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Objective. To compare the effect of various surface treatments on the bonding of luting resin
Methods. Bar specimens (n = 200) (2 mm 5 mm 25 mm) were prepared from zirconia blocks
8 January 2015
(VITA In-Ceram YZ, Vita Zahnfabrik) with the cementation surface (2 mm 5 mm) of
Keywords:
(CC), or left untreated as control (C). Within each treatment, bars were cleaned ultrasoni-
cally for 15 min in ethanol and then deionized water before bonding in pairs with one of
Adhesive cementation
two luting resins: Panavia F 2.0, (Kuraray) (P); RelyX U-200 (3 M/Espe) (R), to form 10 test
specimens for each treatment and lute combination. Mechanical tests were performed
and bond strengths (MPa) were subject, after log transformation, to analysis of variance,
ShapiroWilk and HolmSidak tests; also log-linear contingency analysis of failure mode
distribution; all with = 0.05. Fracture surfaces were examined under light and scanning
electron microscopy.
Results. While the effect of surface treatment was signicant (p = 1.27 109 ), there was no
detected effect due to resin (p = 0.829). All treatments except CC (30.1 MPa / 1.44)* were
signicantly better than the untreated control (24.8 MPa / 1.35) (p = 3.28 109 ). While the
effect of GB which gave the highest mean strength (50.5 MPa / 1.29) was not distinguishable from that of GHF (39.9 MPa / 1.29) (p = 0.082), it was signicantly better than
treatment with either CC or Z (33.1 MPa / 1.48) (p < 0.05). (* After log transformation for
analysis and back; asymmetric error bounds as s.d. in log values.)
Signicance. The novel test method design, which has good discriminatory power, conrmed
the value of gritblasting as a simple and effective treatment with low operator hazard. It gave
the highest bond strengths regardless of the cement type. Glaze layer application followed
http://dx.doi.org/10.1016/j.dental.2015.03.004
0109-5641/ 2015 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.
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d e n t a l m a t e r i a l s 3 1 ( 2 0 1 5 ) 657668
1.
Introduction
Zirconia, or rather yttria-partially stabilized tetragonal zirconia (YTZP), is increasingly used in dentistry in view of its
remarkable strength [1,2]. However, a major impediment to
its effective use is its lack of reactivity since it is a non-polar
and more or less inert material which becomes very dense and
homogeneous on sintering [3]. This means that all the usual
means of bonding (in the broad chemical sense of established
a covalent bond between adhesive material and the substrate),
effective enough for other ceramic systems, do not work [3],
and although phosphate-based systems have shown some
improvement [3], nothing is yet considered reliable enough.
This also includes the mechanical retention afforded by gritblasting, where particle size has to be limited to minimize
subsurface damage and hence the risk of cracking [4]. Thus, it
is of great interest to develop an effective means of bonding
to zirconia to enable long-term retention. For this purpose, a
great number of surface treatment methods have been tried,
for example to roughen the surface with rotary systems, laser
irradiation, or selective inltration etching, or to modify the
surface through silica coating, silane application, hydrouoric
acid etching after fused glass-ceramic application, or nanostructured alumina coating [3,57].
The nature of dentistry, in terms of economy, processing
time, and the fact that all restorative devices are effectively
one-off prototypes, means that the clinical and laboratory procedures to be used for zirconia-based polycrystalline ceramic
restorations to achieve adhesive cementation should be practical and easily handled. We may note that while hydrouoric
acid (HF) etching is an easy if hazardous surface treatment
for silicate-containing ceramics [8], some oxide ceramics, and
in particular zirconia, which contain less than 15 mass% silica
and little or no glass phase [9], cannot be so treated. However, the application of a fused glass-ceramic on the intaglio
surfaces of zirconia restorations, which glaze is then etchable
and so capable of adhesive cementation, has been described
[5,10,11]. The effectiveness of this bonding depends on intimate contact and micromechanical key with grain boundary
topography, rather than chemical interaction as has sometimes been suggested [12], there being no chemical reaction
or elemental migration or diffusion at the interface [13]. Some
studies suggest that compressive stresses arising from a difference in coefcient of thermal expansion (CTE) between a
ceramic and zirconia have a positive correlation with the bond
strength [14]. This is a general principle that should apply
in the present context. Ordinary silane chemistry also may
not improve the afnity of resin cements for zirconia since
it is more stable then silica-based ceramics and cannot be
hydrolysed easily [3]. Zirconate coupling agents have been
introduced with the aim of improving the bonding of zirconia
d e n t a l m a t e r i a l s 3 1 ( 2 0 1 5 ) 657668
659
2.
2.1.
Specimen preparation
Presintered zirconia blocks (Vita In-Ceram YZ-40/19; Vita Zahnfabrik, Bad Sckingen, Germany) were cut with a low-speed
(400 rpm) diamond saw under water cooling (Isomet 1000;
Buehler, Lake Bluff, IL, USA) to give bars with the dimensions
of 31.25 mm 6.25 mm 2.50 mm (each aspect measured at
three places with a digital caliper) using an acrylic jig. These
were then sintered at 1530 C for 7.5 h in a furnace (MOS
160/1; Protherm, Ankara, Turkey) giving nal dimensions
of 25.0 mm 5.0 mm 2.0 mm after shrinkage. These dimensions were decided according to previous remarks on S/d ratio
[27,28] for this test method [29], given the size of the zirconia
blocks.
The zirconia specimens were then ultrasonically cleaned
(Sonorex RK102 Transistor; Bandelin, Walldorf, Germany) for
15 min in 96% ethanol (Smyras, Bornova, Izmir, Turkey) and
15 min in distilled water to ensure the absence of particulate debris immediately before surface treatment. Calculation
indicated that 10 specimens per subgroup would give a power
>90%.
2.2.
Surface treatments
2.2.1.
Control (C)
No surface treatment.
2.2.2.
Gritblasting (GB)
Gritblasting (EasyBlast; Bego, Bremen, Germany) was performed normal to the luting surface with 50 m Al2 O3 (Shera
Werkstoff Technologie, Hannover, Germany) for 13 s at a pressure of 2.8 bar from a distance of 10 mm [32].
2.2.3.
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d e n t a l m a t e r i a l s 3 1 ( 2 0 1 5 ) 657668
at 60 C/min to 725 C, which was held for 1 h before cooling. Glaze that extended beyond the cementation surface was
removed, by grinding at on 600-grit SiC paper under water,
to avoid any supportive effect during the fracture test.
The glazed surfaces were then treated at room temperature with 9.5% hydrouoric acid gel (Porcelain Etch; Ultradent
Products, South Jordan, UT, USA) for 60 s, rinsed with deionized water for 90 s. They were then neutralized with a slurry
of neutralizing powder (CaCO3 , Na2 CO3 ) (IPS Ceramic Neutralizing Powder, Ivoclar Vivadent) for 5 min, washed thoroughly
for 20 s with distilled water, and air dried [5].
2.2.4.
2.2.5.
After cleaning the cementation surfaces by rinsing with deionized water and air drying, two coats of primer (Z-Prime Plus;
Bisco, Schaumburg, IL, USA) were applied uniformly, wetting
the bondable surface, and dried with an air syringe for 35 s to
remove solvent, according to the manufacturers instructions.
2.3.
Luting
from the interface. For resin P, the material was then covered
with an oxygen-inhibiting material (Oxyguard; Kuraray, Tokyo,
Japan), and irradiated for 20 s each from the top and the bottom
(LED Bluephase C5; Ivoclar Vivadent),. Resin R was similarly
irradiated from top and bottom for 10 s each, to prevent movement, then left undisturbed for 5 min (25 C, 5065% relative
humidity) to complete self-curing.
2.4.
3F(L Li )
2wh2
2.5.
Fractographic analysis
2.6.
Statistical analysis
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d e n t a l m a t e r i a l s 3 1 ( 2 0 1 5 ) 657668
Manufacturer
a
Panavia F 2.0
Composition description/mass%
Batch
A paste: BPEDMA/MDP/DMA
B paste:
*
Ba-* B-Si-glass/silica-containing
composite
Glycerin gel
00037A
00020A
3 M/Espe
Seefeld, Germany
315751
Vita In-ceram
YZ-40/19
Zirconia Block
ECYZ40192
P56200
P56200
Z-Prime Plus
(Zirconia Primer)
B-6001P
Ultradent
Porcelain Etch
C123
Oxyguard II
b
Rely-X U200
Base
(Clicker Dispenser)
Rely-X U200
Catalyst
(Clicker Dispenser)
00471A
3.
Results
3.1.
Four-point bending
3.2.
Failure mode and environmental scanning
electron microscopy
The distribution of failures modes is shown in Table 5. In
the 3 CT analysis (Table 6) the interaction (or lack thereof)
between Resin and Surface Treatment has been ignored as the
design was balanced (i.e. not a random distribution of specimens by Resin and Surface Treatment). Thus, the effect of
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d e n t a l m a t e r i a l s 3 1 ( 2 0 1 5 ) 657668
Table 2 Analysis of variance of four-point bending strength: resin surface treatment (log-transformed data).
Source of variation
DF
SS
MS
Resin
Treatment
Resin treatment
Residual
1
4
4
90
0.000841263
1.108007
0.209951
1.620414
0.000841263
0.277002
0.0524878
0.0180046
0.0467
15.385
2.915
Total
99
0.829
1.27 109
0.0256
Table 3 Analysis of variance of four-point bending strength: surface treatment (log-transformed data).
Source of variation
DF
SS
MS
Treatment
Residual
4
95
1.108007
1.831206
0.277002
0.0192759
14.370
Total
99
2.939213
p
3.28 109
Diff. of means
GB vs. C
Z vs. C
GHF vs. C
CC vs. C
GB vs. GHF
GB vs. CC
GB vs. Z
GHF vs. CC
GHF vs. Z
Z vs. CC
0.308124
0.124909
0.205230
0.0838744
0.102894
0.224250
0.183215
0.121355
0.0803203
0.0410349
7.018
2.845
4.674
1.910
2.344
5.108
4.173
2.764
1.829
0.935
<0.000001
0.0322
0.000078
0.167
0.0821
0.000015
0.000466
0.0338
0.136
0.352
p < 0.05
Yes
Yes
Yes
No
No
Yes
Yes
Yes
No
No
Treatment
Total
Total
C
GB
Z
GHF
CC
7
0
1
1
0
3
6
8
9
7
0
4
1
0
3
10
10
10
10
10
6
1
5
5
4
4
9
5
5
2
0
0
0
0
4
10
10
10
10
10
Total
33
50
21
25
50
Table 6 Three-way contingency table analysis (3 CT) of failure mode distribution: log-linear analysis results (G2 )
compared with exact 2 (Treatment = surface treatment).
Treatment mode
Resin mode
Treatment mode|resin
Resin mode|treatment
a
b
G2
df
2
p (exact)
34.92
7.42
52.94
25.44
8
2
16
10
<1 104
0.0245
<1 104
0.0046
32.57a
7.24b
(Not possible)
(Not possible)
5.47 105
0.0254
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Table 7 Failure type discrepancy evidence. Y means: (under A) in an area that appears to be simply an adhesive
failure, there is evidence of remnants of cement; (under C) in an area that appears to be simply a cohesive failure, there is
evidence of the underlying zirconia showing through. N means: not detected in the elds examined. E: as determined
by high magnication ESEM examination. S: as determined by EDX spectrum.
Resin
Treatment
C
GB
Z
GHF
CC
A
Y (E, S)
N
Y (E)
Y (E,S)
N
suggesting an interpenetrating network of lute, glaze and zirconia for both resins. For CC, sharply distinct areas of the
lute, glaze (with visible voids), and the zirconia surface were
found, with apparently relatively clean separation at these
interfaces, while for Z remnants of primer and cement were
found, EDS showing Si from the cement, indicative again of
a degree of cohesive failure of the cement as well as adhesive failure between cement and primer. The results of the
ESEM and EDS checks of the categorization of failure mode
are shown in Table 7, indicating where contrary evidence was
found.
4.
Discussion
The symmetrical four-point test was found to be a straightforward and effective means of testing bond strength, with the
coefcient of variation for the log-transformed data (8.6 2.0)
being acceptable for this class of test (Fig. 1, top) and indicating useful discriminatory power. Technically, the set-up
could be improved to control more precisely the lute or cement
R
C
Y (E)
Y (E,S)
Y (E,S)
N
Y (E,S)
A
Y (E,S)
Y (E,S)
Y (E)
Y (E,S)
Y (E,S)
C
Y (E)
Y (E)
Y (E,S)
Y (E,S)
Y (E)
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d e n t a l m a t e r i a l s 3 1 ( 2 0 1 5 ) 657668
Fig. 2 ESEM images for typical fracture surfaces, low and high magnications.
d e n t a l m a t e r i a l s 3 1 ( 2 0 1 5 ) 657668
665
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d e n t a l m a t e r i a l s 3 1 ( 2 0 1 5 ) 657668
Normal
linear
Normal
log
Weibull
log
0.9334
0.8815
0.9299
0.9415
0.9255
0.9812
0.9613
0.9838
0.9709
0.9497
0.9071
0.8839
0.9076
0.9263
0.8884
5.
Conclusions
d e n t a l m a t e r i a l s 3 1 ( 2 0 1 5 ) 657668
Acknowledgements
This work was submitted in partial fulllment of the requirements for the degree of Ph D for SS. It is dedicated to the
memory of Professor Dr. Cenk Cura (19652011), under whose
tutelage this work was commenced. We gratefully acknowledge the assistance of the Izmir Institute of Technology, Izmir,
Turkey, in the ESEM-EDS analysis.
references
667
[13] Kwon JE, Lee SH, Lim HN, Kim HS. Bonding characteristics
between zirconia core and veneering porcelain. Dent Mater
2009;25(5):e42.
[14] Gstemeyer G, Jendras M, Dittmer MP, Bach FW, Stiesch M,
Kohorst P. Inuence of cooling rate on zirconia/veneer
interfacial adhesion. Acta Biomater 2010;6:45328.
[15] Magne P, Paranhos MPG, Burnett LH. New zirconia primer
improves bond strength of resin-based cements. Dent Mater
2010;26:34552.
[16] Anusavice KJ, Kakar K, Ferree N. Which mechanical and
physical testing methods are relevant for predicting the
clinical performance of ceramic-based dental prostheses?
Clin Oral Implants Res 2007;18:21831.
[17] Scherrer SS, Cesar PF, Swain MV. Direct comparison of the
bond strength results of the different test methods: a critical
literature review. Dent Mater 2010;26(2):e7893.
[18] Ban S, Anusavice KJ. Inuence of test method on failure
stress of brittle dental materials. J Dent Res 1990;69:17919.
[19] Armstrong S, Geraldeli S, Maia R, Raposo LHA, Soares CJ,
Yamagawa J. Adhesion to tooth structure: a critical review of
micro bond strength test methods. Dent Mater
2010;26:e5062.
[20] Timoshenko S. Strength of materials. Part I. Elementary
theory and problems. New York: D. Van Nostrand; 1940. p.
137.
[21] Placido E, Meira JB, Lima RG, Muench A, de Souza RM,
Ballester RY. Shear versus micro-shear bond strength test: a
nite element stress analysis. Dent Mater 2007;23:108692.
[22] Darvell BW. Adhesion strength testingtime to fail or a
waste of time? J Adhes Sci Technol 2009;23:93544.
[23] Della Bona A, Donassollo TA, Demarco FF, Barrett AA,
Mecholsky JJ. Characterization and surface treatment effects
on topography of a glass-inltrated
alumina/zirconia-reinforced ceramic. Dent Mater
2007;23:76975.
[24] Mirmohammadi H, Aboushelib MN, Kleverlaan CJ, Jager N,
Feilzer AJ. The inuence of rotating fatigue on the bond
strength of zirconia-composite interfaces. Dent Mater
2010;26:62733.
[25] Granjon H. Fundamentals of welding metallurgy. Cambridge,
UK: Abington Publishing; 1991. p. 192206.
[26] Staninec M, Kim P, Marshall GW, Ritchie RO, Marshall SJ.
Fatigue of dentincomposite interfaces with four-point
bend. Dent Mater 2008;24:799803.
[27] Carter CB, Norton MG. Ceramic materials: science and
engineering. Springer; 2007. p. 2978.
[28] Jones DW, Jones PA, Wilson HJ. The relationship between
transverse strength and testing methods for dental
ceramics. J Dent 1972;1:8591.
[29] ASTM International. Designation: C1674-11. Standard test
method for exural strength of advanced ceramics with
engineered porosity (Honeycomb Cellular Channels) at
ambient temperatures. West Conshohocken, PA, USA: ASTM
International; 2011.
[30] Song HY, Yi YJ, Cho LR, Park DY. Effects of two preparation
designs and pontic distance on bending and fracture
strength of ber-reinforced composite inlay xed partial
dentures. J Prosthet Dent 2003;90:34753.
[31] Van Noort R. An introduction to dental materials. 4th ed.
London: Elsevier Mosby; 2013. p. 317.
[32] Amaral R, zcan M, Valandro LF, Balducci I, Bottino MA.
Effect of conditioning methods on the microtensile bond
strength of phosphate monomer-based cement on zirconia
ceramic in dry and aged conditions. J Biomed Mater Res B
Appl Biomater 2008;85:19.
[33] Lowry R. Log-linear analysis for an A B C contingency
table; 2001. http://vassarstats.net/abc.html [accessed
01.03.14].
668
d e n t a l m a t e r i a l s 3 1 ( 2 0 1 5 ) 657668
[51]
[52]
[53]
[54]
[55]
[56]
[57]
[58]
[59]
[60]
[61]
[62]
[63]
[64]