d e n t a l m a t e r i a l s 2 7 ( 2 0 1 1 ) 1144–1152

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journal homepage: www.intl.elsevierhealth.com/journals/dema

Synthesis and study of physical properties of dental

light-cured nanocomposites using different amounts of a
urethane dimethacrylate trialkoxysilane coupling agent

Maria M. Karabela, Irini D. Sideridou ∗

Laboratory of Organic Chemical Technology, Department of Chemistry, Aristotle University of Thessaloniki,
Thessaloniki GR-54124, Greece

a r t i c l e i n f o a b s t r a c t

Article history: Objective. The purpose of this work was the study of the effect of the amount of a urethane
Received 10 July 2010 dimethacrylate silane (UDMS) coupling agent on physical properties of dental light-cured
Received in revised form resin nanocomposites based on Bis-GMA/TEGDMA (50/50 wt/wt) matrix and Aerosil OX50 as
29 June 2011 filler.
Accepted 19 August 2011 Methods. Silica nanoparticles (Aerosil OX 50) used as filler were silanized with 5 different
amounts of UDMS 1.0, 2.5, 5.0, 7.5 and 10 wt% relative to silica. The silanizated silica nanopar-
ticles were identified by FT-IR spectroscopy and thermogravimetric analysis (TGA). Then the
Keywords: silanized nanoparticles (60 wt%) were mixed with a Bis-GMA/TEGDMA (50/50 wt/wt) matrix.
Dental nanocomposites Degree of conversion of light cured composites was determined by FT-IR analysis. The static
Urethane dimethacrylate silane flexural strength and flexural modulus were measured using a three-point bending set up.
(UDMS) The dynamic thermomechanical properties were determined by DMA analyzer. Measure-
Bis-GMA/TEGDMA ments were taken in samples stored, immediately after curing, in water at 37 ◦ C for 24 h.
Aerosil OX50 Sorption, solubility and volumetric change were determined after storage of composites in
DMA water or ethanol/water of 75 vol% for 30 days. Thermogravimetric analysis of composites
Flexural strength and modulus was performed in nitrogen atmosphere from 50 to 800 ◦ C.
Sorption Results. Almost all of used amount of silane remained chemically bounded on the surface of
Degree of conversion silica particles, forming a layer around them, which have dense accumulation of methacry-
late groups. No significant statistic difference was found to exist between the degree of
conversion values of composites with different silane contents. The composite with the
lowest amount of UDMS (1.0 wt%) showed the lower flexural strength value, the higher static
and dynamic elastic modulus values and the higher sorbed liquid value and solubility.
Significance. The optimum concentration of UDMS seems to be that of 2.5 wt%. Higher con-
centrations of UDMS did not improve the properties of composites.
© 2011 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

by polymerization of one or more monomer/oligomers, (2)

1. Introduction
Dental polymer composites are interconnected hetero-
geneous materials that generally have three discernable
phases: (1) a polymeric matrix or continuous phase formed
a higher modulus dispersed phase consisting of fillers of
various types (silica, ceramic, organic, etc.) sizes, shapes and
morphologies and (3) an interfacial or interphasial phase
that bonds to both the continuous and dispersed phases,
thereby enhancing the moduli and mechanical properties

∗
Corresponding author. Tel.: +30 31 2310 997825; fax: +30 31 2310 997769.
E-mail address: siderid@chem.auth.gr (I.D. Sideridou).
0109-5641/$ – see front matter © 2011 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.dental.2011.08.008
 d e n t a l m a t e r i a l s 2 7 ( 2 0 1 1 ) 1144–1152
of the weaker polymer phase and also facilitating stress
transfer between these phases by forming a unitary mate-
rial. Adhesion of lower moduli polymer matrices to higher
moduli inorganic fillers can occur as a result of van der Waals
forces, ionic interactions, hydrogen bonding, ionic or covalent
bonding, interpenetrating polymer network formation and
for certain types of fillers by micromechanical interlocking
mechanisms. For most mineral reinforced dental composites
the primary interphasial linkage between the polymer matrix
and the filler is by chemical bond formation, mediated by a
silane coupling agent [1].
Usually the organic matrix is based on methacrylate
chemistry, especially cross-linking dimethacrylates like 2,2-
bis[4-2-hydroxy-3-methacryloyloxypropyl) phenyl] propane
(Bis-GMA) and triethylene glycol dimethacrylate (TEGDMA)
are used. The free-radical polymerization of the matrix
monomers leads to a three-dimensional network. Most of
the contemporary dental polymer composites are light curing
composites, which harden by irradiation with visible light in
the wavelength range 400–500 nm. Nearly all composite man-
ufacturers are using camphorquinone as the photoinitiator.
The absorption maximum of camphorquinone is at 468 nm.
Amines are used as accelerators and thereby the initiation
radicals are formed via proton and electron transfer [2]. The
dispersed inorganic phase may consist of several inorganic
materials such as quartz, borosilicate glass, lithium aluminum
silicate, strontium or zinc glass and colloidal silica. The inor-
ganic phase is treated with an organosilane before being
mixed with the unreacted dimethacrylate monomers. These
organosilanes are called coupling agents because they form a
bond between the inorganic and organic phases of the com-
posite. Although adhesion is the central function of silanes,
there are many factors involved in the silane modification of
the organic-inorganic interface that change the properties of
the composite. The silane protects the filler surface from frac-
ture, strengthens the boundary layer of polymer matrix and
thus has a positive effect on the properties of the compos-
ite even if failure is not at the interface. With the appropriate
coupling agent, fracture of the composite will not occur at the
interface, but will occur through the polymer matrix. Surface
modification of fillers also affects the rheology of the mixture
of monomers and filler by changing wetting characteristics,
dispersion of particles and viscosity [3].
Generally the efficacy of a silane coupling agent is deter-
mined by the overall degrees of reaction of the silane with
the glass filler (oxane bond formation) with itself (by siloxane
formation) and with the polymer matrix (by graft copolymer-
ization). The oxane bond (silicon–oxygen–silicon) that forms
between the silane agent and the mineral filler can be espe-
cially vulnerable to hydrolysis, because this covalent bond has
significant ionic character [1,4]. By contrast, the carbon-carbon
covalent bond that forms between the silane and the polymer
matrix is considerable more stable to hydrolytic attack than
the silicon–oxygen covalent bond.
The most common silane used in dental composites is
␥-MPS. One approach aimed at improving the quality and
durability of the filler/matrix interface involves the use of
more hydrophobic and flexible silane coupling agents than ␥-
MPS such as the 10-(methacryloyloxy)decyltrimethoxysilane
(MDTMS) [5–7]. The decrease in the flexural strength upon
1145
O
O O O
O O
O NH Si
O
O
Fig. 1 – Chemical structure of urethane dimethacrylate
silane (UDMS).
storage of the composite sample in water can be reduced
by surface modification with the more hydrophobic silane
MDTMS. But the overall mechanical properties achieved with
this silane bearing the flexible decyl spacer are worse than
those attained with the silane possessing the propyl spacer. A
further advantage of using fillers silanized with MDTMS is that
this surface treatment enables higher loadings to be achieved
[8].
Another silane which shows promising results
is the adduct of glycerol dimethacrylate and 3-
(isocyanato)propyltriethoxysilane, a urethane dimethacrylate
silane (UDMS) (Fig. 1). This has two methacrylate groups and
therefore enables the preparation of a crosslinked structure.
Less brittleness of the cured composites is observed after
storage in water. Furthermore, the mechanical properties
are better than those achieved with MDTMS [9]. UDMS has
already been used in commercial dental composites. The
commercial hybrid filling material Definite® is based on it
[10].
In this work the effect of the amount of UDMS cou-
pling agent used on physico-mechanical properties of dental
light-cured resin nanocomposites based on Bis-GMA/TEGDMA
(50/50 wt/wt) matrix and Aerosil OX50 as filler was studied.
The organic monomer matrix used is hardened by irradia-
tion with visible light in the wavelength range 400–500 nm,
using camphorquinone as the photoinitiator and ethyl-4-
dimethylaminobenzoate (4EDMAB) as the accelerator.
2. Materials and methods
2.1. Materials
3-Isocyanatopropyltriethoxysilane (IPTES) was from ABCR
GmbH&Co. KG (SII 6455.0) (Karlsruhe, Germany), dibutyltin
dilaurate, 95% (Metatin 812) (Lot no. 13917HC-135) and
glycerol dimethacrylate (85% mixture of isomers) (GDMA)
(Lot no. S32621-495) were from Sigma–Aldrich, hydro-
quinone, >99% (HQ) from Merck (Art 4610, 2606317)
used in the synthesis of the silane UDMS. Propylamine,
99+% (Lot no. 0.4419MS) and cyclohexane, 99+% (Lot no.
S22455-155) used in the silanization of nanoparticles
of silica were received from Sigma–Aldrich GmbH
(Deisenhofen, Germany). The monomers used i.e. 2,2-
bis[4-(2-hydroxymethacryloxypropoxy) phenyl]propane
(Bis-GMA) (Lot no 07210BB) and triethyleneglycol dimethacry-
late (TEGDMA) (Lot no. 09004BC-275) were provided also
from Sigma–Aldrich. The photoinitiator system was
1146 d e n t a l m a t e r i a l s 2 7 ( 2 0 1 1 ) 1144–1152
camphorquinone, 97% (CQ) (Lot no. S12442-053) and ethyl
4-dimethylaminobenzoate, 99+% (4EDMAB) (Lot no. 90909001)
both from Sigma–Aldrich. The filler Aerosil OX50 was from
Degussa (Lot no. 3155092345) and it is fumed amorphous
silica with average specific surface area (BET) 50 (35–65) m2 /g
and an average particle diameter of 40 nm.
All the materials used in this study were used as received
without further purification.
2.2. Synthesis of the silane UDMS
1 mol of IPTES was carefully added to a mixture of 1 mol of
GDMA, 150 mg of HQ and 180 mg of Metatin 812 as described
in Ref. [10]. Then the mixture was stirred at room temper-
ature for 24 h. The prepared silane was identified by FT-IR
and NMR spectroscopy as described in our previous papers
[11,12].
2.3. Silanization of silica nanoparticles
The silica nanoparticles (Aerosil OX50) were silanized follow-
ing the method of Chen and Brauer [4] using as silane the
UDMS. The amount of silane was at 1.0, 2.5, 5.0, 7.5, 10.0%
(wt/wt) relative to silica.
The silica (5.0 ± 0.05 g), the silane (0.50 ± 0.01 g), the solvent
(100 ml cyclohexane) and n-propylamine (0.1 ± 0.01 g) were
stirred at room temperature for 30 min and then at 60 ± 5 ◦ C
for additional 30 min at atmospheric pressure. The mixture
then was placed in a rotary evaporator at 60 ◦ C for the remov-
ing of the solvent and the volatile byproducts. The powder was
then heated at 95 ± 5 ◦ C for 1 h on the rotary evaporator and
finally was dried at 80 ◦ C in a vacuum oven for 20 h.
The silanized silica nanoparticles were identified by FT-
IR spectroscopy (FTIR Spectrum One, Perkin Elmer, resolution
4 cm−1 , 32 scans, 4000–1350 cm−1 ). Spectroscopic grade KBr
and silica powder were pressed together into a pellet using
a KBr palletizer.
Thermogravimetric analysis of the silanized silica
nanoparticles was performed using a Pyris 1 TGA (Perkin
Elmer) thermal analyzer using about 5 mg of each sample.
The particles were heated to 800 ◦ C under air or nitro-
gen atmosphere flow: 20 ml/min) with a heating rate of
10 ◦ C min−1 .
2.4. Preparation of nanocomposites
The resin matrix was consisted of Bis-GMA/TEGDMA mixture
(50:50 wt/wt) which contained the photoinitiator system CQ
(0.2 wt%) and 4EDMAB (0.8 wt%). Bis-GMA was first heated in
an ultrasonic bath at about 40 ◦ C for 10 min and then TEGDMA
containing the photoinitiating system was added. Then the
silanized silica (60 wt%) was mixed with the resin by hand
spatulation, as it is suggested in Refs. [13–16]. Once the pow-
der was completely wetted with the resin, the composite
pastes were sheared against a glass surface with a Teflon
spatula until the pastes were semi-transparent to assure
maximum particle dispersion in the resin. Then the com-
posite pastes were put into an ultrasonic bath for 3 h. This
employment of high shear stress has shown to help the
silanized Aerosil to form stable sol with the dimethacrylate
resin [17]. Then the pastes were placed in a vacuum oven
to remove air bubbles which probably were entrapped inside
the paste.
2.5. FT-IR analysis-degree of conversion
The FT-IR analysis was conducted in a FT-IR spectrometer,
Spectrum One of Perkin-Elmer. Spectra were obtained over
4000–600 cm−1 region and were acquired with a resolution of
4 cm−1 and a total of 32 scans per spectrum. A small amount
of each composite was placed between two translucent Mylar
strips, which pressed to produce a very thin film. The FT-IR
spectrum was recorded at zero time and immediately after
exposure to visible-light (for 80 s). For each spectrum it was
determined the height of aliphatic C C peak absorption at
1637 cm−1 , as well as the aromatic C C peak absorption at
either 1608 cm−1 , utilizing a base line technique which proved
the best fit to the Beer–Lambert law [18]. The aromatic C C
vibration is used as internal standard. The percent monomer
conversion of the cured specimen, which expresses the per-
cent amount of double carbon bond reacted, is determined
according to the equation:
 
(A1637 /A1608 )polymer
degree of conversion (%) = 100 × 1 −
(A1637 /A1608 )monomer
2.6. Mechanical properties
Mechanical properties were measured in accordance with
International Standard Organization (ISO) Specification No.
4049. Bar specimens were prepared by filling a Teflon
mold with unpolymerized material, taking care to mini-
mize entrapped air. The upper and lower surfaces of the
mold were overlaid with glass slides covered with a Mylar
sheet to avoid adhesion with the unpolymerized material.
The completed assembly was held together with spring
clips and irradiated by overlapping, as recommended in ISO-
4049, using a XL 3000 dental photocuring unit (3M-ESPE,
St. Paul, MN, USA). This source consisted of a 75-W tung-
sten halogen lamp, which emits radiation between 420 and
500 nm and has the maximum peak at 470 nm. This unit
was used without the light guide in contact with the glass
slide. Each overlap was light-cured for 80 s. The samples
were irradiated on both sides. Then, the mold was disman-
tled and the composite was carefully removed by flexing
the Teflon mold. Five specimen bars were prepared for each
composite. The bar-shaped specimens had been stored in dis-
tilled water at 37 ± 1 ◦ C in dark for 24 h, immediately after
curing.
2.6.1. Flexural strength and flexural modulus
For flexural tests, bar-specimens were prepared by filling a
Teflon mold 2 mm × 2 mm × 25 mm. The specimens were bent
in a three-point transverse testing rig with 20 mm between
the two supports (3-point bending). The rig was fitted to a
mechanical testing machine (Instron, model 3344). All bend
tests were carried out with a constant cross-head speed of
0.75 ± 0.25 mm/min until fracture occurred. The load and
the corresponding deflection were recorded. The flexural
 d e n t a l m a t e r i a l s 2 7 ( 2 0 1 1 ) 1144–1152
modulus (E), in MPa, and the flexural strength (), in MPa,
were calculated using the following equations:
F1 l3 3Fl
E= and  =
4bdh3 2bh2
where F1 represents the load in Newtons exerted on the
specimen, F the maximum load in Newtons exerted on the
specimen at the point fracture, l the distance in mm between
the supports, h the height of specimen in mm measured
immediately prior to testing, b the width of specimen in mm
measured immediately prior to testing and d is the deflection
corresponding to the load F1 .
2.6.2. Dynamic mechanical analysis (DMA)
For DMA tests, bar specimens were prepared by filling a Teflon
mold (2 mm × 2 mm × 40 mm). DMA tests were performed
on a Diamond dynamic mechanical analyzer (Perkin Elmer
instruments, technology SII) using a dual-cantilever clamp. A
frequency of 2 Hz was applied (approximately average chew-
ing rate) and amplitude of 10 ␮m. A temperature range of
25–185 ◦ C at a heating rate of 2 ◦ C min−1 was selected to cover
mouth temperature and the materials’ likely glass-transition
temperature (Tg ). Elastic modulus (E ), viscous modulus (E )
and tangent delta (tan ı) were plotted against temperature
over this period. After the DMA run was complete, the sample
was allowed to cool naturally to room temperature and the
values of E , E and tan ı at various temperatures were noted.
This method was used for each of the samples and the mean
values were calculated.
2.7. Sorption of water and ethanol/water solution
(75 vol%) – solubility – volumetric change
Sorption and solubility tests were determined according to the
method described in ANSI/ADA Specification No. 27-1993 for
resin based filling materials. Specimen discs were prepared by
filling a Teflon mold (15 mm in diameter and 1 mm in thick-
ness) with the unpolymerized material. The samples were
irradiated for 80 s on each side, using a XL3000 dental pho-
tocuring source (3M-ESPE, St. Paul, MN, USA). The unit was
used without the light guide at the contact with the sam-
ple. Four specimen discs were prepared for each composite
material.
The percentage amount of water or ethanol/water solution
(75 vol%) sorbed (WS (%) or EWS (%)) and desorbed (WD (%) or
EWD (%)), the solubility (SL (%)) in these liquids, the volumet-
ric change (VI (%)) and the fraction of the liquid contributing
to an increase in swelling (f) were determined according
to the method described in detail in our previous work
[19].
2.8. Thermogravimetric analysis
The thermal degradation of composites and the determination
of the weight percentage of fillers were studied by thermo-
gravimetric analysis. Weight changes as a function of time
and temperature were evaluated during a thermal program
from 50 to 800 ◦ C at the heating rate of 10 ◦ C min−1 in nitrogen
atmosphere (flow 20 ml/min) by cooling room temperature.
Thermogravimetric analysis was performed on a Pyris 1 TGA
1147
(Perkin Elmer) thermal analyzer using about 5 mg of each sam-
ple.
2.9. Statistical analysis
The values reported in all following tables and figures repre-
sent mean values ± standard deviation of replicates. One-way
analysis of variance (ANOVA) test, followed by a Tukey’s test,
for multiple comparisons between means to determinate sig-
nificant differences was used at a significance level set at
p ≤ 0.05, for analysis of the experimental results.
3. Results and discussion
3.1. Characterization of silanized silica
Many methods have been used to treat the filler particles
with a silane coupling agent and a general consensus does
not emerge from the literature regarding the best method
of silanization. In this work silanization of Aerosil OX 50
nanoparticles was performed by mixing a certain amount
of UDMS in cyclohexane in the presence of n-propylamine
used as catalyst. The use of n-propylamine accelerates the
silanization of the silica [20,21] and yields the most stable
interfacial silicon-silane bonds [4]. This silanization proce-
dure was followed by Antonucci et al. [13–15] in their attempt
to study the interphase effects in dental nanocomposites.
According to this mechanism (so-called direct condensation
mechanism) the silane molecules would chemically bond
to the surface of filler particles via direct condensation of
–OCH2 CH3 groups of the silane with the surface hydroxyl
groups of the filler to form a covalent bond (oxane bond
formation; Si–O–Si) [20,21]. The –OCH2 CH3 groups on adja-
cent silane can also condense with each other to form
a polymeric siloxane polymer film on the silica surface
(Fig. 2) [1].
The prepared silanized silica nanoparticles were identi-
fied by FT-IR spectroscopy. The FT-IR spectra of Aerosil OX50
treated with various amounts of UDMS are shown in Fig. 3.
They showed (a) an absorption band at 1638 cm−1 due to
the stretching vibration of the C C bond in UDMS and (b) a
strong absorption band at the region 1700–1725 cm−1 due to
the stretching vibration of the C O bond. The free carbonyl
stretching vibration of the neat unhydrolyzed UDMS appears
at 1724 cm−1 . In the Aerosil treated with 10 wt% silane this
absorption is also appeared at 1725 cm−1 , but it is shifted to
lower frequencies (1724, 1719, 1712, 1705 cm−1 ) as the amount
of UDMS is decreased correspondingly (7.5, 5.0, 2.5, 1.0 wt%).
This shift to lower frequencies is most probably due to the
formation of hydrogen bonds between the carbonyl groups
and the hydroxyls of silica or adjacent silane molecules.
Thus silane molecules form a layer around the filler particles
through chemical and physical bonds that may have a signifi-
cant impact on the filler–matrix bond strength, depending on
the amount of the silane used.
TGA of the samples showed first a one-step weight loss due
to the silane decomposition and then a small weight loss at
approximately 500 ◦ C, which is due to condensation of surface
silanols [22]. From the first weight loss the amount of UDMS
1148 d e n t a l m a t e r i a l s 2 7 ( 2 0 1 1 ) 1144–1152

Table 1 – Amount of the silane UDMS attached on the silica surface determined by TGA of silanizated silica in nitrogen or
air atmosphere.
Amount of UDMS used in silanization (wt%) TGA weight loss (%) Silane UDMS

wt% ␮mol/m2 molecules/nm2

From TGA in nitrogen
1.0 0.69 1.00 0.44 0.27
2.5 1.48 2.16 0.95 0.57
5.0 2.70 3.96 1.73 1.04
7.5 4.42 6.48 2.83 1.71
10.0 5.90 8.65 3.78 2.28
From TGA in air
1.0 0.68 1.00 0.44 0.26
2.5 1.51 2.21 0.96 0.58
5.0 3.17 4.64 2.03 1.22
7.5 4.79 7.02 3.07 1.85
10.0 6.24 9.14 4.97 2.31

Ο
Si
ΟΗ ΟΗ
ΗΟ ΟΗ Ο
ΗΟ Ο
R
ΗΟ ΟΗ

ΗΟ ΟΗ OCH2CH3 cyclohexane
Si ΗΟ Ο Si
R
H3CH2CO OCH2CH3 n-propylamine
ΗΟ ΟΗ
ΗΟ ΟΗ Ο
ΟΗ ΗΟ Ο
ΟΗ Si

Ο R
nanoparticle SiO2 silane surface modified nanoparticle SiO 2

Fig. 2 – Simplified representation idealized silanization of silica-filler particles, according to direct condensation mechanism.
In this figure, the sizes of the interphase regions have been exaggerated relative to the size of the silica nanoparticles.

attached on the Aerosil OX50 surface was quantitatively deter-

mined and it is presented in Table 1. This amount is very close
to the amount of the silane used, indicating that almost all the
used amount of silane remained chemically bounded on the
silica particles.

3.2. Degree of conversion

The degree of conversion of prepared composites attained val-

A
ues in the range of 54.8–56.3%, which is not depended on the
10 %
amount of silane used (p ≥ 0.05). The UDMS-silanized nanopar-
7,5 % ticles may have acted more like multifunctional monomers,
due to methacrylate groups, causing gelation to occur at low
5,0 % conversions in a short time and thereby decrease the limiting
degree of conversion.
2,5 %

1,0 % 3.3. Mechanical properties

The mechanical properties of composites containing dif-

2000 1900 1800 1700 1600
ferent amounts of UDMS-coupling agent are summarized
Wavenumber (cm-1) in Table 2. The flexural strength was statistically similar
for all composites, except for the composite with UDMS
Fig. 3 – FT-IR spectra of silane treated silica surface with
1.0 wt%, which had a significantly lower strength (p ≤ 0.05).
increasing amounts of silane (in wt%): 1.0, 2.5, 5.0, 7.5, 10.
The low amount of silane (1.0 wt%) used in silanization,
The silane is UDMS.
was no enough most probably to coat uniformly the silica
particles, causing low flexural strength. As the amount of
 d e n t a l m a t e r i a l s 2 7 ( 2 0 1 1 ) 1144–1152 1149

Table 2 – Mechanical properties of the composites after storage in water 37 ◦ C for 24 h [mean (S.D.)],a n = 5.
Amount of UDMS used (wt%) Flexural strength (MPa) Flexural modulus (GPa)
1.0 (1.00)b 76.4 (8.6) 7.02 (0.16) b
2.5 (2.21)b 100.4 (8.1) a 6.80 (0.16) b
5.0 (4.64)b 103.7 (2.3) a 6.38 (0.15) c
7.5 (7.02)b 99.2 (4.5) a 6.16 (0.15) c
10 (9.14)b 99.3 (11.4) a 6.17 (0.07) c
a
Common corresponding letters indicate no significant difference (p ≥ 0.05).
b
The values in the parentheses are the amount of the silane chemical attached to the silica which has been determined by TGA (Table 1).

Table 3 – Glass transition temperature (Tg ) and dynamic mechanical properties of the composites at 37 ◦ C, after storage in
water (37 ◦ C) for 24 h [mean (S.D.)],a n = 4.
Amount of UDMS used (wt%) Tg (◦ C) Dynamic Dynamic tan ı (×103 ) tan ı (×103 ) at Tg
elastic viscous
modulus, E modulus, E
(GPa) (GPa)
1.0 (1.00)b 124.4 (1.1)a 6.74 (0.04) 0.41 (0.00) 61.5 (0.78) 136.8 (0.8)g
2.5 (2.21)b 127.9 (1.9)a 6.61 (0.05)b 0.43 (0.01)d 65.0 (1.27) 140.9 (1.1)
5.0 (4.64)b 125.3 (0.3)a 6.56 (0.11)b 0.45 (0.01)d 69.8 (2.35)f 138.0 (0.8)g
7.5 (7.02)b 126.5 (1.0)a 5.21 (0.32)c 0.37 (0.01)e 69.4 (1.63)f 133.1 (0.5)h
10 (9.14)b 125.6 (1.1)a 5.46 (0.15)c 0.39 (0.01)e 70.6 (0.42)f 133.6 (1.1)h
a
Common corresponding letters indicate no significant difference (p ≥ 0.05).
b
The values in the parentheses are the amount of the silane chemical attached to the silica which has been determined by TGA (Table 1).

Table 4 – Sorption/desorption parameters of water or ethanol/water solution (75 vol%) for the five composite materials,
after storage in liquids at 37 ◦ C for 30 days [mean (S.D.)],a n = 4.
Amount of UDMS Sorption (wt%) Desorption (wt%) Solubility (wt%) % Volume increase Swelling, f
used (wt%)
Water
1.0 (1.00)b 2.05 (0.00)A 2.06 (0.03)A 0.28 (0.01)d 1.89 (0.08) 0.55 (0.02)g
2.5 (2.21)b 1.85 (0.04)a,B 1.85 (0.04)b,B 0.20 (0.02)e 2.18 (0.03) 0.66 (0.07)
5.0 (4.64)b 1.85 (0.07)a,C 1.76 (0.01)c,C 0.21 (0.05)e 1.61 (0.02)f 0.53 (0.03)g
7.5 (7.02)b 1.91 (0.05)a 1.76 (0.04)c 0.23 (0.01)e 1.62 (0.07)f 0.51 (0.02)g
10 (9.14)b 1.95 (0.06)a 1.79 (0.04)b,c 0.23 (0.01)e 1.54 (0.03)f 0.56 (0.03)g
Ethanol/water solution 75 vol%
1.0 (1.00)b 4.34 (0.27)h 4.16 (0.25)h 0.39 (0.07)k 6.78 (0.21) 0.79 (0.06)n,o
2.5 (2.21)b 3.46 (0.19)i 3.35 (0.23)i 0.11 (0.06)l 5.73 (0.08) 0.81 (0.02)n
5.0 (4.64)b 2.74 (0.53)i,j 2.88 (0.35)i,j 0.16 (0.00)l 4.01 (1.06)m 0.74 (0.01)o
7.5 (7.02)b 3.05 (0.40)i,j 2.95 (0.38)i,j 0.14 (0.01)l 3.87 (0.90)m 0.69 (0.08)o,p
10 (9.14)b 2.64 (0.49)j 2.51 (0.46)j 0.17 (0.02)l 3.26 (0.62)m 0.63 (0.01)p
a
Common corresponding letters indicate no significant difference (p ≥ 0.05).
b
The value in the parentheses is the amount of the silane attached to the silica which has been determined by TGA (Table 1).

UDMS on interface composites increased, it was not observed
increase to strength. Although UDMS molecules can react
with the dimethacrylate monomers during polymerization
via methacrylate groups, creating strong coupling between
the filler and polymer matrix phase, the high amount of
silane limits mobility of the silane methacrylate groups and
therefore it limits their capacity to act like multifunctional
monomers.
The composites with UDMS 1.0 wt% and 2.5 wt% showed
the highest flexural modulus values (Table 2). The other three
composites showed lower modulus values, which are not
statistically different (p ≥ 0.05). Therefore, the capacity of mul-
tifunctional silane UDMS to crosslinking does not contribute
to increase to elastic behavior of composite, as the amount of
UDMS on interface composites increased, due to stereochem-
ical hindrance.
In Table 3 are presented the dynamic mechanical proper-
ties of composites at usual temperature of oral cavity (37 ◦ C).
Dynamic elastic or storage modulus, E , showed a maximum
value (6.74 GPa) for the composite contained the minimum
chemically attached molecules of UDMS (1.00 wt%). At higher
amounts of UDMS the dynamic elastic modulus decreases.
Elastic modulus is an indicator of elastic behavior and reveals
the ability of the material to store elastic energy associated
with recoverable elastic deformation. Therefore, the ability
of the multifunctional coupling agent UDMS to crosslinking
does not lead to increase of the elastic behavior of compos-
ites. Dynamic loss or viscous modulus E , at 37 ◦ C, showed
a maximum value (0.44 GPa) for the composites with UDMS
2.16 and 6.48 wt% correspondingly. A maximum value of loss
modulus suggests a greater ability of the composite to relieve
excess energy build up through moderate viscous flow during
1150 d e n t a l m a t e r i a l s 2 7 ( 2 0 1 1 ) 1144–1152

100 composite
1,0% Bis-GMA/TEGDMA
2,5%
90 5,0% 100
weight loss (%)

7,5%
10 %
80 80

weight loss (%)

70 60

60 40

50 20
100 200 300 400 500 600 700 800
o
Temperature ( C)
0
100 200 300 400 500 600 700
o
0,0 Temperature ( C)
der. weight loss (% / min)

-0,5
composite
-1,0 Bis-GMA/TEGDMA
0
-1,5 o
1,0% -1 610 C

der. weight loss (% / min)

-2,0 2,5%
-2
5,0% o
7,5% -3 312 C o
406 C
-2,5
10 %
-4
-3,0
100 200 300 400 500 600 700 800
-5 o
342 C
o -6
Temperature ( C)
-7
Fig. 4 – Effect of the amount of silane-coupling agent UDMS -8 o
(1.0, 2.5, 5.0, 7.5, 10 wt%) used for the silanization of 416 C
-9
nanosilica on the TGA and DTGA curves of prepared 100 200 300 400 500 600 700
nanocomposites, in nitrogen atmosphere. o
Temperature ( C)

Fig. 5 – Comparison TGA/DTGA curves of polymer matrix

tooth function. On one hand, the viscous flow may help
to reduce or delay failure processes that depend on energy
build up, such as fracture, wear and debonding [23]. On the
other hand, materials with high loss modulus can show small
permanent dimensional change, which may not be desir-
able.
The values of glass transition temperature, Tg , of prepared
composites which were determined by peak tan ı curves,
are presented in Table 3. No significant statistic difference
(p ≥ 0.05) was found to exist between the Tg values of com-
posites with different silane contents. High Tg values indicate
a highly crosslinked nature of the polymeric network of the
composites. However, it is reported [24] that the feature that
is the most sensitive to the structure of the interphase is
the height of the tan ı at the glass transition temperature
(Tg ) and is recommended as the best parameter for charac-
terizing variations in interfacial structure of composites. The
composites with the higher amounts of silane UDMS (7.02
and 9.14 wt% correspondingly) (Table 3) showed the lower
values for the tan ı at the Tg , which are not statistically dif-
ferent (p ≥ 0.05). According to this result these two composites
seem to have better interfacial adhesion between filler and
matrix.
Bis-GMA/TEGDMA and nanocomposite prepared with the
use of 7.5 wt% UDMS, in nitrogen atmosphere.
3.4. Sorption of water or ethanol/water solution
(75 vol%) – solubility – volumetric change
The values of the determined parameters for sorption of water
and ethanol/water solution by the prepared nanocomposites,
after storage in liquids (37 ± 1 ◦ C) for 30 days, are reported in
Table 4. The composite with the lowest amount of silane UDMS
(1.0 wt%), sorbed the highest amount of water followed by the
other four composites, which showed statistically (p ≤ 0.05) the
same values of sorbed water. The composite interface sorbed
water and the presence of a chemisorbed layer of silane at
the silica surface reduces the amount of sorption [25]. In case
of composites without a chemical bonding between the sil-
ica and the matrix the exposed hydrophilic sites on the silica
surface (–SiOH) attract water, forming hydrogen bonds with
sorbed water molecules. However, in case of composites with
silane-treated filler particles, the chemical bonds between the
silane and the silica reduced the number of the hydrophilic
sites and thus the amount of water uptake [24]. Therefore, on
the silica surface of the composite with the lowest amount
of UDMS there are more exposed silanol groups than other
 d e n t a l m a t e r i a l s 2 7 ( 2 0 1 1 ) 1144–1152 1151

composites. A similar behavior was observed for the water

desorption. The amount of water desorbed was no statistically
4. Conclusions
different (p ≥ 0.05) from that sorbed.
After modification with different amount of UDMS silane
The results obtained for the sorption and desorption of the
coupling agent, the UDMS molecules are grafted onto the
ethanol/water solution by the prepared composites are also
surface of silica nanoparticles. Almost all of used amount
presented in Table 4. The composite with the lowest amount of
of silane remained chemically bounded on the surface of
silane UDMS (1.0 wt%) sorbed/desorbed the highest amount of
silica particles, forming a layer around them, which have
solution, as the case water, followed by the other composites,
dense accumulation of methacrylate groups. By introduc-
which showed statistically (p ≥ 0.05) the same values of sorbed
ing silica particles with modification into the dimethacrylate
solution.
monomers, the pastes of composites are prepared.
All composites showed higher values sorbed liquid after
No significant variation in degree of conversion of the cured
immersion in ethanol solution when compared with that
pastes, with increasing silane amount, is observed. A highly
in water. This behavior is due to different chemical affin-
condensed silane interphase that limits mobility of the silane
ity between sorbed liquid and the polymer matrix [26,27].
methacrylate, causing gelation to occur in a short time, would
The higher absorbance of ethanol/water solution 75 wt%
account for the conversion decrease among the composites.
(ı: 3.0 × 10−4 J1/2 m−3/2 ) than water (ı: 4.8 × 10−4 J1/2 m−3/2 )
The capacity of multifunctional silane UDMS to crosslink-
by the resin of composites reveals that the solubility
ing does not contribute to increase to elastic behavior of
parameter, ı, of resins must be closer to that of ethanol
composite, as the amount of UDMS on interface composites
solution.
increased, due to stereochemical hindrance. Even if UDMS
The amount of silane UDMS used for the silanization
molecules can react with the dimethacrylate monomers dur-
of nanosilica was found to affect the volume increase (VI)
ing polymerization via methacrylate groups, creating strong
of composites after immersion in both solvents (Table 4).
coupling between the filler and polymer matrix phase, the
In Table 4 is also shown the dependence of the amount
high amount of silane limits mobility of the silane methacry-
of the coupling agent UDMS on the fraction (f) of sorbed
late groups and therefore it limits their capacity to act like
solution which is accommodated between polymer chains
multifunctional monomers.
and contributed to swelling of composite. The fraction f is
However, in case of composites with silane-treated filler
affected (p ≤ 0.05) by the amount of UDMS on composite
particles, the chemical bonds between the silane and the sil-
interface in both solvents. Comparing the volume increase
ica reduced the number of the hydrophilic sites and thus the
and swelling of composites in both solvents it is observed
amount of water uptake. Therefore, the composite with the
that for all composites show extremely high values in
lowest amount of UDMS sorbed the highest amount of water
ethanol/water solution. This behavior is due to the much
or ethanol solution.
higher amount of ethanol solution than water sorbed by the
The optimum concentration of UDMS seems to be that of
composites.
2.5 wt%. Higher concentrations of UDMS did not improve the
properties of composites.
3.5. Thermogravimetric analysis

The TGA curves and the corresponding differential TGA

(DTGA) curves of all prepared composites containing differ-
ent amounts of UDMS-coupling agent indicated a three-step
degradation process (Fig. 4). The first two steps thermal
degradation of the composites, one around 210–350 ◦ C and
the other one from 350 to 490 ◦ C, is related to the degra-
dation of neat polymeric matrix, Bis-GMA/TEGDMA, while
the third step around 490–770 ◦ C is due to condensation
of surface silanols of silica [22]. These are concerned by
the comparison between the TGA/DTGA curves of polymer
matrix and the curves of the composites (Fig. 5). The appear-
ance of two thermal degradation steps in the matrix based
Bis-GMA/TEGDMA is attributed to inhomogeneities in the
network structure mainly due to the formation of primary
cycles during photopolymerization. The first degradation step,
at low temperatures, corresponds to bond breaking near
the cycling points, while the second to the main network
[28–30].
Thermogravimetric analysis showed that composites con-
tain filler about 60 wt%. It was observed that an increase in
the amount of used silane UDMS, decrease the fraction of inor-
ganic filler of composites. The temperature where degradation
of composites starts is not affected by the amount of UDMS on
composite interface.
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