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journal of the mechanical behavior of biomedical materials 37 (2014) 100 108

Available online at www.sciencedirect.com

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Research Paper

Strengthening of dental adhesives


via particle reinforcement

Renan Bellia, Stefan Kreppelb, Anselm Petschelta, Helga Hornbergerb,


Aldo R. Boccaccinib, Ulrich Lohbauera,n
a
Laboratory for Biomaterials Research, Dental Clinic 1 Operative Dentistry and Periodontology,
Friedrich-Alexander-University of Erlangen-Nuremberg, 91054 Erlangen, Germany
b
Institute of Biomaterials, Department of Materials Science and Engineering, Friedrich-Alexander-University
of Erlangen-Nuremberg, 91058 Erlangen, Germany

ar t ic l e in f o abs tra ct

Article history: The bond between methacrylic polymer adhesives and dental restoratives is not perfect and
Received 12 February 2014 may fail either in the short or in the long term. This study aims to evaluate the effects of
Received in revised form particle incorporation in a self-etch model adhesive on mechanical and physical properties that
24 April 2014 are relevant during application and service. Filled adhesives containing 5, 10, 15 or 25 wt% glass
Accepted 3 May 2014 llers were compared to their unlled counterpart in terms of water sorption and solubility;
Available online 11 May 2014 viscosity and dynamic viscosity during polymerization were recorded using rheological

Keywords: measurements and compared to FTIR analysis of the real-time degree of cure. Elastic modulus

Nanoparticles and ultimate tensile strength measurements were performed in uniaxial tension; the energy to

Bond strength fracture was used to calculate the fracture toughness of the adhesives. Finally, the experimental

Elasticity adhesives were applied on dentin substrate to test the bond strength using the microtensile

Adhesives test. Results showed that the incorporation of 510 wt% nanoller to self-etching dental

Dentin adhesives is efcient in accelerating the polymerization reaction and increasing the degree of
cure without compromising the lm viscosity for good wettability or water sorption and
solubility. Fillers increased the elastic modulus, tensile strength and fracture toughness to a
plateau between 5 and 15 wt% ller concentration, and despite the tendency to form
agglomerations, active crack pinning/deection toughening mechanisms have been observed.
The bond strength between resin composite and dentin was also improved when adhesives
with up to 10 wt% llers were used, with no additional improvements with further packing. The
use of llers to reinforce dental adhesives may therefore be of great practical benet by
improving curing and mechanical properties.
& 2014 Elsevier Ltd. All rights reserved.

n
Corresponding author. Dental Clinic 1 Operative Dentistry and Periodontology, Glueckstr. 11 D-91054 Erlangen, Germany.
Tel.: 49 9131 854 3740; fax: 49 9131 853 4207.
E-mail address: lohbauer@dent.uni-erlangen.de (U. Lohbauer).

http://dx.doi.org/10.1016/j.jmbbm.2014.05.007
1751-6161/& 2014 Elsevier Ltd. All rights reserved.
journal of the mechanical behavior of biomedical materials 37 (2014) 100 108 101

1. Introduction 2. Materials and methods

Tailoring of mechanical and physical properties of materials 2.1. Experimental adhesives


through changes in formulations is a process based on com-
promises between desirable and undesirable effects. For dental Due to the uncertainty surrounding the precise chemical com-
adhesives that join restoratives to tooth tissues, mechanical position and monomer concentrations of marketed dental adhe-
stiffness and stability are the goals in order to endure shrinkage sives, an experimental self-etching adhesive was produced
stresses and cyclic mastication forces (Braga et al., 2005; specically for this study (Voco, Cuxhaven, Germany). The
Frankenberger et al., 2005). The initial state of this bond has following monomers/additives and corresponding weight con-
shown to reach satisfactory levels for currently marketed centrations were stirred until homogeneously mixed and stored
adhesives (Van Meerbeek et al., 2010). Its degradation, however, in a PE beaker: Bis-2-methacryloyoxy)ethylphosphate (Bis-MEP;
is rather expedited by the susceptibility to water diffusion from 33.3 wt%), Bisphenol A diglycidyl methacrylate (Bis-GMA; 33.3 wt
the underlying wet substrate and the environment, and is %), 2-hydroxyethyl methacrylate (HEMA; 32.5 wt%), Camphoro-
mainly dictated by the hydrophilicity of the adhesive quinone (0.3 wt%), Ethyl-4-dimethyllaminobenzoate (DABE;
composition (Tjderhane et al., 2013). Prevailing strategies to 0.45 wt%) and Butylhydroxytoluene (BHT; 0.01 wt%). From this
preserve the bond integrity focus on minimizing the polymer composition, four lled versions (5, 10, 15 and 20 wt%, or 2.5, 5,
water uptake by using more hydrophobic compositions (Tay 7.5 and 10 vol%, respectively) were produced by incorporation of
et al., 2007; Tjderhane et al., 2013). This should be achievable SiO2BaO glass llers (NanoFines NF180 of glass GM27884,
using monomer solutions that maintain a uidic character Schott, Landshut, Germany) with grain size of d50/d99 180/
for proper substrate wettability and still reach adequate 500 nm and irregular shape. Silanization of llers was under-
degrees of cure. taken by the company delivering the llers (Schott) by using
Improvements in bond strength can also be accomplished 13 wt% relative to silica of the organosilane -methacryloxypro-
by reinforcing the adhesive polymer with llers. In a previous pyltrimethoxysilane as a coupling agent. Further specications
report (Lohbauer et al., 2010a) we showed that uncoated of the used particles can be found in the product information
spherical zirconia (ZrO2) nanoparticles can be added to either sheet (Schott, 2010). Dispersion of ller in the resin was achieved
components of a particular 3-step dental adhesive as an in three steps via kneading, rolling and ultrasonication.
attractive strategy to improve the dentin-composite bond.
That study corroborated previous attempts to reinforce the
bond between resin-based restoratives and tooth tissues 2.2. Water sorption and solubility
through ller incorporation into dental adhesive agents
(Miyazaki et al., 1995; Kim et al., 2005b; Sadat-Shojai et al., Five disc-shaped specimens ( 15 mm; thickness 1 mm) were
2010). Meanwhile nano- and micro-sized particles (mainly produced according to ISO 4049 for each adhesive. The adhesives
colloidal silica or glass llers) compose many marketed were poured into a silicon mold, covered with a glass cover slip,
dental adhesives in concentrations between 5 and 48 wt% clamped and light-activated for 5 min using a light-curing oven
(Van Landuyt et al., 2007). (Unilix AC, Heraeus Kulzer, Wehrheim, Germany). The speci-
Consequences of incorporating llers into dental adhesives mens were dried in a desiccator at 37 1C for 22 h and transferred
go beyond mechanical effects, and may further alter physical to another desiccator at 23 1C for 2 h. The specimens were
aspects that have a potential clinical relevance during applica- subsequently weighted using a high accuracy balance (YDK01
tion and service. One of these parameters is the lm viscosity, model, Sartorius, Goettingen, Germany). After a stable mass
which is increased by ller incorporation with the purpose of reading was obtained, this value was taken as the initial mass
thickening the adhesive lm and preventing full-thickness (minitial). The dimensions of the specimens were measured by
oxygen inhibition (Frankenberger et al., 2002). Overdoing in ller taking 2 points for the diameter and 5 points for the height to
loading may increase the adhesive viscosity to a point that resin calculate the volume V of the specimens. The specimens were
inltration into the demineralized substrate is compromised. then put in containers with distilled water and stored for 7 days
That represents a bigger issue for etch-and rinse adhesives, at 37 1C. It was made ascertained that the minimum distance
since the self-etching formulations promote resin inltration at between the specimens was Z3 mm and at least 10 ml water
the pace of etching (Van Meerbeek et al., 2011). In increasing the was supplied per specimen. After the storage period the speci-
viscosity, llers may further affect the polymerization kinetics mens were rinsed, gently air-dried and weighted within 1 min.
of the resin by acting as rigid centers for chain initiation during The weight measured is referred as mwet. To determine the
polymerization, with expected accompanying effects on the solubility in water (representing the amount of diluted mono-
degree of cure. mer), the rst step needed to be repeated with the wet samples,
The present study aims to clarify these questions. Here we obtaining the weight mdry. For the calculation of water sorption
address the effects of incorporating silanized sub-micrometer and solubility, the following equations were used:
glass llers into an experimental self-etch adhesive formulation
in terms of viscosity, dynamic viscosity during curing, degree of
mwet minitial
conversion, water sorption/solubility, elastic modulus develop- Wsorption 1
V
ment, ultimate tensile strength, fracture toughness and bond
strength to dentin. The null hypothesis tested was that ller minitial mdry
Wsolubility 2
concentration has no effect in the aforementioned parameters. V
102 journal of the mechanical behavior of biomedical materials 37 (2014) 100 108

2.3. Viscosity and polymerization kinetics stressstrain curve (Wf), to obtain the work-of-fracture f Wf/
2S, where S is the cross-sectional area of each respective
The viscosities of the unlled and lled adhesives were specimen. For materials with negligible dissipation of energy
measured using a rheometer (Physica MCR301, AntonPaar, in the form of plastic deformation (which can be assessed
Ostldern, Germany) and processed with the software Rheo- from the stressstrain curve linearity), the work-of-fracture
plus 3.40 (AntonPaar). The plate-on-plate testing set-up used equals the critical energy release rate Gc, which can be used
a oscillating cylinder ( 28 mm) at 2 Hz over an aluminum to calculate the fracture toughness, or critical stress intensity
plate at a distance of 1 mm. The lower plate was cooled to factor KIc from the relationship proposed by Irwin (1964):
23 1C by a Peltier water cooling system (HWE, Huber, Offen-  
Gc E 1=2
burg, Germany) and the tests were conducted in light- KIc 3
1 2
protected environment.
To evaluate the dynamic viscosity of the adhesives during where E is the elastic modulus measured for each adhesive
polymerization, an integrated-controlled custom LED light- loading level, and the Poisson's ratio of the adhesives (all
source was built in the lower chamber of the rheometer to assumed to be 0.35 in this study) (Greaves et al., 2011).
provide polymerizable energy 1 mm beneath the glass plate
(1 mm-thick) over which the adhesives were placed. The light 2.6. Microtensile bond strength to dentin
energy provided by the light source was measured using a
Ulbricht integrating sphere (Gigahertz-Optik, Tuerkenfeld, Bovine incisors were stored in 0.5% Chloramine-T solution at
Germany) to 500 mW/cm2. The dynamic viscosity during 4 1C and used within 3 months of extraction. From each tooth
light-activation was measured using the same above descri- the buccal enamel was grinded at until dentin exposure,
bed set-up and measuring parameters. which was further wet grinded for 30 s with a 600-grit SiC
paper to create a clinically relevant smear layer.
2.4. Real-time degree of conversion For the application as a dentin adhesive system, the
formulated adhesive blends were diluted in a mixture of
In order to evaluate the effect of ller concentration on the water and acetone (50 vol% of adhesive, 25 vol% water and
conversion rate, the degrees of conversion (DC) of the unlled 25 vol% acetone) to be applied as a primer solution. The
and lled adhesives were measured after different light- primer was applied over the dry substrate in two consecutive
activation times by Fourier transform infrared reectance coats 20 s apart and dried with oil-free air-spray for 20 s. Non-
spectroscopy (FTIR). A FTIR spectrometer (Nicolet 6700, diluted solutions of the monomer formulations were applied
Thermo Scientic, Waltham, USA), operated under 0.5 cm  1 on top of the primer as an adhesive, following the so-called
resolution and 64 scan coadditions, was used to capture the two-step self-etch approach. After application, the adhesive
ongoing curing process using the two frequency technique, was polymerized for 40 s (Elipar Trilight) with an output
where the net peak absorbance areas of the aliphatic CQC intensity of 850 mW/cm2. A resin composite (Grandio Flow,
stretching vibrations at 1638 cm  1 and the reference aromatic Voco) was then placed incrementally in four 1-mm horizontal
C    C stretching vibrations at 1608 cm  1 were recorded. increments; each individually cured for 40 s with the same
Continuous readings were made every 10 s over 50 s of light- light-curing unit.
activation (Elipar TriLight, 3MESPE, output intensity: 850 mW/ For the microtensile bond strength (TBS) testing, each
cm2) on 1-mm-thick samples. The baseline method was tooth was longitudinally sectioned in both x and y direc-
employed for the peak area ratios, where the quotient of areas tions across the bonded interface with a low-speed diamond
of the aromatic C    C peak with the methacrylic CQC peak saw under substantial water lubrication. This procedure
was plotted against curing time. resulted in specimens with cross-sectional area of 0.957
0.05 mm2. After cutting, the specimens were stored for 7 days
2.5. Elastic modulus, tensile strength and fracture in distilled water at 37 1C before testing. The specimens were
toughness measurements then xed to microtensile bond strength testing jigs with
cyanoacrylate glue and loaded in tension using a universal
Glass-hour-shaped specimens were produced by pouring the testing machine (Z2.5, Zwick) with a 100 N load cell traveling
adhesives into a custom built silicon mold. A thin plastic foil at a cross-head speed of 0.5 mm/min. After beam fracture,
covered the adhesive and glass plates were xed with clamps the dimensions of the cross-sectional area were measured
on both sides to retain constant specimen dimensions using a digital caliper and used to calculate the TBS by
(3871 mm3). Curing was performed in a light-curing oven dividing the imposed force (in N) at the time of fracture by the
(Unilux AC) for 5 min. Specimens were stored in distilled bonded area (in mm2). The failure modes were evaluated at
water at 37 1C for 24 h. Specimens were tested in uniaxial 20  in a light microscope (SV-6, Zeiss, Oberkochen, Ger-
tension using a low-compliance universal testing machine many) and classied as cohesive (failure entirely within
(Z2.5, Zwick, Ulm, Germany) until fracture. Stressstrain dentin substrate or resin composite), mixed (failure mainly
curves were used to derive the Elastic modulus (E) from the in the adhesive resin with excursion to the dentin/adhesive
linear elastic range. Loads at fracture and specimens cross- interface) or adhesive (failure only at the dentin/adhesive
section areas were used to calculate the ultimate tensile interface). Only specimens presenting adhesive or mixed
strength. failure modes were included in the calculation of mTBS
At the moment of fracture, the total external work applied means, and a minimum of n 30 was assured for the
to the specimen can be retrieved from the area under the calculation.
journal of the mechanical behavior of biomedical materials 37 (2014) 100 108 103

Values of water sorption, monomer solubility, elastic The FTIR spectrum of the unlled and the 20 wt% lled
modulus, tensile strength, fracture toughness and microten- adhesive are shown in Fig. 3 for the different curing times. The
sile strength were evaluated for normality and statistically decrease in resin content with increase in ller incorporation
treated using a one-way Analysis of Variance and LSD post- was also conrmed from the progressive decline of the peaks at
hoc test at pr0.05 (SPSS 21.0 software, IBM, Chicago, IL, USA). 1455 cm  1 and 1510 cm  1, related to CH2 and CQO, respec-
tively (not shown).
From the SEM images of the fractured specimens, a homo-
geneous ller distribution was observed for all lled adhesives
3. Results despite their tendency to form agglomerations. Maximum
cluster sizes were found to reach up to 10, 20, 50 and 80 mm
In Table 1 the values for viscosity, water sorption, monomer
solubility and for the mechanical testing are summarized. An
increasing trend of water uptake was observed for adhesives
with a ller concentration higher than 5 wt%, although no
signicant statistical differences between them and the
unlled adhesive could be observed. When the water sorption
is normalized by the monomer fraction in weight, the values
for the 15 and 20 wt% lled adhesives become statistically
higher than the unlled resin (Fig. 1). Monomer solubility
values showed a different trends, with the unlled adhesive
showing signicantly higher values in comparison to adhe-
sives with 10 and 15 wt% ller concentration. However when
the obtained values are again normalized by the monomer
fraction, no statistically signicant differences were found
between unlled and 5, 15 or 20 wt% lled adhesives.
The viscosity of the different adhesives increased with
ller concentration, which also signicantly inuenced their
dynamic viscosity during polymerization. Fig. 2a illustrates
the changes in viscosity of the unlled and lled adhesives
during polymerization. The artifacts in the graph are the
result of the spontaneous peeling of some samples after full
cure was achieved. The peak value represents the full state of
hardening, from which the distance to the time of light
activation may be taken as the curing time. While the unlled
resin took 10 s to cure, the adhesive containing 20 wt% llers
is fully cured after 2 s of light activation. The addition of 5 wt
% ller reduced the curing time to 4 s. The reduction in
polymerization time with increasing ller content could also
be observed from the values obtained from the real-time
degree of conversion (Fig. 2b). The unlled adhesive showed
to polymerize linearly with curing time (i.e., energy density
provided) until no signicant changes in conversion were
detected, whereas lled adhesives showed an exponential
behavior. After 20 s of light-activation, the unlled adhesive Fig. 1 Values for the sorption and solubility measured for
showed approximately 50% of its maximum conversion; at the unlled and lled adhesives. Absolute values and values
this stage all lled adhesives had achieved their nal normalized by the wt% of resin phase are plotted side
curing state. by side.

Table 1 Mean values (S.D.) for viscosity, water sorption, water solubility, elastic modulus (E), ultimate tensile strength
(UTS), fracture toughness (KIc) and microtensile bond strength (TBS) measurements for the tested adhesives.

Viscosity (Pa s) Water sorption Water solubility Emod (GPa) UTS (MPa) KIc (MPa m0.5) lTBS (MPa)
(lg/mm3) (lg/mm3)

Unlled 1 20.5 (5.1) ab 28.7 (3.7) a 0.57 (0.09) c 1.23 (0.21) c 0.74 (0.13) c 18.4 (8.5) c
5 wt% 1.4 15.5 (3.8) b 27.3 (7.1) ad 1.24 (0.27) b 2.66 (0.72) a 1.18 (0.26) a 26.9 (9.4) b
10 wt% 3.4 21.9 (5.1) ab 19.5 (1.4) bc 0.97 (0.20) b 1.93 (0.50) b 0.89 (0.22) bc 39.7 (10.5) a
15 wt% 7.3 24.4 (5.5) a 22.2 (1.8) bd 1.58 (0.42) a 2.33 (0.97) ab 1.03 (0.41) ab 39.1 (14.6) a
20 wt% 20.3 26.1 (6.3) a 23.8 (1.6) acd 1.58 (0.33) a 2.01 (0.68) ab 0.95 (0.24) ab 37.9 (16.2) a

Different letters in columns designate groups with different statistical subsets at 0.05.
104 journal of the mechanical behavior of biomedical materials 37 (2014) 100 108

Fig. 2 (a) Viscosity curves during polymerization of the unlled and lled adhesives. (b) Conversion vs. curing time measured
by FTIR.

Fig. 3 FTIR spectra for every measuring time interval of (a) the unlled adhesive and (b) the 20 wt% lled adhesive.

Fig. 4 SEM images in backscattered mode of the fracture surfaces of the 10 wt% (a and b) and 20 wt% (c) lled adhesives. In
(a) unidirectional microcracks around one hemisphere of a particle agglomeration is pointed by the arrow. In (b) and (c) the
fracture surfaces show increased roughness due to crack deection around particles, which fractured partally or completely.
journal of the mechanical behavior of biomedical materials 37 (2014) 100 108 105

Fig. 5 Mean values (error bars are standard deviations) of the mechanical properties of the adhesives and microtensile bond
strength to dentin. The same letters designate the same statistical subsets.

for the 5, 10, 15 and 20 wt% ller concentration, respectively. At failure of either substrate was observed with the increase in ller
preferential hemispheres of agglomerations of diameters larger incorporation (not shown).
than 10 mm, unidirectional microcracks were observed occa-
sionally (Fig. 4a). In general, fracture surfaces became rougher
with the increase in ller content, and crack deection fracto-
graphic markings were visible around particles and agglomera-
tions, revealing the crack trajectory (Fig. 5b and c). Agglome- 4. Discussion
rations involved in the crack path were observed to be partially
or completely fractured. In the present study the incorporation of glass llers to a self-
A summary of the results from the mechanical tests are etch adhesive has shown to produce signicant effects in all
illustrated in Fig. 5. The ultimate tensile strength of the tested properties, leading us to reject the null hypothesis.
adhesives markedly increased with the addition of llers, The testing of dental adhesives under pure tension is
but not further beyond a 5 wt% ller level, which in fact lead perhaps of higher practical relevance given the high shrinkage
to a slight decrease in strength. A 5 wt% incorporation of stress undergone by the adhesive interface during polymeriza-
llers signicantly increased the elastic modulus of the tion. To that adds the higher susceptibility of materials show-
adhesive to approximately 2 times the values of the neat ing brittle-like fracture response to tensile stresses. Packing of
resin, reaching a 3-fold increase when 15 wt% llers were a more compliant material, such as methacrylate-based poly-
added. Elastic modulus increase found a plateau at 15 wt% mers for dental use, with stiffer llers leads clearly to an
ller level, with a signicant decrease when the ller con- increase in the elastic modulus of the composite. Locally, a
centration was further increased to 20 wt% (Table 1). Fracture well-bonded particle constrains the surrounding matrix
toughness results followed the trend observed for the elastic against deformation. Under uniaxial loading, closely packed
modulus and tensile strength, once these properties shape the particles act by hindering the transverse strain of the matrix in
fracture behavior of brittle materials. The mTBS to dentin showed the interstitial spaces. The global effect is the decrease of the
a signicant increase for ller levels Z5 wt% (Table 1). mTBS Poisson0 s ratio of the composite as the ller loading increases
values for the adhesives containing 10, 15 and 20 wt% were not (Chabrier et al., 1999; Chung et al., 2004; Masouras et al., 2008).
statistically different (Fig. 5a). A trend of increasing cohesive Following the trend of the elastic modulus, further packing
106 journal of the mechanical behavior of biomedical materials 37 (2014) 100 108

also increases the bulk modulus, rendering dental composites collective unidirectional elongation, is suggestive of cohesive
also more resistant to shear stresses (Masouras et al., 2008). cracking of the polymer matrix resulting from a tensile stress
Bond strength increases as a consequence of ller addition zone created during copolymerization of resin monomers
was expected from past results. Particles in adhesives may with the silanized llers. These cracks may be a repercussion
increase the debonding energy in different ways. In a favor- of inhomogeneities in the local onset of the curing reaction,
able scenario where the dentinadhesive interface is strong, leading to stress competition zones around an agglomeration
aws responsible for failure may rather origin in the adhesive axis. The increase in size of agglomerations may aggravate
resin, with the crack propagating therein. Consequently, as it this effect in more highly loaded systems. At an interface
occurs in resin composite restoratives, particles provide under stress this is critical, and may explain the increase in
obstacles at the crack front, consuming energy during crack bond strength scatter for the adhesives having ller loading
extension (Lohbauer et al., 2013). In a low stiffness Bis-GMA/ levels beyond 10 wt%.
TEGDMA-based polymer, the high modulus of a particle (e.g., Comparatively, KIc values of pure Bis-GMA and TEGDMA
glass) has the potential to attract an offset traveling crack, polymers were measured to 1.45 and 1.97 MPam (Cook and
causing a temporary reduction in the energy release rate due Moopnar, 1990), respectively, and 0.22 MPam for a blend of
to changes in crack trajectory (Wang et al., 2008). In compo- 37.5 wt% Bis-GMA, 37.5 wt% Bis-EMA and 25 wt% TEGDMA
sites composed of 40120 nm spherical silica particles or (Chan et al., 2007). Considering the low cross-linking potential
0.4 mm irregular glass particles, crack deection was found of our monomer mixture, a nearly 60% increase in fracture
to be the main mechanisms of polymer toughening, with the toughness values took place from 0 to 5 wt% ller loading.
particlematrix interface playing an important role (Chan Higher mTBS means for lled adhesives may reect the
et al., 2007). In (Lohbauer et al., 2010a), complementary observed enhancements in UTS and KIc, but the relation
particle-induced toughening mechanisms have been detected ship between these properties is not at all straightforward.
contributing to the increase in debonding energy. Differences in specimen dimensions create clear volume
Particle clustering is an important obstacle when adding dependent aw population size and distribution effects.
llers to adhesives, since particles aggregate before incor- Additionally, lm thickness, geometry and elastic moduli
poration or in suspension. By increasing particle concentra- ratio at the interface, all affect the stress distribution during
tion in a medium the distances between particles are microtensile testing, as highlighted by Soderholm (2010). The
reduced, and inter-particle interactions become more likely. contribution of llers to higher bond strengths to dentin may
Secondary cluster formation as response to increases in ller be rather associated with the increase in interface stiffness,
loading was related to bond strength deterioration in several as found by Tam and Pilliar (2000). From a subsequent work it
studies of the kind (Kim et al., 2005b; Sadat-Shojai et al., 2010; could also be shown the important role of adhesive packing
Chen et al., 2011; Solhi et al., 2011). Spherical particles are in increasing the fracture toughness of the adhesivedentin
advantageous in this respect since few contacts can be interface (Tam et al., 2001). The change in fracture mode
established to neighboring particles, an less energy is needed patterns observed herein also point to a crack trajectory
to break those interactions. Geometries that increase the moving away from the adhesive joint constituents toward
potential area for contact with other particles will be there- the adhesivedentin interface as a result of increased resis-
fore more prone to form agglomerations. When using rod- tance to fracture propagation.
shaped hydroxyapatite nanollers we also observed severe The tendency to form agglomerations is mainly regulated
particle agglomeration already at low ller concentrations, by the zeta () potential of the particles in suspension, which
which prevented meaningful improvements in bond strength is in turn dependent on the particle surface charge and pH of
(Wagner et al., 2013). In that study, parabolic markings (Kies the solution. These properties in an adhesive solution are of
gures) (Kies et al., 1950) associated with micrometer-size high relevance when dealing with particles that may be sur-
agglomerations pointed to independent crack initiation sites face modied and embedded in solutions that undergo wide
in front of the running crack, indicating that particle agglom- changes in pH during application, as is the case for self-etching
erations may potentially act as stress concentrating defect systems. For the application as primer, the monomer Bis-MEP
sites. There, agglomerations reached a critical size (450 mm) in our self-etch adhesive is ionized by water and dissociates
beyond 5 wt% of loading level, which led to a signicant into phosphoric acid and two HEMA molecules. During this
decrease in bond strength. Particle cluster dimensions up to period, before the phosphoric acid is completely neutralized by
80 mm were found in the present study for the 20 wt% lled calcium from the dentin surface, the pH of the solution drops
adhesive. In the availability of KIc values, the critical aw size considerably and particles become more mobile due to a
(ac) for unstable fracture initiation can be calculated using the decrease in viscosity. Below a pH of  3, silica particles become
basic fracture mechanics relation of Irwin (Irwin, 1964) highly unstable (Kim and Lawler, 2005a). Silanization of silica
KIc Ysfac, where Y is the crack geometric factor ( 1.3 for particles helps to increase the stability of the dispersion at
elongated agglomerations) and sf the ultimate tensile lower pH values by shifting the isoelectric point toward higher
strength. For the 20 wt% lled adhesive aco10 mm, showing pH (Jesionowski, 2003). During neutralization, an incre-
that large agglomerations although not readily benecial, ase in pH beyond 5 may destabilize the suspension, as the -
apparently did not act as weakening sites. Flaws matching potential of silanized particles enter a range of higher instabil-
the theoretical ac dimensions were occasionally found around ity (Jesionowski, 2003). Our adhesive solution was, however,
particle clusters 415 mm, as shown in Fig. 4a. Their morphol- only ionized for application onto dentin for the mTBS test.
ogy, namely the nonorthogonal orientation of the cracks in Nonetheless, deeper knowledge of this dynamic in self-etching
relation to the surface of the agglomeration, but rather a systems is of high interest and warrants further research.
journal of the mechanical behavior of biomedical materials 37 (2014) 100 108 107

Monomer composition also regulates the overall hydro-


philicity of the resin mixture and consequently the quantity 5. Conclusions
of water that is absorbed by the cured polymer (Ito et al.,
2005). In the monomer blend used in the present study, Considering the limitations of the methods used in the
carbonyl groups in HEMA/Bis-MEP along with the two hydro- present study, we can conclude that the incorporation of
xyl groups in Bis-GMA and in the phosphate functional group nanoparticle llers in a particular self-etching monomer
of Bis-MEP form polar sites to which water molecules are able mixture has the potential to promote the strengthening of
to form hydrogen bonds. With the incorporation of silanized the adhesive resin and the adhesive interface, with improve-
particles to the monomer solution, additional OH that ments to the degree of conversion and polymerization ef-
remain available from free silanol groups at the glass particle cacy. As drawbacks, llers may substantially increase the
surface, as well as carbonyl groups from the silane backbone viscosity of the resin and expedite water sorption into the
molecule add to the hydrophilicity of the resin (Karabela and adhesive layer and the elution of solubilized components.
Sideridou, 2008; Sideridou and Karabela, 2009). Water sorp-
tion then increases for the lled adhesives, even though they
show higher monomer conversion (Figs. 1 and 2). Since a small Acknowledgments
amount of resin cannot absorb more water than a large amount
of the same resin, the elevated water sorption values were Experimental adhesives were supplied by Voco, Germany.
normalized by the wt% of resin phase to reveal the contribution
of the ller and silane polar groups to the water uptake in the r e f e r e nc e s
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