The effect of hydrofluoric acid surface

treatment and bond strength of a

zirconia veneering ceramic
Yada Chaiyabutr, DDS, MSD, DSc,a Steve McGowan, CDT,b
Keith M. Phillips, DMD, MSD,c John C. Kois, DMD, MSD,d and
Russell A. Giordano, DMD, DMSce
School of Dentistry, University of Washington, Seattle, Wash;
Goldman School of Dentistry, Boston University, Mass
Statement of problem. Clinicians are frequently faced with a challenge in selecting materials for adjacent restorations,
particularly when one tooth requires a zirconia-based restoration and the next requires a veneer. While it may be desir-
able to use the same veneering ceramic on adjacent teeth, little information is available about the use of veneering
ceramics over a zirconia-based material.

Purpose. The purpose of this study was threefold: (1) to study the influence of hydrofluoric acid-etched treatment on
the surface topography of the zirconia veneering ceramic, (2) to test the bond strength of zirconia veneering ceramic
to enamel, and (3) to evaluate the flexural strength and the elemental composition of ceramic veneers.

Material and methods. Three zirconia veneering ceramics (Cerabien CZR (CZ), Lava Ceram (L), and Zirox (Z)) and
4 conventional veneering ceramics (Creation (C), IPS d.Sign (D), Noritake EX-3 (E), and Reflex (R)) were evaluated.
Twenty ceramic bars of each material were fabricated and surface treated with hydrofluoric acid according to the
manufacturer’s recommendations. Ten specimens from each group of materials were examined with a profilometer,
and a sample of this group was selected for quantitative evaluation using a scanning electron microscope (SEM).
Another 10 acid-etched specimens from each group of materials were treated with silane prior to cementing with resin
cement (Variolink II) on enamel surfaces. These luted specimens were loaded to failure in a universal testing machine
in the shear mode with a crosshead speed of 0.05 mm/min. The data were analyzed with a 1-way ANOVA, followed
by Tukey’s HSD test (a=.05). An additional 10 ceramic bars from each material group were fabricated to evaluate
flexural strength and elemental composition. The flexural strength (MPa) of each specimen was determined by using a
4-point-1/4-point flexure test. A Weibull statistic tested the reliability of the strength data; pairwise differences among
the 7 groups were evaluated at confidence intervals of 95%. The chemical composition of each bar was determined by
energy dispersive spectroscopy (EDS).

Results. There was a significant difference in the surface roughness in all testing groups. Conventional veneering
ceramics (groups C and R) had a mean surface roughness higher than the groups of zirconia veneering ceramics
(P<.001). Group D showed no difference in surface roughness compared with the groups of zirconia veneering ceram-
ics. The SEM micrographs revealed differences in the acid-etched surfaces of ceramics. Zirconia veneering ceramics
were smooth, with some groove formations, while conventional veneering ceramics had an amorphous, spongy-like
structure with numerous microporosites. The mean bond strength (SD) of zirconia veneering ceramics to enamel re-
vealed a significant difference. Group R (25.16 (3.40) MPa) followed by group C (22.51 (2.82) MPa) had significantly
higher mean bond strength than the groups of zirconia veneering ceramics (P<.001, P=.009 respectively). Groups
D (16.54 (2.73) MPa) and E (17.92 (3.39) MPa) showed no differences. Only group L (9.45 (1.62) MPa) exhibited
significantly lower mean bond strength when compared with conventional veneering ceramics (P<.001). For flexural
strength, only 1 group, group CZ, had a significantly lower flexural strength than all other groups (P<.001).

a
Affiliate Instructor, Department of Restorative Dentistry, School of Dentistry, University of Washington; Clinical Research Scien-
tist, Seattle, Wash.
b
Dental Technologist, Seattle, Wash.
c
Assistant Professor and Associate Director, Graduate Prosthodontics, Department of Restorative Dentistry, School of Dentistry,
University of Washington.
d
Affiliate Professor, Department of Restorative Dentistry, School of Dentistry, University of Washington; Private practice, Tacoma,
Wash.
e
Associate Professor and Director, Division of Biomaterials, Department of Restorative Sciences and Biomaterials, Goldman School
of Dentistry.
The Journal of Prosthetic Dentistry Chaiyabutr et al
September 2008 195
Conclusions. Effective ceramic interface management, such as acid etching and enamel bonding, is essential for suc-
cessful ceramic laminate veneer restorations. Not all zirconia veneering ceramics display the same quality of surface
roughness after hydrofluoric acid etching and the same bond strength to enamel when used as laminate veneer mate-
rials. (J Prosthet Dent 2008;100:194-202)

Clinical Implications
Clinicians should choose those zirconia veneering ceramics that, when
etched, create a maximum rough surface, demonstrate high bond
strength to enamel, and demonstrate necessary flexural strength.

In clinical situations that require
highly demanding esthetic restora-
tions, all-ceramic restorations have
the potential to be a more effective
selection when compared to metal
ceramic restorations. The alloy struc-
ture in metal restorations may create
an opaque appearance, while ceramic
materials seem to generally produce a
more translucent look that replicates
the appearance of the natural tooth
(Fig. 1).
There is a growing interest in the
use of zirconia oxide ceramics as sub-
stitutes for metal core structures. This
is due to the fact that zirconia oxide
ceramic has superior mechanical
properties, including a high flexural
strength (1.0-1.2 GPa) and toughness
(7-8 MPa x m0.5).1,2 In addition, the
development of new technology, such
as computer-aided design/computer-
aided manufacturing (CAD/CAM), al-
lows the fabrication of zirconia-based
restorations for all-ceramic crowns
(or fixed partial dentures) to be more
a practical process.3-8 The zirconia-
based core structure is veneered with
zirconia veneering ceramic that has
a suitable coefficient of thermal ex-
pansion matching the core ceramic.
When one tooth requires an all-ce-
ramic crown (zirconia based) and an-
other requires a veneer, clinicians are
frequently faced with the challenge of
selecting materials for the adjacent
restorations. While it may be desir-
able to use the same veneering ceram-
ic on adjacent teeth, little information
is available about zirconia veneering
ceramic.
The retention of the veneer can be
satisfactorily achieved by 3 factors:
(1) ceramic surface treatment from
acid etching, (2) an application of si-
lane coupling agent prior to cement-
ing with a resin cement,9-16 and (3)
alumina oxide-particle abrasion.17 In
general, the structure of veneering ce-
ramic has been described as an amor-
phous and glassy matrix that consists
of a random network of cross-linked
silica in a tetrahedral arrangement,
which is embedded in varying amounts
of undissolved feldspar and leucite
crystals. For ceramic surface treat-
ment, the acid reacts with the glassy
matrix that contains silica and forms
hexafluorosilicates. This glassy matrix
is selectively removed and the crystal-
line structure is exposed. As a result,
the surface of the ceramic becomes
rough, which is expected for micro-
mechanical retention on the ceramic
surface.18-20 This roughly etched sur-
face also helps to provide more sur-
face energy prior to combining with
the silane solution.21,22 The applica-
tion of the silane coupling agent onto
the etched ceramic surface increases
the chemical bonding between the
ceramic and resin materials due to its
bifunctional characteristics. This pro-
cess also promotes cement wettability
on the ceramic surface, which in turn
enhances its cohesiveness with the
resin cements.23,24 The subsequent use
of the alumina oxide-particle abra-
sion on ceramic surfaces prior to acid
etching may substantially increase the
surface area and enhance the poten-
tial for micromechanical retention,
and increases the bond strength of
the ceramic veneer on the tooth.17
Although numerous in vitro stud-
ies have reported the positive effect
of acid etching and the application of

A B
1 Ceramic veneer restoration restored with conventional veneering ceramic in esthetic zone area.
Chaiyabutr et al
196
silane on the ceramic veneer, most of
the veneering ceramics used in these
studies were either conventional ve-
neering ceramics or heat-pressed
ceramics.9-16,19-21 Zirconia veneering
ceramics have not been investigated
in this way. Therefore, in the first part
of this study, the influence of hydro-
fluoric acid-etching treatment on the
surface topography of zirconia ve-
neering ceramic was examined. The
surface roughness of the veneering
ceramic after acid etching was de-
termined, followed by a qualitative
evaluation using scanning electron
microscopy (SEM). The second part
of this study involved bond strength
tests of the etched ceramic bonded to
enamel using a resin cement.
Most veneering ceramic requires
a lower coefficient of thermal expan-
sion than the core structure, which
places the weaker veneering ceramic
under slight compression.25 The zir-
conia veneering ceramic has a coef-
ficient of thermal expansion of ap-
proximately 8-10 µm/mxK,26 which
is considerably lower than the aver-
age for the conventional veneering
ceramic (13-14 µm/mxK) used for a
metal ceramic crown as well as lami-
nate veneer restorations.27 Altera-
tions in ceramic elemental composi-
tion may occur in zirconia veneering
ceramic in order to adjust the coeffi-
cient of thermal expansion to a level
more compatible with the core struc-
ture. This difference in composition
could also directly affect the ceramic
strength properties.28-30 Therefore,
the third part of the present study
aimed to evaluate the strength prop-
erties (4-point-1/4-point flexure test)
of zirconia veneering ceramic and the
chemical composition of the ceramic
using energy dispersive spectroscopy
(EDS).
The first null hypothesis was that
the use of zirconia veneering ceramic
as a ceramic laminate veneer mate-
rial would not result in different bond
strengths between the ceramic-tooth
interface compared with conven-
tional veneering ceramics. The sec-
ond null hypothesis was that zirconia
veneering ceramic would exhibit no
difference in mechanical properties
(flexural strength) compared with
conventional veneering ceramics.
MATERIAL AND METHODS
Seven commercially available ve-
neering ceramics were investigated
(Table I). Three are used for veneering
zirconia-based restorations (Noritake
Cerabien CZR (Noritake, Aichi, Japan)
(CZ), Lava Ceram (3M ESPE, St. Paul,
Minn) (L), and Zirox (Wieland Dental
Systems, Inc, Danbury, Conn) (Z)),
Volume 100 Issue 3
and 4 are used for ceramic laminate
veneers (Creation (Jensen Industries,
North Haven, Conn) (C), IPS d.Sign
(Ivoclar Vivadent, Amherst, NY) (D),
Noritake EX-3 (Noritake) (E), and
Reflex (Wieland Dental Systems, Inc)
(R)). Thirty ceramic bars of each ma-
terial were fabricated, using a silicone
mold with a length of 30 mm, a width
of 5 mm, and a height of 3 mm. Ve-
neer powders were mixed with deion-
ized water, vibrated, and excess water
was removed with absorbent paper to
condense the ceramic. All specimens
were fired according to the manufac-
turer’s instructions (Table I) in a pro-
grammable vacuum furnace (Dekema
Austromat 3001; Dekema Service
GmbH, Freilassing, Germany). The
fired bars were polished to standard-
ized dimensions (L: 25 ±0.2 x W: 4
±0.1 x H: 2 ±0.1 mm) prior to glaz-
ing by using a variable-speed grinder-
polisher machine (Ecomet 3; Buehler
Ltd, Lake Bluff, Ill). Diamond grinding
discs (Buehler ULTRAPREP 45 μm, no.
15-6145, and 15 μm, no. 15-6115;
Buehler Ltd) were used at 30 rpm. The
specimens were gently pressed onto
the polishing surface under continu-
ous water flow. The purpose of this
standardized polishing procedure was
to remove external irregular scratches
and defects.
Twenty specimens of each material

Table I. Firing temperature and hydrofluoric acid etch, based on manufacturer’s recommendations
Dentin Firing Cycles Glazing Cycles HF Acid Etch
Dry Ramp High Hold Ramp High Hold Acid Etch
Time Rate Temp Time Rate Temp Time Conc. Time
Ceramic Veneer (sec) (sec) (°C) (sec) (sec) (°C) (sec) (%) (sec)

Conventional Group C 8 55 925 60 55 930 0 9.5 300

Group D 9 60 870 60 60 870 60 5.0 90
Group E 9 45 930 0 50 930 0 9.5 120
Group R 9 75 905 120 75 880 60 9.5 120

Zirconia Group CZ 9 45 940 60 50 930 30 9.5 120

Group L 7 45 820 60 45 820 0 9.5 420
Group Z 9 45 905 120 45 880 60 9.5 180

The Journal of Prosthetic Dentistry Chaiyabutr et al

September 2008
were selected to evaluate the influence
of hydrofluoric acid-etch treatment.
In order to assess the microstructure
surface alteration after a hydrofluoric
etch, the surface roughness before
and after acid etching was deter-
mined using a profilometer (Mitu-
toyo Surftest SJ-201P NW; Mitutoyo
USA, Aurora, Ill), and the parameter
Ra was calculated. The Ra value de-
scribes the average roughness value
for a surface that has been traced by
the profilometer. A lower Ra value in-
dicates a smoother surface. The cut-
off length of the profilometer was
set at 0.8 mm. The transverse length,
which is the length of the surface ex-
amined by the instrument, was set to
4.5 mm and the measuring range to
0-12.5 mm. Each specimen was then
stabilized on a flat surface, and the
roughness was measured with a stylus
that moved across the surface. Each
specimen was scanned 3 times by 5
parallel tracings in different areas of
the specimen. After the initial baseline
measurements, each specimen was
etched with hydrofluoric acid in ac-
cordance with manufacturer protocol
(Table I). The etched specimens were
rinsed with water, air dried, and the
Ra value was remeasured. One inves-
tigator prepared all of the specimens
and measured the surface roughness.
After the surface roughness measure-
ment, specimens in each group of
materials were selected for additional
examination qualitatively for the mi-
crostructure morphology of the ce-
ramic surface using a scanning elec-
tron microscope (SEM XL20; Philips
Electronic Instruments Co, Mahwah,
NJ). The specimens were attached to
SEM stubs with cyanoacrylate cement
(UHU GmbH, Buehl, Germany) and
sputter coated with gold-palladium
(Technics Hummer Sputter Coater;
Anatech, Hayward, Calif ) for 60 sec-
onds. One-way analysis of variance
(ANOVA), followed by Tukey’s HSD
test (α=.05) was used to assess the
statistical difference of surface rough-
ness among the different veneering
ceramics after hydrofluoric acid etch
on the ceramic surfaces.
Chaiyabutr et al
Ten acid-etched specimens from
each group of materials were selected
for bond strength tests. The methods
used for the shear bond test in this
study were similar to those described
in a previous study.31 Extracted molar
teeth were selected, given their rela-
tively large surface area that resists
fracture when stressed and diverging
roots which resist removal from the
embedding acrylic resin during test-
ing. Immediately following the extrac-
tion, teeth were cleaned of surface
debris, sterilized in 0.5% sodium hy-
pochlorite, and kept in a liquid steri-
lant (0.5% sodium hypochlorite) until
tested. Teeth were then selected from
the sterilization liquid based on the
following criteria: no evidence of car-
ies, no restorations, and no cracks or
fractures in the crown. The roots of
the selected teeth were notched for
retention, and a vertical planar enam-
el-bonding surface was prepared on
the buccal or lingual enamel with a
high-speed handpiece and a diamond
rotary cutting instrument (KS1; Bras-
seler USA, Savannah, Ga). The teeth
were then attached with sticky wax
(Sticky Wax; Kerr Corp, Orange, Ca-
lif ) to a dental surveyor (J.M. Ney Co,
Bloomfield, Conn) rod on a vertically
prepared surface so as to maintain
a perpendicular plane between the
bonding surface and the shear loading
axis of the universal testing machine.
The teeth were then lowered into a
copper cylinder, and positioned in the
center of the cylinder with the buccal
cementoenamel junction 3 mm above
the top of the copper mounting cylin-
der. Premixed autopolymerizing resin
(Pattern Resin; GC America, Alsip, Ill)
was injected into the cylinder until it
was completely full. After acrylic resin
polymerization, the dental surveyor
rod was detached and the specimens
were stored in distilled water at room
temperature. Seventy enamel speci-
mens were divided into 7 groups for
bonding with the various veneering
ceramics. The enamel-prepared sur-
faces were mechanically cleaned with
a 27-µm aluminous oxide-particle
abrasion (40 psi at a 2-mm distance)
197
(PrepStart; Danville Materials, Inc,
San Ramon, Calif ), then rinsed with
water and dried gently. The specimens
were etched with 37% phosphoric acid
gel (Total Etch; Ivoclar Vivadent, Am-
herst, NY) for 15 seconds, rinsed with
water spray for 30 seconds, and then
air dried until a frosty white appear-
ance was observed. Following this, an
adhesive bonding agent (ExciTE DSC;
Ivoclar Vivadent) was applied on the
prepared tooth surface, and light po-
lymerization (Mini LED SP; Aceton,
Mount Laurel, NJ) was performed
with a light intensity of 480 nm and
a power of 1100 mW/cm2 (±10%) for
20 seconds at a 10-mm distance from
the specimens. Ceramic bars were cut
to a small block (L: 2 ±0.2 x W: 2 ±0.2
x H: 2 ±0.1 mm). This was accom-
plished using diamond disks (Brasseler
USA, Savannah, Ga) to avoid causing
any damage on the ceramic surface,
which already had been glazed and
prepared for bonding to enamel. The
ceramic surface was then treated with
9.5% hydrofluoric acid (Porcelain
Etch; Ultradent, South Jordan, Utah),
according to each manufacturer’s
protocol (Table I), except for group
D, as the manufacturer recommended
treatment with 5% hydrofluoric acid
(IPS Etching Gel; Ivoclar Vivadent).
Silane solution (Monobond-S; Ivoclar
Vivadent) was applied on the ceramic
surface for 60 seconds, then air dried
gently, and an adhesive bonding agent
(ExciTE DSC; Ivoclar Vivadent) was
applied on the ceramic surface. Resin
cement (Variolink II; Ivoclar Vivadent)
was mixed according to the manufac-
turer’s recommendations. The mixed
cement was applied directly to both
the prepared enamel and the ceram-
ic. The ceramic was placed upon the
flattened enamel surface with finger
pressure. The excess cement was re-
moved with an explorer after the ini-
tial polymerization; the resin cement
was light polymerized with a light
intensity of 480 nm and a power of
1100 mW/cm2 (±10%) for 40 seconds
at a 10-mm distance from the speci-
mens. The bonded specimens were
stored at room temperature with
198
100% relative humidity for 48 hours
prior to the shear bond strength test.
Each specimen was then mounted on
a metal holder in the universal test-
ing machine (Model 5585H; Instron
Corp, Norwood, Mass), equipped
with a 1-kN load cell and at a cross-
head speed of 0.05 mm/min. All of
the specimens were tightened and sta-
bilized to ensure that the edge of the
shearing rod was positioned as close
to the ceramic-tooth interface as pos-
sible. A shear load was applied until
failure occurred. The ultimate load to
failure was recorded in newtons (N).
The average bond strength (MPa) was
calculated by dividing the maximum
ultimate load to failure (N) by the
bonded cross-sectional area (mm2).
The means and standard deviations
were recorded. The fractured surfaces
were then examined under an optical
microscope (Wolfe Contour Cord-
less Binocular Microscope; Carolina
Biological Supply, Burlington, NC) to
obtain the mode of failure. The fail-
ure mode was classified in accordance
with one of the following mode crite-
ria: (I) adhesive failure along the ce-
ramic surface, (II) cohesive failure with
a thin layer of resin cement remaining
on the ceramic surface, or (III) cohe-
sive failure in the luting cement. The
data was then subjected to a 1-way
ANOVA followed by Tukey’s multiple
range tests to define the significant
differences (α=.05). This determined
whether or not significant differences
Table II. Mean (SD) of surface roughness of veneering ceramics with untreated
surface and after hydrofluoric surface treatment
Ceramic Veneer
Conventional
Zirconia
Values with same lowercase letter are not significantly different at P<.05
The Journal of Prosthetic Dentistry
existed in the bond strength of the
various type of veneering ceramics.
An additional 10 specimens from
each group were fabricated to evalu-
ate flexural strength and elemental
composition of the veneering ce-
ramic. Ceramic bars were tested for
flexural strength using a 4-point-1/4-
point flexure test performed in a uni-
versal testing machine (Model 4202;
Instron Corp), equipped with a 10-kN
load cell and at a crosshead speed of
0.5 mm/min. The flexural strength
was calculated based on the follow-
ing equation32:
Flexural strength = 3(PL)/4(wh2)
where P is the applied load (new-
tons), L is outer span of the 4-point
bend apparatus (mm), w is the width
of specimen (mm), and h is the height
of specimen (mm). The flexural-test
device was self-aligning, with an inner
span of 10 mm and an outer span of
20 mm. The ceramic bars were then
positioned to ensure that the top and
bottom surfaces were aligned perfect-
ly with a uniform contact to the roll-
ers. This uniform contact was verified
visually and then the rollers were fixed
with a diameter of 2.4 mm. A Weibull
regression analysis was performed on
the strength data to determine the
Weibull modulus (m value) and the
strength levels at a 5% probability of
failure for assessing the reliability of
each material. The description of the
Weibull distribution is given by the
formula33:
Untreated Surface Acid-Etch Surface Treatment
Group C 0.20 (0.01)
Group D 0.24 (0.03)
Group E 0.19 (0.02)
Group R 0.17 (0.03)
Group CZ 0.30 (0.06)
Group L 0.21 (0.03)
Group Z 0.24 (0.03)
Volume 100 Issue 3
P(σ) = 1-exp (-σ/σ0)m
where P(σ) is the fracture probability,
σ is the fracture strength, σ0 is the
characteristic strength at the fracture
probability of 63.21%, and m is the
Weibull modulus, which is the slope
of the line (line 1/1-P) versus in σ
plots. Pairwise differences among the
testing groups were evaluated by us-
ing confidence intervals for scale and
shape parameters. Overlapping con-
fidence intervals for the parameters
would indicate that the Weibull dis-
tributions did not differ. In addition,
an EDS analysis (EDS INCA system;
Oxford Instruments, High Wycombe,
UK) was performed to quantify the
elemental composition of veneering
ceramics.
RESULTS
The mean surface roughness (Ra)
(SD) of the ceramic before and after
acid etching is presented in Table II.
Before acid etching, group CZ (0.30
(0.06)) presented the highest mean
surface roughness values relative to
other testing groups. After acid-etch-
ing surface treatment, an increase in
surface roughness was detected in all
groups. One-way ANOVA revealed
significant differences between the
group means (df of 6, F of 135.63,
P<.001). As for conventional veneer-
ing ceramics, groups C (1.18 (0.09))
and R (1.28 (0.06)) had higher mean
surface roughness values, while D
1.18 (0.09)a
0.56 (0.07)d
0.74 (0.05)b,c
1.28 (0.06)a
0.66 (0.05)c,d
0.58 (0.05)d
0.55 (0.07)d
Chaiyabutr et al
September 2008
(0.56 (0.07)) and E (0.74 (0.05)) had
a mean of roughness value that was
comparable with the group of zirconia
veneering ceramics, CZ (0.66 (0.05)),
L (0.58 (0.05)), and Z (0.55 (0.07)).
There were no significant differences
in surface roughness among all zirco-
nia veneering ceramics. The SEM im-
ages of the external acid-etched sur-
faces of specimens provided valuable
information concerning the porous
structure of ceramic materials (Fig. 2).
From these 2-dimensional images, an
amorphous spongy-like microstruc-
ture with numerous microporosities
on the surface was found in the con-
ventional veneering ceramic, while the
zirconia veneering ceramic exhibited a
smooth surface structure with some
striation formation. These striations
were detected as elongated pores in
the subsurface under higher magni-
fication and appeared to be larger
and deeper when compared with the
porosities found on the acid-etched
conventional veneering ceramic speci-
mens.
The means and standard devia-
tions of the bond strength are pre-
sented in Table III. One-way ANOVA
for the results of the shear bond
strength revealed that there were sig-
nificant differences between the mean
groups (df of 6, F of 11.07, P<.001).
The highest mean (SD) shear bond
strength was obtained from the con-
ventional veneering ceramics, group
R (25.16 (3.40) MPa), followed by C
199
(22.51 (2.82) MPa). This is approxi-
mately 50-60% more than the weakest
mean bond strength obtained from
zirconia veneering ceramics, found in
group L (9.45(1.62) MPa). The mode
of failure data demonstrated that
zirconia veneering ceramics had the
most adhesive failures along the ce-
ramic veneer surface, group L (100%),
CZ (75%), and Z (50%), while conven-
tional veneering ceramics had mixed
cohesive failures, with a thin layer of
resin cement remaining on the ceram-
ic surface and at the luting cement.
The means and standard devia-
tions of the flexural strength data and
the Weibull statistical analysis for
testing groups are presented in Table
IV. The Weibull analysis provided 2

A B
2 SEM micrographs of acid-etch surface. A, Zirconia veneering ceramic. B, Conventional veneering ceramic (x1000
magnification).

Table III. Mean (SD) of shear bond strength. For mode of failure: Type I, adhesive failure
along ceramic surface; Type II, cohesive failure with thin layer of resin cement remaining on
ceramic surface; Type III, cohesive failure in luting cement

Mode of Failure (%)

Ceramic Veneer Shear Bond Strength (MPa) Type I Type II Type III

Conventional Group C 22.51 (2.82)a,b – 75 25

Group D 16.54 (2.73)b,c – 50 50
Group E 17.92 (3.39)a,b,c 25 25 50
Group R 25.16 (3.40)a – 25 75

Zirconia Group CZ 13.02 (3.42)c,d 75 25 –

Group L 9.45 (1.62)d 100 – –
Group Z 13.03 (5.07)c,d 50 50 –

Values with same lowercase letter are not significantly different at P<.05
Chaiyabutr et al
200 Volume 100 Issue 3
Table IV. Mean (SD) of flexural strength and Weibull analysis
4-Point–1/4-Point Weibull Weibull
Flexure Strength Modulus Characteristic 95% CI
Ceramic Veneer (MPa) (m) Strength σ0 for σ0

Conventional Group C 76.82 (6.73) 11.91 79.87 75.88-84.07

Group D 82.77 (10.77) 8.72 87.44 81.53-93.78
Group E 91.31 (11.42) 8.90 96.39 90.00-103.23
Group R 93.27(12.91) 7.11 99.74 91.54-108.68

Zirconia Group CZ 62.33 (5.15) 11.94 64.55 62.20-67.94

Group L 80.36(7.80) 11.79 83.86 79.63-88.32
Group Z 85.71 (9.30) 10.45 89.85 84.75-95.25

Table V. EDS analysis of major components of element surface composition (%wt) in different
ceramic veneering materials

Element Composition in % by Weight

Ceramic Veneer Si C O F Na Mg Al K

Conventional Group C 9.90 23.37 55.37 0.66 4.28 0.14 3.86 1.41
Group D 12.07 15.24 58.61 1.80 7.05 0.05 4.18 0.99
Group E 8.83 19.56 52.35 0.95 6.94 0.33 3.41 0.53
Group R 16.39 11.29 58.13 0.86 6.04 0.05 4.69 2.03

Zirconia Group CZ 6.84 25.64 59.23 1.50 4.37 0.10 2.07 0.24
Group L 8.50 14.12 66.22 2.17 6.10 0.00 2.62 0.27
Group Z 6.09 20.58 63.16 1.69 5.72 0.00 2.77 0.00

parameter estimates for each group;
the Weibull modulus m and the nor-
malizing parameter σ strength, which
corresponds to the 63.21 probability
of failure. Based on the mean strength
data (SD), a conventional veneering
ceramic, group R, was the strongest
(93.27 (12.91) MPa), though values
did not differ significantly from other
groups: E (91.31 (11.42) MPa), D
(82.77 (10.77) MPa) (overlap con-
fidence intervals for parameter σ0),
with the exception of C (76.82 (6.73)
MPa). For the zirconia veneering ce-
ramics, groups Z (85.71 (9.30) MPa)
and L (80.36 (7.80) MPa) had flexural
strength mean values that were com-
parable to conventional veneering
ceramic; however, group CZ (62.33
The Journal of Prosthetic Dentistry
(5.15) MPa) was significantly lower
than the others (P<.001).
The elemental composition analy-
sis revealed that the major component
elements included high concentrations
of oxygen (O), carbon (C), and silica
(Si), followed by sodium (Na), alumi-
num (Al), potassium (K), magnesium
(Mg), and fluoride (F) (Table V). The
composition of silica (Si) ranged from
6.09 to 8.50% by weight in the zirco-
nia veneering ceramics, which demon-
strated similar quantities to groups C
(9.90%) and E (8.83%). The 2 highest
concentrations of silica composition
were found in the conventional ve-
neering ceramic, group R (16.39 %),
followed by D (12.07%).
DISCUSSION
The surface morphology of con-
ventional veneering ceramics, which
are subjected to hydrofluoric acid-etch
treatments, conform to those report-
ed in the literature.10-12 As described
by Yen et al,12 hydrofluoric acid can re-
act preferentially with the silica phase
in a glassy matrix to form hexafluo-
rosilicates. As a result, the surface of
the ceramic becomes rough, which is
required for micromechanical reten-
tion. In the present study, EDS analy-
sis revealed that there were 3 ranges
of percent by weight silica content
in ceramic veneers: a high amount
of silica (groups D and R) (12-16%),
medium amount of silica (groups C,
Chaiyabutr et al
September 2008
E, and L) (8.5-9%), and low amount
of silica (groups CZ and Z) (6-7%). In
most situations, the amount of silica
content in the ceramic may represent
the possibility of a hydrofluoric acid-
etch reaction. However, in the present
study, the surface roughness values of
some veneering ceramics are depen-
dent on silica contents while some are
not. For example, group D had higher
percent by weight silica content, but
demonstrated significantly lower val-
ues in surface roughness when com-
pared with other conventional veneer-
ing ceramics. One possible reason for
the lower surface roughness values
may be that the hydrofluoric acid
concentration that was used to etch
group D specimens is only 5%, while
other ceramics were recommended
to be etched with concentrations of
9.5%. At low hydrofluoric acid con-
centrations, the crystalline phase
could have greater durability.10,12,15
Therefore, using a lower concentra-
tion may cause less of an etching ef-
fect on the ceramic surface, thereby
resulting in a lower surface roughness
value. It is also interesting to note that
group L had a medium silica content;
however, the surface roughness val-
ues were lower and comparable to
the groups with low silica content,
such as groups CZ and Z. In regard to
the etching effect in group L, surface
roughness measurements alone may
not fully explain the particular distri-
bution of the porosity. Future research
is required to evaluate the volumetric
porosity and the pore size rather than
a function of roughness.
The present study confirmed that
insufficient surface modification and
the difference in surface texture after
acid etching could affect the reten-
tion of ceramic. This information was
supported by SEM evaluation, which
showed a different retentive surface
topography in the zirconia veneer-
ing ceramic groups compared with
the conventional veneering ceramics.
The zirconia veneering ceramic acid-
etched surface consists of 2 separate
parts: a smooth surface (representing
insufficient acid etching) and a rough
Chaiyabutr et al
surface with groove formation. This
surface texture may influence the dis-
tribution of the silane coupling agent
on the ceramic surface. Jardel et al21
reported that etching with hydro-
fluoric acid alone without the silane
coupling agent is not sufficient to
produce a strong bond. It appeared
that the silane solution may not have
been distributed well on the zirconia
veneering ceramic surface when it was
compared with the surface of the con-
ventional veneering ceramic, which
exhibited an amorphous spongy-like
microstructure with numerous mi-
croporosities. Thus, the overall mean
bond strength of zirconia veneering
ceramic was at least 25% lower than
that of conventional veneering ce-
ramic. The lower values in shear bond
strength may be a result of the weak
link between the composite resin lut-
ing agent and the ceramic. The post
failure survey after the strength test
also revealed that zirconia veneering
ceramic had the most adhesive failure
at the ceramic interface. Although the
overall mean bond strength of the zir-
conia veneering ceramic is lower than
conventional veneering ceramic, the
statistical analysis demonstrated that
only 2 groups of zirconia veneering
ceramic (groups CZ and Z) had bond
strengths comparable to the group
of conventional veneering ceramics.
Therefore, the first null hypothesis
was rejected.
The flexural strength of the ceram-
ic veneer was also evaluated in the
present study. It is well known that
investigating only the mean flexural
strength does not result in accurate
characterization of the properties of
a ceramic. In order to evaluate the
strength data for ceramics, a Weibull
regression analysis is indicated, since
ceramics have a wide variability in
their failure rates. This is directly re-
lated to flaws incorporated when
the specimens are processed.33,34 The
variability of strength was considered
by estimating the Weibull modulus,
m, which considers the flaw size dis-
tribution in ceramic. In the present
study, the m values of the groups were
201
within the range of 5 to 15 cited for
dental ceramics.34 For the most part,
the strength data support rejection
of the second null hypothesis, since
a significant difference was detected
in one group of zirconia veneering ce-
ramic (group CZ). Although groups of
veneering ceramic received the same
surface treatment (polishing/glaz-
ing), it was found that group CZ had
the highest surface roughness values
at the untreated surface, and these
values were 20-40% higher than the
other group of veneering ceramics.
De Jagar et al21 reported that surface
roughness results in nonuniform stress
distribution, and applied stress will
concentrate locally, which will lead to
incongruous surface layers. The dis-
tribution of cracks in group CZ may
not have developed or propagated
randomly, but formed at the rough-
est spots, which also had the highest
stress concentration, resulting in a
significantly lower flexural strength.
There are limitations to the pres-
ent study. The veneering ceramics se-
lected (zirconia or conventional) were
used based on their commercial avail-
ability. The results are applicable to
only the veneering ceramic and luting
system evaluated. Although surface
roughness was measured, the volu-
metric porosity and the average pore
size of each ceramic were not estimat-
ed. That information may help explain
more about the features of the etch-
ing effect on ceramic surfaces. Two-
dimensional SEM images were made
in the present study. Additional infor-
mation on z dimension (3-D) would
be beneficial to understand the pore
distribution in acid-etched ceram-
ics. The effect of differences in acid
concentration and differences in acid
application periods were not deter-
mined in the present study, since the
study methods were intended to repli-
cate the most practical methods used
in the laboratory and clinic. These
influencing factors may need to be
considered in future research. In the
present study, low pressure alumina
oxide-particle abrasion on the ceram-
ic surface was not used as a regular
202
mechanical cleansing protocol for the
ceramics prior to acid etching. The
subsequent use of the alumina oxide-
particle abrasion on ceramic surfaces
may substantially increase the surface
area and enhance the potential for
micromechanical retention, and in-
creases the bond strength of the ce-
ramic veneer on the tooth.17
CONCLUSIONS
Effective ceramic interface man-
agement, such as acid etching and
enamel bonding, is considered es-
sential for successful ceramic lami-
nate veneer restorations. This study
demonstrated that not all zirconia
veneering ceramics display the same
quality of surface roughness after hy-
drofluoric acid etching and the same
bond strength to enamel when used
as laminate veneer materials.
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Corresponding author:
Dr Yada Chaiyabutr
1001 Fairview Ave N, Suite 2200
Seattle, WA 98109
Fax: 206-621-7609
E-mail: yada@koiscenter.com
Acknowledgements
The authors thank the manufacturers for
the donation and provision of the ceramic
substrates. The authors also thank Mr Ron
L’Herault, Department of Biomaterials/Re-
storative Sciences, Boston University, and Mr
William Kuykendall, Department of Mechani-
cal Engineering, University of Washington, for
their technical assistance.
Copyright © 2008 by the Editorial Council for
The Journal of Prosthetic Dentistry.
Chaiyabutr et al