The Effects of Surface Conditioning and Aging on the

Bond Strength Between Composite Cement and Zirconia-

reinforced Lithium-Silicate Glass-Ceramics
Wolfgang Bömickea / Peter Rammelsbergb / Johannes Krisamc / Stefan Ruesd

Purpose: To determine the effects of ceramic-surface conditioning and aging on the bond strength between com-
posite cement and zirconia-reinforced lithium-silicate glass-ceramics (ZLS) under simulated clinical conditions.
Materials and Methods: ZLS disks (Celtra Duo, Dentsply Sirona, n = 110 test group n = 10, diameter: 8.3 mm,
height: 3.4 mm) were assigned to four surface-conditioning groups: (I) 30 s of ~5% hydrofluoric-acid etching (Vita
Ceramics Etch, Vita; HF), silanization (Calibra Silane; SIL); (II) successive contamination with saliva and silicone
(CONT), HF, SIL; (III) CONT, tribochemical silicatization (CoJet), SIL; (IV) HF, SIL, application and light polymerization
of an adhesive (Prime&Bond Active), CONT, reapplication and light polymerization of the adhesive. The ZLS disks
were bonded to composite-resin cylinders in acrylic tubes (inner diameter: 3.3 mm) using self-adhesive composite
cement (Calibra Universal). The tensile-bond strength (TBS) was measured after both 24 h and 6 months of water
storage (WS). Additional aging protocols were tested for group I (3-day WS; 30-day WS including 7500 thermocy-
cles between 6.5 and 60°C; 150-day WS including 37,500 thermocycles).
Results: After 24 h, the mean TBS ranged between 21 MPa (group III) and 30–35 MPa (remaining groups). With
the exception of 3-day WS, TBS was statistically significantly reduced by aging. The greatest reduction was ob-
served for silicatized specimens (group III, mean TBS after aging: 9.8 MPa).
Conclusion: Both ceramic surface conditioning and aging had a statistically significant effect on the bond strength
between composite cement and ZLS. A treatment protocol based on tribochemical silicatization cannot be recom-
mended for the adhesive cementation of ZLS.
Keywords: acid etching, adhesive cementation, aging, air abrasion, all-ceramic, bond durability, composite cement,
tensile bond strength.

J Adhes Dent 2019; 21: 567–576. Submitted for publication: 21.02.19; 29.09.19
doi: 10.3290/j.jad.a43650

I n addition to good biocompatibility and esthetics, the me-

chanical strength of a ceramic material must be sufficient
to ensure its clinical success without major limitations.25 In
a Assistant Professor, Department of Prosthetic Dentistry, University Hospital
Heidelberg, University of Heidelberg, Heidelberg, Germany. Study concept,
wrote the manuscript.
b Director, Department of Prosthetic Dentistry, University Hospital Heidelberg,
University of Heidelberg, Heidelberg, Germany. Proofread the manuscript.
c Statistician, Institute of Medical Biometry and Informatics, University of Hei-
delberg, Heidelberg, Germany. Statistical consultation and evaluation, proof-
read the manuscript.
d Biomaterials Engineer, Section of Biomaterial Research, Department of Pros-
thetic Dentistry, University Hospital Heidelberg, Heidelberg, Germany. Contrib-
uted substantially to the study, proofread the manuscript.
Correspondence: PD Dr. Wolfgang Bömicke, Department of Prosthetic Den-
tistry, University Hospital Heidelberg, University of Heidelberg, Im Neuenheimer
Feld 400, 69120 Heidelberg, Germany. Tel: +49-6221-56-6052;
e-mail: Wolfgang.Boemicke@med.uni-heidelberg.de
this context, zirconia-reinforced lithium silicate (ZLS) was
recently introduced. The material consists of very fine lith-
ium metasilicate with crystals of an average size of 0.5–
1.0 μm and nanometric-sized lithium orthophosphate em-
bedded in a glassy matrix containing approximately 10 wt%
zirconia in solution.4,24 ZLS is available for machining in
both a pre-crystallized (Vita Suprinity, Vita Zahnfabrik; Bad
Säckingen, Germany) and fully crystallized state (Celtra
Duo, Dentsply Sirona; Bensheim, Germany). At approxi-
mately 600 MPa, the Weibull strength of these two mater-
ials has been determined to be similar to that of a high-
strength CAD/CAM lithium disilicate ceramic.30 However,
the comparatively low Weibull modulus (ca 5.5) recorded for
both materials as well as the damage caused by diamond-
coated grinding instruments during machining of the pre-
crystallized material might be sources of concern.30 Accord-
ing to the manufacturer’s specifications, restorations
fabricated from the fully crystallized material only need to
be polished prior to placement. However, the strength of

Vol 21, No 6, 2019 567

Bömicke et al

Table 1 Specifications of materials

Material Brand Lot Composition Manufacturer

Ceramic Celtra Duo FC 18016865, Zirconia-reinforced lithium-silicate Dentsply Sirona;
18020569 Bensheim, Germany

Ceramic etchant Vita Ceramics 51950 4.8% hydrofluoric acid, 7.8% sulfuric acid, 3.2% Vita Zahnfabrik;
Etch ethyl alcohol Bad Säckingen, Germany

Silane Calibra Silane 140723, n.a. Dentsply Sirona

150401

Adhesive Prime&Bond 1506004120 n.a. Dentsply Sirona

Active

Composite Calibra Universal 141008, Urethane dimethacrylate, 2,2’-ethylenedioxydiethyl Dentsply Sirona

cement 150716 dimethacrylate, phosphoric-acid-modified acrylate,
initiators (dibenzoyl peroxide), stabilizers,
silanized barium glass, fumed silica, pigments

Core buildup Core-X flow 140919, Di- and tri-functional methacrylates, barium boron Dentsply Sirona
composite 1511000340 fluoroalumino-silicate glass, camphorquinone
photoinitiator, photoaccelerators, silicon dioxide,
benzoyl peroxide

mately 10 wt% dissolved in the glass phase was also re-

Fig 1 Diagram of the test setup for tensile-bond strength
measurement.
the material can be significantly increased by firing and
glazing.18,33 The flexural strength of fired Celtra Duo was
determined to be higher than that of fired Vita Suprinity.24
However, tests with anatomical crowns and ZLS disks
bonded to dentin analogues showed that the highest frac-
ture strength/fatigue failure load was achieved when the
material was processed in the pre-crystallized state.22,33
More recently, a pressable variant of the material (Celtra
Press, Dentsply Sirona) has been introduced. After hot
pressing, the main phase is lithium disilicate, followed by a
secondary phase of lithium orthophosphate with crystals
approximately 1.8 μm in size; a zirconia content of approxi-
corded.13 At 450 MPa, the flexural strength of Celtra Press
was similar to that of another high-strength lithium-disilicate
glass-ceramic, and its strength was further increased by
means of an additional heat treatment.13 In terms of frac-
ture toughness and hardness, ZLS is comparable to other
zirconia-based ceramics.28 The current range of indications
for ZLS includes partial crowns, inlays, onlays, and veneers.
The prognosis of these types of restoration depends not
least on effective adhesive cementation.8 As expected, high
adhesion values were found for ZLS after it had been condi-
tioned using hydrofluoric acid (HF).12 Although HF can be
safely used in dentistry under certain conditions, it can po-
tentially have both local and systemic toxic effects on hu-
mans. Additionally, concentration-dependent usage restric-
tions are in place in several countries: in Japan, the
chairside use of hydrofluoric acid is completely prohib-
ited.20 Some manufacturers exclude the intraoral use of
their products (eg, for veneer repairs).20 Here, airborne-
particle abrasion using 50-μm alumina or 30-μm silica-mod-
ified alumina (tribochemical silicatization) might be an alter-
native to HF etching.1,3,12,23,26 A more experimental
method that avoids chairside HF etching and still protects
the freshly etched and silanized surface from clinical con-
tamination is to “seal” it directly in the laboratory using a
bonding agent. After clinical try-in, the adhesive surface is
“reactivated” by re-applying the bonding agent. Although
such a sealing technique has not yet been described in the
literature, the authors are aware that it is being practiced in
some countries. No data are yet available regarding how
contamination (for example, with saliva and low-viscosity
silicone) affects the bond strength between composite ce-
ment and ZLS in conjunction with subsequent chairside HF

568 The Journal of Adhesive Dentistry


Fig 2 Overview of the procedures in the
four conditioning groups and the aging sub-
groups.
etching or tribochemical silicatization, or the sealing tech-
nique described above. In addition, no data are currently
available on the long-term cement-ZLS bond, because only
short-term water storage or thermocycling with <20,000
cycles have been used for aging thus far.1,3,12,14,19,23,26,29
The primary objective of this study was therefore to eval-
uate the effects of ceramic-surface treatment (HF etching,
tribochemical silicatization, laboratory sealing) and long-
term aging on the bond strength between composite ce-
ment and ZLS after intermediate exposure to contamina-
tion. A secondary objective was to compare different aging
protocols for one selected ceramic-surface treatment group.
The null hypothesis was that none of the variables tested
would affect the bond strength between the resin and ZLS.
In addition, to improve the interpretability of the bond-
strength results, roughness values of the ceramic surfaces
subjected to testing in the experimental groups were mea-
sured, and their surface morphology was qualitatively ana-
lyzed by means of scanning electron microscopy (SEM).
MATERIALS AND METHODS
The study was conducted in accordance with ISO
11405:2015(E): Dentistry—Testing of adhesion to tooth
structure. The lot numbers, composition, and manufactur-
ers of the substrates and adhesives used in this study are
listed in Table 1. A tensile test was performed using stan-
dardized test specimens consisting of ZLS disks adhesively
cemented to resin cylinders contained in acrylic tubes
(Fig 1). All surface-conditioning and cementation procedures
were performed by the same person and in accordance with
the manufacturer’s specifications, where available.
Specimen Preparation
Cylinders (14 mm in length and 8.3 mm in diameter) were
milled from ZLS ceramics (C14 blocks, Celtra Duo FC LT
Vol 21, No 6, 2019
Bömicke et al
A2, Dentsply Sirona) using a laboratory milling unit (Brain
MC XL, DeguDent; Hanau, Germany) and sectioned into
disks 3.4 mm thick using a precision cutting machine
(IsoMet High Speed Pro, Buehler; Lake Bluff, IL, USA). After
3 min of cleaning in an ultrasonic bath with a 70% ethanol
solution, the disks were randomly subdivided into four sur-
face-conditioning groups (Fig 2):
Group I: clinical workflow without contamination
(control group)
y Disinfection: immersion of the disks in 70% ethanol solu-
tion for 1 min and subsequent drying for 5 s using oil-
free air
y HF etching: etching of the ceramics for 30 s with ~5% HF
gel (Vita Ceramics Etch, Vita Zahnfabrik), rinsing with
water spray for 20 s, and thorough drying for 5 s using
oil-free air
y Silanization: application of a silane coupling agent (Calibra
Silane, Dentsply Sirona; Konstanz, Germany) for 60 s
and air drying for 5 s
Group II: clinical workflow with contamination
y Disinfection
y Contamination and cleaning: The disks were stored in
human saliva for 60 s, rinsed with water spray for 20 s,
and air dried for 5 s. A silicone disclosing agent (Xanto-
pren blue, Heraeus Kulzer; Hanau, Germany) was subse-
quently applied to the bonding surface and removed
after 4.5 min. The ceramic surface was then cleaned
using a two-step process: (I) rinsing with water spray for
20 s followed by air drying for 5 s and (II) wiping with cot-
ton pellets soaked with 70% ethanol solution for 20 s
followed by air drying for 5 s.
y HF etching
y Silanization
569
Bömicke et al
a b
Fig 3 Categorization of qualitative failure mode (optical area of sharpness at level of ceramic surface for a and b). a: near-surface fracture
pattern (wafer-thin cement layer remains on ceramic disk); b: oblique fracture pattern involving or near the interface (fracture through
cement and composite resin cylinder); c: far from the surface fracture pattern (fracture through composite resin cylinder only).
Group III: workflow for intraoral repairs
y Disinfection
y Contamination and cleaning
y Tribochemical silicatization: airborne-particle abrasion of
the ZLS disks with 30-μm silica-modified alumina particles
applied by means of a handpiece (CoJet system; 3M Oral
Care) at a 90-degree angle and a distance of 10 mm for
15 s at a pressure of 0.28 MPa. Particle residues were
removed using oil-free air.
y Silanization
Group IV: workflow with HF etching conducted in the
dental laboratory/laboratory-sealing technique
y HF etching
y Silanization
y Sealing of the silanized surface: application of an adhe-
sive (Prime&Bond Active; Dentsply Sirona) for 20 s,
evaporation of solvent for 5 s using a gentle air stream,
light polymerization for 10 s (SmartLite Focus, Dentsply
Sirona, irradiance output of 800 mW/cm2)
y Storage in a hermetically sealed plastic box under dry,
dark conditions for 14 days to simulate delivery of the
restoration to the dental practice
y Disinfection
y Contamination and cleaning
y Re-application of the adhesive and light polymerization
as described above.
Composite-resin cylinders were fabricated by filling acrylic
tubes (inner diameter: 3.3 mm) with a dual-polymerizing
composite-resin foundation material (Core-X flow, Dentsply
Sirona). This was left to polymerize for at least 10 min with-
out the additional use of a polymerization light-curing unit
because the composite resin was exposed to light later on
during the polymerization of the adhesive cement.
The composite-resin cylinders were bonded to the ZLS
disks with self-adhesive composite cement (Calibra Univer-
sal; Dentsply Sirona) under a constant load of 7.5 N for
10 min. After excess cement had been removed using
foam pellets, light polymerization was performed at right
570
c
angles for 20 s from four directions with an LED light-curing
unit (SmartLite Focus).
For each conditioning group, subgroups of n = 10 test
specimens per group were artificially aged either by means
of 24-h or 6-month storage in 37°C deionized water accord-
ing to ISO 11405:2015(E) (Fig 2).
For conditioning group I (control group), three additional
subgroups (n = 10 test specimens per group) with other
aging protocols commonly used for bond-strength investiga-
tions were added (Fig 2): 3-day water storage, 30-day water
storage including 7500 thermocycles, and 150-day water
storage including 37,500 thermocycles (distributed over
five intervals of 7500 cycles each, starting after 25-, 50-,
75-, 100-, and 125-day water storage). Thermocycling was
performed in deionized water at 6.5 and 60°C (Thermocy-
cler TC 1, SD Mechatronik [Feldkirchen, Germany], water
bath dwell-time 45 s, total transfer time 7.5 s).
Tensile Bond Strength Test
The test specimens were separated at a crosshead speed
of 1 mm/min in a universal testing device (Zwick/Roell
Z005, Zwick; Ulm, Germany). A pull-off device with a spheri-
cal joint in the lower transducer and a chain in the upper
transducer ensured no torque or transverse forces could
act on the adhesive joint (Fig 1). Test specimens that
debonded spontaneously before tensile testing were as-
signed a bond strength of 0 MPa.
Morphological and Optical Assessment of
Conditioned ZLS Surfaces
To quantitatively characterize both the initial ceramic surface
morphology produced by cutting the ceramic cylinder into
disks and the surface morphology after HF etching or tribo-
chemical silicatization, the mean surface roughness Ra and
roughness depth Rz were determined for three representative
ZLS disks (Marsurf Perthometer M2, Mahr; Esslingen, Ger-
many). A track 5.6 mm in length and perpendicular to the cut-
ting direction was recorded five times for each disk. For the
evaluation, the track was divided into seven parts, and the
outer two parts were discarded when calculating Ra and Rz.
The Journal of Adhesive Dentistry
 Bömicke et al

Table 2 Mean surface roughness (Ra) and roughness depth (Rz) for study disks and additionally fabricated crowns
after different surface conditioning methods

Surface Surface conditioning Disk Crown

roughness after cutting (disk)/
(μm) milling (crown) Mean SD n Mean SD n

None 1.76 0.11 15 2.08 0.58 15*

~5% HF (Vita Ceramics
1.39 0.07 15 1.30 0.47 20
Ra Etch), 30 s
Tribochemical
1.20 0.07 15 1.81 0.59 15*
silicatization (CoJet)
None 11.44 0.26 15 10.46 2.47 15*
~5% HF (Vita Ceramics
9.14 0.49 15 6.65 1.97 20
Rz Etch), 30 s
Tribochemical
7.79 0.52 15 8.54 2.00 15*
silicatization (CoJet)
HF = hydrofluoric acid. SD = standard deviation. n = number of measurements. *For technical reasons, only three of the four crown segments planned could
be measured profilometrically.

To estimate the extent to which the surfaces created in
the test by cutting the ceramic were representative of the
ceramic surfaces expected in clinical practice, three identi-
cal molar crowns were milled from a ZLS block using a la-
boratory milling unit (Brain MC XL, Degudent). The intaglio
surfaces of the crowns were either left as milled, HF-
etched, or tribochemically silicatized. For the analysis, the
circumferential wall of each crown was segmented into four
parts (mesial, distal, oral, buccal), and the surface rough-
ness values were determined in the direction of insertion
of the crown. For these segments, a track length of
1.75 mm was chosen. Ra and Rz were calculated as de-
scribed above.
Following the roughness measurements, the disk speci-
mens were coated with gold, and SEM images (JSM-6510
JEOL; Tokyo, Japan) were captured at magnifications of
100X, 1000X, and 5000X.
Optical Assessment of Debonded Test Specimens
Debonded specimens were evaluated under a light micro-
scope (Stemi SR, Carl Zeiss; Jena, Germany) at 70X magni-
fication. Using specialized software (AxioVision V4.8.2, Carl
Zeiss), the failure mode was quantitatively expressed in %
in terms of the adhesive failure area relative to the total
bonding area. The failure mode was also qualitatively as-
sessed according to the position or orientation of the frac-
ture surface within the resin-cement/composite resin cylin-
der relative to the ceramic interface (Fig 3).
Statistical Analysis
Statistical software was used (SPSS v 25 [IBM; Armonk,
NY, USA], SAS v 9.4 [SAS; Cary, NC, USA]). The effects of
ceramic-surface conditioning and aging on bond strength
were assessed using two-way and one-way ANOVA. Pairwise
comparisons within the models were conducted using the
LSD (least significant difference) test. The level of statis-
tical significance was set at _ = 0.05 for all analyses.
RESULTS
Morphological and Optical Assessment of
Conditioned ZLS Surfaces
The highest roughness values were recorded after cutting/
milling (Table 2). Conditioning of the surface by means of
HF etching or tribochemical silicatization reduced surface
roughness. In terms of the surface roughness generated by
different machining processes, the roughness of a cut disk
was similar to that of the intaglio surface of a milled crown.
In the SEM images, differences were observed between
the structures of the four ZLS surfaces, particularly be-
tween that of the etched ceramic surface and those of the
cut and the silicatized surfaces. The etching process re-
sulted in partial exposure of the lithium-silicate crystals and
channel-like depressions (Fig 4), whereas the cut (Fig 5)
and silicatized (Fig 6) specimens were characterized by
rather chunk-like breakouts of the ceramic and an absence
of exposed crystals. In the silicatized sample, deposits of
the abrasive could also be detected.
Bond Strength
No spontaneous cement debonding occurred during water
storage or thermocycling; thus, all specimens could be
tested in the tensile test. For test specimens aged in ac-
cordance with the ISO standard, mean bond strengths
ranged from 20 to 35 MPa after 24 h of water storage
(Table 3, Fig 7). The lowest bond strengths were found for
silicatized test specimens. After six months of water stor-
age, mean bond strengths ranged from 9 to 16 MPa, with
the lowest values again observed for silicatized specimens.

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Bömicke et al

a b c
Fig 4 Scanning electron micrographs of ceramic surface after 30 s 5% hydrofluoric-acid etching. a: 100X magnification;
b: 1000X magnification; c: 5000X magnification. Accelerating voltage = 5 kV.

a b c
Fig 5 Scanning electron micrographs of ceramic surface after cutting. a: 100X magnification; b: 1000X magnification; 5
c: 5000X magnification. Accelerating voltage = 5 kV.

a b c
Fig 6 Scanning electron micrographs of ceramic surface after chairside tribochemical silicatization for 15 s. a: 100X magnification,
b: 1000X magnification, c: 5000X magnification. Accelerating voltage = 10 kV.

The type of surface conditioning (F-value = 8.7, p < 0.0001)
and aging protocol (F-value = 134.9, p < 0.0001) – and how
these interacted (F-value = 3.0, p = 0.0357) – had a statis-
tically significant effect on bond strength. Pairwise testing
revealed that after 24-h water storage, the bond strength of
silicatized specimens was significantly lower (p < 0.0027)
than that of specimens in all other surface-conditioning
groups. No statistically significant difference was found be-
tween these other groups (p > 0.1275). Statistically, the
bond strength of all study groups stored in water for six
months was significantly lower (p < 0.0002) than that of
their counterpart groups stored in water for 24 h. Among
the 6-month WS groups, a statistically significant difference
(p = 0.0190) was only found when comparing the silicatized
group with the laboratory-sealed group. The latter had the
highest bond strength in this particular aging group.
The bond strength of the controls (conditioning protocol I)
– which were also stored in water for 3 or 30 days including
7500 thermocycles, or 150 days including 37,500 thermo-
cycles – decreased continuously as the storage time in-
creased (Table 3, Fig 7). One-way ANOVA revealed that the
aging protocol used had a statistically significant effect (F-
value = 41.9, p < 0.0001) on tensile bond strength. No sta-
tistically significant difference in bond strength was observed
between test specimens stored in water for 24 h or 3 days
(p = 0.0567) or between test specimens stored in water

572 The Journal of Adhesive Dentistry

 Bömicke et al

Table 3 Results for bond strength, relative adhesive failure, and failure mode

Relative
Study group adhesive failure
(n = 10/group) Bond strength (MPa) (%) Failure mode (%)

Condi-
tioning Aging Lower Upper Mini- Maxi-
protocol protocol Mean SD quartile Median quartile mum mum Mean SD a b c
Study groups aged in accordance with ISO standard
24-h WS 34.16A 6.10 29.35 34.16 39.56 24.11 41.94 0.30 0.91 0 20 80
I
6-month WS 10.79CD 2.39 8.22 11.13 12.86 7.36 13.95 1.72 4.37 100 0 0
24-h WS 29.70A 6.52 24.87 28.22 34.14 22.16 41.14 0.15 0.47 0 90 10
II
6-month WS 14.47CD 7.28 9.73 13.60 18.89 4.11 28.41 0.39 0.89 60 40 0
24-h WS 20.69B 8.37 16.40 20.54 24.74 6.58 33.53 0.00 0.00 0 100 0
III
6-month WS 9.34D 4.08 7.37 9.22 11.38 1.86 17.02 36.92 10.85 100 0 0
24-h WS 33.58A 5.93 27.86 36.06 37.64 23.98 40.59 0.79 1.00 0 70 30
IV
6-month WS 16.29BC 8.65 9.38 13.53 22.00 7.36 31.45 11.04 12.28 10 90 0
Study groups with surface conditioning protocol I aged in accordance with ISO standard and alternative aging protocols
24-h WS 34.16a 6.10 29.35 34.16 39.56 24.11 41.94 0.30 0.91 0 20 80
3-day WS 29.29a 8.21 22.76 30.14 33.86 15.22 40.71 2.78 2.94 0 100 0
30-day WS 23.86b 5.62 19.83 23.04 27.09 15.79 35.00 4.33 8.58 0 100 0
incl. 7500
I TCL
6-month WS 10.79c 2.39 8.22 11.13 12.86 7.36 13.95 1.72 4.37 100 0 0
150-day WS 8.12c 3.62 6.49 7.25 8.89 3.78 15.45 2.11 3.70 100 0 0
incl. 37,500
TCL

Conditioning protocol: I = no contamination, chairside HF etching, silanization (control); II = contamination, chairside HF etching, silanization; III = contamina-
tion, chairside silicatization, silanization; IV = laboratory HF etching, silanization, application of adhesive, contamination, re-application of adhesive.
WS = water storage. TCL = thermocycles. Failure mode categories: a = near-surface fracture pattern (wafer-thin cement layer remains on ceramic disk);
b = oblique fracture pattern involving or near the interface (fracture through cement and composite resin cylinder); c = fracture pattern far from the surface
(fracture through composite resin cylinder only). Different superscript uppercase letters denote statistically significant differences between study groups aged
in accordance with ISO standard. Different superscript lowercase letters denote statistically significant differences between study groups with conditioning pro-
tocol I (controls).

for 6 months or 150 days with additional thermocycling DISCUSSION

(p = 0.2896). Remaining pairwise comparisons revealed sta-
tistically significantly lower bond strength (p < 0.0346) for
test specimens aged for a longer period of time.
Failure Mode
Test specimens predominantly failed cohesively within the
resin-based components; ceramic fractures were not ob-
served. Prolonged water storage was associated with an
increase in adhesive failure (Table 3). The highest propor-
tion of adhesive failure was found for silicatized specimens
after 6-month WS.
In initial tests (after 24 h or 3 days of water storage), the
qualitative failure mode was characterized by an oblique
fracture pattern well below the surface (Table 3). With pro-
longed aging, a fracture pattern nearer the surface was ob-
served, with the remaining cement layer measuring
87 ± 66 μm in height (determined with a digital micrometer,
Micromar 40 EWRi, Mahr). For the laboratory-sealed test
specimens, however, a predominantly oblique fracture pat-
tern was observed, again after 6 months of water storage.
The first part of this study determined the effects of ceramic
surface conditioning and aging on the bond strength be-
tween self-adhesive cement and ZLS. Because both param-
eters had a statistically significant effect, the null hypothe-
sis was rejected. In addition to HF-etching and silanization
of the ceramic material, two alternative conditioning meth-
ods were also investigated. These were (I) laboratory etch-
ing using HF followed by silanization, application and poly-
merization of an adhesive and (II) chairside tribochemical
silicatization and silanization. HF etching is regarded as the
reference method for conditioning of glass-ceramic restor-
ations2,27 and has also proved suitable for increasing the
adhesion of various composite cements to ZLS.12,14,23,26
Accordingly, high bond strengths were achieved in the pres-
ent investigation for the study groups based on HF etching.
It should be noted that the etchant used in this study was
found to be more aggressive than other 5% HF gels.21 When
used on lithium disilicate, this produced an etching pattern
suggestive of over-etching, probably due to the additional

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Bömicke et al

50

40
Bond Strength [MPa]

30

20

10

Study group

Fig 7 Box and whisker plots of bond strengths in study groups. I = no contamination, chairside HF etching, silanization (control);
II = contamination, chairside HF etching, silanization; III = contamination, chairside silicatization, silanization; IV = laboratory HF etching,
silanization, application of adhesive, contamination, re-application of adhesive. WS = water storage. TCL = thermocycles.

component of 7.8% sulfuric acid. 21 Therefore, bond
strengths might have been different if other etchants con-
taining only HF had been used. Tribochemically silicatized
test specimens generally had the lowest bond strengths in
this dataset, and after 6 months of water storage, a bond
strength of less than 10 MPa was observed. Tribochemical
silicatization therefore cannot be recommended as a condi-
tioning method for non-retentive ZLS restorations. In this
context, the silicatized surface appeared less retentive in
SEM examination than the etched surface because of the
absence of undercuts, such as those present in the area of
crystals exposed by etching. Furthermore, the etched sur-
faces had channel-like structures and thus differed from the
tribochemically silicatized surfaces, which did not. Other
studies testing tribochemical silicatization and HF etching
for the conditioning of ZLS yielded comparable results, also
recording the lowest bond strengths after silicatization.23,26
Using a microtensile test after 1 week of water storage,
these values were only half as high as those recorded after
HF etching,23 and silicatized samples proved particularly
susceptible to aging after 10,000 thermocycles.26 In con-
trast, for the pre-crystallized material (Vita Suprinity), the
highest microtensile bond strengths after 5000 thermocy-
cles were determined after tribochemical silicatization,
whereas HF-etched, silanized test specimens had the worst
performance.1 The etching time used might account for this
result, because a 5% hydrofluoric acid solution was used
for 60 s instead of the 30 s specified by the manufacturer.
It was shown elsewhere that an extended etching time
(40 s) for a 10% hydrofluoric acid solution negatively af-
fected the ZLS adhesive bond.26
For this test, an unconditioned ZLS-disk surface was in-
tended which closely corresponds to that encountered in
clinical practice. This was achieved to the extent that the
surface roughness of the ZLS disks was in a range compa-
rable to that of milled ZLS crowns. The greater variability of
the roughness values recorded for crowns – reflected in a
larger standard deviation – can be interpreted as the result
of a less-standardized dental milling process compared with
cutting using a precision-cutting machine during test speci-
men preparation.
Contamination with human saliva and condensation-
crosslinked silicone most probably had no negative effect
on bond strengths in conjunction with the surface condition-
ing methods used. However, this could only be shown di-
rectly for chairside HF etching, because groups I and II were
the only ones that differed solely with regard to the con-
tamination variable. HF etching was shown to be particularly
suitable for removing saliva residues from glass ceramics
and creating an effective bonding surface.17,32 But silicone
contamination might be more problematic than saliva con-
tamination. Silicone leaves a thin film on ceramic, thus pre-

574 The Journal of Adhesive Dentistry


venting stable micromechanical retention or chemical bond-
ing.31 Whereas phosphoric acid effectively removed saliva
contamination from a glass ceramic, only hydrofluoric acid
enabled high bond strengths on a glass-ceramic surface
additionally contaminated with silicone; other cleaning
media such as phosphoric acid, alcohol, or sodium bicar-
bonate powder were insufficient for this purpose.16 For the
laboratory-sealed specimens, it was not the ceramic sur-
face that was contaminated, but a previously light-polymer-
ized adhesive. Cleaning consisted of simply spraying the
ceramic surface with water and wiping with an alcohol-
soaked cotton pellet before a new bonding agent was ap-
plied. Test specimens treated in this way had the highest
long-term bond strengths and were not statistically signifi-
cantly different from chairside-etched specimens. It can be
assumed that the re-application of adhesive resulted in ef-
fective wetting of the surface by the composite cement, as
well as chemical activation through restoration of the oxy-
gen-inhibition layer.5 The application of an adhesive has
previously been considered essential for achieving optimum
adhesion to saliva- or blood-contaminated composites.9,10
Prolonged aging statistically significantly reduced the
bond strength of the specimens in the study groups tested
according to ISO standards, and it increased the relative
adhesive failure, particularly for the silicatized test group.
Contrary to expectations from experiments with the same
experimental setup, in which a decrease in bond strength
was clearly associated with an increase in relative adhesive
failure,6 the bond strengths measured here could only be
associated to a limited extent with relative adhesive failure,
but all the better with the qualitatively observed failure
mode. In particular, near-surface fractures were associated
with low bond strength and were predominant among test
specimens without additional bonding. It can therefore be
assumed that the silane–self-adhesive cement interface
was more prone to aging by water storage than the silane-
adhesive and adhesive–self-adhesive cement interfaces.
The comparatively high bond strengths of laboratory-
sealed test specimens might be the result of better inter-
locking of the less-viscous adhesive with the ceramic sur-
face compared to composite cement, also expressed by the
deep oblique fracture pattern prevailing in these samples.
Other studies of ZLS, lithium-disilicate, and feldspar ceram-
ics also recorded improved bond strength when an adhe-
sive was applied after etching with 5% or 8% HF using ce-
ramic-specific etching times (range: 20 s to 2 min) and
silanization.1,7,11 However, high bond strength could only
be permanently maintained if a hydrophobic adhesive was
used.11 Conversely, the present study used adhesives that
inevitably had distinct hydrophilicity due to their self-adhe-
sive or self-etching properties, which might explain the
aging processes observed. It is important to bear in mind
that there are currently no instructions for use (IFUs) regard-
ing the combined use of Prime&Bond Active and Calibra
Universal. Available IFUs recommend that Prime&Bond Ac-
tive be used with Self Cure Activator (SCA, Dentsply Sirona)
when combined with auto- or dual-polymerizing composite
resin. However, in combination with self-adhesive Calibra
Vol 21, No 6, 2019
Bömicke et al
Universal, this is not necessary, as Prime&Bond Active is
chemically compatible with Calibra Universal without the
use of SCA (Dr. Frank Pfefferkorn, Dentsply Sirona, per-
sonal communication). Finally, the laboratory-sealing tech-
nique requires that the layer of adhesive is taken into ac-
count when designing the indirect restoration, especially
when planning the cement and marginal gap, and that the
correct fit of the restoration on the master model is verified
again after the adhesive has been applied. However, before
recommendations can be made regarding the clinical ap-
plicability of the method, the associated fit and clinical
prognosis of restorations treated in this way must be inves-
tigated.
The second part of the study suggests that testing long-
term bond strength in accordance with ISO 11405:2015
does not necessitate the use of thermocycling. The de-
crease in bond strength observed after 6 months of water
storage differed only non-significantly from that observed for
an alternative long-term aging protocol involving 150 days
of water storage in combination with 37,500 thermocycles.
For this comparison, the null hypothesis was thus ac-
cepted. Inokoshi et al,15 who investigated the bonding of
zirconia ceramic, reported similar results. They found a
stronger correlation between water-storage time and de-
crease in bond strength than between thermocycling and
decrease in bond strength.
CONCLUSIONS
In a simulated clinical environment with saliva and silicone
contamination, conditioning protocols based on HF etching
were used for ZLS with acceptable success in terms of long-
term bond strength. Chairside tribochemical silicatization of
ZLS cannot be recommended because this was associated
with low bond strength after long-term aging. Compared with
initial bond strengths, the aging protocols with either
6-month water storage or 150-day water storage including
37,500 thermocycles led to a similar decrease in bond
strength. Therefore, both might be considered suitable for
testing long-term adhesion.
ACKNOWLEDGMENTS
The authors thank Dentsply Sirona for financially supporting the
study and providing adhesives and ceramic materials free of charge,
and ZTM Cornel Weber (Owingen, Germany) for the introduction of
the laboratory-sealing technique used in this study. They also thank
Hazel Davies for English-language editing of the manuscript.
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Clinical relevance: By etching the ceramic surface
using ~5% hydrofluoric acid solution for 30 s, it was
possible to effectively remove contamination and
generate a long-term, durable bond between the self-
adhesive composite resin and ZLS.
The Journal of Adhesive Dentistry