Dental Materials (2006) 22, 258–267

www.intl.elsevierhealth.com/journals/dema

Dynamic visco-elastic properties of dental

composite resins
Renata V. Mesquita*, Detlef Axmann, Jürgen Geis-Gerstorfer

Department of Prosthodontics, Section Medical Materials and Technology, University Hospital Tuebingen,
Osianderstr. 2-8, D-72076 Tuebingen, Germany

Received 12 August 2004; received in revised form 17 March 2005; accepted 4 April 2005

KEYWORDS Summary Objectives: This study aimed to examine the visco-elastic properties of
Composites; dental composites by dynamic mechanical analysis under the influence of clinically
Visco-elastic relevant temperatures and variable frequencies, after being stored in air or distilled
properties; water for up to 3 months.
Water sorption; Methods: Two direct (Diamond Lite and Grandio) and two indirect (Artglass and Vita
Temperature; Zeta LC) composites were used. Samples were immediately tested (baseline) or
Frequency stored at 37 8C, either in air or distilled water for 1 day, 7 or 90 days before testing.
During dynamic testing, elastic modulus, viscous modulus and loss tangent were
determined over a frequency range from 0.1 to 10 Hz at constant temperatures
between 5 and 55 8C.
Results: Results were analyzed by one-way ANOVA and Tukey’s-test. Elastic and
viscous moduli were higher for direct than for indirect composites. No such
evidence was found for loss tangent. Only the elastic modulus showed statistically
relevant differences in the direct and indirect materials groups: Grandio showed
higher modulus than Diamond Lite, while Artglass had higher modulus than Vita
Zeta LC. The elastic modulus reduced with increasing temperature and decreasing
frequency, while the loss tangent showed the opposite trend. The influence of
temperature and frequency on viscous modulus was not conclusive. The elastic
modulus was more sensitive to moisture than viscous modulus and loss tangent but
all three properties showed no overall consistent trend in the results following the
storage periods.
Significance: Dynamic mechanical analysis was a valuable tool to characterize the
visco-elastic properties of dental composites, thus giving us a greater insight into
material behavior.
Q 2005 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Introduction
* Corresponding author. Tel.: C49 7071 29 83995; fax: C49
7071 29 5775.
Elastic modulus is a very sensitive parameter for
E-mail address: renata.mesquita@med.uni-tuebingen.de (R. evaluating and ranking particle reinforced compo-
V. Mesquita). sites [1]. Typically, dental composites with low
0109-5641/$ - see front matter Q 2005 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.dental.2005.04.019
Dynamic properties of dental composite resins
modulus will more readily elastically deform under
functional stresses, which may result in cata-
strophic fracture of the surrounding tooth structure
[2]. In such cases, enamel and dentin will be forced
to carry more forces than originally intended,
increasing the risk of cusp fracture [3]. Addition-
ally, a composite’s elastic deformation may also
disrupt the interfacial tooth/restoration bonding,
which may lead to gap formation and contribute to
microleakage, secondary caries and post-operative
sensibility [2,4].
Conversely, composite materials with extremely
high elastic modulus are unable to absorb occlusal
vertical loading stresses. Consequently, mastica-
tory stresses will be almost totally transmitted to
the cavity walls, which can have a potential
destructive effect on the prepared brittle tooth
structure. Moreover, these materials cannot flow
and compensate for the volumetric contraction
stresses developed during polymerization, putting
at risk the integrity of the adhesive interface
between tooth and restoration, and also increasing
the risk of tooth fracture [5].
Ideally, the elastic modulus of dental composites
should be matched to those of the dental tissue
they are supposed to replace [2,4]. Since enamel
and dentin have distinct elastic properties and
generally must be simultaneously replaced, two
distinct restorative materials should be combined.
Then a more realistic concept would be choosing
one of either enamel or dentin, as a standard.
Polymers are characterized as visco-elastic
materials, so that dental composite resins should
be expected to exhibit some visco-elastic response.
This gives a mismatch with the behavior of enamel at
body temperature, but a closer match to that of
dentin. Consequently, the dental tissue to be chosen
as standard should preferably be the dentin [6].
Therefore, in order to survive in stress bearing areas
in the oral environment, the elastic modulus of
dental composites should at least be as high as dentin
modulus [4], which is about 18 GPa, or higher [7].
Traditionally, the mechanical properties of
dental composites have been investigated using
static tests. However, this approach has led to
difficulties in assessing and comparing materials
that show visco-elastic behavior under load [8],
since it focuses only on the elastic component of
the material. Dynamic tests such as dynamic
mechanical analysis, on the other hand, are
particularly well suited for visco-elastic materials,
since they can determine both the elastic and
viscous responses of the sample.
Since dental composites are exposed to dynamic
loading rather than static loading, dynamic tests
have become increasingly relevant. While static
259
tests obtain data related to a longer time scale than
that of mastication [9], which can be a source of
misleading results [10]; dynamic tests better mimic
the cyclic masticatory loading to which dental
composites are clinically subjected [10]. Besides
the masticatory stresses, composites are exposed
to organic food acids, plaque-forming bacteria and
other secretions, also being susceptible to pH and
temperature variations.
The first aim of this study was to monitor the
changes in the visco-elastic properties of current
dental composite resins over a range of clinically
relevant temperatures and variable frequencies,
including an approximate masticatory frequency
(1 Hz). Within this experimental setting, the second
objective was to study the influence on those
properties of aging in air and in water for up to 3
months. The wet condition was selected to simulate
the moisture in the oral environment, while the dry
condition was taken for comparison to reveal
changes in the properties due to water sorption.
Materials and methods
Materials and preparation of the specimens
Two direct (Diamond Lite and Grandio) and two
indirect (Artglass and Vita Zeta LC) light-activated
composite materials were selected for this study.
Their specifications are listed in Table 1.
Bar shape specimens were prepared using a
Teflon mold of internal dimensions 30!2.5!
2 mm. The mold was lubricated with a thin layer
of Vaseline and filled to excess, the material
surface covered with a Mylar sheet and a glass
slide. Moderate digital pressure was applied to the
slide to extrude excess material. The glass slide was
removed and the sample polymerized.
Diamond and Grandio specimens were cured at
room temperature (22G1 8C) by placing the tip
(9 mm diameter) of the hand light curing unit
(Elipar Trilight, 3M/Espe, USA) in contact with the
Mylar sheet at the surface of the mold. The samples
were irradiated at four 60-second overlaps along
the length of the upper surface. A stepped cure was
performed, initially with a period of low-intensity
(200 mW/cm 2 ) followed by a period of high
intensity irradiance (900 mW/cm2).
For the indirect composites, Artglass and Vita
Zeta LC, the mold was placed in a light curing unit
(DentacolorwXS, Heraeus Kulzer, Germany) and
exposed from the top for 3 min. The mold was
disassembled, allowing free retrieval of the sample,
260
Table 1 List of materials and their respective compositions.
Material/supplier Shade/batch
Artglass, Heraeus Kulzer, B3/040110
Germany
Diamond Lite, DRM B3/900050-1
Laboratory, USA
Grandio, Voco, Germany -/V21513
Vita Zeta LC, Vita 2M2/6698
Zahnfabrik, Germany
All information provided by the manufacturer.
which was also irradiated from the reverse side for
another 3 min.
Following polymerization, the specimens were
examined, and those presenting irregularities such
as bubbles and cracks were discarded. Finally, both
faces of the specimens were ground flat on 600 grit
emery paper under water with a polishing machine
(TG 200, Jean Wirtz, Düsseldorf, Germany) and
adjusted to the final dimensions.
Composing the groups of samples
A total of 35 samples were prepared from each
composite and equally distributed into 7 groups.
One group was tested immediately after prep-
aration (baseline). Three other groups were con-
ditioned in distilled water for either 1 day, 7 or
90 days. The last three groups were stored in air,
also either for 1 day, 7 or 90 days. Each stored group
was kept separately in a closed plastic receptacle at
37 8C. Distilled water was changed weekly. After
the storage period, each specimen was tested in a
dynamic mechanical analyzer.
Theory about dynamic mechanical analysis
(DMA)
During dynamic testing, a sample is subjected to a
sinusoidal deformation (strain) at one frequency or
range of frequencies over a specific temperature
range or isothermically as a function of time, and
the corresponding forces are measured. The sample
can be also subjected to an amplitude force and the
resulting deformation is measured.
When a sinusoidal stress is applied to a perfectly
elastic solid the deformation occurs exactly in
phase with it. A completely viscous material will
respond with the deformation lagging 908 behind
the applied stress. However, when the stress is
applied to a visco-elastic material, it will behave
neither as a perfectly elastic nor as a perfectly
R.V. Mesquita et al.
Monomer matrix Filler content Filler wt%
Multifuncional metha- Ba-Al-Silicate-Glass 70
crylates and SiO2
PEX (Phenol-epoxy- Borosilicate glass 78–84
monomer)
Bis-GMA, UDMA and Glass ceramic 87
TEGDMA particles and SiO2
Bis-GMA, UDMA and Multiphase feldspar 44.7
TEGDMA frits and SiO2
viscous body and the strain will lag behind the stress
by some angle s, where s!908 [11].
The stress that is in phase with the applied strain
is used to determine the elastic or storage modulus
(E 0 ), which is an indicator of elastic behavior, and
reveals the ability of the material to store elastic
energy associated with recoverable elastic defor-
mation. The stress that is out of phase with the
applied strain is used to calculate the viscous or loss
modulus (E 00 ), which indicates the ability of the
material to dissipate mechanical energy through
conversion into heat by molecular motion, being
associated with unrecoverable viscous loss [12]. The
loss tangent (tan d) is the phase angle between the
dynamic strain and stress in the oscillating exper-
iment, and is given by the ratio of the viscous
modulus to the elastic modulus. The lower the loss
tangent the quicker the material will respond to load
(more elastic like), returning faster to its original
shape, whereas the higher it is the higher the amount
of energy lost as heat (more viscous like).
Experimental method
The dynamic mechanical analysis of the materials
was carried out using a DMA Q800 (TA Instruments,
New Castle, USA) and nitrogen as coolant. The device
was set up for single cantilever mode with an
oscillation amplitude of 35 mm. In the test, the
sample was clamped inside an environmental
chamber and periodically subjected to a series of
discrete frequencies (0.1, 1, 2, 5 and 10 Hz). Data
were obtained every 5 8C over the 5–55 8C range. A
5-min soak time was used at each temperature to
ensure isothermal conditions. During the experiment
the elastic modulus, viscous modulus and loss tangent
were collected and plotted versus temperature.
Statistical analysis
Three frequencies (0.1, 1 and 10 Hz) were selected
for statistical analysis, which was performed at two
Dynamic properties of dental composite resins 261

Table 2 Summary of mean and (standard deviation) of the elastic modulus values (GPa) at 5 8C for Diamond Lite
(D), Grandio (G), Artglass (A) and Vita Zeta LC (V) at the frequencies 0.1, 1 and 10 Hz.
Group Baseline 1 day 7 days 90 days
– Air Water Air Water Air Water
a b a b
D-0.1 10.8 (0.3) 13.6 (0.3) 12.3 (0.4) 14.2 (0.5) 13.3 (0.3) 12.3 (0.3) 11.6 (0.2)
D-1 11.8 (0.3)a 14.4 (0.3)b,c 13.1 (0.4)d 14.9 (0.4)b 14.0 (0.4)c 13.0 (0.3)d 12.4 (0.2)a,d
D-10 12.7 (0.2)a 14.9 (0.3)b,c 13.7 (0.4)d 15.3 (0.5)b 14.5 (0.4)c 13.6 (0.3)d 13.0 (0.2)a,d
G-0.1 15.2 (0.2) 16.9 (0.2)a 16.4 (0.1)b 18.1 (0.2) 16.4 (0.1)b 17.5 (0.3) 17.0 (0.4)a
G-1 16.1 (0.2) 17.5 (0.2)a,b 17.1 (0.1)a,c 18.6 (0.2) 17.0 (0.2)c 17.9 (0.3)b 17.6 (0.4)b
G-10 16.9 (0.2) 18.0 (0.2)a,b 17.7 (0.1)a,c 19.1 (0.2) 17.5 (0.2)c 18.3 (0.2)b 18.1 (0.4)a,b
A-0.1 9.4 (0.1)a,b 10.7 (0.1)c 10.2 (0.2)c 10.3 (0.5)c 9.2 (0.5)a 10.1 (0.3)b,c 9.0 (0.3)a
A-1 10.1 (0.1)a,b 11.1 (0.1)c 10.8 (0.2)c 10.7 (0.5)a,c 9.8 (0.5)b 10.5 (0.3)a,c 9.6 (0.1)b
A-10 10.7 (0.1)a,b 11.5 (0.1)c 11.2 (0.2)a,c 11.1 (0.4)a,c 10.3 (0.4)b,d 10.9 (0.3)a 10.0 (0.2)d
V-0.1 3.7 (0.1) 6.2 (0.3)a,b 5.7 (0.2)c 5.9 (0.3)a,c 4.9 (0.2) 6.6 (0.0)b 5.7 (0.2)c
V-1 4.4 (0.1) 6.8 (0.2)a,b 6.3 (0.2)c 6.5 (0.3)a,c 5.6 (0.2) 7.0 (0.0)b 6.1 (0.3)c
V-10 5.0 (0.1) 7.2 (0.1)a 6.7 (0.2)b,c 6.9 (0.3)a,b 6.1 (0.2)d 7.3 (0.0)a 6.4 (0.3)c,d
*Values in the same line not connected by the same letter are significantly different.

extreme temperatures (5 and 55 8C) at which
materials could be exposed to clinically. Results
are condensed in tables to means and standard
deviations (Tables 2–7). The elastic and viscous
modulus confidence intervals at 5 and 55 8C for
baseline and 1 day water-stored samples are
presented at 1 Hz for all composites tested
(Figs. 1 and 2). All results were analysed by means
of one-way analysis of variance (ANOVA) and
Tukey’s test for multiple comparison of means
(test level aZ0.05).
Results
Direct composites showed statistically significant
higher elastic modulus than the indirect composites
tested. Differences were also found within these
groups: Grandio showed higher elastic modulus than
Diamond Lite, while Artglass exhibited higher
modulus than Vita Zeta LC, considering the same
storage and testing conditions.
Viscous modulus results were also statistically
significantly different when direct and indirect
composites were compared. Once more, the
direct composites showed the highest modulus
values. But no statistically relevant differences
were found between composites belonging to the
same group. Loss tangent results, on the other
hand, showed no statistically significant differ-
ences at all.
The elastic modulus decreased substantially for
all composites as the temperature was raised. This
temperature dependence was even greater for

Table 3 As Table 2, but for 55 8C.

Group Baseline 1 day 7 days 90 days
– Air Water Air Water Air Water
a b a b a,b
D-0.1 7.5 (0.2) 8.7 (0.5) 7.6 (0.2) 9.7 (0.6) 8.5 (0.3) 8.1 (0.2) 8.1 (0.2)a,b
D-1 8.5 (0.2)a 9.7 (0.5)b 8.5 (0.3)a 10.6 (0.5) 9.4 (0.3)b,c 9.0 (0.2)a,c 8.9 (0.2)a,c
D-10 9.6 (0.2)a 10.8 (0.4) b
9.6 (0.3)a 11.6 (0.5) 10.4 (0.3)b,c 9.9 (0.2)a,c 9.8 (0.2)a,c
G-0.1 12.0 (0.8)a 13.0 (0.4) b,c
12.8 (0.3)a,b,c 14.2 (0.2)d 12.7 (0.2)a,b 14.2 (0.3)d 13.6 (0.5)c,d
G-1 13.0 (0.8)a 13.8 (0.4) b
13.7 (0.3)a,b 15.0 (0.2)c 13.5 (0.2)a,b 14.8 (0.3)c 14.3 (0.5)b,c
G-10 13.8 (0.7)a 14.6 (0.3)a,b,c 14.4 (0.2)a,b 15.7 (0.2)d 14.2 (0.2)a,b 15.4 (0.3)c,d 15.0 (0.5)b,c,d
A-0.1 5.9 (0.1)a,b 6.8 (0.1)a,c 6.2 (0.2)a,b 7.4 (0.8)c 5.6 (0.4)b 6.4 (0.2)a,b 5.5 (0.6)b
A-1 6.7 (0.1)a,b,c 7.4 (0.1) a,d
6.9 (0.2)a,b 7.9 (0.7)d 6.3 (0.4)b,c 7.0 (0.2)a,b 6.1 (0.6)c
A-10 7.4 (0.1)a,b,c 8.1 (0.1) a,d
7.7 (0.2)a,b 8.5 (0.7)d 7.0 (0.4)b,c 7.7 (0.2)a,b 6.8 (0.5)c
a
V-0.1 1.8 (0.0) 2.5 (0.1) 2.3 (0.1)a 2.5 (0.2)a 2.4 (0.2)a 4.1 (0.1) 3.1 (0.1)
a
V-1 2.3 (0.0) 3.1 (0.1) 2.8 (0.1)a 3.1 (0.2)a 2.9 (0.2)a 4.6 (0.1) 3.5 (0.1)
V-10 2.9 (0.1) 3.7 (0.1)a 3.5 (0.1)a,b 3.7 (0.2)a,b 3.4 (0.2)b 5.1 (0.1) 4.1 (0.2)
*Values in the same line not connected by the same letter are significantly different.
262 R.V. Mesquita et al.

Table 4 Summary of mean and (standard deviation) of the viscous modulus values (GPa) at 5 8C for Diamond Lite
(D), Grandio (G), Artglass (A) and Vita Zeta LC (V) at the frequencies 0.1, 1 and 10 Hz.
Group Baseline 1 day 7 days 90 days
– Air Water Air Water Air Water
a,b a b a,b b
D-0.1 0.90 (0.04) 0.69 (0.03) 0.74 (0.06) 0.63 (0.06) 0.68 (0.01) 0.61 (0.03) 0.67 (0.02)a,b
D-1 0.80 (0.03) 0.58 (0.04)a,b,c 0.62 (0.07)a 0.49 (0.05)c 0.52 (0.01)b,c 0.56 (0.03)a,b,c 0.60 (0.03)a,b
D-10 0.63 (0.03) 0.43 (0.03)a,b 0.46 (0.06)a 0.36 (0.04)c 0.37 (0.01)b,c 0.42 (0.03)a,b,c 0.43 (0.03)a,b,c
G-0.1 0.82 (0.04) 0.58 (0.02)a,b 0.60 (0.05)a 0.51 (0.05)b 0.53 (0.05)a,b 0.39 (0.02) 0.52 (0.02)b
G-1 0.73 (0.04) 0.51 (0.02)a,b 0.54 (0.05)a 0.46 (0.04)b 0.48 (0.05)a,b 0.36 (0.02) 0.47 (0.02)a,b
G-10 0.64 (0.04) 0.46 (0.01)a,b 0.48 (0.05)a 0.41 (0.04)b 0.43 (0.05)a,b 0.32 (0.02) 0.42 (0.02)a,b
A-0.1 0.58 (0.05)a 0.45 (0.05)b,c 0.51 (0.02)a,b 0.39 (0.01)c 0.50 (0.04)b 0.41 (0.04)c 0.45 (0.02)b,c
A-1 0.51 (0.04)a 0.37 (0.04)b 0.43 (0.03)b,c 0.36 (0.03)b 0.47 (0.05)a,c 0.38 (0.03)b 0.39 (0.05)b,c
A-10 0.39 (0.05)a 0.27 (0.04)b,c 0.32 (0.02)b,c 0.26 (0.02)b 0.35 (0.04)a,c 0.28 (0.02)b 0.29 (0.04)b,c
V-0.1 0.52 (0.03)a 0.44 (0.02)b,c 0.48 (0.02)a,b 0.41 (0.02)c 0.48 (0.01)b 0.35 (0.01) 0.41 (0.03)c
V-1 0.48 (0.04)a 0.36 (0.05)b 0.38 (0.02)b 0.38 (0.02)b 0.45 (0.02)a 0.26 (0.01)c 0.30 (0.02)c
V-10 0.39 (0.04) 0.25 (0.03)a 0.26 (0.01)a 0.27 (0.02)a 0.32 (0.02) 0.17 (0.01)b 0.19 (0.02)b
*Values in the same line not connected by the same letter are significantly different.

Table 5 As Table 4, but for 55 8C.

Group Baseline 1 day 7 days 90 days
– Air Water Air Water Air Water
a a a b b b
D-0.1 0.76 (0.01) 0.73 (0.02) 0.72 (0.04) 0.66 (0.04) 0.65 (0.01) 0.65 (0.03) 0.61 (0.03)b
D-1 0.77 (0.02)a 0.74 (0.02)a,b 0.73 (0.03)a,b 0.67 (0.05)c,d 0.70 (0.01)b,c 0.66 (0.03)c,d 0.62 (0.03)d
D-10 0.82 (0.02)a 0.77 (0.03)a,b 0.78 (0.04)a,b 0.69 (0.05)c 0.74 (0.01)b,c 0.70 (0.03)c 0.69 (0.03)c
G-0.1 0.83 (0.03) 0.71 (0.03)a 0.71 (0.03)a,b 0.65 (0.05)b 0.66 (0.03)a,b 0.53 (0.02) 0.60 (0.02)
G-1 0.73 (0.03) 0.63 (0.02)a 0.63 (0.02)a 0.59 (0.03)a,b 0.60 (0.03)a,b 0.47 (0.02) 0.55 (0.02)b
G-10 0.69 (0.02) 0.59 (0.02)a 0.59 (0.03)a 0.55 (0.03)a,b 0.57 (0.03)a,b 0.45 (0.02) 0.53 (0.02)b
A-0.1 0.58 (0.02)a 0.53 (0.02)a 0.56 (0.03)a 0.42 (0.07)b 0.52 (0.01)a,c 0.52 (0.01)a,c 0.45 (0.05)b,c
A-1 0.54 (0.03)a 0.50 (0.03)a,b,c 0.54 (0.02)a,b 0.41 (0.05)d 0.50 (0.01)a,b,c 0.48 (0.01)b,c 0.45 (0.04)c,d
A-10 0.56 (0.03)a 0.52 (0.03)a,b 0.57 (0.02)a 0.44 (0.04)c 0.54 (0.01)a,b 0.50 (0.02)b 0.49 (0.04)b,c
V-0.1 0.35 (0.01)a 0.40 (0.01)b 0.38 (0.01)c 0.39 (0.01)b,c 0.34 (0.01)a 0.30 (0.01)d 0.28 (0.01)d
V-1 0.40 (0.01)a 0.43 (0.01) 0.41 (0.01)a 0.41 (0.01)a 0.37 (0.01) 0.35 (0.01)b 0.34 (0.02)b
V-10 0.44 (0.02)a,b 0.48 (0.01)c 0.46 (0.01)a,c 0.46 (0.01)a,b,c 0.43 (0.01)b 0.38 (0.01)d 0.39 (0.02)d
*Values in the same line not connected by the same letter are significantly different.

Table 6 Summary of mean and (standard deviation) of the loss tangent values at 5 8C for Diamond Lite (D), Grandio
(G), Artglass (A) and Vita Zeta LC (V) at the frequencies 0.1, 1 and 10 Hz.
Group Baseline 1 day 7 days 90 days
– Air Water Air Water Air Water
a,b c a b,d a,b
D-0.1 83 (5) 51 (3) 60 (4) 44 (4) 51 (1) 50 (3) 58 (2)c,d
D-1 68 (3) 40 (3)a 47 (5)b 33 (3)c 37 (1)a,c 43 (3)a,b 48 (2)b
D-10 50 (3) 29 (2)a,b 34 (4)a 23 (3)c 26 (1)b,c 31 (2)a,b 33 (2)a
G-0.1 52 (3) 34 (1)a,b 37 (3)a 28 (2)c 32 (3)a,b,c 22 (1) 30 (1)b,c
G-1 44 (2) 29 (1)a,b 32 (3)a 25 (2)c 28 (3)a,b,c 20 (1) 27 (1)b,c
G-10 37 (2) 25 (1)a 27 (3)a 21 (2)b,c 25 (3)a,b 18 (1)c 23 (1)a,b
A-0.1 61 (6)a 42 (4)b 50 (2)c 38 (3)b 55 (4)a,c 41 (4)b 50 (4)c
A-1 51 (5)a 33 (3)b 40 (3)b,c 35 (4)b 48 (6)a,c 36 (3)b 41 (6)b,c
A-10 37 (4)a 24 (3)b 29 (2)b,c 26 (6)b 34 (4)a,c 26 (2)b 29 (4)b,c
V-0.1 142 (13) 72 (8)a 84 (2)b,c 70 (4)a 97 (2)b 53 (2) 72 (2)a,c
V-1 110 (11) 54 (9)a,b 61 (3)a 59 (5)a,b 81 (3) 37 (2)c 48 (2)b,c
V-10 78 (9) 36 (6)a,b 40 (1)a 39 (4)a 52 (2) 23 (2)c 30 (2)b,c
All loss tangent values are multiplied by 103. *Values in the same line not connected by the same letter are significantly different.
Dynamic properties of dental composite resins 263

Table 7 As Table 6, but for 55 8C.

Group Baseline 1 day 7 days 90 days
– Air Water Air Water Air Water
a b a c b,c b
D-0.1 101 (4) 84 (6) 94 (3) 68 (8) 77 (3) 81 (5) 76 (2)b,c
D-1 91 (3)a 76 (5)b 86 (3)a 64 (7)c 74 (2)b 73 (4)b 71 (2)b,c
D-10 85 (4)a 71 (5)b 81 (3)a 60 (6) 71 (2)b 71 (3)b 71 (2)b
G-0.1 68 (8) 55 (3)a 55 (3)a 46 (2)b,c 52 (2)a,b 37 (1)d 44 (3)c,d
G-1 56 (6) 46 (3)a 46 (2)a 39 (2)b 45 (2)a,b 32 (1) 39 (2)b
G-10 49 (4) 40 (2)a 41 (2)a 35 (2)b 40 (1)a,c 29 (1) 36 (2)b,c
A-0.1 98 (8)a 78 (5)a,b 89 (6)a 58 (16)b 93 (7)a 81 (3)a 82 (18)a
A-1 81 (6)a 67 (4)a 76 (4)a 52 (11) 79 (5)a 68 (3)a 74 (12)a
A-10 76 (5)a,b 64 (3)a 72 (3)a,b 52 (9) 77 (3)b 65 (2)a,b 73 (11)a,b
V-0.1 193 (3) 162 (6)a 163 (5)a 158 (9)a,b 145 (11)b 72 (3) 93 (2)
V-1 172 (3) 140 (5)a 143 (5)a 134 (8)a,b 129 (7)b 76 (2) 97 (2)
V-10 153 (2) 128 (4)a,b 134 (4)a 124 (7)b 127 (5)a,b 74 (1) 96 (2)
*Values in the same line not connected by the same letter are significantly different.

composites with lower filler content. Vita Zeta LC, composite, had the lowest rates that ranged from
the least filled composite tested, showed the 16 to 25%.
highest modulus decreasing rates (30–60%) between Loss tangent values, on the other hand, signifi-
5 and 55 8C, while Grandio, the heaviest filled cantly increased between 5 and 55 8C for all sample
groups. Grandio exhibited the lowest increasing
18 5˚C 55˚C 5˚C 55˚C 5˚C 55˚C 5˚C 55˚C rates, while Vita Zeta LC the highest, ranging from
17 27 to 77% and 29 to 255%, respectively.
16 Between 5 and 55 8C, viscous modulus values
increased for all Grandio and Artglass sample
15
groups, except for Artglass/Water/90 days at 0.
14 1 Hz. The viscous modulus values of Diamond Lite
13
Elastic Modulus E' [GPa]

12 1.0 5˚C 55˚C 5˚C 55˚C 5˚C 55˚C 5˚C 55˚C

11

10 0.9
9

8 0.8
7
Viscous Modulus E'' [GPa]

6 0.7
5

4 0.6
3

2 0.5
A D G V

Figure 1 95% elastic modulus confidence interval (C.I.) 0.4

for Artglass (A), Diamond Lite (D), Grandio (G) and Vita
Zeta LC (V) at 5 and 55 8C. For baseline groups, the CI is
represented by the distance between the pairs of 0.3
horizontal lines. For 1 day water-stored groups it
corresponds to the length of the vertical lines, where
the mean C.I. is horizontally illustrated. Additionally, the 0.2
elastic modulus of each 1 day water-stored sample is A D G V
separately presented at 5 8C (circles) and 55 8C
(triangles). Figure 2 As Fig. 1, but for viscous modulus.
264
increased for most sample groups except for
baseline at 0.1 and 1 Hz and for all water-stored
groups at 0.1 Hz. All Vita Zeta LC samples
decreased their modulus when tested at 0.1 Hz,
while for two groups their viscous modulus reduced
when tested at 1 Hz (baseline and Water/7 days).
All the other groups increased their modulus
between 5 and 55 8C. These results were not always
statistically significant.
Higher testing frequencies enhanced the elastic
modulus of all groups of samples at both tempera-
tures, although these results were not always
statistically relevant. In contrast, loss tangent
values dropped over increasing testing frequencies
for all groups of samples, except Vita Zeta
LC/Air/90 days and Vita Zeta LC/Water/90 days,
when tested at 55 8C. Their loss tangents increased
as frequency was raised from 0.1 to 1 Hz, and then
decreased again from 1 to 10 Hz. Also for the loss
tangent, the results were not always statistically
significant. The non-significant differences among
the three frequencies occurred in 74% of the cases at
55 8C.
Grandio samples invariably decreased their
viscous modulus between 0.1 and 10 Hz, which
only happened to Artglass, Diamond Lite and Vita
Zeta LC samples at 5 8C. When tested at 55 8C,
Diamond Lite and Vita Zeta LC increased their
viscous modulus; while Artglass first decreased it
between 0.1 and 1.0 Hz, and then raised it again at
10 Hz. These results were not always statistically
significant.
Samples produced from the same material,
stored for a similar period of time and tested
under identical conditions showed a higher elastic
modulus when stored in air than in water. These
findings were statistically relevant, except for
Grandio/90 days at all frequencies and Diamond
Lite/90 days at 1 Hz, when tested at 5 8C, and
Diamond Lite/90 days, Grandio/1 day, Grandio/90 -
days and Vita Zeta LC/7 days, at all frequencies,
when tested at 55 8C.
When tested at 5 8C, all samples stored in water
showed higher viscous modulus and loss tangent
than the corresponding samples stored in air. At
55 8C most groups of samples still exhibited the
same trend for loss tangent, but not for viscous
modulus.
During the three months in air or water, the
elastic modulus (Tables 2 and 3), viscous modulus
(Tables 4 and 5) and loss tangent (Tables 6 and 7) of
the composites followed different patterns.
Regarding their elastic modulus, the only trend
identified for all composites was a statistically
significant increase between baseline and 1 day air
or water at 5 8C (Fig. 1), except for Artglass/Water/
R.V. Mesquita et al.
10 Hz (Table 2). A similar trend was observed at
55 8C, although most of the results were not
statistically relevant (Table 3 and Fig. 1).
In contrast, loss tangent values substantially
decreased between baseline and 1 day, either in
air or water, for all sample groups (Tables 6 and 7).
The same happened to the loss modulus (Tables 4
and 5; and Fig. 2), except for Vita Zeta LC/55 8C at
all testing frequencies. Also these results were not
always statistically significant.
Discussion
Direct comparisons between composites are diffi-
cult because information regarding their compo-
sition and fabrication is often not available.
However, a positive association could be found
between elastic modulus and percentage of filler by
weight. This might be the main reason why the
more heavily filled direct composites showed higher
elastic modulus than the indirect composites, and
also why Grandio showed higher modulus than
Diamond Lite, while Artglass exhibited higher
modulus than Vita Zeta LC.
In this study Grandio was the only material that
approached the rigidity of dentin. Even so, its
elastic modulus represents only one-fifth the
rigidity of enamel. Hence, a conservative prep-
aration is preferred, so that the tooth rather than
the composite absorbs most of the stress. For
instance, Diamond Lite may cause the restorations
to deform excessively under masticatory stresses,
which limits its indications. However, it could be
very satisfactorily used for the restoration of
anterior teeth, subjected to lower functional
stresses when normal occlusion is considered, and
also for large Class V restorations.
When indicated as inlays or onlays, indirect
composite resins might work as direct composites,
requiring a high elastic modulus to withstand the
masticatory stresses. The use of low modulus
materials in such cases might stress the tooth/
restoration interface over time, which can result in
marginal breakdown and loss of marginal seal
[13–15]. On the other hand, a low elastic modulus
can be advantageous when indirect composites are
used for esthetic veneering of partial dentures. In
such cases, a flexible composite is needed due to
the low deformability of the metallic framework.
Instead of transmitting the masticatory stresses to
the metal/composite interface, the flexible com-
posite deforms and dissipates the stresses itself, so
that the veneer does not flake off. In considering
the elastic modulus of the indirect composites, Vita
Dynamic properties of dental composite resins
Zeta LC veneers seem to have greater chances of
survival without flaking off than Artglass veneers.
Direct composites showed the highest viscous
modulus values in this study, suggesting their
greater ability to relieve excess energy build up
through moderate viscous flow during tooth func-
tion. This can be attributed to their higher filler
content, since friction between the particles and
the polymer matrix has been suggested as an
important source of energy dissipation during
deformation under stress [16,17]. 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 [18]. On the other
hand, materials with high loss modulus can show
small permanent dimensional change, which may
not be desirable.
The low loss tangent values presented by all
composite materials ranged from 0.018 to 0.142 at
5 8C, and 0.032 to 0.193 at 55 8C. The fact that the
loss tangent approached ‘0’ means the materials
have almost no viscous component over the
temperature and frequency ranges investigated,
which is suggestive of more elastic-like materials.
The detrimental influence of increasing testing
temperatures on elastic modulus can be explained by
the changes in a material’s free volume. At lower
temperatures the molecular motion of the chains is
impeded due to the lack of free volume. Under
heating, the free volume expands, thus increasing the
available space for the molecules to slip between
each other. Consequently, the material will flow more
easily under external forces, which decreases its
elastic modulus. It is possible that reinforcing filler
particles can act as cross-links and restrain the
material from flowing. This might explain why
composites with higher filler loading, such as Grandio,
were less sensitive to temperature in this study.
Although drops in elastic modulus were observed
for all composites as a function of temperature, no
glass transition was indicated. This might be due to
the high filler loads and the highly cross-linked
structure of the composites, which are responsible
for the shift of the transitions to higher
temperatures.
The great temperature dependence observed for
loss tangent can be attributed to the fact that at
higher temperatures materials behave more vis-
cous-like, responding more slowly to deforming
forces. This was especially noticeable for Vita Zeta
LC. Probably, its degree of cross-linking and low
filler content did not offer enough resistance to
viscous flow at higher temperatures. The opposite
might be true for Grandio.
The dependence of viscous modulus upon
temperature was higher for Grandio and Artglass
265
than for Diamond Lite and Vita Zeta LC.
Presumably, Grandio and Artglass experienced
low internal friction and energy dissipation
when tested at 5 8C, which produced low viscous
modulus values. At this temperature, their cross-
links might have acted as anchors between the
molecules restraining their motion. At 55 8C, on
the other hand, the free volume might have
expanded enough to facilitate molecular motion,
thus increasing modulus values. For Diamond
Lite, and especially for Vita Zeta LC, the viscous
modulus values at 5 8C did not statistically
significantly differ from those at 55 8C for many
of the groups. It suggests the inability of their
cross-links to restrain molecular motion at both
testing temperatures, particularly at lower
frequencies.
Cycling the materials at a loading frequency
close to that of chewing is an important
requirement for visco-elastic materials. In the
present study, the elastic modulus of all compo-
sites sloped upward towards higher frequency,
what is typical of more elastic-like materials. The
low-frequency range is where the viscous or
viscous-like behavior predominates, since the
material will have enough time to flow. As
frequency rises, the material acts in a more
elastic way, thus increasing the modulus.
Increasing frequencies reduced the loss tangent
of all tested composites. This might be related to
restrictions of chain motions in polymer at higher
frequencies, thus decreasing a material’s energy
absorption capacity. At higher temperatures, chain
motion is facilitated by an expanded free volume,
becoming less dependent on frequency. This might
justify why most non-relevant differences between
frequencies occurred at 55 8C.
At higher frequencies the material does not have
enough time to flow, which decreases its energy
dissipation capacity through internal friction and
lowers the viscous modulus. This phenomenon was
observed for Grandio at both testing temperatures,
suggesting the ability of its cross-links and fillers to
restrain molecular motion even at 55 8C, when the
free volume is expanded. Artglass was almost as
effective as Grandio in restraining molecular
motion, but its viscous modulus increased between
1 and 10 Hz at 55 8C. Diamond Lite and Vita Zeta LC,
however, were only able to limit molecular motion
at 5 8C, so that their modulus increased over higher
frequencies at 55 8C.
Especially for the direct composites that were
polymerized at approximately 22 8C, some post-
curing effect was expected during the storage
period at 37 8C, since conversion in light-activated
dental composites is still incomplete [19]. Usually,
266
the cross-linked network formed contains signifi-
cant numbers of pendant groups. As temperature is
raised, the mobility of the molecules is increased,
and this leads to further bonding of these groups
[8]. The progressive cross-linking increases the
rigidity of the sample by restricting the movement
of large molecular segments and the microscopic
movement of polymer segments.
Between baseline and 1 day, the increase in
elastic modulus and decrease in viscous modulus
and loss tangent can be mainly attributed to the
higher cross-linking density in the samples
following post-curing. Changes occurring between
1 day and 90 days, however, were confusing and
specific for each composite. Then, in order to
understand the conflicting trends of increases or
decreases in the visco-elastic properties over time,
the effect of water and air-storage should be
considered.
Water sorption may alter the values of visco-
elastic properties due to plasticizing and degrada-
tional effects—two distinctly different mechanisms.
Absorbed water causes sorption expansion, increas-
ing the effective free volume and the ease of
movement of chain segments, thus reducing the
elastic modulus and increasing the viscous modulus
and loss tangent. Degradation, on the other hand, is
presumed to be due to leaching of the material’s
components in water [20].
The less impressive effect of water on loss
tangent and especially on viscous modulus values
at 55 8C might also be attributed to changes in the
free volume. At this temperature the expanded
free volume might facilitate molecular motion
independently of the presence of water, which
yielded similar results for air and water-stored
samples.
Although air-storage seems to be a stable
condition when compared to water and was used
as reference in this study, it should not be
considered so. Freshly prepared composites are
expected to lose volatile compounds by evapor-
ation and absorb water vapour from the surround-
ings, depending on their hydrophilicity and the
humidity of the environment [20]. Therefore,
although the detrimental influence of distilled
water is expected to be greater for water-stored
samples, some effect should not be excluded on air-
stored samples.
Conclusions
The possibility of monitoring the visco-elastic
properties of dental composite materials under
R.V. Mesquita et al.
conditions that simulate the oral environment
seems to be an important tool to obtain more
clinically significant experimental results.
The frequency of non-relevant statistical
results in this study might be attributed to the
improvement in materials properties, reflected in
the limited degradation in distilled water and
storage periods, and the absence of phase
transitions in the temperature and frequency
ranges studied.
The differences in the visco-elastic properties
between the composites do not necessarily mean
that one material is better than the other, but that
each material would better suit a certain clinical
application.
Acknowledgements
This work has been partially supported by Vita
Zahnfabrik/Germany. R.V. Mesquita acknowledges
a fellowship from CAPES, Brasilia/Brazil. The
authors are also indebted to F. Rupp and
N. Kournetas for critical reading of the manuscript
and valuable discussions.
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