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Resin Bonding to a Feldspar Ceramic After Different lication
te ot

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Ceramic Surface Conditioning Methods: Evaluation ss e n c e fo r

of Contact Angle, Surface pH, and Microtensile Bond

Strength Durability
Regina Amarala/Mutlu Özcanb/Marco Antonio Bottinoc/Luiz Felipe Valandrod

Purpose: To evaluate the surface pH, contact angle and microtensile bond strength (MTBS) of a resin-cement to
feldspathic ceramic after various surface conditioning methods (SC).
Materials and Methods: For pH measurements, 96 glass-ceramic disks were assigned into 12 groups (n = 8):
SC1-pH: No ceramic surface conditioning (control); SC2-pH: hydrofluoric-acid (HF) 9% 1 min; SC3-pH: SC2-
pH+wash/dry; SC4-pH: SC3-pH+silane; SC5-pH: HF 4% 1 min; SC6-pH: SC5-pH+wash/dry; SC7-pH: SC6-pH
+silane; SC8-pH: HF 5% 1 min; SC9-pH: SC8-pH+wash/dry; SC10-pH: SC9-pH+silane; SC11-pH: SC9-pH
+neutralizer+wash/dry+sonic-cleaning; SC12-pH: SC11-pH+silane. For contact angle analysis, 40 disks were
divided into 5 groups (n = 8): SC1-ca: no conditioning; SC2-ca: HF 9%+wash/dry; SC3-ca: HF 4%+wash/dry; SC4-
ca: HF 5%+wash/dry; SC5-ca: HF 5%+neutralizer+wash/dry+ultrasonic-cleaning. To evaluate the MTBS, 40 blocks
were distributed into 4 groups SC (N = 10): SC1-bond: HF 9% 1 min+silane; SC2-bond: HF 4% 1 min+silane;
SC3-bond: HF 5% 1 min+silane; SC4-bond: HF 5% 1 min+neutralizer+wash/dry+ultrasonic cleaning+silane. The
resin cement was applied on the treated surfaces and bar specimens were produced that were submitted to 2
conditions: dry: immediate MTBS; TC: storage for 150 days and thermocycling 5000x. Fifty bar specimens were
produced per group (n = 50). Contact angle and pH results were submitted to one-way ANOVA and Tukey’s test
(_ = 0.05). Microtensile data were submitted to two-way ANOVA and Tukey’s test (_ = 0.05).
Results: pH values were significantly higher for SC6-ph (11.5 ± 2.6) when compared to those of SC5-pH (2.7
± 0.4), SC8-pH (2.7 ± 0.2) and SC2-pH (2.2 ± 0.2) (p < 0.00, ANOVA). SC1-ca had the largest contact angle
(48 ± 16 degrees) and SC3-ca the smallest (9.4 ± 7.7 degrees). The results of the MTBS test were as follows:
independent of the storage condition, SC2-bond = SC1-bond > SC3-bond = SC4-bond. SC4-bond had the lowest
MTBS value after TC (10.6 ± 2.6 MPa).
Conclusion: The acid neutralization step appears to be dispensable, since the washing/drying promoted similar pH
values. That condition promoted a high contact angle and unstable resin microtensile bond strength to glass ceramic.
Keywords: glass ceramic, resin cement, pH, contact angle, bond durability.
J Adhes Dent 2011; 13: 551–560 Submitted for publication: 19.05.10; accepted for publication: 01.08.10.
doi: 10.3290/j.jad.a19815

a Dentist, Department of Dental Materials and Prosthodontics, São José dos

Campos Dental School, São Paulo State University (UNESP), São José dos
Campos, SP, Brazil.
b Professor, Head of Dental Materials Unit, Center for Dental and Oral Medi-
cine, Clinic for Fixed and Removable Prosthodontics and Dental Materials
Science, University of Zürich, Switzerland.
c Professor, Department of Dental Materials and Prosthodontics, São José
dos Campos Dental School, São Paulo State University (UNESP), São José
dos Campos, SP, Brazil.
d Associate Professor, Department of Restorative Dentistry (Prosthodontics),
Faculty of Odontology, Graduate Program in Oral Sciences, Federal University
of Santa Maria, Santa Maria, Rio Grande do Sul State, Brazil; Department of
Dental Materials and Prosthodontics, São José dos Campos Dental School,
São Paulo State University (UNESP), São José dos Campos, SP, Brazil.
Correspondence: Luiz Felipe Valandro, Federal University of Santa Maria,
Faculty of Odontology, Department of Restorative Dentistry, Division of Pros-
thodontics, R. Marechal Floriano, 1184, 97015-372, Santa Maria, Rio Grande
do Sul State, Brazil. Tel: +55-55-3220-9275, Fax: +55-55-3220-9272. e-mail:
lfvalandro@hotmail.com
F eldspar ceramics, such as Vita VM7 (Vita Zanhfabrik;
Bad Säckingen, Germany) micro-particulate ceramic,
can be used for inlay/onlay restorations and veneers.
Using SEM and energy-dispersive x-ray spectroscopy,
Leite22 verified that this ceramic is based on a silica
net (SiO2) and potassium (K2O-Al2O3-6SiO2) or sodium
(Na2O-Al2O3-6SiO2) feldspar. The clinical success of
these restorations is based on a durable bond to dental
structure, promoted by adhesive cementation.17,18
Conditioning with hydrofluoric acid produces a micro-
morphological pattern on the ceramic surface, which
seems to have a significant influence on the formation
and maintenance of chemical and mechanical adhesion
to resin-based materials due to the creation of micropores
that allow interconnection with low viscosity polymers in
resin cements, while simultaneously optimizing the sur-

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Amaral et al
face wettability, which promotes better contact between
resins and the ceramic surface.19 Greater numbers and
types of irregularities on previously conditioned ceramic
surfaces have been associated with enhancing the bond
strength;29 additionally, conditioned areas seem to mod-
ify the surface wettability through enhancing the surface
energy and adhesion potential to resins.10,29 The surface
energy of a material is one of the physical characteristics
related to bond strength, and can be naturally or artifi-
cially changed through acid conditioning and silanization.
Therefore, conditioning with hydrofluoric acid promotes
bonding to resins and can be enhanced with a silane cou-
pling agent. Both conditioning methods can enhance the
cement surface wettability,23,25,29 improving the contact
with resin cements. However, when used alone, these
agents do not provide satisfactory results.5,24,38,42
Silane provides bonding between the silica in ceram-
ics and the organic matrix of resin cements through si-
loxane bonds.9,11,13,23,42 The reaction occurs between
3-methacrylpropyl tris(trimethylsiloxy)silane (MPS) meth-
oxy groups (Si-OCH3) and ceramic surface OH groups; it is
initiated and accelerated by an acidic catalyst, eg, acetic
acid. A pH of 4 is required for condensation between mol-
ecules that is sufficient to stabilize the silane solution. In
the majority of commercial silane products, acidic mono-
mers are used to catalyze this reaction.24,32,33
Foxton et al16 verified that the surface pH of a feldspar
ceramic increases (tending to be neutral) with a longer
rinse period. They also observed that when increasing
the rinse period, the groups treated with a ceramic primer
and without an acid catalyst had increased pH values
and decreased bond strengths. These results show the
necessity of H+ ions, working as acidic monomers in the
hydrolysis of the silane coupling agent, for the formation
of siloxane bonds.
There is great concern about neutralizing or cleaning
the surface after conditioning to remove residual acid, ar-
resting the surface degradation process and topographic
changes, and removing the impurities (from the reaction
precipitate) that are formed in the ceramic microreten-
tions.22,35,36 Therefore, sonic devices and neutralizing
agents have been employed.6 However, there is no con-
sensus about the influence of these procedures on the
bond strength of resin-based materials to ceramics. Some
studies have shown that ultrasonic cleaning optimizes ad-
hesion,1,6 while other studies demonstrate no influence.1
Thus, this purpose of the current study was to evaluate
the pH and contact angle (wettability) of a ceramic surface
submitted to different conditioning strategies, while also
evaluating the bond strength durability between a resin
cement and feldspar ceramic. Two main test hypotheses
were: 1. The different strategies of surface conditioning of
feldspar ceramic reduce the contact angle; 2. The differ-
ent strategies of surface conditioning of feldspar ceramic
promote stable bond strength.
552
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MATERIALS AND METHODS rP
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pH Measurement
lica
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To accomplish pH measurement on thet e ceramic sur- on
ot
n
face, 96 ceramic disks of Vita VM7 Dentinss
fo re
e n c(Vita
5M2
Zahnfabrik; Bad Säckingen, Germany) were manufac-
tured according to the manufacturer’s instructions. The
ceramic mass was inserted into the template (diameter:
8 mm; thickness: 3 mm), and the green blocks were
sintered. Due to the sintering contraction (around 20%),
the post-sintering samples obtained were approximately
6.4 mm x 2.4 mm.
The surface to be analyzed was flattened and polished
in a machine (Labpol 8-12, Extec; Enfield, CT, USA) using
silicone carbide papers in a sequence of 600-, 800- and
1200-grit (3M ESPE; St Paul, MN, USA). All samples were
cleaned in an ultrasonic device with isopropyl alcohol
for 10 min.12 The ceramic samples were divided into
12 groups (n = 8) according to the surface conditioning
method (Table 1; SC-pH).
The surface pH of each sample was obtained using
a HANNA micro-processed digital potentiometer (In-
gold - Mettler Toledo, model HI9224; Sao Paulo, Brazil)
equipped with a surface glass electrode with a flat mem-
brane of 6 mm diameter, which responds directly to the
hydrogen ion concentration. This device employs an elec-
trode, with a reference system to Ag/AgCl base.
Contact Angle Measurement
Forty (N=40) disks (diameter = 6.5 mm, h = 2.5 mm)
of Vita VM7 Dentin 5M2 ceramic (Vita Zahnfabrik) were
manufactured as described above for pH analysis. The
surface to be analyzed was flattened and polished in
a machine (Labpol 8-12, Extec) using silicone carbide
papers in a sequence of 600-, 800-, and 1200-grit (3M
ESPE). All samples were cleaned in an ultrasonic device
with isopropyl alcohol for 10 min.12
The ceramic samples were randomly divided into 5
groups (n = 8) according to the surface conditioning
method (Table 1; SC-ca). The contact angle was meas-
ured using a goniometer (Contact Angle Goniometer, 100-
00, Ramé-Hart; Mountain Lakes, NJ, USA) under con-
trolled temperature and connected to a computer with
specialized software for measuring the contact angle and
surface energy (Software RHI 2001 Imaging; Metcong, NJ,
USA). One drop of deionized water was put on the ceramic
surface with a syringe, and after 5 s, the contact angle
was measured.20
Bond Strength
Forty-eight (N = 48) ceramic blocks (6.4 x 6.4 x 4.8 mm)
of Vita VM7 Dentin 5M2 were prepared (40 blocks for
the bond strength test and 8 blocks for the micromorpho-
logical analysis after ceramic surface conditioning). The
cementation surface (6.4 x 6.4 mm) was flattened and
polished in a machine (Labpol 8-12, Extec) using silicone
carbide papers in a sequence of 600-, 800-, and 1200-
grit (3M ESPE).
Impressions were made from each ceramic block us-
ing addition silicone putty (Elite HD, Zhermack; Badia
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Table 1 Surface conditioning (SC), pH, contact angle, and bond strength measurements rP

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Measured parameters tio
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pH groups Contact Bond ss e n c e fo r
angle groups strength
Ceramic surface conditioning (SC) groups
No conditioning SC1-pH SC1-ca

Etching with gel 9% hydrofluoric acid* for 1 min SC2-pH

SC2-pH + washing with air-water spray for 30 s + drying SC3-pH SC2-ca

SC3-pH + silanization** waiting 5 min SC4-pH SC1-bond

Etching with gel 4% hydrofluoric acid*** forw 1 min SC5-pH

SC5-pH + washing with air-water spray for 30 s + drying SC6-pH SC3-ca

SC6-pH + silanization** waiting 5 min SC7-pH SC2-bond

Etching with liquid 5% hydrofluoric acid**** for 1 min SC8-pH

SC8-pH + washing with air-water spray for 30 s + drying SC9-pH SC4-ca

SC9-pH + silanization** waiting 5 min SC10-pH SC3-bond

SC9-pH + application of neutralizer***** + washing/drying + sonic cleaning for SC11-pH SC5-ca

5 min in distilled water

SC11-pH + silanization** waiting 5 min SC12-pH SC4-bond

* Ultradent Porcelain Etch, Ultradent; South Jordan, UT, USA.** Porcelain Primer, Bisco.*** Porcelain Etchant, Bisco.**** IPS Ceramic Etching, Ivoclar
Vivadent.***** IPS Ceramic Neutralizing powder, Ivoclar Vivadent.

Polesine, Italy; batch # 19915) in order to achieve 3 mm
of distance between the upper portion of the mold and
the surface of the block. The cement, Panavia F (Kura-
ray; Okayama, Japan), was injected into this space after
ceramic surface conditioning. The ceramic blocks were
randomly divided into 4 groups (N = 10), according to the
surface conditioning method (Table 1; SC-bond).
A coupling agent (Porcelain Primer, Bisco; Schaumburg,
IL, USA) was applied on all conditioned ceramic surfaces
and allowed to sit for 5 min. Each treated ceramic block
was placed in its silicone mold, with the cementation face
exposed. The resin cement, Panavia F, was mixed follow-
ing the manufacturer’s instructions and injected into the
mold, onto the treated surface of the ceramic block.27,28
The cement was light polymerized for 40 s (XL 3000,
3M/ESPE). After 10 min, the ceramic block/resin cement
assembly was removed from the mold and the cement
was once again submitted to light polymerization from five
aspects of the block (upper and lateral) for 40 s per side.
The blocks were rinsed with water and stored in distilled
water at 37°C for 24 h until preparation of the specimens.
Sectioning was performed using a diamond disk at
low speed under water cooling in a sectioning machine
(Labcut 1010, Extec). Initially, the cemented blocks were
fixed using cyanoacrylate adhesive gel (Super Bonder
Gel; Düsseldorf, Germany) on a metallic base that was
attached to the sectioning machine. The blocks were
positioned as perpendicularly as possible in relation to
the diamond disk of the machine. Four to five sections,
measuring 0.8 ± 0.1 mm in thickness, were produced.
The specimen was rotated 90 degrees and cut again
to produce four to five other sections, also measuring
0.8 ± 0.1 mm in thickness.5 The outer samples of the
specimen were discarded due to the possibility of excess
or the absence of cement at the interface that might alter
the results.21 Thus, only the central samples were used
for the experiments.
Specimens presented the following characteris-
tics: i) beam shape with non-machined adhesive zone
(nontrimmed); ii) bonded area as square as possible (ca
0.8 mm x 0.8 mm) with an area of ca 0.64 mm2, iii) ap-
proximate length of 8 mm.3,4,7,14,40,47
The bar-shaped specimens obtained from each ceramic
block were randomly divided into two groups, according
to storage/aging conditions: 1. without thermal cycling
(dry) – specimens were submitted to microtensile test-
ing immediately after sectioning; 2. with thermal cycling
(TC) – specimens were stored in distilled water at 37°C
for 150 days and submitted to thermocycling (12,000
cycles; 5°C to 55°C; dwell time: 30 s; transfer time: 2 s).

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Table 2 Test groups according to the factors of bond strength measurements (surface conditioning SC [4
r Plevels]

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Surface conditioning Storage conditions teGroups n ot

n
ss e n c e fo r
SC1-bond Etching with gel 9% hydrofluoric acid for 1 min + washing for 30 s + Without aging* Gr1
drying
With aging Gr2

SC2-bond Etching with gel 4% hydrofluoric acid for 1 min + washing for 30 s + Without aging Gr3
drying
With aging Gr4

SC3-bond Etching with liquid 5% hydrofluoric acid for 1 min + washing for 30 s + Without aging Gr5
drying
With aging Gr6

SC4-bond SC3-bond + application of neutralizer + washing/drying + sonic clean- Without aging Gr7
ing for 5 min in distilled water
With aging Gr8

* Aging = storage for 150 days and thermocycling.

Considering the “surface treatment” factor in four lev-
els (SC1, SC2, SC3, SC4), and “storage condition” factor
in two levels (dry and TC) (factorial 4 x 2), eight groups
were formed (Table 2).
Each specimen was fixed with cyanoacrylate gel to the
rods of a device adapted for this test. The specimens
were positioned parallel to the long axis of the device in
order to reduce the bending stress on the adhesive zone.
Only the extremities of the specimens were fixed, keep-
ing the bonded area free of adhesive. The device was
fixed in the universal testing machine (EMIC DL-1000),
as parallel as possible to the application of tensile load.
Testing was performed at a crosshead speed of 1 mm/
min.3,4,14,25,40,47 Pre-test failures were discarded.
The bond strength was calculated according to the
formula R = F/A, where “R” is the strength (MPa), “F” is
the load required for failure of the specimen (N) and “A”
is the interface area of the specimen (measured with a
digital caliper before the test; mm2).
All of the specimens submitted to the microtensile
test were analyzed using a light microscope at 50X to
200X magnification. Some specimens were selected for
analysis under a scanning electron microscope (SEM)
(JEOL JSM 6360; Tokyo, Japan) at 100X and 5000X mag-
nification).
Initially, the fractured region of each specimen was
analyzed to verify whether failure occurred at the adhesive
zone, presenting 3 regions: 1a) adhered interface; 2a)
ceramic region closer to interface; 3a) resin cement por-
tion closer to interface. Failures were classified as one of
4 types:14 1) between ceramic and cement (ADHES); 2)
cohesive failure in the cement (COHES-cem); 3) cohesive
failure in the ceramic (COHES-cer); 4) adhesive failure and
cohesive failure of the cement (MIX).
For the SEM topographic analysis, two samples were
conditioned per method (SC1, SC2, SC3, SC4) but not
silanized.
Statistical Analyses
Contact angle and pH data were submitted to one-way
ANOVA and post-hoc Tukey’s test (_ = 0.05). Microten-
sile data were submitted to two-way ANOVA and post-
hoc Tukey’s test (_ = 0.05). MINITAB (Minitab, version
14.12, 2004; State College, PA, USA), STATISTICA
(StatSoft, version 5.5, 2000; Hamburg, Germany) and
STATISTIX (Analytical Software, version 8.0, 2003; Tal-
lahassee, FL, USA) were used for statistical analysis.
RESULTS
pH Measurement
One-way ANOVA found a statistically significant differ-
ence between the different types and techniques of
surface conditioning in the surface pH analysis (p <
0.0001; statistical hypotheses had to be rejected).
SC6-pH obtained the highest pH value when compared
to the other conditioning methods (Tukey’s test, Table 3).
Groups SC11-pH, SC4-pH, SC7-pH, SC3-pH and SC9-pH
were similar to each other and different from the other
groups. Groups SC5-pH, SC8-pH, and SC2-pH had the
lowest pH values and were similar to each other.
Contact Angle
One-way ANOVA showed that the conditioning methods
had a significant influence (p < 0.0001) on the contact
angle results, and thus the first null hypothesis had to
be rejected.

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Table 3 Means and standard deviation for pH meas- Table 4 Means and standard deviation for contact
rP

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urements with different surface conditioning (SC) angle measurements (in degrees) ub

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SC Means ± SD SC Means ± SD* t e n ot

n
ss e n c e fo r
SC6-pH 11.5 ± 2.6a SC1-ca 48 ± 16a

SC11-pH 9.6 ± 2.0b SC5-ca 35.1 ± 20.8b

SC4-pH 9.3 ± 0.8b SC4-ca 16.5 ± 10.5c

SC7-pH 8.7 ± 1.9b SC2-ca 11.3 ± 10.2cd

SC3-pH 8.6 ± 2b SC3-ca 9.4 ± 7.7d

SC9-pH 8 ± 0.3b The same superscript letters indicate no significant differences and differ-
ent letter mean difference significant statistically (Tukey’s test, _ = 5%.
SC12-pH 5.6 ± 0.8c

SC1-pH 5.4 ± 0.9c

SC10-pH 5.4 ± 0.7c

SC5-pH 2.7 ± 0.4d

SC8-pH 2.7 ± 0.2d

SC2-pH 2.2 ± 0.2d

The same superscript letters indicate no significant difference and differ-
ent letters mean statistically significant difference (Tukey’s test, _= 5%).
Representative micrographs of samples conditioned
with hydrofluoric acid (without silane application) are pre-
sented in Fig 1. The different conditioning strategies of
the ceramic surface yielded similar micromorphologies.

DISCUSSION

The unconditioned group (SC1-ca) achieved the highest
contact angle, followed by SC5-ca (conditioning + neutral-
izing + ultrasonic cleaning). The lowest contact angle
values were, in descending order, SC3-ca, SC2-ca, and
SC4-ca, which corresponds to conditioning with hydro-
fluoric acids in different concentration (4%, 9%, and 5%,
respectively), without neutralization + ultra sonic cleaning
(Table4).
Bond Strength
Two-way ANOVA revealed that the factors “conditioning”
(p < 0.0001) and “storage” (p = 0.0099) were statisti-
cally significant, therefore requiring rejection of the 2nd
statistical hypothesis. The interaction between them
was also significant (p < 0.0001).
Tukey’s test (Table 5) indicated that: (1) considering
only the conditioning factor, independent of storage, SC2-
bond = SC1-bond > SC3-bond = SC4-bond; (2) consider-
ing only storage, independent of the conditioning factor,
without TC > with TC; (3) after aging, SC4-bond had the
lowest values of bond strength compared to SC1-bond
and SC2-bond; (4) Only SC4-bond showed a significant
decrease of the bond strength after aging when compared
to the results in the “dry” group.
Table 6 presents the numbers and percentage of the
type of failure of specimens submitted to microtensile
testing. No adhesive failure was found under optical mi-
croscopy. Cohesive failures in cement and ceramic were
found in some cases. The majority of fractured surfaces
exhibited the presence of resin cement on the ceramic.
Acid etching and silanization are often recommended
for adhesive cementation of a cement resin to silica-
based ceramic restorations (feldspar ceramic) to obtain
a micromechanically retentive surface.34,46 Conditioning
with hydrofluoric acid followed by the application of a
silane coupling agent enhances the adhesion of resin
cements to feldspar ceramics.6,19
pH results obtained in the present study showed that,
during conditioning with acids of different concentrations,
the surface pH decrease drastically (SC2-pH, SC5-pH and
SC8-pH) when compared with SC1-pH (no conditioning).
After rinsing and drying, there was a significant enhance-
ment of pH. These results suggest that only rinsing the
ceramic surface, without neutralization, is enough to sig-
nificantly enhance the pH of the ceramic surface.
Foxton et al16 observed that the acid treatment and
rinsing duration of a ceramic surface causes different
surface pH values when using two acids (40% phosphoric
acid and 20% hydrofluoric acid). When a longer period of
rinsing was utilized, the surface pH was enhanced and
the bond strength decreased in groups where the silane
without acidic monomers was used; however, there was
no significant difference in bond strength in groups with
an acidic monomer. Acid etching of silica-based ceramic
surfaces probably increased the concentration of H+ ions
on the surface, which can activate a-MPS derived from
silane when the silane coupling agent contains no phos-
phate monomers.
The present study also found that the pH values in-
creased after acid removal through surface rinsing for

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Table 5 Means and standard deviation of the bond strength data (MPa) rP

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SC Storage Total tio
te n
ot

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Without TC With TC ss e n c e
fo r
SC1-bond 14.4 ± 2.7Aa 13.9 ± 4.5Aab 14.1 ± 3.7

SC2-bond 14.3 ± 3.1Aa 15.5 ± 3.2Aa 14.9 ± 3.2

SC3-bond 12.7 ± 3.6Aa 12.4 ± 2.7Abc 12.6 ± 3.2

SC4-bond 14.2 ± 3.1Aa 10.6 ± 2.6Bc 12.4 ± 3.4

Total 13.9 ± 3.2 13.1 ± 3.8

n = 50 bar specimens/group. Superscript capital letters for comparison in rows, lower-case letters for comparison
in the columns. The same letters indicate no significant differences and different letters mean statistically signifi-
cant differences (Tukey’s test, _= 5%).

Table 6 Number and percentages of the types of fractures in the beam specimens submitted to the microtensile
test

Groups Total no. of Type of fracture (%)*

beams
ADHES COHEScem COHEScer MIX
Gr1 45 0 (0%) 1 (2.2%) 0 (0%) 44 (97.8%)

Gr2 45 0 (%) 2 (4.4%) 1 (2.2%) 42 (93.4%)

Gr3 45 0 (%) 0 (0%) 0 (0%) 45 (100%)

Gr4 45 0 (0%) 0 (0%) 4 (8.8%) 41 (9.2%)

Gr5 45 0 (0%) 0 (0%) 3 (6.6%) 42 (93.4%)

Gr6 45 0 (0%) 1 (2.2%) 2 (4.4%) 42 (93.4%)

Gr7 45 0 (0%) 0 (0%) 0 (0%) 45 (100%)

Gr8 45 0 (0%) 3 (6.6%) 0 (0%) 42 (93.4%)

Total 360 (100%) 0 (0%) 7 (1.9%) 10 (2.7%) 343 (95.4%)

*ADHES: Adhesive fracture at cement/ceramic interface; COHEScem: cohesive fracture of the resin cement; COHEScer: cohesive fracture of the ceramic;
MIX: mixed adhesive failure and cohesive of resin cement.

30 s and drying (SC3-pH, SC6-pH, and SC9-pH), resulting
in pH values higher than the unconditioned surface. The
higher pH can be caused by products (acid precipitate and
salt) resulting from the chemical reaction between the
acid and ceramic. The control and limitation of the attack
by the hydrofluoric acid though neutralization and ceramic
surface cleaning (pH increase) with ultrasonic equipment
has been associated with the creation of a regular and
uniform conditioning pattern.35 The present study con-
cluded that a 30-s rinse and drying of the ceramic surface
was enough to significantly increase the pH values of the
ceramic surface (SC3-pH = 8.6; SC6-pH = 11.5; SC9-pH
= 8; SC11-pH = 9.6), indicating that pH increase can be
attained without a neutralization process.
When applying the silane to an etched surface, the
ceramic surface showed significantly higher values of pH
than (SC4-pH, SC7-pH) or remained statistically similar
to (SC10-pH and SC12-pH) the unconditioned ceramic
surface. SC12-pH represents the conditioned, neutral-
ized, sonically cleaned, and silanizated ceramic sur-
face, and its pH was similar to a ceramic surface with
no conditioning. This could indicate the effectiveness of

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Fig 1a Representative micrograph (3000X) of the conditioned
surface (not silanized). SC1: Etching with gel 9% hydrofluoric
acid [HF] + washing + drying. Porous and lattice of voids and
channels are noted, with probable presence of precipitates
from acid conditioning (irregular white residues).
Fig 1b Representative micrograph (3000X) of the conditioned
surface (not silanized). SC2: Etching with gel 4% HF + washing
+ drying.

Fig 1c Representative micrograph (3000X) of the conditioned
surface (not silanized). SC3: Etching with liquid 5% HF + wash-
ing + drying.
Fig 1d Representative micrograph (3000X) of the conditioned
surface (not silanized). SC4: SC3 + neutralization + washing/
drying + sonic cleaning for 5 min in distilled water. Similar
topographic patterns can be observed (with precipitates also)
in Figs 1b and 1c.

conditioning neutralization. However, pH values of the
surfaces that were not submitted to neutralization and
sonic cleaning remained similar to or were higher than
SC12-pH, demonstrating that neutralization as an op-
erative step after conditioning with hydrofluoric acid may
be unnecessary. Relating these findings of pH to the
bond strength results, a probable positive relationship
between high pH values and the highest bond strength
values was found, since the surface conditioning of
SC4-pH and SC7-pH (highest pH values) corresponded to
SC1-bond and SC2-bond, respectively, which generated
high and stable bond strength values. Conversely, low pH
values (SC2-bond and SC10-pH) were associated with the
lowest bond strength values (SC3-bond and SC4-bond).
These results are based on chemical phenomena relative
to surface acidity, with subsequent chemical incompatibil-
ity between resin cement and ceramic surface.8,26,35,41
Studies have previously described this possible chemical
incompatibility between adhesive systems with low pH
and resinous materials.8,26,37,44 Decreased microtensile
bond strengths of chemically initiated polymerizing resin
composites bonded to dentin have been reported, due

Vol 13, No 6, 2011 557


Amaral et al
to the acidity of the adhesive system.37 It is known that
acidic resin monomers retard the polymerization of chemi-
cally and/or light initiated polymerizing resins that are
initiated via peroxide-amine type binary redox catalysts.
The interaction between acidic adhesive resin monomers
and the basic composite tertiary amines results in the
consumption of the latter in acid-base reactions, negating
their ability to generate free radicals in subsequent redox
reactions.43-45
Table 5 shows that only SC1-bond and SC2-bond dem-
onstrated stable bond strengths, and SC3-bond and SC4-
bond had a significant decrease in values after aging.
Evaluating only the conditioning factor (right column in
Table 5), SC2-bond = SC1-bond > SC3-bond = SC4-bond,
indicating that conditioning with 5% acid and its use as-
sociated with neutralization seems to be ineffective in es-
tablishing stable bonding to the studied feldspar ceramic.
The contact angle of a liquid on a substrate acts as
an indicator of total surface energy and wettability of the
adherent (adhesive, resin cement, composite resin).50
Enhancing the free energy of a substrate and the wettabil-
ity of adherent causes the adherent to flow more easily
on the substrate.23
Jardel et al19 related the surface topography to bond
strength of two ceramics conditioned with 10% hydro-
fluoric acid and silane. Their results showed that the com-
bination of acid conditioning + silanization provided higher
bonding values. A subsequent study,20 using the same
experimental conditions, evaluated the surface energy
related to topographic roughness caused by acid condi-
tioning in ceramics. Those results showed that acid condi-
tioning enhanced the bond potential on tested ceramics.
The highest bonding potentials presented in the cur-
rent study were found with 4% (9.4 degrees), 9% (11.26
degrees) and 5% (16.46 degrees) hydrofluoric acid. Sam-
ples conditioned with 5% hydrofluoric acid followed by
neutralization + ultra sonic cleaning achieved the highest
contact angle (35.13 degrees) and therefore the lowest
bonding potential, especially when compared to condi-
tioning with the same acid without neutralization. The
lowest bonding potential, statistically different from other
treatments (48.01 degrees), was presented by the group
“without conditioning”.
Findings of bonding potential related to contact angles
were reflected in the bond strength results: the neutral-
ized group had the lowest bonding potential (highest con-
tact angle) and obtained the lowest bond strength in the
present study.
Thus, the 2 test hypotheses were rejected in view of
the fact that: 1) etching with liquid 5% hydrofluoric acid fol-
lowed by neutralization had a mean contact angle statisti-
cally similar to that of the control group (without ceramic
surface treatment), while other acid etching approaches
reduced the contact angle significantly compared to con-
trol group; 2) etching with liquid 5% hydrofluoric acid fol-
lowed by neutralization procedure promoted lower bond
strength compared to the other acid etching approaches,
which yielded higher bond strength.
Other studies15,20 corroborate with the current results
on contact angles, which were statistically lower when
558
pyrig
No Co
ht
t fo
etching the ceramic surface with hydrofluoric
r acid
Pu when
by N
compared to control group (polishing only). Thosebli two
Q ui
cat
previous studies15,20 found that the larger the pores,
sulci, and cracks are (analyzed micromorphologically),
ion
te ot
n
ss e nofc ethe
the higher the surface area and bonding potential
fo r
ceramic surface. In the current study, groups conditioned
with different strategies did not seem to present differ-
ences in micromorphological patterns (Fig 1). However,
different values of contact angle were obtained from dif-
ferent strategies, demonstrating that other factors can
affect bonding potential of a ceramic surface. Perhaps the
presence of residual products of acid neutralization are
responsible for the reduced bonding potential, resulting
in high values of contact angle and lower bond strength,
such as occurred in the neutralized group.
Neutralization and water rinsing are performed to neu-
tralize and remove the deposited precipitate on a ceramic
surface after conditioning.17,18,22 However, in this current
study, this procedure was found to decrease the wettabil-
ity of the ceramic surface, presenting contact angle val-
ues statistically higher than the values of only conditioned
and not neutralized samples. Ceramic surface neutraliza-
tion was introduced to optimize ceramic/cement bonding,
but some studies have demonstrated that this procedure
does not influence the results.1,35,36
Bond strength results showed a statistical difference
between the 4% and 9% hydrofluoric conditioned groups
and the 5% hydrofluoric conditioned groups, even when
including conditioning + neutralization and sonic cleaning.
Acid conditioning happens when hydrofluoric acid reacts
with the silica of feldspar ceramics (such as Vita VM7),
forming fluorosilicates.14
Based on the current results, neutralization of the in-
ner surfaces of restorations made of feldspar ceramic
(inlays/onlay/veneers) that have been conditioned with
hydrofluoric acid seems to be unnecessary. Hydrofluoric
conditioning + water rinse + silanization could be the
indicated strategy of pretreatment of glass ceramics for
adhesive cementation.
However, in vitro studies have inherent limitations,
since some clinical conditions cannot be simulated. Thus,
these findings must be interpreted with caution, because
results from laboratory studies should not be immediately
extrapolated to clinical situations. Although the neutrali-
zation group showed reduced microtensile bond strength,
it can have no significance from the clinical point of view
– only a controlled randomized clinical trial will be able to
determine clinical relevance.
The microtensile test was chosen for evaluation of
cement-ceramic adhesion. For the test to be able to ac-
curately measure the bond strength values between an
adherent and a substrate, it is crucial that the bonding in-
terface should be the most stressed region, regardless of
the test methodology being employed.7,21,39,48,49 Many
studies that employed stress distribution analyses have
reported that microtensile bond strength tests stress the
interfacial zone appropriately, leading to failures at that
zone.30,31 Nevertheless, sectioning the glass ceramic/
cement assembly should be performed carefully, as criti-
cal defects can be generated in specimens during cutting.
The Journal of Adhesive Dentistry

CONCLUSIONS
1. pH values decrease during acid action; however,
the ceramic surface returned to a basic (higher)
pH with rinsing and drying, and remained basic
after silanization.
2. Even if neutralization increases the pH, strong
resin bonds are not promoted.
3. The highest bonding potential (low contact an-
gles) was observed in groups conditioned with
different acid concentrations when compared to
the unconditioned group and the group with acid
neutralization after conditioning.
4. Higher bond strengths were obtained when ce-
ramic surfaces were conditioned with 9%, 5%
and 4% hydrofluoric acid, while a significant de-
crease of bond strength was observed when ce-
ramic surfaces were submitted to neutralization
and sonic cleaning after conditioning.
5. Low bond strength values seem to be related to
low pH values. Lower contact angles (high ad-
hesive potential) are related to higher values of
bond strength.
Randomized clinical trials should be performed to
determine the clinical impact of these findings.
ACKNOWLEDGMENTS
This study was supported in part by a research grant from
the Sao Paulo Research Foundation (FAPESP). This study is
based on a master’s thesis submitted to the São José dos
Campos Dental School, São Paulo State University (UNESP),
Brazil, in partial fulfillment of the requirements for the M.S.D.
degree in Restorative Dentistry (Prosthetic Dentistry).
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Clinical relevance: Acid neutralization of the etched
glass ceramic appears to be unnecessary, since it
promoted a high contact angle and reduced resin mi-
crotensile bond strength to glass ceramic.

560 The Journal of Adhesive Dentistry