed that SIE produced a rougher surface with more retentive features than sandblasting and therefore enhanced mechanical retention. ...
... SEM analysis confirmed that SIE produced a rougher surface with more retentive features than sandblasting and therefore enhanced mechanical retention. Notably, adhesive failures were more common in untreated and sandblasted groups, whereas SIE-treated groups exhibited mixed failures, indicating stronger bonds between zirconia and resin cement [56]. ...
Article
Full-text available
The increasing use of zirconia in dental restorations necessitates a comprehensive understanding of effective bonding techniques to ensure long-term clinical success. Zirconia's unique chemical composition presents challenges in achieving a durable bond as it lacks the glass phase necessary for traditional etching and silanization processes. This review evaluates current methods and emerging innovations for enhancing zirconia bond strength to resin cements. Our findings emphasize the importance of mechanical surface treatments such as air-particle abrasion and tribochemical silica-coating, which significantly improve micromechanical retention. Laser irradiation, while less commonly used, also shows promise in enhancing bond strength without compromising zirconia's structural integrity; 10-methacryloyloxydecyl dihydrogen phosphate (10-MDP) primers emerged as critical agents in forming stable P-O-Zr bonds, particularly when used with resin cements containing 10-MDP. However, variations in formulation and application methods impact their overall efficacy. Resin cement demonstrated superior bond strength compared to conventional cement, but clinical outcomes varied, highlighting the importance of cement-primer compatibility and strict procedural adherence. Emerging technologies such as polymer-infiltrated ceramic networks (PICNs) and additive manufacturing (AM) of zirconia offer potential for future advancements, although they require further research to address mechanical and aesthetic challenges. In conclusion, while established methods such as sandblasting and the use of MDP primers remain reliable, ongoing research into novel materials and techniques continues to offer opportunities for enhancing zirconia bonding. Clinicians must balance effectiveness, procedural complexity, and clinical practicality when selecting the most appropriate bonding protocols for zirconia restorations.
... In recent years, zirconia ceramics treated by hot acid etching have become a new technology that is gradually being applied in the eld of dental prosthesis. Hot acid etching is the use of high temperature heating strong acid acts on the surface of zirconia; the irregular high-energy atoms around zirconia are corroded and a large number of porous structures are formed on the surface to increase the roughness, which increases the effective area of the bonding, provided a more stable bonding strength for zirconia and resin adhesive, and thus enabled a satisfactory bonding strength of zirconia that meets the requirements of clinical application 4,5 . ...
... This action corrodes the irregular high-energy atoms surrounding the zirconia, forming numerous porous structures on its surface to increase roughness. This increase in roughness enhances the effective bonding area, providing a more stable bonding force for the adhesion of zirconia to resin materials 4,5 . ...
Preprint
Full-text available
In recent years, zirconia ceramics have been widely used as in prosthodontics because of their good aesthetics and mechanical properties. At present, the thermal acid etching technology for treating zirconia ceramics has gradually emerged as a new method. In this study, the effect of thermal acid etching surface treatment on the shear strength and flexural properties was investigated. In the fourth sentence, it might be clearer to specify that the zirconia ceramics were divided into five groups: "In the experiment, the zirconia ceramics were divided into five groups, each receiving a different treatment: blank, 110µm alumina sandblasting, 10-minute thermal acid etching, 30-minute thermal acid etching, and 60-minute thermal acid etching.The surface morphology, crystal structure, and the initial shear bonding strength of zirconia were analyzed by scanning electron microscope (SEM), X-ray diffractometer (XRD), and Instron3345 micro-force testing machine, respectively.SPSS19.0 software was used for the statistical analysis of experimental data, and the statistical difference was set as P < 0.05. The experimental results show that the thermal acid etching technology can effectively increase the surface roughness of zirconia and the shear bonding strength of zirconia and resin adhesive, the effect is obviously better than that of sandblasting, and there is no obvious correlation with the time of technology. This conclusion is of significant importance for guiding oral clinical treatment.
... SIE involves coating the zirconia surface with a conditioning agent containing glass, heating it to facilitate glass infiltration into grain boundaries, and subsequently rinsing with an acid bath to enhance retention [29]. The glass percentage in the conditioning agent may influence its melting temperature and efficiency in infiltrating the zirconia surface [39]. The current analysis underscores SIE's efficacy in establishing a robust and enduring zirconia-resin bond, likely attributed to the highly retentive surfaces it generates, facilitating resin-based luting agent penetration and interlocking. ...
... Hot etching ranked second in SUCRA but did not exhibit a significant difference when compared to air abrasion. This method entails placing samples in a reaction kettle and heating them in a hot-etching solution, typically composed of 800 mL of methanol, 200 mL of 37 % HCl, and 2 g of ferric chloride [39,72]. It dissolved the outermost grain structure of the zirconia surface, enhancing nanoscale roughness [132]. ...
Article
Full-text available
This review examined the efficacy of surface treatments and adhesive monomers for enhancing zirconia-resin bond strength. A comprehensive literature search in PubMed, Embase, Web of Science, Scopus, and the Cochrane Library yielded relevant in vitro studies. Employing pairwise and Bayesian network meta-analyses, 77 articles meeting inclusion criteria were analyzed. Gas plasma was found to be ineffective, while treatments including air abrasion, silica coating, laser, selective infiltration etching, hot etching showed varied effectiveness. Air abrasion with finer particles (25–53 µm) showed higher immediate bond strength than larger particles (110–150 µm), with no significant difference post-aging. The Rocatec silica coating system outperformed the CoJet system in both immediate and long-term bond strength. Adhesives containing 10-methacryloyloxydecyl dihydrogen phosphate (10-MDP) were superior to other acidic monomers. The application of 2-hydroxyethyl methacrylate and silane did not improve bonding performance. Notably, 91.2 % of bonds weakened after aging, but this effect was less pronounced with air abrasion or silica coating. The findings highlight the effectiveness of air abrasion, silica coating, selective infiltration etching, hot etching, and laser treatment in improving bond strength, with 10-MDP in bonding agents enhancing zirconia bonding efficacy.
... To ensure long-term success of zirconia restorations, it is crucial to establish a strong adhesion between zirconia and the luting cement [5,6]. Various techniques have been employed to physically and/or chemically modify the surface of zirconia, thereby enhancing the bonding capability and resulting in long-lasting restorations [7,8]. Airborne particle abrasion is an example of a mechanical treatment that entails impacting the intaglio surface of zirconia with alumina particles μm) under pressure, resulting in higher surface roughness, facilitating micromechanical retention and expanding the available surface area for bonding. ...
... However, other studies have observed that while tribochemical silica-coating initially results in high bond strength between resin cement and zirconia, values decrease after long-term storage or thermocycling [7,11,[16][17][18][19][20]. The weakening of bond strength has been suggested to be linked to the presence of a thin layer of silica deposited on the zirconia surface. ...
... 22 This study was aimed to examine the effectiveness of one of the universal adhesives to substitute the chemical conditioning step -including 10-MDP monomer after air blasting or Silane coupling agent after silica depositionproducing a durable zirconia resin bond strength. conventional flowable nanohybrid composite was used in this investigation to standardize the samples and guard against any potential issues that may arise from using tooth structure, 23 avoid the contribution of any functional monomers in the resin part to exclude its effect in evaluating the used adhesive promoters, 24 and this helped partly to simulate a repair scenario besides being used to replace resin cement whenever higher filler content is needed to secure mechanical properties. ...
... One of the advances in dental ceramics is the development of high-strength zirconia, which has superior fracture toughness and durability compared to other available mineral and nonmetallic alternatives [1]. Zirconia ceramic is currently used in several dental applications, such as the fabrication of orthodontic brackets, intracanal posts, abutments, singleunit crowns, and fixed partial dentures [2,3]. ...
Article
Full-text available
Objectives: Durable bonding to zirconia is a challenging issue in dentistry. This study aimed to assess the effect of bioglass coating of zirconia on the microshear bond strength of resin cement to zirconia and to study the effect of thermocycling on this bond. Materials and Methods: This in-vitro experimental study was conducted on 60 yttria-stabilized tetragonal zirconia blocks in six groups (N=10) based on surface pretreatment and thermocycling. Surface pretreatments included no treatment control, alumina particle abrasion, and bioglass-coating of zirconia. Resin bonding was performed with Panavia F2.0 cements. Then, half of the specimens underwent a 24-hour incubation in 37°C water, while the other half were subjected to thermocycling (12000 cycles, 5-55°C, 60s for each batch) following the same incubation period. Subsequently, the microshear bond strength of the specimens was measured. Additionally, one block from each group was subjected to scanning electron microscopy and X-ray diffraction. The data were analyzed using Kruskal-Wallis and Mann-Whitney U tests. Results: There was a significant difference between the bond strength values of different groups (P<0.001). Alumina particle abrasion and bioglass coating equally increased the bond strength compared to the untreated control group (P<0.001). Thermocycling caused significant decreases in bond strength in all the groups (P<0.001); however, the bond strength value of the thermocycled bioglass-coated group was significantly higher than that reported for the thermocycled alumina particle abraded group (P=0.015). Conclusion: Despite the decrease in the bond strength values after thermocycling, the long-term efficacy of the bioglass coating of zirconia was promising.
Article
Background Limited evidence suggested different outcomes of surface treatment methods on zirconia abutments and crowns. Therefore, we investigated the effect of grooving, hot etching, and airborne particle abrasion (APA) methods on zirconia crowns over Ti-base zirconia abutments retention and fracture strength. Materials and methods In this in vitro study, 110 zirconia crowns and abutments were divided into five groups, including APA for crown and grooved zirconia abutment (APACr-GrAb), APA for crown and hot etching zirconia abutment (APACr-HtAb), grooved modified zirconia crown and APA for zirconia abutments (GrCr-APAAb), hot etching modified zirconia crown and APA for zirconia abutments (HtCr-APAAb), and APA for both crown and zirconia abutments (control group). The retention and fracture strength were measured. Data were analyzed by ANOVA, Tukey, Kruskal-Wallis, and Mann-Whitney with Bonferroni correction tests (α = 0.05). Results Hot etching and grooving on the crown or abutment significantly resulted in higher retention (P < 0.001). The fracture strength significantly differed among the five groups (P = 0.041), with the highest fracture strength observed in the GrCr-APAAb group and the lowest for the APACr-GrAb group; however, no significant differences were found in pairwise comparisons between groups (P > 0.05). By considering both fracture strength and retention, grooving, hot etching, and APA were confirmed for better crown and abutment function, respectively. Conclusion Grooving surface treatment was the best method due to its high fracture strength and retention, followed by hot etching due to its high retention compared to APA, which can be considered a suitable method for cementing zirconia crown on zirconia abutments.
Article
The surface of zirconia was treated with hot-acid etching of different durations to improve its shear bond strength to resin. Zirconia discs were subjected to untreated, sand-blasting, and hot-etching treatments for 10, 30 and 60 min. The discs were bonded to the surface of bovine enamel specimens using RelyX Ultimate resin cement. The bonded specimens were divided into immediate and thermocyling aging groups according to whether they underwent thermal cycling. A universal mechanical testing machine was used to measure the shear bond strength of the specimens. One-way analysis of variance was used to determine the effect of hot-etching time on the shear bond strength. In the immediate and thermocyling aging groups, 60 min of hot-etching provided significantly higher shear bond strength than the other conditions (p<0.05).
Article
Full-text available
To investigate the influence of chemical and enzymatic degradation on the stability of zirconia resin bond strength using micro-shear bond strength test. Zirconia discs were airborne particle abraded (SB) or selective infiltration etched (SIE) while no surface treatment served as control. Resin composite (Filtek Z250) microdiscs were bonded to zirconia using self-adhesive universal resin cement (RelyX UniCem). Micro-shear bond strength (microSBS) test was conducted after immersion in the following degrading media: 24 hours and 2 weeks of water storage, and 2 weeks in NaOH, alcohol, or esterase enzyme (n=10). There was a significant influence of the surface finish (P < 0.001, F=154.5), biodegradation medium (P < 0.001, F=52.9), and their interaction (P < 0.001, F=6.0) on zirconia resin bond strength. In general SIE group revealed the highest microSBS values (8.1 - 34.5 MPa) after degradation in different media, followed by SB group (8.7 - 28.5 MPa), while the control group showed significantly lower bond strength (0.4 - 9 MPa).
Conference Paper
High-strength all-ceramic systems for fixed partial dentures (FPDs) are available for replacing a missing tooth. New core/framework materials have been developed and have evolved in the last decade. With the advancement of CAD/CAM technology, various fabrication techniques have been developed for fabricating improved, consistent, and predictable restorations in terms of strength, marginal fit, and esthetics and for managing core/framework materials that could not otherwise be managed. This article reviews the evolution and development of materials and technologies for all-ceramic FPDs through data published between 1966 and 2004 in the English language. Peer-reviewed articles were identified through a MEDLINE search and a hand search of relevant textbooks and annual publications. The available information suggests that clinical data on the success of these restorations are limited, and that the results of long-term clinical studies are critical to the assessment of these restorations to provide more specific guidelines for usage.
Article
Selective infiltration etching (SIE) is a newly developed surface treatment used to modify the surface of zirconia-based materials, rendering them ready for bonding to resin cements. The aim of this study was to evaluate the zirconia/resin bond strength and durability using the proposed technique. Fifty-four zirconia discs were fabricated and divided into three groups (n = 18) according to their surface treatment: as-sintered surface (control group), airborne-particle abrasion (50-mum aluminum oxide), and SIE group. The zirconia discs were bonded to preaged composite resin discs using a light-polymerized adhesive resin (Panavia F 2.0). The zirconia/resin bond strength was evaluated using microtensile bond strength test (MTBS), and the test was repeated after each of the following intervals of accelerated artificial aging (AA): thermocycling (10,000 cycles between 5 and 55 degrees C), 4 weeks of water storage (37 degrees C), and finally 26 weeks of water storage (37 degrees C). Silver nitrate nanoleakage analysis was used to assess the quality of zirconia/resin interface. A repeated measures ANOVA and Bonferroni post hoc test were used to analyze the data (n = 18, alpha= 0.05) There were significant differences in the MTBS values between the three test groups at each of the test intervals (p < 0.001). AA resulted in reduction in the bond strength of the as-sintered and the particle-abraded groups (5.9 MPa and 27.4, MPa, respectively). Reduction in the bond strength of these groups was explained by the observed nanoleakage across the zirconia/resin interface. The bond strength of the SIE specimens was stable after completion of AA (51.9 MPa), which also demonstrated a good seal against silver nitrate penetration across the zirconia/resin interface. SIE established a strong, stable, and durable bond to zirconia substrates. Conservative resin-bonded zirconia restorations are now possible using this new technique.
Article
The popularity of high-strength ceramic systems is increasing, and the range of their clinical indications is expanding constantly. Glass-infiltrated aluminum oxide ceramic (eg, InCeram® Alumina, Vita Zahnfabrik, Bad Säckingen, Germany), densely sintered aluminum oxide ceramic (eg, Procera® AllCeram, Nobel Biocare AB, Gothenburg, Sweden), and zirconium oxide ceramic (eg, Procera AllZirkon®, Lava® 3M ESPE, St. Paul, MN, USA, Cercon®, Dentsply Ceramco, Burlington, NJ, USA) are popular oxide-based high-strength ceramic materials that offer favorable esthetic characteristics, mechanical properties, and biocompatibility. Proper selection and application of luting agents for final cementation of all-ceramic restorations are keys for their clinical success. The few clinical trials on full-coverage, high-strength ceramic restorations report acceptable success rates with conventional luting agents. However, an article discussed in Part I of this Critical Appraisal reviewed available in vitro and in vivo studies on this topic and recommended adhesive cementation of ceramic and even high-strength ceramic restorations. These findings contradict many manufacturers’claims and clinicians’preferences because resin bonding is a technique-sensitive and time-consuming procedure. However, resin bonding has a number of advantages (eg, increased retention, improved marginal adaptation, and higher fracture resistance of the restored tooth and the restoration itself) and is required for some minimally invasive treatment options, such as resin-bonded fixed partial dentures and laminate veneers.
Article
Purpose: To compare the flexural strength of two glass-infiltrated high-strength ceramics and two veneering glass-ceramics. Materials and methods: Four ceramic materials were tested: two glass-infiltrated high-strength ceramics used as framework in metal-free restorations [In-Ceram Zirconia IZ (Gr1) and In-Ceram Alumina IA (Gr2)], and two glass-ceramics used as veneering material in metal-free restorations [Vita VM7 (Gr3) and Vitadur-alpha (Gr4)]. Bar specimens (25 x 5 x 2 mm3) made from core ceramics, alumina, and zirconia/alumina composites were prepared and applied to a silicone mold, which rested on a base from a gypsum die material. The IZ and IA specimens were partially sintered in an In-Ceram furnace according to the firing cycle of each material, and then were infiltrated with a low-viscosity glass to yield bar specimens of high density and strength. The Vita VM7 and Vitadur-alpha specimens were made from veneering materials, by vibration of slurry porcelain powder and condensation into a two-part brass Teflon matrix (25 x 5 x 2 mm3). Excess water was removed with absorbent paper. The veneering ceramic specimens were then removed from the matrix and were fired as recommended by the manufacturer. Another ceramic application and sintering were performed to compensate the contraction of the feldspar ceramic. The bar specimens were then tested in a three-point bending test. Results: The core materials (Gr1: 436.1 +/- 54.8; Gr2: 419.4 +/- 83.8) presented significantly higher flexural strength (MPa) than the veneer ceramics (Gr3: 63.5 +/- 9.9; Gr4: 57.8 +/- 12.7). Conclusion: In-Ceram Alumina and Zirconia were similar statistically and more resistant than VM7 and Vitadur-alpha.
Article
The effect of surface treatment using tribochemical silica coating/silane coupling on the shear bond strengths of (1) a glass-infiltrated, zirconia-reinforced alumina (In-Ceram Zirconia) and (2) a yttria-stabilized zirconia ceramic (YZ Zirconia) to human dentin was studied. Twelve specimens of each ceramic were randomly assigned to one of three surface treatments: (1) no surface treatment (control group); (2) a chairside tribochemical silica coating/silane coupling system (CoJet group); and (3) a laboratory tribochemical silica coating/silane coupling system (Rocatac group). The mode of failure of each specimen was determined under magnification. The shear bond strengths (mean ± SD) of In-Ceram Zirconia of the control, CoJet and Rocatec groups were 5.7 ± 4.3 MPa, 11.4 ± 5.4 MPa, and 6.5 ± 4.8 MPa, respectively. The corresponding figures for YZ Zirconia were 8.2 ± 5.4 MPa, 9.8 ± 5.4 MPa, and 7.8 ± 4.7 MPa. Two-way ANOVA revealed significant differences in bond strength due to the difference in surface treatment (p= 0.02), but the bond strengths between the two ceramics were not significantly different (p= 0.56). Post hoc tests showed that In-Ceram Zirconia treated with CoJet had significantly higher shear bond strengths than those untreated (p < 0.05) or treated with Rocatec (p < 0.05). Surface treatment did not affect the shear bond strength of YZ Zirconia significantly (p > 0.05). The bonding of In-Ceram Zirconia can be improved by the chairside surface treatment system.
Article
Ceramics have a long history in fixed prosthodontics of achieving optimal esthetics. Yttrium tetragonal zirconia polycrystal (Y-TZP)-based systems are a recent addition to the high-strength, all-ceramic systems used for crowns and fixed partial dentures. CAD/CAM-produced, Y-TZP-based systems are in considerable demand in esthetic and stress-bearing regions. The highly esthetic nature of zirconia coupled with its superior physical properties and biocompatibility have resulted in restorative systems that meet the demands of today's patients. Undoubtedly, these systems are considered to be prospective replacements for metal-ceramic restorations. This article reviews relevant contemporary literature regarding all-ceramic materials and systems and discusses their material properties, biocompatibility, advances in cementation, and more with special emphasis on clinical survival. The article also aims to provide recommendations for their use.
Article
This report presents a novel pretreatment technique, whereby the zirconia surface is converted to a more reactive zirconium oxyfluoride, enabling improved chemical bonding to other dental substrates via conventional silanation approaches. The study leverages a novel gas-phase fluorination process that creates a thin oxyfluoride conversion layer on the surface of zirconia, making it more reactive for conventional adhesive bonding techniques. Zirconia specimens, polished and roughened, were pretreated and composite cylinders bonded using conventional adhesive techniques. All specimens were subjected to a force at a crosshead speed of 0.5mm/min in an electro-mechanical testing device. Single-factor analysis of variance (ANOVA) at a 5% confidence level was performed for the bonding strength data. Optical microscopy and scanning electron microscopy (SEM) were used to evaluate and quantify failure surfaces. Shear bond strengths were analyzed using single-factor ANOVA (p<0.05). Mechanical testing results revealed that fluorinated zirconia specimens (both rough and polished) displayed the highest shear bond strengths as compared to other commercially available treatments. X-ray photoelectron spectroscopy analysis helped determine that this novel pretreatment created a more reactive, 2-4nm thick oxyfluoride conversion layer with approximate stoichiometry, ZrO(3)F(4). Simple shear bond mechanical tests demonstrated that a fluorination pre-treatment is a viable method to chemically modify zirconia to produce a reactive surface for adhesive bonding.