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Effect of tribochemical treatments and silane

reactivity on resin bonding to zirconia

Raphael Pilo a , Maria Dimitriadi b , Anna Palaghia b , George Eliades b,∗

a Department of Prosthodontics, School of Dentistry, Tel Aviv University, Israel
b Department of Biomaterials, School of Dentistry, University of Athens, Greece

a r t i c l e i n f o a b s t r a c t

Article history: Objective. The aim of the study was to assess the roughness, structure and bond strength with
Received 7 October 2017 zirconia of four grit-blasting treatments combined with three silane types, the reactivity of
Received in revised form which was evaluated, as well.
5 November 2017 Methods. The grit-blasted treatments performed on zirconia (Lava) were alumina (ALU),
Accepted 9 November 2017 CoJet (COJ), SilJet (SLJ) and SilJet Plus (SJP, with silica-encapsulated silane). The other two
Available online xxx silanes selected were the S-Bond (SB, prehydrolyzed) and Clearfil Ceramic Primer Plus (CP,
prehydrolyzed with 10-MDP). The activity of the silanols in the silanes was evaluated by
Keywords: FTIR spectroscopy. Optical profilometry and Raman microspectroscopy were used for the
Zirconia assessment of roughness (Sa, Sz, Sdr parameters) and structure (monoclinic volume-Vm) of
Tribochemical treatments zirconia, before (REF) and after grit-blasting, and a shear bond strength (SBS) with a flowable
Roughness resin composite, for the investigation of the bonding capacity of the treatments.
Structure Results. Only SB demonstrated reactive silanols. CP and the SJP silanes were mostly in
Silane reactivity a polymerized siloxane state. Roughness was increased after grit-blasting as follows:
FTIR ALU > SLJ,SJP > COJ > REF (Sa,Sz) and ALU > SLJ,COJ,SJP > REF (Sdr). ALU demonstrated the
Raman spectroscopy highest Vm (7.52%) from all other treatments (4.16–4.81%) and the REF (0%). COJ and SLJ
showed the highest SBS (14–15.94 MPa) regardless of the silane type used. SJP showed no
significant differences from SLJ-SB and COJ-SB. Weibull analysis showed a reliability (ˇ)
ranking of COJ, SJP, SLJ, ALU-CP > ALU-SB > REF and a characteristic life () ranking of COJ,
SLJ, ≥SLJ-SB, SJP, ALU ≥ ALU-SB,REF-CP > REF-SB.
Significance. The reactivity of the silanes used showed great variations to support a pre-
dictable effect in all treatments. CP with deactivated silanols demonstrated a) the most
reliable and strongest treatment with a silica-rich powder (COJ), despite the lowest Sa,Sz
substrate values and b) high strength with a low-silica powder (SLJ) with higher Sa,Sz sub-
strate values. Therefore, it may be concluded that 10-MDP greatly contributes to the bonding
mechanism of the silane containing primers.
© 2017 The Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

∗
Corresponding author at: Department of Biomaterials, School of Dentistry, National and Kapodistrian University of Athens, 2 Thivon St.,
Goudi, 115 27 Athens, Greece.
E-mail address: geliad@dent.uoa.gr (G. Eliades).
https://doi.org/10.1016/j.dental.2017.11.006
0109-5641/© 2017 The Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

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humidity) [19], it can be assumed that siloxane polymers have

1. Introduction
Grit-blasting of dental zirconia surfaces with alumina or
silica–alumina particles followed by the use of properly func-
tionalized methacrylate coupling agents have been accepted
as the most efficient and durable surface treatments for resin
bonding [1,2]. The main advantages of this combined pro-
cedure are a) the chemical bonding of coupling agents with
zirconia and the surface retained particles, and b) the mechan-
ical interlocking of the luting agents or restoratives on the
rough surface, following polymerization and shrinkage. This
combination has been shown to overwhelm the deficiencies
of using only coupling agents for chemical bonding [3,4] or
grit-blasting without coupling agents [5]. Use of low pressures
(<0.3 MPa) and small particle sizes (<70 ␮m) has been advo-
cated to reduce the extent of microcrack formation and control
the tetragonal (t) to monoclinic (m) phase transformation,
at the surface and subsurface zones [6,7]. This is important,
since the advantages of increased zirconia strength due to the
transformation-induced residual compressive stresses after
grit-blasting [8] are minimized by microcrack formation and
structural destabilization [9,10].
For zirconia surfaces grit-blasted with crystalline alumina
(␣-Al2 O3 ), phosphate functionalized methacrylate monomers
have been proposed as coupling agents, which bond with alu-
mina implanted particles and the uncoated zirconia surface
[2]. For tribochemical treatments, where silica-treated alu-
mina particles are included in the alumina powder, silane
coupling agents are used, which bond with the fractions of
the hydroxylated amorphous silica particles retained on the
zirconia surface [2]. However, the tribochemical coating is not
uniform with only small fraction of zirconia surface coverage
[11]. Because of the low bonding capacity of silanes to zir-
conia [12], acidic ethanol solutions of silane with phosphate
coupling agents have been introduced [13]. In these products
hydrolyzed ␥-methacryloxypropyl trimethoxysilane (MPTMS)
is usually mixed with 10-methacryloyloxydecyl dihydrogen
phosphate (10-MDP). MPTMS is the most commonly silane
used in dental applications, since its methacrylate functional-
ity matches that of most dental resins [14], whereas 10-MDP is
a phosphate monomer capable of bonding with a wide range of
substrates [12]. MPTMS has been incorporated, as well, in uni-
versal adhesives containing 10-MDP, in order to expand their
applications in ceramic bonding and repair. However, it has
long been stated that mixing hydrolyzed silanes with den-
tal monomers possessing −OH groups, deactivates the silanol
(Si–OH) groups via condensation reactions [14]. This has been
confirmed in silane containing universal adhesives, where no
Si–OH groups were traced [15], resulting in inferior bonding
of these adhesives with silica-rich substrates as compared to
that of separate MPTMS treatments [15,16].
Recently, a new tribochemical treatment, containing
encaplulated MPTMS in silica microspheres, has been intro-
duced for simultaneous roughening and silanization of the
substrate. This treatment has been found equally efficient
to traditional tribochemical methods for resin bonding to a
Co–Cr alloy [17] and zirconia [18]. The status of the encap-
sulated silane is unknown. Based on the sealing procedure
of the silane-filled silica microspheres (exposure to ambient
been formed.
The aim of the present study was a) to evaluate the silanol
reactivity of two commercially available silane primers (based
on MPTMS and MPTMS/10-MDP), and a silica-encapsulated
MPTMS silane, b) to assess the effects of the grit-blasting
treatments on zirconia roughness and structure, and c) to
investigate the bond strength of a resin composite to zirconia,
as mediated by four grit-blasting treatments and the corre-
sponding silanes. The null hypothesis was that no differences
are expected in the silanol reactivity, grit-blasting effects on
zirconia roughness and structure, and bond strength between
the grit-blasting/silane treatments employed.
2. Materials and methods
The materials used in the study are listed in Table 1.
2.1. Silanol reactivity
A drop of each of the CP and SB silanes were applied on an
infrared Ge window. The solvents were evaporated with a
stream of nitrogen gas for 20 s and immediately after trans-
mission FTIR spectra were obtained employing a spectrometer
(Spectrum GX, Perkin-Elmer, Bacon, UK) under the following
conditions: 4000–600 cm−1 wavenumber range, 4 cm−1 reso-
lution and 30 scans co-addition. The presence of methoxy
(2840, 1190, 1083, 850–800 cm−1 ), siloxane (1120–900 cm−1 ) and
silanol groups (3430, 904 cm−1 ), were considered as an indica-
tor of the activity of freshly applied silane films. As controls
served a non-hydrolyzed MPTMS silane (Dynasylan, Evonik
Industries AG, Essen, Germany), an aged SB solution (SBA, 2
years at 37 ◦ C) and a 10-MDP sample (Ivoclar Vivadent, Schaan,
Liechtenstein). For SJP, which contains silane in a silica-
encapsulated form, a small amount of the powder was placed
on the diamond crystal of an attenuated total reflectance (ATR)
accessory with ZnSe lenses (Golden Gate, Specac, Kent, UK),
crashed under pressure applied with a metallic anvil and spec-
tra were taken as before. The depth of the ATR analysis was
estimated as to 2 ␮m at 1000 cm−1 . These tests were performed
in triplicate.
2.2. Roughness measurements
Disk-shaped zirconia specimens (Ø = 10 mm, h = 2 mm, n = 20)
were prepared and polished with SiC papers (320–1000
grit size) in a grinding-polishing machine (Dap-V, Struers,
Ballerup, Demark) and ultrasonicated for 5 min, in distilled
H2 O. The specimens were randomly assigned into four groups
(n = 4/group) corresponding to the grit-blasting treatments
with 50 ␮m ␣-Al2 O3 (ALU), CoJet (COJ), SilJet (SLJ), SilJet Plus
(SJP), and a reference polished zirconia group (REF). The cen-
tral part of the specimens was blasted for 5 s with each powder
using an intraoral sandblaster (Microetcher IIA, Danville Mate-
rials) operated at 2.3 bar air pressure (0.23 MPa, 0.47 L/s flow
rate), 5 mm distance and 90◦ angle. All specimens were dried
with oil-free dry air for 20 s and then examined by optical inter-
ferometric profilometry. An optical profiler (Wyko NT1100,
Veeco, Tuscon, AZ, USA) was used as follows: Mirau lens, 40×

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Table 1 – The materials used in the study (composition according to manufacturers’ information).
Product Composition Manufacturer
Tribochemical systems
CoJet (Lot: 385026) 30 ␮m silica/alumina particles 3 M ESPE, Seefeld, Germany
SilJet (Lot: 078-096B) 30 ␮m silica/alumina particles Danville Materials Inc., S. Ramon,
CA, USA
SilJet Plus (Lot:112148B) 30 ␮m silica/alumina particles, Danville Materials Inc., S. Ramon,
silica-encapsulated ␥-MPTMS CA, USA
(␥-methacryloxypropyl trimethoxy silane)
Medical Grade Alpha Alumina (Lot: 50 ␮m alumina particles Danville Materials Inc., S. Ramon,
21063) CA, USA

Silane agents
Clearfil Ceramic Primer Plus Ethanol, prehydrolyzed ␥-MPTMS, 10-MDP Kuraray Noritake Dental Inc.,
(Lot:17C) (10-methacryloyloxydecyl dihydrogen Okayama, Japan
phosphate)
S-Bond (Lot:19620) Ethanol, prehydrolyzed ␥-MPTMS Danville Materials Inc., S. Ramon,
CA, USA

Zirconia
Lava Frame 3Y-TZP 3M ESPE, Seefeld, Germany

Composites
StarFlow A2 (19887) BisGMA, Ba-glass, amorphous SiO2 (61% wt, Danville Materials Inc., S. Ramon,
0.7 ␮m size) CA, USA

magnification, vertical scanning imaging mode, 5 mm scan-
ning length, 113.3 × 148.5 ␮m2 analysis area, and tilt correction
with 0.1 nm (z-axis) and 0.2 ␮m (x-axis and y-axis) resolu-
tion. The surface roughness parameters measured were: i) the
amplitude parameter Sa (the arithmetic average of the abso-
lute values of the surface height deviations measured from the
best fitting plane), ii) the amplitude parameter Sz (the 10 point
height over the surface, representing the average difference
between the 5 highest peaks and 5 lowest valleys), and iii) the
hybrid parameter Sdr (the developed area due to the surface
texture versus an ideal plane area ratio). On each specimen
three measurements were performed and averaged, yielding
the representative value.
2.3. Zirconia phase transformation
To evaluate the effect of the grit-blasting treatments on
the stability of the tetragonal zirconia phase, four zirco-
nia specimens from each group were examined by Raman
microspectroscopy. A Raman microscope was used (InVia
Raman Microscope, Renishaw, Gloucestershire, UK), oper-
ated under the following conditions: Ar+ laser ( = 514.5 nm),
0.45/50× (LWD) objective, 900–100 cm−1 Raman shift range,
4 cm−1 resolution, 2400 grit/mm grating, 60 s acquisition time
and 10 mW laser power on target. Two 50 × 50 ␮m2 randomly
selected regions were analyzed on the grit-blasted area of each
sample, using 10 ␮m step scans and an average spectrum was
obtained per region. The peaks at 179 and 189 cm−1 , attributed
to the m-phase, were used as evidence of t- → m-phase
transformation, triggered by the grit-blasting procedure. The
percentage of the monoclinic phase volume (Vm%) was esti-
mated by the Katagiri et al method [20], according to the
equation:
Vm = 0.5×(I179 +I189 )/[2.2×I147 +0.5×(I179 +I189 )]
where I179 , I189 are the peak intensities of the m-phase and I147
of the t-phase.
2.4. Bond strength testing
For the bond strength study, zirconia specimens were prepared
as above and randomly classified into 9 groups of 10 speci-
mens each. Two polished groups received no treatment (REF),
a pair of groups was subjected to each of the ALU, COJ, SLJ
treatments and one group was treated with SJP. At the cen-
tral part of each specimen a 100 ␮m-thick masking tape was
placed, leaving a free circular area (Ø = 2 mm) for bonding. One
group of the REF, ALU, COJ and SLJ specimens was treated with
the S-Bond (SB) silane, whereas the second with the Clearfil
Ceramic Primer Plus (CP) silane. Silanes were applied with a
microfiber brush, left intact for 60 s and then air-dried for 10 s.
Cylindrical molds (Ø = 2.4 mm, h = 2 mm) were placed over the
treated surfaces, filled with the light-cured flowable compos-
ite and irradiated for 30 s with a LED curing unit (Bluephase
16i, Ivoclar Vivadent, Schaan, Liechtenstein) operated in stan-
dard mode (1600 mW/cm2 ). All specimens were stored in
distilled water (5 days/37 ◦ C), then thermal-cycled (3000×,
5/55 ◦ C water baths, 2 cycles/min, 10 s dwell time, 5 s trans-
fer time) and finally debonded under shear loading, applied at
the zirconia-composite interface with the notched-edge blade
method. A universal testing machine (Tensometer 10, Mon-
santo, Swindon, UK) was employed, operated at 1.0 mm/min
crosshead speed. Debonded zirconia surfaces were subjected
to failure mode analysis under a stereomicroscope (M80, Leica
Microsystems, Wetlzar, Germany) at 10× magnification and
a light microscope (DM 4000B, Leica) operated in reflection
at 100× magnification. Failure mode was classified as Type I
(adhesive at the zirconia-composite interface), Type II (cohe-
sive within the composite) and Type III (mixed of type I and
(1) II).

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Fig. 1 – Transmission FTIR spectra of the CP and SB silane films, along with the aged SB silane (SBA) and the controls
(non-hydrolyzed MPTMS and 10-MDP). The spectrum of CP shows a small peak of H-bonded OH groups, no methoxy groups
(Si–O–CH3 ), and siloxane (Si–O–Si) peaks, resembling that of aged SBA. The contribution of 10-MDP in CP is clearly seen at
∼1000 cm−1 (P–O) (a: 4000–2000 cm−1 range and b: 1800–650 cm−1 range).

2.5. Statistical analysis
Statistical analysis of the roughness parameters and Vm%
values were performed by one-way ANOVA plus Holm-Sidak
multiple comparison tests. For the shear bond strength
results, a two-way ANOVA plus Tukey test (independent
parameters: types of treatment and silane, for comparisons
among REF, ALU, COJ, SLJ) and one-way ANOVA plus Tukey
test for comparisons of the groups corresponding to each
silane treatment with SJP. Moreover, a Weibull analysis was
performed. The shape or modulus parameter (ˇ, defines the
variability of the results, by expressing the size distribution of
the flaws) and the scale or B63.2 parameter, frequently defined
as characteristic life (, indicates the strength value for which
the 63.2% of the sample size will be debonded) of the Weibull
distributions were calculated. A Chi-square test was used for
the failure mode analysis. Finally, Pearson correlation coef-
ficient was used to evaluate statistical correlations between
roughness parameters, Vm and shear bond strength. The sta-
tistical analyses were performed by SigmaStat software (v3.1,
Jandel Scientific Software Inc, S. Raphael, CA, USA, for rough-
ness, SBS, failure mode and Pearson correlation) and Develpe
software (v. 3.12, Velp, The Netherlands, for Weibull analysis).
For all cases a 95% confidence level was used (˛ = 0.05).
3. Results
3.1. Silanol reactivity
FTIR spectra of CP, SB, and of the SBA, MPTMS, 10-MDP controls
are shown in Fig. 1(a, b). The original methoxy (Si–O–CH3 ) peak
of MPTMS (2843 cm−1 ) was not identified in CP and SBA, due
to complete hydrolysis (Fig. 1a). Only in SB, a small peak was
found at 2843 cm−1 , indicating incomplete hydrolysis. Based
on the peak height ratios of the methoxy groups normalized
against the C C peaks at 1636 cm−1 , a ∼60% hydrolysis was
estimated for SB relative to MPTMS. The broad OH peak at
(3750–3100 cm−1 ) in SB should be attributed to various states
of hydrogen bonded silanols (Si–OH) with other silanols, resid-
ual water or ester (C O) groups. This may explain, as well, the
lower band shoulder (∼1703 cm−1 ) of the strong C O peak at
1715 cm−1 found in CP, SB and SBA, which is typical of hydro-
gen bonded C O groups [21]. The contribution of water to the
3750–3100 cm−1 region should be minimal, since there are no
important interferences at 1640 cm−1 (bending vibrations of
water −OH), which usually overlap the C C peak at 1636 cm−1 .
Therefore, the broad peak should be rather attributed to H-
bonded Si–OH vibrations. Interestingly, this broad peak is
reduced in CP and diminished in SBA, indicating the absence
of H-bonded silanols. No such peak appeared in MPTMS and
10-MDP controls. In the 1250–800 cm−1 region, characteristic
vibrations of Si–O–C, Si–O–Si and Si–OH appear [21,22] along
with the P–O and P–O–C vibrations of 10-MDP [23,24]. The
peaks at 1164 cm−1 are assigned to C–O–C groups of C O,
at 1190 cm−1 , 1083 cm−1 and 815 cm−1 to methoxy groups, at
1120, 1040 cm−1 to Si–O–Si, at 935 cm−1 to C C and at 904 cm−1
to Si–OH [21,22]. Also, the P–O peaks appear at 1014 cm−1 and
the P–O–C at 1043 cm−1 [24]. The broad and strong peaks of CP
and SBA at 1130 and 1097 cm−1 imply the formation of siloxane
bonds. In SB, the shoulder at 1120 cm−1 indicates the presence
of siloxanes at a smaller extend.
Spectra of crushed SJP particles (Fig. 2) demostrated noise,
due to the hard nature of the particles to succeed good con-
tact with the crystal. The spectra mostly resembled that of
amorphous silica [25], with a peak of ester at 1720 cm−1 . After
subtraction of the spectrum of amorphous silica, the peaks
at 1120 and 1040 cm−1 revealed the presence of polymerized
silanols (Si–O–Si).
3.2. Roughness measurements
3D-profilometric images of reference and grit-blasted zirco-
nia surfaces are exhibited in Fig. 3. A rough surface was

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Fig. 2 – ATR-FTIR spectra of SJP powder (4000–750 cm−1 range) with the characteristic peak of Si–O–Si vibrations at
1090 cm−1 (black arrow). The insert shows expanded spectra (1850–850 cm−1 range) of SJP, amorphous silica, SiO2 (a), and
the subtraction spectrum (SUB). The peaks at 1720 cm−1 (C O), 1110 and 1030 cm−1 (Si–O–Si) of the subtracted spectrum
(grey arrows) imply the presence of polymerized silanols.

established after all grit-blasting treatments. Table 2 summa-
rizes the results of the roughness parameters. The polished
group showed the lowest values in all the roughness parame-
ters tested (p < 0.05). The ranking of the statistically significant
differences was ALU > SLJ,SJP > COJ for Sa,Sz and ALU > SLJ, COJ,
SJP for Sdr.
3.3. Zirconia phase transformation
Raman spectra of reference and the grit-blasted zirconia sur-
faces are illustrated in Fig. 4. No peaks were identified at
179 and 189 cm−1 in the reference group. After grit-blasting,
all specimens demonstrated the m-phase. The results of
the Vm% are summarized in Table 3. From the grit-blasted

Fig. 3 – 3D-profilometric images of the reference (REF; 0,83 to −1,39 ␮m scale range) and the grit-blasting treatments tested
(40× magnification). ALU: ␣-Al2 O3 (3,07 to −4,1 ␮m scale range), COJ: CoJet (2,09 to −2.93 ␮m scale range), SLJ: SilJet (2,59 to
−4,85 ␮m scale range), SJP: SilJet Plus (1.88 to −4,11 ␮m scale range).

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Table 2 – Results (means and standard deviations) of the Table 3 – Results (means and standard deviations) of the
roughness parameters tested. Same letters show means monoclinic volume fraction (Vm%) in the grit-blasted
with no statistically significant differences per groups and the reference. Same letters show means
parameter (p > 0.05). with no statistically significant differences per
parameter (p > 0.05).
Treatment Sa (nm) Sz (␮m) Sdr (%)
Treatment Vm (%)
REF 99.75 (13.07) a 1.34 (0.18) a 1.75 (0.09) a
ALU 483.5 (17.52) b 4.27 (0.29) b 47.72 (1.33) b REF 0a
COJ 360.5 (15.69) c 3.16 (0.10) c 41.78 (1.13) c ALU 7.52 (1.27) b
SLJ 427.25 (13.2) d 3.72 (0.19) d 42.23 (1.51) c COJ 4.16 (0.43) c
SJP 420 (10.22) d 3.37 (0.15) d 41.67 (0.83) c SLJ 4.81 (0.34) c
SJP 4.99 (0.46) c

groups, ALU demonstrated significantly higher Vm% (7.52%).

No statistically significant differences were found between the
remaining grit blasted groups, with Vm% mean values rang-
ing from 4.16% (COJ) to 4.99% (SJP). No statistically significant
differences were found among the grit-blasted groups.

3.4. Bond strength testing

The results of SBS and failure mode analysis are presented in

Fig. 4 – Representative Raman spectra of reference (REF)
and grit-blasted zirconia with ␣-Al2 O3 (ALU), CoJet (COJ),
SilJet (SLJ) and SilJet Plus (SJP). The peaks at 179 and
189 cm−1 are characteristic of the monoclinic phase and at
147 cm−1 of the tetragonal phase at the region.
Table 4. Comparison between REF, ALU, COJ and SLJ treatments
with CP and SB silanes showed a statistically significant differ-
ence in the treatment and silane parameters (p < 0.001), with
an insignificant interaction (p = 0.082). CP was more effective
in REF than SB. There was no significant difference between
the two silanes in ALU, which provided higher SBS than REF.
COJ and SLJ resulted in significantly higher strength than ALU,
regardless of the type of silane used, with no statistically
significant differences between them. SJP manifested no sta-
tistically significant differences from COJ-SB, SLJ-SB and ALU
treated with both silanes. Significant differences were regis-
tered in favor of SJP (greater than REF) and against SJP (lower
than COJ-CP and SLJ-CP). The Weibull graphs for the refer-
ence and the grit-blasted groups treated with CL, SB, and the
SJP are illustrated in Fig. 5(a, b). The most reliable treatment
(ˇ), according to Weibull analysis, was the COJ-CP but with no
statistically significant differences from COJ-SB, SJP, SLJ (both
silanes) and ALU-CP, and the least reliable the REF-SB with
no statistically significant difference from ALU-SB (Table 4).
COJ-CP was the treatment with the highest characteristic life
(), with no statistically significant differenes from COJ-SB, SLJ
(both silanes) and SJP, whereas REF-SB was the treatment with
the lowest one. Microscopic images of representative deboned
zirconia surfaces are illustrated in Fig. 6. In most specimens of
REF group, adhesive failures were encountered (Fig. 6a, b, f). In
cases of mixed failures, resin fragments were most frequently
located at the opposing quartile to the loading site (Fig. 6c, d)
and sporadically at the center (Fig. 6e). All reference specimens
showed adhesive failures (Type I). Mixed failures (Type III) were
found in all grit-blasted specimens ranging from 10 to 30%
(Table 4). No statistically significant difference in the failure
mode was registered among these groups (p = 0.383 > 0.05).
Statistically significant correlations (p < 0.05) were found
between Sa–Vm (r = 0.97, p = 0.006), Sz–Vm (r = 0.982, p = 0.003),
Sdr–Vm (r = 0.892, p = 0.04) for the treatments REF, COJ, SLJ, SJP,
and between Sdr-SBS (r = 0.887, p = 0.045) for the same treat-
ments combined with the MTMPS silane (SB and SJP).

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Table 4 – Results of the shear bond strength test (means, standard deviations, Weibull parameters) and failure mode
analysis (percentage of adhesive failures). Same letters show mean values with no statistically significant differences per
column (p > 0.05).
Treatment Mean (SD) Weibull Weibull -parameter Weibull Adhesive
(MPa) ˇ-parameter (95% C.I.) (MPa) -parameter r2 failures (%)
(95% C.I.)
REF + CP 7.95 (1.67) a 4.43 (3.35–5.51) a 8.65 (7.03–9.88) a 0.92 100
REF + SB 3.39 (1.36) b 2.48 (2.18–2.79) b 3.83 (2.75–4.72) b 0.99 100
ALU + CP 11.73 (2.15) c 5.80 (5.06–6.54) a,c 12.61 (10.65–14.04) c 0.98 90
ALU + SB 9.14 (3.07) a,c 3.27 (2.59–3.96) b 10.11 (7.59–12.15) a,c 0.94 80
COJ + CP 15.94 (2.03) d 8.49 (6.14–10.84) c,d 16.73 (15.05–17.89) d 0.90 60
COJ + SB 14 (2.39) d,e 6.13 (5.3–6.96) c,d 16 (12.78–16.61) d,e 0.97 70
SLJ + CP 14.95 (2.99) d 5.34 (4.49–6.18) c,d 16.13 (13.46–18.11) d,e 0.96 70
SLJ + SB 14.21 (2.56) d,e 6.13 (4.20–7.35) c,d 15.19 (13.33–16.5) d,e 0.90 80
SJP 12.45 (1.86) c,e 7.17 (5.59–8.73) c 13.18 (11.59–14.31) e,c 0.92 90

Fig. 5 – Weibull graphs for the treatments with SPJ, SB (a) and CP (b) silanes. CP treatment improved the reliability (slop of
the graph) and the characteristic life (intersection of the graph with the 63.2% probability horizontal line) in reference (REF)
and ␣-Al2 O3 blasted (ALU) zirconia specimens.

the encapsulated spheres immediately after fracture. The SB

4. Discussion spectrum was typical of a prehydrolyzed silane [21,26] demon-
strating a degree of hydrolysis ∼60%, which is in agreement
The grit-blasting treatments selected include all the systems
with previous findings [26]. Upon application to a dry substrate
introduced for chairside zirconia preparation related to bond-
and solvent evaporation, the condensation reaction of silanols
ing and repair procedures. The silane primers used in the
proceeds, catalyzed by environmental humidity. A thin layer is
study belong to two categories; the pure prehydrolyzed (SB)
mandatory to avoid intermolecular condensation rather than
and the prehydrolyzed with phosphate monomers (CP), repre-
bonding with the substrate [27]. Nevertheless, concerns about
senting the vast of the commercially available products. Based
the pot stability and shelf-life of prehydrolyzed silanes have
on the results of the current study, the first part of the hypoth-
been expressed, due to the tendency of silanols to condense
esis should be rejected, since there were differences in the
in the solution overtime [21]. For silanes applied in thin films,
silanol reactivity among CP, SB and SJP. The second part, relat-
pH 4 is considered as the best to minimize condensation reac-
ing to grit-blasting effects, should be accepted only for SLJ, SJP
tions during storage [28]. In the aged SB sample (SBA), the
(Sa, Sz) and SLJ, COJ, SJP (Sdr and Vm). The third part, relating
small hydroxyl peak, the absence of methoxy peaks and the
to bond strength, should be rejected for ALU as compared to
strong siloxane peaks, imply that silanol groups have reacted
with COJ and SLJ (both silanes), and for SJP as compared to to
forming siloxanes. Evidence of such a reaction has been found
COJ-CP and SLJ-CP.
also in CP, which implies that the silanol component of the
The transmission FTIR study was performed on Ge win-
primer has been deactivated to a great extend. The incompat-
dows to avoid interferences of the acidic silane solutions with
ibility between silanes and dental monomers with hydroxyl
the salts of traditional windows (KBr, NaCl, etc.). The ATR study
groups, due to formation of oligomeric silsesquioxanes or silyl
was employed for direct analysis of the silane released from

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(2017), https://doi.org/10.1016/j.dental.2017.11.006
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Fig. 6 – Microscopic images of debonded zirconia surfaces. Adhesive failures from polished (a) and grit-blasted (b) zirconia
(10×, bar = 500 ␮m), mixed failures from grit-blasted zirconia (c–e, 100×, bar = 100 ␮m) and adhesive failure from polished
zirconia (f, 100×, bar = 100 ␮m).

ethers, has already been documented [14]. The presence of
the reactive 10-MDP in the same vial with the MPTMS, may
lead to formation of Si–O–P intermediates, which, however,
are hydrolyzable [29]. Nevertheless, it has been postulated that
the presence of silanols impair the strength of 10-MDP with
zirconia [30].
In SJP, porous silica elongated spheres with ∼30 ␮m wall
thickness are included, which are filled with MPTMS, during
the manufacturing process. These are sealed by the superfi-
cial MPTMS condensates induced by environmental humidity
[19]. The encapsulated silanols are in a polymerized state as
confirmed by the ATR analysis. The conditions of silanization
with encapsulated silane during grit-blasting are completely
different, due to the high temperatures created locally during
the impaction of the airborne particles. These temperatures
may lead to rapid removal of loosely H-bound water from the
surface, encapsulated siloxane depolymerization and estab-
lishment of new bonds between reformed residual silanol
groups of siloxane chains with the strongly H-bound water of
silica and alumina particles. Reactions of this type may apply,
since it has been shown that SJP treatment created a more
hydrophobic surface on a grit-blasted Co–Cr alloy than sil-
ica/alumina powders, establishing thus a more energetically
compatible surface for hydrophobic resin composites [17].
The COJ, SLJ and SJP powders, except from crystalline
␣-Al2 O3 contain 30 ␮m silica/alumina particles, mainly pro-
duced by sol–gel precipitation of tetraethyl orthosilicate on
alumina particles [19]. There are differences in the silica to
alumina ratio between these powders. The Si/Al atomic ratios,
as previously calculated by EDX analyses, were: 0.13 (COJ),
0.03 (SLJ) and 0.06 (SJP) [17]. These differences may explain
the lowest amplitude roughness values of COJ in comparison
with the alumina-rich grit-blasting treatments (ALU, SLJ, SJP),
which complies with previous findings [31]. The amplitude
parameters Ra, Rz were found most sensitive in discriminating
the grit-blasting effects on zirconia roughness, since the sta-

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tistical ranking included three homogeneous groups, instead
of two for the hybrid parameter Sdr.
In the present study the air-blasting period was reduced
to 5 s, from the 15 s indicated by the manufacturers, since
the bonding area was small. All the grit-blasting treatments
induced phase transformation, as documented from the char-
acteristic m-phase peaks. The highest amount was found after
alumina grit-blasting which is in agreement with previous
findings [32]. The greater particle size and hardness of pure
␣-Al2 O3 treatment may explain the more abrasive capacity of
the treatment and the greater extent of t-phase transforma-
tion. The significantly higher statistical correlation between
the Sa,Sz parameters and Vm, rather than the hybrid param-
eter Sdr, indicates that amplitude deviations more precisely
define the effect of air-abrasion than a hybrid parameter with
more sensitivity to the surface slopes.
The possible contribution of this phase transformation to
the bond strength has not been investigated. It has been stated
that the transformed region extending to a depth of ∼10 ␮m
[7], strengthens zirconia by the development of residual com-
pressive stresses at the subsurface zone. However, this might
be outbalanced by the m-phase which is weaker, with much
lower hardness than the t-phase [33], prone to further desta-
bilization by environmental factors and possesses structural
discontinuities.
The composite bond strength values on polished zirconia
surfaces have been used as negative controls, to evaluate the
bonding capacity of the two types of silanes (CP and SB) on zir-
conia, without mechanical retention. These treatments along
with ALU-SB showed the least reliability (ˇ-parameter) and
characteristic life (-parameter). A major reason for the low
effectiveness of MPTMS is the limited surface hydroxylation
of zirconia to promote siloxane interfacial bonding [34]. The
significantly higher SBS of CP on polished zirconia implies a
main effect of 10-MDP rather than a synergistic effect with
MPTMS. This is in agreement with the polymerized nature of
CP silanols, as documented by the FTIR study. Despite the fact
that the aging conditions included thermal-cycling in water,
the low bond strength of SB treatment did not show prema-
ture failures on polished specimens, which gives a credit to
the hydrolytic stability of silanol bonding in water [21].
Treatments with ALU, COJ, SLJ (including both silanes) and
SJP showed higher SBS from the controls, highlighting the role
of micromechanical retention in bonding, regardless of the
silane type used. The increased surface area for bonding (Sdr)
and the increased amplitude parameter values (Sa,Sz), cre-
ate a more retentive surface for the resin composite, which
anchors strongly on the substrate assisted by the rheological
characteristics and polymerization shrinkage of the flowable
consistency. From these treatments, statistically significant
differences were found only between ALU and the group of
COJ, SLJ, independently of the silane type used (CP or SB),
which is in agreement with previous findings [35]. The lower
SBS strength of ALU-SB treatment should be attributed to the
limited reactivity of MPTMS silanols to the surface located
hydroxyl groups of alumina (Al–OH) in comparison with Si–OH
groups [36], and the minimal reactivity to the −OH deficient
zirconia surface [34]. The higher strength of ALU-CP over
ALU-SB is explained by the increased reactivity of the 10-MDP
phosphate groups towards the more basic nature of the hydra-
Please cite this article in press as: Pilo R, et al. Effect of tribochemical treatments and silane reactivity on resin bonding to zirconia. Dent Mater
(2017), https://doi.org/10.1016/j.dental.2017.11.006
9
tion layer of alumina (Al–OH) forming stable Al–O–P bonds [29]
and the documented capacity of the phosphate monomers to
bond with zirconia [37,38]. The statistically insignificant differ-
ences of COJ and SLJ with the two silanes, may have a twofold
explanation: first, for the SB treatment, with a high yield of
reactive silanols, more efficient chemical bonding is expected
after COJ, since the blasting powder has ∼4.5 times more silica
than SLJ, and may provide more silica-rich domains on hard
materials like zirconia. This may be counterbalanced by the
higher extend of micromechanical retention expected after
SLJ treatment, which creates a rougher substrate due to the
increased power content in highly abrading alumina. Second,
for the CP treatment, the reduced silanol yield in CP may be
counterbalanced by the presence of the reactive phosphates in
10-MDP, which may readily interact with alumina implanted
particles, the free zirconia surface and possibly with silica par-
ticles via the surface hydrated silica groups (Si–OH). However,
because of the acidity of the Si–OH groups, the Si–O–P adduct
is unstable [29]. Based on the Weibull analysis, the COJ-CP
treatment showed the highest ˇ-value, although with no sta-
tistically significant differences from COJ-SB, SLJ, ALU-CP, and
the greatest -value between COJ and SLJ treatments treated
with the two silanes. This enlightens the role of 10-MDP in the
bonding mechanism.
After SJP treatment, the surface left was primed with
polymerized silanols. The treatment showed high reliability,
ranked second after COJ-CP. This may be associated with the
simultaneous grit-blasting and silanization procedure, which
minimizes the variations in silane film thickness after manual
application. SJP demonstrated significantly lower character-
istic life from COJ-CP, possibly attributed to the higher Si/Al
ratio of COJ powder and the 10-MDP content of CP. Although
no statistically significant differences were found between
SJP, COJ-SB and SLJ (both silanes) in characteristic life, SJP
was ranked last within this group, which may pinpoint the
role of polymerized silanols in the tribochemical process.
The fact that a statistically significant correlation was found
only between Sdr and MPTMS silanated surfaces (SB and SJP)
implies that the nature of interfacial bonding is more depen-
dent on the developed area due to surface texture, than the
MPTMS/10-MDP treatments.
The reactivity of polymerized silanols towards silica mod-
ified surfaces is a matter of concern, since many new
multicomponent adhesives and primers contain silanols,
which may exist in a polymerized state. It has been shown that
surficial siloxanes formed on amorphous silica films exhibit
interconversion to silanols at room temperature dependent
on the pH and hydration state [39]. Also, it has been postu-
lated that an ionic nature prevails the bonding mechanism
of silanols with inorganic materials, which is highly based
on equilibrium constants [40]. This provides the basis for the
reversible hydrolytic bonding mechanism of silanes by for-
mation and rapture of siloxane bonds [28]. Experimentally it
has been shown that Si–O–CH3 groups are regenerated after
extended periods of silanol hydrolysis, proving the cycling
nature of the process [22]. It is unclear, though, what hap-
pens when a polymerized silane, with limited or no silanol
reactivity at all, is used for a momentary treatment of a
substrate that is immediately restored with a resinous mate-
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rial copolymerizing with the silane, as in dental practice. Most
of the dental silanes currently used, are based on MPTMS kept
in a low pH alcoholic environment, either pure prehydrolyzed
or in mixtures with other reactive monomers of primers and
adhesives. These conditions do not favor depolymerization of
any siloxanes formed, since the latter is activated at pH 4–8
[41]. Considering that several MPTMS containing primers and
adhesives used for ceramic bonding and repair purposes have
a pH <3, a limited contribution of the silane component to
bonding is anticipated.
The results of the present study reveal the problem of
silane reactivity, not only in universal adhesives, as previously
documented [15], but also in silane primers with phosphate
monomers, like 10-MDP and in tribochemical systems with
encapsulated silane. The role of the deactivated silanols in
the bonding mechanism is unclear. This is important since
deactivation not only diminishes the bonding potential with
the substrate, but also may hinder formation of horizontal
intermolecular siloxane crosslinks along the interface, which
stabilizes the interfacial structure by covalent bonds. Such a
mechanism is missing from 10-MDP, where only H-bonding
intermolecular interactions may occur [38]. Grit-blasting of
zirconia with increased Si/Al ratio powder (COJ) and appli-
cation of a MPTMS/10-MDP silane (CP) was found to be the
strongest treatment with highest reliability and characteristic
life, regardless the lower Sa, Sz of the substrate in comparison
with the other treatments. These findings highlight the impor-
tant role of 10-MDP in bonding on a rough substrate, with a low
monoclinic content, induced by the grit-blasting procedure.
Further research should focus on the stability of these
silanes and their performance in the presence of compounds
capable of deactivating silanols, in order to understand the
reaction mechanism of multicomponent systems and, if
required, to modify the clinical steps accordingly.
Acknowledgements
Part of the study was funded by Danville Materials Inc., S.
Ramon, CA, USA.
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