Braz Dent J (2011) 22(1): 45-50 Ceramic properties after HF etching ISSN 0103-6440

45

Effect of Hydrofluoric Acid Etching Duration on

the Roughness and Flexural Strength of a Lithium
Disilicate-Based Glass Ceramic
Lucas Villaça ZOGHEIB1
Alvaro DELLA BONA1
Estevão Tomomitsu KIMPARA2
John F. MCCABE3

1Department of Restorative Dentistry, Dental School, University of Passo Fundo, Passo Fundo, RS, Brazil
2Department of Dental Materials and Prosthodontics, São José dos Campos Dental School,
UNESP - Univ. Estadual Paulista, São José dos Campos, SP, Brazil
3Dental Materials Unit, Newcastle University, Newcastle upon Tyne, United Kingdom

The aim of this study was to examine the effect of different acid etching times on the surface roughness and flexural strength of a
lithium disilicate-based glass ceramic. Ceramic bar-shaped specimens (16 mm x 2 mm x 2 mm) were produced from ceramic blocks.
All specimens were polished and sonically cleaned in distilled water. Specimens were randomly divided into 5 groups (n=15). Group
A (control) no treatment. Groups B-E were etched with 4.9% hydrofluoric acid (HF) for 4 different etching periods: 20 s, 60 s, 90 s
and 180 s, respectively. Etched surfaces were observed under scanning electron microscopy. Surface profilometry was used to examine
the roughness of the etched ceramic surfaces, and the specimens were loaded to failure using a 3-point bending test to determine the
flexural strength. Data were analyzed using one-way ANOVA and Tukey’s test (α=0.05). All etching periods produced significantly
rougher surfaces than the control group (p<0.05). Roughness values increased with the increase of the etching time. The mean flexural
strength values were (MPa): A=417 ± 55; B=367 ± 68; C=363 ± 84; D=329 ± 70; and E=314 ± 62. HF etching significantly reduced
the mean flexural strength as the etching time increased (p=0.003). In conclusion, the findings of this study showed that the increase
of HF etching time affected the surface roughness and the flexural strength of a lithium disilicate-based glass ceramic, confirming
the study hypothesis.

Key Words: hydrofluoric acid, CAD/CAM, lithium disilicate glass ceramic, roughness, flexural strength.

INTRODUCTION is embedded in varying amounts of undissolved feldspar

and reinforcement crystals like lithium disilicate (1,4).
Dental ceramic restorations are extensively used, For ceramic surface treatment, the acid reacts
because they are durable, esthetically appealing, and with the glass matrix that contains silica and forms
provide excellent biocompatibility (1). This preference hexafluorosilicates. This glass matrix is selectively
is directly related to the success of ceramic resin bond removed and the crystalline structure is exposed. As a
that contributes to the restoration longevity. result, the surface of the ceramic becomes rough, which
The retention of the lithium silicate ceramic is expected for micromechanical retention on the ceramic
veneer can be satisfactorily achieved by two factors: surface (5,6). This roughly etched surface also helps to
ceramic surface treatment from acid etching, and provide more surface energy prior to combining with
silane coupling agent application prior to cementation the silane solution (7).
with a resin cement (1-4). In general, the structure of In vitro studies have reported positive effects of
veneering ceramic has been described as an amorphous hydrofluoric acid (HF) etching on the strength of glasses
and glass matrix that consists of a random network of by removing or stabilizing surface defects and on surface
cross-linked silica in a tetrahedral arrangement, which topography increasing roughness for adhesive bonding

Correspondence: Prof. Lucas Villaça Zogheib, Faculdade de Odontologia, Universidade de Passo Fundo, Campus I, São José, BR 285 - Km 171,
99052-900 Passo Fundo, RS, Brasil. Tel:+55-54-3316-8402. Fax: +55-54-3316-8403. e-mail: [email protected]

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46 L.V. Zogheib et al.

(2,8,9). On the other hand, HF etching can weaken the ceramic specimens were etched in a laboratory cupboard
flexural strength of ceramics (10). under ventilation, wearing acid resistant gloves, coat
The addition of lithium disilicate crystals in cover with plastic apron and face shield. The etching gel
glass ceramics aimed to improve strength and durability was rinsed in a polyethylene cup for 30 s and the diluted
over conventional dental ceramics (12). In addition, the solution was neutralized using the neutralizing powder
development of new technologies, such as computer- (calcium carbonate, CaCO3 and sodium carbonate,
aided design/computer aided manufacturing (CAD/ Na2CO3) for 5 min. The treated specimens were sonically
CAM), allowed for an easier and more practical cleaned in distilled water for 5 min.
fabrication of lithium silicate-based all-ceramic Randomly selected specimens from each group
restorations (11). were prepared for morphological examination under a
Although some studies have reported on the effect scanning electron microscope (FEI/Philips XL30 ESEM;
of different HF etching times on bond strength (6,7), Philips Electronic Instruments Co, Mahwah, NJ, USA).
roughness (2) and flexural strength (1,2), none of these In all groups, surface roughness was determined
studies addressed such effects on lithium disilicate-based using a profilometer (Mitutoyo Surftest SV-2000;
glass ceramics. Therefore, the purpose of this study was Mitutoyo, Andover, Hampshire, UK), and the Ra
to examine the effect of different HF etching times on parameter values were recorded. Ra is the average
the roughness and flexure strength of a lithium disilicate- roughness value of a surface. The lower the Ra value
based glass ceramic, testing the hypothesis that different the smoother the surface. The profilometer parameters
HF etching times produces different roughness patterns were set as follows: cutoff length of 0.8 mm, transverse
and flexural strength values for this ceramic. length of 4.0 mm, and a measuring range of 0-12.5 mm.
Each specimen was scanned 4 times in different areas
MATERIAL AND METHODS of the specimen and average the Ra value.
The flexural strength was determined with a
Seventy-five bar-shaped ceramic specimens (16 3-point bending test in a universal testing machine
mm x 2 mm x 2 mm) were fabricated from partially (Model 5567; Instron Ltd, Buckinghamshire, England).
crystallized lithium disilicate-based glass blocks (IPS The specimens were placed flat on a mountain jig with
e.max CAD; Ivoclar Vivadent, Schaan, Liechtenstein). rounded supporting rods 12 mm apart, and the center of
The ceramic blocks were cut in rectangular slices (16 mm the specimens was loaded (load cell 1 KN) with a rounded
x 2 mm) using a low speed diamond wheel saw (Model chisel (radius 3 mm) at a crosshead speed of 0.5 mm/
650; South Bay Tech Inc, San Clemente, CA, USA). The min until fracture occurred. The following equation was
ceramic slices were wet polished up to 1000-grit silicon used for flexural strength (σ) calculation: σ=3 Pl/2wb2,
carbide paper and polishing liquid on a grinding device where P is the fracture load (in N); l is the test span (12
(Metaserv; Metallurgical Services, Betchworth, Survey, mm); w is the width of the specimen (in mm); and b is
England) to remove external irregular scratches and the thickness of the specimen (in mm).
defects. The ceramic slices were further cut in bar-shaped One-way ANOVA and Tukey’s HSD test
specimens using the same low speed diamond wheel (α=0.05) were used to assess the statistically significant
saw. All ceramic specimens were sonically cleaned in differences of ceramic surface roughness and flexural
distilled water for 15 min. Specimens were crystallized strength values among the different HF etching times.
following the firing program and vacuum pump furnace
recommended by the manufacturer. RESULTS
The ceramic specimens were randomly divided
into 5 groups (n=15) according to the following ceramic The mean and standard deviation values for Ra
surface treatment: and flexural strength of all experimental groups are
Group A (control) - no ceramic surface treatment; presented in Table 1.
Group B - HF etched (4.9% hydrofluoric acid gel; Significant differences in mean Ra values were
Ivoclar-Vivadent) for 20 s; Group C - HF etched for 60 found among the groups. Group A (0.06 ± 0.01) showed
s; Group D - HF etched for 90 s; Group E - HF etched the lowest mean Ra value, while Group E (0.16 ± 0.1)
for 180 s. showed the highest mean Ra value (p<0.05). There
As HF offers hazardous effects to health, the were no significant differences (p>0.05) between the

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 Ceramic properties after HF etching 47

mean Ra values of groups B and C, groups C and D, improve the surface energy by cleaning the ceramic
and groups D and E. surface (14).
Significant differences in mean flexural strength Ceramic etching is a dynamic process and the
values were also found (Table 1). The control group impact is dependent on substrate constitution, surface
showed significantly higher (p>0.05) mean values than topography, acid concentration and etching time (2,15).
groups D and E. There were no significant differences Regarding the etching time, many studies have
(p>0.05) among groups A, B and C, and among groups B, been done with different kinds of ceramics and HF
C, D and E. However, the mean flexural strength values etchants (3,5,6,15). Chen et al. (5) evaluated two HF
decreased with the increase HF etching time increasing. etchants (2.5 and 5%) and seven different etching times
There was a positive correlation between Ra and flexural (0, 30, 60, 90, 120, 150, and 180 s). Etching periods
strength values (r2=96%) (Fig. 1). above 30 s effectively enhanced the bond strength to
Analysis of the different ceramic surface resin. Of the two etching agents applied to the unsilanated
treatments by scanning electron microscopy (SEM) porcelain, the buffered 2.5% HF produced higher bond
provided valuable information concerning the resulting strengths to resin than the 5% HF for all etching time
topography. The untreated ceramic surface is smooth and periods, except for 180 s. Guler et al. (3) evaluated the
homogeneous (Fig. 2A), becoming increasingly porous effect of different 9.6% HF etching times (30 s, 30+30
and irregular because of the dissolution of the glass phase s, 60 s, 60+60 s, 120 s, and 180 s) on porcelain and
after HF etching (Figs. 2B-E). As a consequence, voids 2 adhesive systems on shear bond strengths to resin
and channels appeared larger and deeper, as the etching composite. The authors concluded that HF etching for
period increases. HF etching patterns appeared more 120 s provided adequate bond strength of porcelain to
pronounced and aggressive in groups D and E, where resin.
lithium disilicate crystals can be easily seen protruded It is known that HF etching of porcelain
from the glassy matrix. provides the necessary surface roughness to mechanical
interlocking but overetching could have a weakening
DISCUSSION effect on the porcelain (15-17). Therefore, it is
important to know the adequate HF etching time
Standard adhesive protocol for ceramic for micromechanical retention without weakening
restorations requires etching and silanating the fitting the ceramic. this is the reason why the present study
surface of the porcelain (13). Acid etching of porcelain investigated the adequate etching protocol for a lithium
has been widely used to enhance the retention between disilicate-based glass ceramic.
bonding resins and ceramic restorations. Some studies Since HF etching was first suggested as a
have suggested that etching is needed preferably with ceramic surface treatment for resin bonding, many
HF than with phosphoric acid (4,13). Notwithstanding, different combinations between etching periods and
phosphoric acid does not etch ceramics but it may

Table 1. Mean values and standard deviations for surface

roughness and flexural strength in all experimental groups.

Surface treatment Surface roughness Flexural strength

(HF etching time) (Ra; µm) (MPa)

Untreated (A) 0.06 ± 0.01 a 417 ± 55 a

20 s (B) 0.09 ± 0.05 b   367 ± 68 ab
60 s (C)   0.12 ± 0.05 bc   363 ± 84 ab
90 s (D)   0.14 ± 0.06 cd 329 ± 70 b
180 s (E) 0.16 ± 0.10 d 314 ± 62 b

Different letters indicate statistically significant difference Figure 1. Fitted line plot of flexural load at failure and surface
(Tukey’s test; p<0.05). roughness (Ra; µm).

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48 L.V. Zogheib et al.

acid concentration have been suggested and used (1- time, which agreed with other studies (2,19) and with
6,8,14,18-20). Wolf et al. (8), evaluated the surface the present study.
roughness of a feldspathic porcelain etched with 9.5% HF In the present study, HF etching increased ceramic
for 30, 60, 150, and 300 s and the tensile bond strength to roughness in all experimental groups, even for periods as
resin. The authors found a positive correlation between short as 20 s, which is the etching time recommended by
ceramic surface roughness and increasing HF etching the manufacturer. Significantly higher mean Ra values

Figure 2. Panel of representative SEM micrographs of

the surface of HF-etched lithium disilicate-based glass
ceramic after application of the different etching times
evaluated in the study. Original magnification ×5,000.

A = not etched

B = 20-s etching

C = 60-s etching

D = 90-s etching

E = 180-s etching

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 Ceramic properties after HF etching 49

were found for groups D and E. The mean Ra values for etching times and acid concentrations are necessary.
the etching times of 0, 20, 60, 90 and 180 s were 0.06, Future studies should consider clinical conditions like
0.09, 0.12, 0.14, and 0.16 µm respectively. Chen et al. wet environment and cyclic load of bonded ceramic
(6), using 2.5% HF, observed that etching periods for restorations.
more than 30 s effectively enhanced the bond strength The findings of this study showed that the increase
between a feldspathic porcelain and a resin cement. of HF etching time affected the surface roughness and
Different results were found and explained by Della the flexural strength of a lithium disilicate-based glass
Bona et al. (15,18). The authors suggested that etching ceramic, confirming the study hypothesis.
mechanisms change according to the type of etchant
and ethcing time, and the ceramic microstructure and RESUMO
composition (18). Therefore, it is difficult to compare
the present results to those of previous studies that used O objetivo deste estudo foi avaliar o efeito de diferentes tempos de
condicionamento ácido na rugosidade de superfície e resistência
different ceramics and etching protocols. However,
flexural de uma cerâmica à base de disilicato de lítio. Espécimes
associating the mean Ra values with the SEM images cerâmicos em forma de barra (16 mm x 2 mm x 2 mm) foram
it is possible to suggest that the ceramic used in the produzidos a partir de blocos cerâmicos. Todos os espécimes foram
present study need more than a 60-s HF etching time polidos e limpos em banho de ultrasom em água destilada. Os
espécimes foram aleatoriamente divididos em 5 grupos (n=15).
to produce adequate retentive surface for resin bonding.
Grupo A (controle) sem tratamento. Grupos B-E condicionamento
The SEM micrographs clearly revealed the effect of the com ácido fluorídrico 4,9% (HF) por 4 diferentes períodos de
different etching periods on the microstructure of the condicionamento: 20 s, 60 s, 90 s e 180 s, respectivamente. As
ceramic (Figs. 2A-E). For cementation of e-max CAD superfícies condicionadas foram observadas sob microscopia
eletrônica de varredura. Perfilometria de superfície foi utilizada
restorations, the manufacturer recommends an etching
para examinar a rugosidade das superfícies condicionadas, e os
time of 20 s using a 4.9% HF gel. The ceramic surface espécimes foram carregados até a falha pelo teste de flexão três
roughness produced by this etching time is significantly pontos. Os valores foram analisados usando ANOVA um fator e
lower than etching for either 90 or 180 s (Table 1 and teste de Tukey (α=0,05). Todos os períodos de condicionamento
produziram superfícies significantemente mais rugosas do que o
Figs. 2 B-E). In addition, Figures 2B and 2C (ceramic
grupo controle (p<0,05). Os valores de rugosidade aumentaram
etched for 20 and 60 s, respectively) show minor surface com o tempo de condicionamento. Os valores médios de
disruptions compared to Figures 2D and 2E (ceramic resistência à flexão foram (MPa): A=417 ± 55; B=367 ± 68;
etched for 90 and 180 s, respectively). This suggests C=363 ± 84; D=329 ± 70; e E=314 ± 62. O condicionamento com
HF reduziu significativamente os valores médios de resistência
different abilities for micromechanical retention and
à flexão conforme o tempo de condicionamento aumentou
bond strength to resin. Further studies on the bond (p=0,003). Os achados deste estudo mostraram que o aumento
strength are necessary to confirm this hypothesis. do tempo de condicionamento ácido influenciou a rugosidade
In the current investigation the flexural strength de superfície e resistência flexural de uma cerâmica à base de
disilicato de lítio confirmando a hipótese do mesmo.
of the lithium disilicate-based glass ceramic decreased
after HF etching. The reason of this could be explained
because the amount of the glass phase involving ACKNOWLEDGEMENTS
the lithium disilicate crystals. SEM images clearly
The authors acknowledge Ivoclar-Vivadent for providing the
revealed less amount of glassy matrix in the control necessary materials used in this study and CAPES (Brazilian
group compared with all experimental groups. Similar Federal Agency for the Support and Evaluation of Graduate
results testing different ceramics have been described, Education) for the financial support provided (grant #3242/08-0).
The authors also acknowledge ACMA unit at School of Chemistry
confirming the weakening effect of HF etching (1,8,12).
and the School of Chemical Engineering and Advanced Materials,
It should be noted that this study has some Newcastle University for the SEM analysis.
limitations. First, the 3-point bending test used does
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