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JPOR 411 No. of Pages 9

journal of prosthodontic research xxx (2017) xxx–xxx

Contents lists available at ScienceDirect

Journal of Prosthodontic Research

journal homepage: www.elsevier.com/locate/jpor

Original article

Self-etching ceramic primer versus hydrofluoric acid etching: Etching

efficacy and bonding performance
Hatem M. El-Damanhourya,b,* , Maria D. Gaintantzopoulouc
a
Department of Preventive and Restorative Dentistry, College of Dental Medicine, University of Sharjah, Sharjah, United Arab Emirates
b
Department of Operative Dentistry, Faculty of Dentistry, Suez Canal University, Ismailia, Egypt
c
Department of Biomaterials, School of Dentistry, National and Kapodistrian 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: Aim: This study assessed the effect of pretreatment of hybrid and glass ceramics using a self-etching
Received 9 November 2016 primer on the shear bond strength (SBS) and surface topography, in comparison to pretreatment with
Received in revised form 31 May 2017 hydrofluoric acid and silane.
Accepted 5 June 2017
Methods: 40 rectangular discs from each ceramic material (IPS e.max CAD;EM, Vita Mark II;VM, Vita
Available online xxx
Enamic;VE), were equally divided (n = 10) and assigned to one of four surface pretreatment methods;
etching with 4.8% hydrofluoric acid followed by Monobond plus (HFMP), Monobond etch & prime (Ivoclar
Keywords:
Vivadent) (MEP), No treatment (NT) as negative control and Monobond plus (Ivoclar Vivadent) with no
Adhesion
CAD/CAM ceramics
etching (MP) as positive control. SBS of resin cement (Multilink-N, Ivoclar Vivadent) to ceramic surfaces
Hybrid ceramics was tested following a standard protocol. Surface roughness was evaluated using an Atomic force
Bond strength microscope (AFM). Surface topography and elemental analysis were analyzed using SEM/EDX. Data were
Surface treatment analyzed with two-way analysis of variance (ANOVA) and post-hoc Bonferroni test at a significance level
Self-etching ceramic primer of a=0.05.
Results: Pretreatment with HFMP resulted in higher SBS and increased surface roughness in comparison
to MEP and MP. Regardless the method of surface pretreatment, the mean SBS values of EM ceramic was
significantly higher (p < 0.05) than those recorded for VM and VE, except when VE was treated with MEP,
where the difference was statistically insignificant. Traces of fluoride ion were detected when MEP was
used with VE and VM.
Conclusion: Under limited conditions, using MEP resulted in comparable SBS results to HFMP; meanwhile
HFMP remains the gold standard for pretreatment of glass ceramics for resin-luting cementation.
© 2017 Japan Prosthodontic Society. Published by Elsevier Ltd. All rights reserved.

1. Introduction leucite-reinforced glass ceramics, lithium disilicate glass ceramics,

Dental CAD/CAM has rapidly gained popularity among dental
practitioners during the last decade. CAD/CAM generated dental
restorations that may have several advantages over conventionally
fabricated restorations; the ability to deliver the restoration in a
single visit seems to be the most important advantage [1]. Other
advantages of these systems include the uniform material quality,
better physic-mechanical properties, the ability to reproduce the
restorations and a significant reduction in production costs and
time [2,3]. A wide range of CAD/CAM blocks are available for
esthetic dental restorations including feldspathic glass ceramics,
* Corresponding author at: College of Dental Medicine, University of sharjah,
room # m28-129, P.O. Box: 27272, Sharjah, United Arab Emirates.
Fax: +971 6 558 5641.
E-mail addresses: hdamanhoury@sharjah.ac.ae, damanhoury414@yahoo.com
(H.M. El-Damanhoury).
aluminum-oxide and yttrium tetragonal zirconia polycrystals,
composite resins [4] and hybrid ceramics [5]. The difference in the
chemical nature of these materials leads to variations in their
mechanical properties and their bonding performance to different
luting cements [6].
The success of all-ceramic restorations leans on establishing a
strong bond between the ceramic material and the tooth structure,
especially for non-retentive restorations such as veneers and
endocrowns [7]. This bond depends on understanding the internal
structure of the restorative material and properly selecting the
suitable surface treatment and resin adhesive. The main idea of
ceramic pretreatment is inducing surface micro-roughness and
then placement of a ceramic primer that facilitates the bonding to a
more hydrophobic luting cement [8]. The method of surface
pretreatment of ceramics before cementation plays a very
important role in the success and longevity of ceramic restorations
[9].

http://dx.doi.org/10.1016/j.jpor.2017.06.002
1883-1958/ © 2017 Japan Prosthodontic Society. Published by Elsevier Ltd. All rights reserved.

Please cite this article in press as: H.M. El-Damanhoury, M.D. Gaintantzopoulou, Self-etching ceramic primer versus hydrofluoric acid etching:
Etching efficacy and bonding performance, J Prosthodont Res (2017), http://dx.doi.org/10.1016/j.jpor.2017.06.002
G Model
JPOR 411 No. of Pages 9
2 H.M. El-Damanhoury, M.D. Gaintantzopoulou / journal of prosthodontic research xxx (2017) xxx–xxx
The protocol of pretreatment varies from one material to the
other; while feldspathic glass ceramics and leucite-reinforced
glass ceramics require 60 s of 5–10% hydrofluoric acid etching,
lithium disilicate glass ceramics require 20 s only. Aluminum-
oxide, zirconia based and composite resin are commonly treated
with airborne-particle abrasion before adhesive cementation [10].
The novel hybrid resin-ceramics vary from one brand to the other,
as some require hydrofluoric acid etching and others require
micro-abrasion according to their composition and method of
manufacturing [11,12].
The most common method for pretreatment of glass ceramics is
etching with hydrofluoric acid followed by a primer containing
organo-silane, where the acid reacts with the glass matrix that
contains silica and forms hexafluorosilicates. This glass matrix is
selectively removed and the crystalline structure is exposed. As a
result, the surface of the ceramic becomes rough, which is
expected for micromechanical retention on the ceramic surface
[13]. This roughly etched surface also helps to provide more surface
energy prior to combining with the silane solution [14].
Alternative methods like, micro-abrasion or air abrasion
followed by tribochemical coating of the microblasted surface
modified silica, laser etching and non-thermal plasma treatment
have been investigated and promoted for pretreatment of metal
ceramics [15,16].
A self-etching ceramic primer (Monobond Etch & Prime, Ivoclar
Vivadent, Schaan, Liechtenstein) has been introduced to the
market as a single-component ceramic primer, alternative to
hydrofluoric acid etching/silane coupling agent routine treatment.
The novel material aims to eliminate the toxic potential of the
hydrofluoric acid, reduce the time required and the technique
sensitivity of etching ceramic with the conventional methods.
Other than the internal data of the manufacturer, there are very
few published research work about the newly introduced self-
etching ceramic primer and the effect of its use on the bonding
efficiency to different types of ceramics. Additionally, very little
information is available in the literature about the bonding
efficiency of the novel hybrid ceramics to luting resin cements [17].
Therefore, the aim of this study was to assess the effect of using
self-etching ceramic primer on the shear bond strength and
surface topography of different hybrid and glass ceramics, in
comparison to the conventional technique of hydrofluoric acid
etching followed by silane application. The null hypothesis was
that pretreatment technique will have no significant influence on
the surface topography or bonding performance of the CAD/CAM
esthetic materials tested to the resin luting cements.
2. Materials and methods
The materials tested and their respective compositions are
displayed in Table 1.
2.1. Specimen Preparation
CAD/CAM blocks from each tested material were used and each
block was cut transversely using a low-speed diamond wheel saw
(Isomet 1000, Buehler, Lake Bluff, IL) under water irrigation to
obtain rectangular discs, 2 mm in thickness. After ultrasonic
cleaning in a distilled water bath for 15 min, IPS e.max CAD (EM)
specimens were fired following the crystallization program
recommended by the manufacturer. All specimens were posi-
tioned in polyvinyl chloride (PVC) plastic rings and embedded in
epoxy resin (Fastray, Harry J. Bosworth Co., Skokie, IL, USA) and wet
polished with up to 600- grit silicon carbide paper discs in a semi-
automatic polisher/grinder (MetaServ 250, Buehler, Lake Bluff, IL)
for one minute. After polishing, the samples were ultrasonically
cleaned in a bath of 80% ethyl alcohol for 15 min and dried to
Please cite this article in press as: H.M. El-Damanhoury, M.D. Gaintantzopoulou, Self-etching ceramic primer versus hydrofluoric acid etching:
Etching efficacy and bonding performance, J Prosthodont Res (2017), http://dx.doi.org/10.1016/j.jpor.2017.06.002
remove surface debris. 40 discs from each material were randomly
selected and equally divided into 4 groups (n = 10) and assigned to
one of the combinations of surface etching and priming methods
below:
1. No treatment (NT). This group was used as negative control.
2. Monobond Plus (Ivoclar Vivadent) with no etching. The ceramic
primer was applied with a microbrush and allowed to react for
60 s. Subsequently, the excess was dispersed with a strong
stream of air to ensure the solvent evaporation (MP). This group
was used as positive control.
3. Etching with 4.8% hydrofluoric acid for 60 s for VE and VM and
20 s only for EM. The acid was thoroughly rinsed off with a
strong jet of air/water spray for 20 s and dried with oil-free air
for 10 s, and application of Monobond Plus (Ivoclar Vivadent)
following the same procedures mentioned above (HFMP).
4. Monobond Etch & Prime (Ivoclar Vivadent), a Self-etching glass-
ceramic primer was applied on the adhesive surface using a
microbrush, agitated into the surface for 20 s then allowed to
react for another 40 s, thoroughly rinsed off with a strong jet
of air/water spray for 20 s and dried with oil-free air for 10 s
(MEP).
A special metal clip was used to fix a Teflon mold (Ultradent Inc,
South Jordan, UT), with a cylindrical cavity of 2 mm width and
2 mm depth, to the pre-treated ceramic surface. Dual-cure resin
cement (Multilink-N Automix, Ivoclar Vivadent) base and catalyst
pastes were mixed using an auto-mixing tip and injected using an
ultra-fine tip 1 mm in diameter into the mold. The excess cement
was removed using a micro-brush and the luting resin was
polymerized using LED light curing unit (Bluephase, Ivoclar
Vivadent) operating at 1200 mW/cm2 in standard mode for 20 s
to fabricate cylindrical luting resin rods. The intensity of the curing
unit was checked every 10 samples. The mold was disassembled
and resultant rods were examined for any composite flashes, which
were removed with a sharp blade. Each specimen was examined
using magnifying loupes to identify specimens containing possible
defects (bubbles or cracks in resin composite or flow of resin
cement beyond the limits of the bonding area).
2.2. Shear Bond Strength Testing (SBS)
The samples were stored in distilled water at 37  C for 24 h and
thermos-cycled (TC) between 5 and 55  C for 5000 cycles with 30-s
dwell times before being tested for SBS using a table-top Shear
Bond Strength Tester (Bisco Inc., Schaumburg, IL, USA). The
semicircular metal attachment of the machine applied shear forces
at the resin-ceramic interface, running at a crosshead speed of
1.0 mm/min, till complete failure of the resin composite and
debonding. The force required for failure was recorded in Newton
and was divided by the surface area (mm2) to calculate the SBS in
MPa.
The debonded specimens were examined under a stereomicro-
scope to determine the failure mode that was classified as adhesive
between resin cement and ceramic (A), mixed (M), cohesive in
resin cement (CR), or cohesive in ceramic (CC).
2.3. Surface roughness measurement
Nine ceramic discs for each material tested were prepared for
surface roughness measurement and were divided into three
subgroups; in the first subgroup specimen were left untreated and
was considered as control, the second subgroup was treated with
hydrofluoric acid with no application of silane, the last subgroup
was treated with MEP following the same protocol mentioned
previously. All specimens were washed with double distilled water,
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H.M. El-Damanhoury, M.D. Gaintantzopoulou / journal of prosthodontic research xxx (2017) xxx–xxx 3

Table 1
Materials used, codes, compositions and lot numbers.

Material Code Manufacturer Composition Lot #

Vita Enamic
IPS e.max CAD
Vita Blocs Mark II
IPS ceramic etching gel
Monobond Plus, glass-ceramic
primer
Monobond Etch & Prime, self-
etching glass-ceramic primer
Multilink automix dual-cure
luting resin cement
VE Vita Zahnfabrik H. Rauter GmbH, Bis-GMA, UDMA, Bis-EMA, TEGDMA, SiO2 (20 nm), ZrO2 (4–11 nm), 86 wt% 38630
Bad Säckingen, Germany aggregated ZrO2/SiO2 cluster (SiO2 = 20 nm, ZrO2 = 4–11 nm)
EM Ivoclar Vivadent, Schaan, Lithium disilicate glass ceramic U26002
Liechtenstein
VM Vita Zahnfabrik H. Rauter GmbH, Feldspar ceramic 7197
Bad Säckingen, Germany
HF Ivoclar Vivadent, Schaan, 4.8% hydrofluoric acid U01182
Liechtenstein
MP Ivoclar Vivadent, Schaan, Ethanol, 3-trimethoxysilylpropyl methacrylate, 10-MDP, disulfide acrylate U25466
Liechtenstein
MEP Ivoclar Vivadent, Schaan, Tetrabutyl ammonium dihydrogen trifluoride, methacrylated phosphoric acid U12508
Liechtenstein ester, trimethoxysilylpropyl methacrylate, alcohol, water
– Ivoclar Vivadent, Schaan, Dimethacrylates, HEMA, t-amine, silicon dioxide filler, ytterbium trifluoride, U02278
Liechtenstein catalysts, stabilizers, pigments, dibenzoyl peroxide

Bis-GMA (2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy)phenyl]propane), UDMA (urethane dimethacrylate), Bis-EMA (2,2-Bis[4-methacryloxypolyethoxyphenyl)pro-

pane]), TEGDMA (triethylene glycol dimethacrylate), 10-MDP(10-methacryloyloxydecyl dihydrogen phosphate), HEMA (2-hydroxyethyl methacrylate).

Table 2
Mean shear bond strength values (MPa  standard deviation [SD]) and failure mode (%) of the tested ceramic materials with no treatment (NT), pretreatment with Monobond
Plus only (MP), hydrofluoric acid and Monobond Plus (HFMP) or Monobond Etch & Prime (MEP).

Surface pretreatment Mean SBS  SD Failure mode %

IPS e.max CAD (EM) Vita Blocs Mark II (VM) Vita Enamic (VE) Adhesive (A), mixed (M), cohesive in resin
cement (CR), or cohesive in ceramic (CC).
NT 1.62  2.0a,A 1.82  3.18a,A 3.43  4.06a,A EM: A = 100; M = 0; CR = 0; CC = 0
VM: A = 100; M = 0; CR = 5; CC = 0
VE: A = 100; M = 0; CR = 0; CC = 0

MP 27.19  5.54b,A 17.22  6.77b,B 14.69  6.78b,B EM: A = 30; M = 70; CR = 0; CC = 0

VM: A = 25; M = 10; CR = 5; CC = 60
VE: A = 45; M = 55; CR = 0; CC = 0

HFMP 37.60  10.68c,A 27.97  6.38c,B 21.33  5.03bc,B EM: A = 20; M = 50; CR = 30; CC = 0
VM: A = 20; M = 0; CR = 0; CC = 80
VE: A = 0; M = 0; CR = 0; CC = 100

MEP 28.06  10.61b,A 14.74  4.81b,B 25.96  11.58c,A EM: A = 20; M = 70; CR = 0; CC = 0
VM: A = 10; M = 20; CR = 0; CC = 70
VE: A = 0; M = 0; CR = 0; CC = 100

Within a column, same lower case superscript letters show mean values with no statistically significant difference (p > 0.05).
Within a row, same upper case superscript letters show mean values with no statistically significant difference (p > 0.05).

cleaned in an ultrasonic water bath for 3 min and dried with oil-
free air stream for 20 s.
Specimens were evaluated under an Atomic force microscope
(AFM), under a non-contact mode using an AFM cantilever with
magneto-resistive sensors integrated in its tip (Flex-Axiom,
Nanosurf AG, Liestal, Switzerland). Four measurements were
collected from each pre-treated ceramic disc using a standardized
rectangular spot (25  25 mm). Changes in vertical position provide
the height of the images, were registered as bright and dark
regions. The tip-specimens distance was maintained stable
through constant oscillation amplitude (set-point amplitude).
The AFM micrographs were analyzed using a scanning probe
microscopy data analysis software (C3000 control software,
version 3.7.2.8, Nanosurf AG, Liestal, Switzerland). The average
surface roughness (Ra), Valley Depth (lowest value—Rv) and Peak
Height (highest value—Rp) of the pre-treated ceramics, expressing
it as a numeric value in nanometers.
7620 Mini Sputter Coater, Hatfield, PA). The effect of each
treatment protocol on the surface topography of each sample
was examined under 2000 magnification, using scanning
electron microscope (VEGA3 XM—TESCAN, Kohoutovice, Czech
Republic) under operating at 20 kV acceleration voltage and 15 mm
working distance.
Elemental analysis of the untreated and treated surfaces using
SEM-coupled energy dispersive X-ray microanalyser (EDX—TES-
CAN, Kohoutovice, Czech Republic) operating at a take-off angle of
35 with both map and point modes at the same operating voltage.
Each ceramic surface was analyzed at five different fixed locations,
one at the center of the specimen and one at each corner of the
specimen surface. The average values of the five readings
composition were calculated. Compositional element concentra-
tions above 1.0 wt% were recorded.
2.5. Statistical analysis

2.4. Surface topography examination and elemental analysis
Representative specimens of each group were randomly
selected for surface topography examination. After treatment, all
specimens were air dried for 60 s, and then mounted on aluminum
stubs and sputter coated with 100 Å Gold-Palladium (EMS
Statistical analysis of the results for the SBS was performed by
two-way analysis of variance (ANOVA) and post hoc Bonferroni test
as a function of CAD–CAM material and surface treatment
technique. A 95% confidence level was applied for all the statistical
tests (a = 0.05). The statistical analysis was performed by the
software SPSS (Version 15.0, SPSS Inc., Chicago, IL, USA).

Please cite this article in press as: H.M. El-Damanhoury, M.D. Gaintantzopoulou, Self-etching ceramic primer versus hydrofluoric acid etching:
Etching efficacy and bonding performance, J Prosthodont Res (2017), http://dx.doi.org/10.1016/j.jpor.2017.06.002
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4 H.M. El-Damanhoury, M.D. Gaintantzopoulou / journal of prosthodontic research xxx (2017) xxx–xxx
Table 3
Mean surface roughness value (Ra), highest peak value (Rp) and lowest valley value
(Rv) of the material tested after no treatment (NT), hydrofluoric acid etching (HF) or
Monobond Etch and Prime (MEP) pre-treatment.
Material Surface pre-treatment Ra (nm) Rp (nm)
IPS e.max CAD (EM) NT 3.94 44.09
HF 134.80 1155.90
MEP 26.05 223.70
Vita Mark II (VM) NT 29.96 209.22
HF 575.37 2399.70
MEP 235.78 641.55
Vita Enamic (VE) NT 74.50 377.45
HF 152.74 676.20
MEP 161.38 866.26
3. Results
The mean SBS values and fracture analyses are summarized in
Table 2. During SBS measurements of all groups, no pre-testing
failures occurred. Pretreatment with HFPM resulted in significant-
ly higher bond strength (P < 0.05) in all groups except for VE,
where there was no significant difference.
Regardless the method of surface treatment, the mean SBS
values of EM ceramic were significantly higher (p < 0.05) than
those recorded for VM and VE, except when VE was treated with
MEP, where the difference was statistically insignificant.
Failure mode was also influenced by the type of surface
treatment and type of material. For all tested ceramics, the highest
percentage of adhesive failure was associated with NT followed by
pretreatment with MP only, and this percentage was reduced when
HFMP and MEP were used. High percentage of cohesive failure in
ceramic was observed when VM and VE were treated by HFMP and
MEP, meanwhile, most of the failures of EM groups were of mixed
type, regardless the method of surface pretreatment.
The AFM surface roughness test results are listed in Table 3 and
presented graphically in Fig. 1. The surface etching with hydro-
fluoric acid etching induced higher mean surface roughness values
(Ra) for all tested materials in comparison to treatment with MEP,
which induced less roughness in all the tested materials
respectively. EM was the least affected, while VM was the most
affected by the surface treatment methods manifested as
significantly increased (Ra).
Representative SEM micrographs of non-treated and pretreated
EM, VM and VE surfaces are presented in Figs. 2–4 respectively.
Treatment with hydrofluoric acid resulted in increased surface
roughness with irregularities and pores on the treated surfaces of
all materials tested. shallower micro-porosities were evident when
pre-treating EM with HFMP or MEP in comparison to VM or VE.
Etching with hydrofluoric acid resulted in honeycomb-like porous
surfaces, consisting of gross irregularities and pores. MEP
generated a less pronounced etching pattern than hydrofluoric
acid in all cases, this etching effect of MEP was the least noticed on
the surface of lithium disilicate (EM).
Elemental analysis with SEM/EDX of surface composition (wt%)
of the tested ceramic materials is presented in Table 4. The analysis
revealed the presence of fluorine residue (2.4 and 1.5 wt% for VE
and VM respectively) after treatment with MEP. No fluorine traces
were found after treatment when using HFMP in any of the tested
materials.
The carbon contents were significantly affected by the method of
treatment; pretreatment with HFMP resulted in higher Carbon
contents in all the tested materials (23.5, 48.4 and 18.7 wt% for EM, VE
and VM respectively), meanwhile, MEP exhibited lower carbon
contents when used with EM and VE (5.8 and 33.7 wt% respectively)
and comparable results when used with VM (18.6 wt%).
Please cite this article in press as: H.M. El-Damanhoury, M.D. Gaintantzopoulou, Self-etching ceramic primer versus hydrofluoric acid etching:
Etching efficacy and bonding performance, J Prosthodont Res (2017), http://dx.doi.org/10.1016/j.jpor.2017.06.002
4. Discussion
This study was conducted to evaluate the effect of surface
pretreatment of CAD/CAM glass and hybrid ceramics with hydro-
Rv (nm)
fluoric acid etching versus self-etching ceramic primer. The
62.93 bonding efficacy was evaluated using shear bond strength test
632.65
and the effect of pretreatment on different ceramic substrates was
291.96
evaluated by AFM and SEM topographical analysis. Main surface
820.34 elemental analysis was done with energy dispersive x-ray. It was of
2710.6 special interest to test whether simplification of the pretreatment
1211.8 process using the self-etching ceramic primer would give
comparable results to the recommended hydrofluoric acid/silane
826.78
793.21 pretreatment procedures. Besides the determination of the bond
675.70 strength values, the failure modes were also examined in this study
to get further information about the probable success or failure of a
pretreatment method under clinical conditions. In general, a
cohesive failure mode within the ceramics indicates that the
adhesion of the resin material to the ceramic is higher than the
cohesive shear strength of the ceramic.
The results of the current study revealed that the effect of
surface treatments on the SBS of the CAD/CAM materials tested to
resin material was material dependent. Therefore, the null
hypothesis that pretreatment technique would have no significant
influence on the surface topography or bonding performance of the
tested CAD/CAM materials to the resin luting cement should be
rejected.
Adhesion has been well documented to play a role in the
strengthening of esthetic adhesive indirect restorations [18]. Weak
bond strength between restorations and resin cement could lead to
a non-homogeneous distribution of forces that could result in
cohesive failure of the resin cement leading to weakening of the
unsupported restoration under the occlusal forces [19].
The individual mechanical properties of the materials involved
(ceramic restoration, resin cement, bonding agent, tooth structure)
and the surface optimization of the bonding substrates are the
main factors which interact in the process of establishing a strong
bond between the restoration and the tooth structure [20]. To
establish a strong bond appropriate treatment of the tooth
structure and the intaglio surface of the restoration is crucial.
The AFM analysis revealed that all surface treatments increased
the roughness of surface compared with the control groups as
shown in Fig. 1 and Table 3. These results were also confirmed by
the SEM topographical analysis (Figs. 2–4). The effect of treatment
with hydrofluoric acid was significantly clear in the surface
roughness/topographic analysis and was signified as increased
surface roughness with irregularities and pores on the treated
surfaces regardless the material tested.
The SBS results revealed that etching with HFMP resulted in
improved adhesion in comparison to pretreatment with MP only or
MEP. The increase of bond strength values using an etching step
with HFMP can be attributed to the increased surface area and
higher surface roughness that is caused by this method of
pretreatment.
Hydrofluoric acid etching of feldspathic and lithium disilicate
ceramics, followed by priming with a silane coupling agent has
been considered as the golden standard for the treatment of the
silica-based ceramics [10]. Etching with hydrofluoric acid leads to
preferential dissolution of one of the glassy phases of porcelain to
create an appropriate microstructure for bonding. Meanwhile, the
application of a silane coupling agent to the pretreated ceramic
surface provides a chemical covalent hydrogen bond that is a major
factor in creating a sufficient resin bond to silica-based ceramics.
This treatment protocol offers the opportunity of improved
micromechanical retention and/or increased physical interactions
and wettability with the luting resin material, which is generally
hydrophobic in nature [12].
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H.M. El-Damanhoury, M.D. Gaintantzopoulou / journal of prosthodontic research xxx (2017) xxx–xxx 5

Fig. 1. AFM Micrographs of the materials tested after no treatment (NT), hydrofluoric acid etching/Monobond Plus (HFMP) or self-etching ceramic primer Monobond Etch and
Prime (MEP) pretreatment.

The decreased roughness of the lithium disilicate ceramic (EM)
is attributed to hydrofluoric acid dissolving of the glassy phase,
leaving behind an active surface, rich in silica due to the
preservation of lithium disilicate crystals. In the current study,
20 s of 5% hydrofluoric acid etching of EM was done, following the
recommendations of the manufacturer. Several articles studied the
etching protocol of lithium disilicate, and extending the etching
time was found to negatively affect the flexure strength of the
material [21], and increasing the etching time or concentration did
not significantly enhanced the bond strength [10].
The bond strengths of all EM groups were significantly higher
than VE and VM, except when VE was treated with MEP, where the
difference was not statistically significant. These results are
consistent with several previous studies [22–24]. Although the
hydrofluoric acid etching, as seen in AFM analysis (Fig. 1 and
Table 3) and the SEM analysis (Fig. 2), was less significant in this
material in contrast to feldspathic ceramic (VM) and Hybrid
ceramic (VE). Therefore, the superior bonding performance of resin
luting materials to lithium disilicate should be mainly attributed to
better chemical interaction between the hydrophobic resin and the
EM surface rather than the mechanical interlocking to the rough
surface.
The results revealed a strong association between the failure
mode and the type of surface treatment and type of material. The
highest percentage of adhesive failure was associated with
pretreatment with MP only, which can be easily explained due
to the absence of micro-porosities created by etching the ceramic
surface. A high percentage of cohesive failure in ceramic was
observed when VM and VE were treated by HFMP and MEP, in
comparison to EM groups, where most of the failures were of
mixed type. These findings could be attributed to the difference in
the microstructure of EM in comparison to feldspathic glass
ceramics, which led to better bond between resin luting materials
and lithium disilicate in addition to higher intrinsic strength of this
material. The addition of lithium disilicate long crystals result in
greater flexural strength and fracture resistance due to the spatial
configuration of their crystalline grid and resistance to crack
propagation through crystals [25].
Although the ideal treatment procedures of hybrid ceramics
have not been well documented yet, a similar pretreatment
protocol is recommended for hybrid ceramics (also referred to as
Polymer infiltrated Ceramic Network—PICN). The effect of etching
on hybrid ceramics and the reaction between the silane primer and
the etched material is different [17]. The acid etching removes part

Please cite this article in press as: H.M. El-Damanhoury, M.D. Gaintantzopoulou, Self-etching ceramic primer versus hydrofluoric acid etching:
Etching efficacy and bonding performance, J Prosthodont Res (2017), http://dx.doi.org/10.1016/j.jpor.2017.06.002
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Fig. 2. SEM Micrograph of IPS e.max CAD surface after (a) no treatment (NT), (b) application of ceramic primer Monobond Plus (MP), (c) hydrofluoric acid for 20 s followed by
Monobond Plus (HFMP), or (d) application of self-etching ceramic primer Monobond Etch & Prime for 60 s (MEP).

of the glass matrix as well, as it dissolves part of the polymer,
producing microporosities and microchannels. The surface rough-
ness analysis in this study revealed shallow porosities after
pretreatment of VE after hydrofluoric acid etching averaging less
than 1.0 mm deep, other studies reported microporosities up to
10 mm deep [11]. The methoxy groups of silane-containing primer
chemically bonds with both the SiO2 and integrated polymer
components of the PICN, polymerizing with the methacrylate
groups of the resin composite available in the matrix [26].
In the current study, the mode of failure analysis revealed more
cohesive failures in VE than VM when pretreated with HFMP or
MEP, meanwhile there was more adhesive and mixed failure when
treated with MP only. VE was expected to show less cohesive
failure within the material due to the polymer–ceramic associa-
tion, which should significantly decreases the material's brittle-
ness compared to feldspathic porcelain [27], but it seems that the
cohesive strength of the resinous infiltrated ceramic is weaker than
the bond strength to the luting cement.
Monobond Etch & Prime is a newly introduced one-bottle
system combining ammonium polyfluoride and silane without
hydrofluoric acid. Although it is named self-etching ceramic
primer, the applied primer should be rinsed with water. This

Please cite this article in press as: H.M. El-Damanhoury, M.D. Gaintantzopoulou, Self-etching ceramic primer versus hydrofluoric acid etching:
Etching efficacy and bonding performance, J Prosthodont Res (2017), http://dx.doi.org/10.1016/j.jpor.2017.06.002
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H.M. El-Damanhoury, M.D. Gaintantzopoulou / journal of prosthodontic research xxx (2017) xxx–xxx 7

Fig. 3. SEM Micrograph of Vita Mark II after (a) no treatment (NT), (b) application of ceramic primer Monobond Plus (MP), (c) hydrofluoric acid for 60 s followed by Monobond
Plus (HFMP), or (d) application of self-etching ceramic primer Monobond Etch & Prime for 60 s (MEP).

system is introduced to simplifies the bonding procedure by
etching and priming glass-ceramics in a single step, and without
compromising the bonding performance of the ceramic material to
the luting cement [28]. In the present study, MEP groups showed
significantly lower SBS values with EM and VM than those
obtained when treated with HFMP, these findings are in agreement
with the study by Swank et al. [29], who also found that the new
self-etching primer exhibited less bond strength values than
hydrofluoric acid/silane when used for pretreatment of lithium
disilicate. In contrast, Román-Rodríguez et al. [28] also assessed
the bond strength of resin luting cement to lithium disilicate and
reported no statistically significant difference between MEP and
hydrofluoric acid etching. These findings can be attributed to the
difference in pretreatment method, as the later study used an
additional application of ortho-phosphoric acid to eliminates the
micro-precipitates that appear after hydrofluoric acid etching
before silane application.
MEP contains ammonium polyfluoride, which is an acid salt
that is usually used in the etching of glass and related silicates to
achieve a rough pattern for micro-mechanical retention. Ammo-
nium polyfluoride has milder acidity in comparison to hydrofluoric
acid, which is expected to result in weaker etching pattern. The

Please cite this article in press as: H.M. El-Damanhoury, M.D. Gaintantzopoulou, Self-etching ceramic primer versus hydrofluoric acid etching:
Etching efficacy and bonding performance, J Prosthodont Res (2017), http://dx.doi.org/10.1016/j.jpor.2017.06.002
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8 H.M. El-Damanhoury, M.D. Gaintantzopoulou / journal of prosthodontic research xxx (2017) xxx–xxx

Fig. 4. SEM Micrograph of Vita Enamic after (a) No treatment (NT), (b) application of ceramic primer Monobond Plus (MP), (c) hydrofluoric acid for 60 s followed by
Monobond Plus (HFMP) or (d) application of self-etching ceramic primer Monobond Etch & Prime for 60 s (MEP).

AFM surface roughness measurement and SEM micro-topographic
analysis in the current study confirmed this assumption, where
etching with MEP resulted in less roughness and shallower etching
pattern than HFMP in all cases, and this etching effect was least
noticed on the surface of lithium disilicate (EM).
In the meantime, the silane system in MEP (based on
trimethoxypropyl methacrylate) leaves a chemically bonded thin
layer of silane that remains after thorough washing off with water
and drying of the treated surface. Although the mechanism of
action of MEP is not very clear, it was evident by the EDX elemental
analysis that some fluorine residue is present on the surface after
pretreatment with MEP. Considering the accuracy of EDX analysis
and difficulty of determination of the light element contents (e.g. C,
O, and F), the presence of F ions residue can be attributed to the
reaction of the material with the glassy part, producing insoluble
silica–fluoride salts, which remains as residue or deposit on the
surface [30], or due to F being trapped within the silane layer left
on the surface of the restoration of VE and VM. This study used only
one method of post-etching cleaning. Other methods of cleaning,
like cleaning in an ultrasonic bath, may result in different
outcomes [31]. The clinical significance of these F residue is still
unclear and requires further investigation.
One limitation of this study is that the shear bond test method
may underreport actual stress due to uneven stress distribution

Please cite this article in press as: H.M. El-Damanhoury, M.D. Gaintantzopoulou, Self-etching ceramic primer versus hydrofluoric acid etching:
Etching efficacy and bonding performance, J Prosthodont Res (2017), http://dx.doi.org/10.1016/j.jpor.2017.06.002
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H.M. El-Damanhoury, M.D. Gaintantzopoulou / journal of prosthodontic research xxx (2017) xxx–xxx 9

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Please cite this article in press as: H.M. El-Damanhoury, M.D. Gaintantzopoulou, Self-etching ceramic primer versus hydrofluoric acid etching:
Etching efficacy and bonding performance, J Prosthodont Res (2017), http://dx.doi.org/10.1016/j.jpor.2017.06.002