d e n t a l m a t e r i a l s 2 7 ( 2 0 1 1 ) 598–607

available at www.sciencedirect.com

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

Physical properties of current dental nanohybrid and

nanofill light-cured resin composites

Irini D. Sideridou ∗ , Maria M. Karabela, Evangelia Ch. Vouvoudi

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: Objectives. The purpose of this work was the detailed study of sorption characteristics of
Received 12 March 2010 water or artificial saliva, the determination of flexural strength and the flexural modu-
Received in revised form lus, and the study of the thermal stability of some current commercial dental light-cured
3 February 2011 nanocomposites containing nano-sized filler particles.
Accepted 4 February 2011 Methods. Three nanohydrid dental composites (Tetric EvoCeram (TEC), Grandio (GR) and
Protofill-nano (PR)) and two nanofill composites (Filtek Supreme Body (FSB) and the Filtek
Supreme Translucent (FST)) were used in this work. The volumetric shrinkage due to poly-
Keywords: merization was first determined. Also the sorption, solubility and volumetric increase were
Dental nanohybrid measured after storage of composites in water or artificial saliva for 30 days. The flexural
Dental nanofill strength and flexural modulus were measured using a three-point bending set-up according
Sorption-solubility-volumetric to the ISO-4049 specification, after immersion of samples in water or artificial saliva for 1
change day or 30 days. Thermal analysis technique TGA method was used to investigate the thermal
Volumetric shrinkage stability of composites.
Flexural strength and modulus Results. GR and TEC composites showed statistically no difference in volumetric shrinkage
Thermogravimetric analysis (%) which is lower than the other composites, which follow the order PR < FSB < FST. The
amount of sorbed water and solubility is not statistically different than those in artificial
saliva. In all the composites studied the amount of water, which is sorbed (% on composite) is
not statistically different than the amount of water, which is desorbed and follows the order:
GR < TEC < PR < FSB < FST. After immersion in water for 1 day the highest flexural strength
showed the FSB and the lowest TEC. GR, PR and FST showed no statistically different flexural
strength. The flexural modulus of composites after immersion for one day follows the order
TEC < PR≤FST < FSB < GR.
Significance. Among the composites studied, Grandio had the lowest polymer matrix content,
consisting mainly of Bis-GMA. It showed the lowest polymerization shrinkage and water
sorption and the highest flexural strength and flexural modulus after immersion in water or
artificial saliva for 30 days. The water and artificial saliva generally showed the same effect
on physical properties of the studied composites. Thermogravimetric analysis gave good
information about the structure and the amount of organic polymer matrix of composites.
© 2011 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

∗
Corresponding author. Fax: +30 210 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.2011.02.015
 d e n t a l m a t e r i a l s 2 7 ( 2 0 1 1 ) 598–607
1. Introduction
The term “nanotechnology” has evolved over the years via
terminology drift to mean “anything smaller than microtech-
nology” such as nano powders and other things that are
nanoscale in size, but not referring to mechanisms that
have been purposefully built from nanoscale components.
This evolved version of the term is more properly labeled
“nanoscale bulk technology” while the original meaning is
more properly labeled “molecular nanotechnology [1].
The most traditional dental composites for restorative
purposes are hybrid and microfill types. Hybrids offer interme-
diate esthetic properties but excellent mechanical properties
by the incorporation of fillers with different average particle
sizes (15–20 ␮m and 0.01–0.05 ␮m). Microfill composites were
launched in the market to overcome the problems of poor
esthetic properties. These materials are usually formulated
with colloidal silica (around 50% in volume) with an average
particle size of 0.02 ␮m and a range of 0.01–0.05 ␮m. Unfor-
tunately the mechanical properties are considered low for
application in regions of high occlusal force [2].
Based on the definition “nanoscale bulk technology” new
classes of dental composites, so-called nanocomposites, have
been developed and marketed during recent years. Nanocom-
posites are claimed to combine the good mechanical strength
of the hybrids [3–5] and the superior polish of the microfills [6].
Other positive features reported are high wear resistance [7–9]
improved optical characteristics [4] and reduced polymeriza-
tion shrinkage [3,10].
Nanocomposites are available as nanohybrid types con-
taining milled glass fillers and discrete nanoparticles
(40–50 nm) and as nanofill types, containing both nano-sized
filler particles, called nanomers and agglomerations of these
particles described as “nanoclusters” [4]. The nanoclusters
provide a distinct reinforcing mechanism compared with
the microfill or nanohybrid systems resulting in significant
improvements to the strength and reliability [11].
This work is concerned first with the determination of the
volumetric shrinkage after polymerization of three current
commercial nanohybrids – Tetric EvoCeram (TEC), Grandio
(GR) and Protofill-nano (PR) – and two nanofill composites –
Filtek Supreme Body (FSB) and Filtek Supreme Translucent
(FST). The composites were then immersed in water or artifi-
cial saliva 37 ◦ C for 30 days for the determination of the sorbed
liquid and volume increase. After that the composites were
put into a desiccator at 37 ◦ C for 30-days and desorption of the
absorbed water or artificial saliva was determined. Based on
this experimental data the amount of unreacted monomers
extracted by water or artificial saliva during immersion for 30
days, known as “solubility” of the composites in these liquids,
was calculated.
In an aqueous oral environment, polymer composites
absorb water and release unreacted monomers. The release
of unpolymerized monomers from polymer composites may
stimulate the growth of bacteria around the restoration and
promote allergic reactions in some patients. Also the water
ingress into dental composites in the oral cavity can, over time,
lead to deterioration of the physical/mechanical properties
due to hydrolytic breakdown of the bond between the silane-
599
filler particles, filler matrix debonding or even hydrolytic
degradation of the fillers. However, some water ingress may
have a positive side effect, such as the expansion of the com-
posite compensating for polymerization shrinkage leading to
improved marginal sealing. Thus the solvent uptake by dental
composite is generally a very important property which must
be investigated. In the authors’ previous work the sorption of
water [12–15] or ethanol/water solution [14] or ethanol [15] by
light-cured dental resins and commercial polymer compos-
ites, was studied. Also the sorption kinetics of ethanol/water
solution by dental resins and composites, was investigated
[16].
In the present study the flexural strength and modulus
were also determined, using a three-point bending set-up
according to the ISO-4049 specification, after immersion of
samples in water or artificial saliva for 1 day or 30 days. The
weight changes of the above composites were also measured
as a function of temperature by Thermogravimetric Analysis
(TGA). TGA is a technique in which the mass of the sample is
monitored as a function of temperature, while the sample is
subjected to a controlled program. TGA has been used for the
study of the thermal stability of dental composites [17–19].
2. Materials and methods
2.1. Materials
Five commercially available dental light-cured composites
were studied; Tetric EvoCeram (TEC; Ivoclar-Vivadent, Schaan,
Liechtenstein), Grandio (GR; VOCO, Cuxhaven, Germany),
Protofill-nano (PR; Germany), Filtek Supreme Body (FSB; 3M-
ESPE, St. Paul, MN, USA) and Filtek Supreme Translucent (FST;
3M-ESPE, St. Paul, MN, USA). Their specifications are listed in
Table 1.
2.2. Artificial saliva
The SAGF medium used as artificial saliva in this work and
its composition is given in Table 2 [20]. The pH of the SAGF
medium was adjusted to 6.8, because this value was closer to
that of saliva in the mouth after its emission from the canals.
The artificial saliva and the samples were sterilized together
(0.5 atm/120 ◦ C/20 min) to avoid colonization of microorgan-
isms. The use of the SAGF medium required special care,
because the solution was supersaturated in carbon dioxide
with regard to the air. As a result it tended to lose CO2 gas,
which led to an increase in pH, so before each experiment,
the pH of solution was controlled.
2.3. Volumetric shrinkage
The volumetric shrinkage was measured based on
Archimedes’ Principle, as described in Refs. [21,22]. The
densities of uncured composites were first measured, using
a Mettler-Toledo AG64 balance. From each test material,
uncured sphere-shaped specimens were carefully formed in
such a way that trapped air bubbles were avoided. Since the
uncured materials were rather sticky, a thin polyester film
(thickness 0.05 mm) was fixed on the special holder of the
600 d e n t a l m a t e r i a l s 2 7 ( 2 0 1 1 ) 598–607

Table 1 – Summary of the constituents and quantities/ratios of components contained in the five composites
investigated.a
Composite Classification Lot no. Shade Matrix Filler Total filler content
Tetric Nanohybrid K34042 A1 Bis-GMA, Barium glass, ytterbium 82–83 wt% 82.5 vol%
EvoCeram UDMA trifluoride, mixed oxide and
(TEC) prepolymer; 40–3000 nm,
550 nm
Grandio (GR) Nanohybrid 780610 A2 Bis-GMA, Silica: 20–60 nm; barium- 87.0 wt% 71.4 vol%
TEGDMA aluminaborosilicate:
0.1–2.5 ␮m
Protofill-nano Nanohybrid 8W603A A1 Bis-GMA, Strontium aluminum 81.9%
(PR) TEGDMA, borosilicate: 0.6 ␮m;
UDMA nanoparticles 20 nm
Filtek Nanofill 5AM A2D Bis-GMA, Silica: 5–20 nm nanoparticle 79 wt% 59.5 vol%
Supreme TEGDMA, (8 wt%); zirconia/silica:
Body (FSB) UDMA, 0.6–1.4 ␮m nanocluster
Bis-EMA (71 wt%)
Filtek Nanofill 7BN GT Bis-GMA, Silica: 75 nm nanoparticle 70 wt% 57.5 vol%
Supreme TEGDMA, (40 wt%); silica: 0.6–1.4 ␮m
Translucent UDMA, nanocluster (30 wt%)
(FST) Bis-EMA
Bis-GMA, bisphenol A diglycidyl ether dimethacrylate; Bis-EMA, bisphenol A polyethylene glycol diether dimethacrylate; UDMA, urethane
dimethacrylate; TEGDMA, triethyleneglycol dimethacrylate.
a
These are the data provided by the manufacturers.

balance and its mass measured in air and in water. Next, pared by filling a Teflon mold (15 mm in diameter and 1 mm
the respective material samples were carefully placed on in thickness) with the unpolymerized material. Samples were
the polyester film and the mass of the whole assembly was irradiated for 60 s on each side, using the XL3000 (3M-ESPE,
measured again in air and in water. Slight deformations of St. Paul, MN, USA) dental photocuring source. The unit was
the materials during the test were of no importance since used without the light guide in contact with the sample. Four
they do not influence density. The mass of each material specimen discs were prepared for each composite material.
was calculated by subtracting the mass of the polyester film The percentage amount of water or artificial saliva sorbed
from the mass of the whole assembly. Now the density of (WS (%) or ASS (%)) and desorbed (WD (%) or ASD (%)), the sol-
the uncured material (uncured ) was computed. The volumetric ubility (SL (%)) of these liquids, the volumetric change (VI (%))
shrinkage (V) was calculated using the following equation: were determined according to the method described in detail
 uncured
 in our previous works [14,15].
V% = 100 × 1 − (1) All the specimens were placed in a desiccator and trans-
cured ferred to a pre-conditioning oven at 37 ◦ C. After 24 h they were
removed, stored in the desiccator for 1 h and weighed to an
where uncured is the density of the uncured composite and
accuracy of ±0.00001 g using a Mettler H54AR balance. This
cured (d ) is the density of the cured composite.
cycle was repeated until a constant mass (mi ) was obtained.
The densities of all samples were measured in dry (d ) or
2.4. Sorption and desorption of water or artificial
saturated conditions (s ) using a Mettler-Toledo AG64 balance
saliva – solubility – volumetric change
and they were calculated based on Archimedes’ principle.
Subsequently, the discs were immersed in water or artificial
Sorption and solubility tests were determined according to
saliva at 37 ± 1 ◦ C. At fixed time intervals they were removed,
the method described in ANSI/ADA Specification No. 27-1993
blotted dry to remove excess liquid, weighed and returned
(ISO 4049) regarding filling materials. Specimen discs were pre-
to the liquid. The uptake of the liquid was recorded for 30
days. The percentage weight increase in specimens, WI (%),
was calculated using the following formula:
Table 2 – Composition of the artificial saliva (SAGF
medium) [20]. ms − mi
WI(%) = 100 (2)
Components Concentration (mg l−1 ) mi
NaCl 125.6
KCl 963.9 where ms represents the weight of the saturated specimen
KSCN 189.2 after 30 days of immersion. This is an apparent value for the
KH2 PO4 654.5
liquid sorbed, because unreacted monomer is simultaneously
Urea 200.0
extracted resulting in a decrease of specimen weight.
NaSO4 .10H2 O 763.2
NH4 Cl 178.0
For the determination of monomer extracted, the samples
CaCl2 .2H2 O 227.8 were transferred to a drying oven maintained at 37 ◦ C and a
NaHCO3 630.8 similar process to that of sorption repeated during desorption.
 d e n t a l m a t e r i a l s 2 7 ( 2 0 1 1 ) 598–607
The percentage amount of water or artificial saliva desorbed
from specimens, WD (%) or ASD (%), was calculated using the
following formula:
ms − md
WD(%) or ASD(%) = 100
ms
in which md represents the weight of the specimen after
30-days desorption. The amount of unreacted monomer
extracted by water or artificial saliva, during immersion for
30 days, known as “solubility” (SL) of the composite in these
solvents, was calculated from the equation:
mi − md
SL(%) = 100
mi
The percentage amount of water or artificial saliva
absorbed is then given by the formula:
WS(%) or ASS(%) = WI(%) + SL(W or AS) (%)
The percentage amount of water or artificial saliva
absorbed was also calculated as % sorption on polymer matrix
(WSR (%) or AASR (%)) using the equation:
WS(%) AASR (%)
WSR (%) = or AASR (%) =
a a
where a is the %-wt amount of polymer matrix in the compos-
ite. Also the absorbed amount of water or artificial saliva was
calculated in ␮g/mm3 using the equation:
WS(g/mm3 ) = WI(␮g/mm3 ) + SL(g/mm3 )
where WI(g/mm3 ) = 106 ((ms − mi )/V), SL(g/mm3 ) =
10 ((mi − md )/V) and V the volume of discs in cubic millimeters
6 d is the deflection corresponding to the load F1 .
was determined from the diameter and the thickness of the
specimen disc measured at five points.
Furthermore, the % volume increase VI (%) is calculated
using the available data of densities for the dry (d ) and satu-
rated (s ) specimens:
100 (d − s ) + wd
VI(%) =
s
where w represents the % sorbed water (WS%) or artificial
saliva (ASS%).
2.5. Flexural properties
Flexural properties were determined according to the method
described in ANSI/ADA Specification No. 27-1993 for resin
based filling materials or ISO 4049. Specimens were pre-
pared by filling a Teflon mold (2 mm × 2 mm × 25 mm) with
the unpolymerized composite, taking care to minimize the
untrapped air. The upper and ower surfaces of the mold were
overlaid with glass slides covered by a Mylar sheet to avoid
adhesion with the unpolymerized material. The completed
assembly was held together with spring clips and irradiated
by overlapping, using a XL 3000 dental photocuring unit (3M-
ESPE, St. Paul, MN, USA). This source consisted of a 75 W
tungsten halogen lamp, which emits radiation between 420
601
and 500 nm and has the maximum peak at 470 nm. The unit
was used without the light guide at a contact point on the
glass slides. The samples were irradiated for 60 s on each side.
Then the mold was dismantled and the composite carefully
removed by flexing the Teflon mold. Twenty five specimen bars
(3)
were prepared for each composite.
The specimens were divided into five groups of five sam-
ples each. The first group consisted of dry samples measured
immediately after preparation. The second and third group
consisted of samples, which had been stored in distilled water
at (37 ± 1) ◦ C in dark for periods 1 and 30 days, correspond-
ingly. The fourth and fifth group consisted of samples, which
had been stored in artificial saliva at (37 ± 1) ◦ C in the dark for
(4)
periods 1 and 30 days, correspondingly. The samples of groups
II–V were immersed in their solution immediately after prepa-
ration. 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
(5) (Instron, model 3344). All bend tests were carried out with a
constant cross-head speed of 0.75 ± 0.25 mm/min until frac-
ture occurred. The load and the corresponding deflection were
recorded. The flexural modulus (E), in MPa, and the flexu-
ral strength (), in MPa, were calculated using the following
equations:
(5a)
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 of fracture, l the distance in mm
(5b) between the supports, h the height of specimen in mm
measured immediately prior to testing, b the width of the
specimen in mm measured immediately prior to testing and
2.6. Thermogravimetic analysis
Thermogravimetric Analysis was performed on a Pyris 1 TGA
(Perkin Elmer) Thermal Analyzer using about 5 mg of each
sample. It evaluated weight changes as a function of temper-
ature during a thermal program ranging from 30 to 700 ◦ C at
(6)
the heating rate of 10 ◦ C min−1 in nitrogen atmosphere (flow
20 ml/min) followed by cooling to room temperature.
2.7. Statistical analysis
The values reported in tables and figures represent mean val-
ues ± standard deviation of replicates. One-way analysis of
variance (ANOVA) test, followed by Tukey’s test, for multiple
comparisons between means to determine significant differ-
ences was used at a significance level set at p ≤ 0.05.
3. Results
The determined mean values and standard deviations of the
percentage of volumetric shrinkage of the studied composites
are shown in Fig. 1.
In Table 3 the sorption of water (37 ± 1 ◦ C) by the studied
composites after immersion in water for 30 days is shown.
602 d e n t a l m a t e r i a l s 2 7 ( 2 0 1 1 ) 598–607

Table 3 – Sorption/desorption of water (37 ± 1 ◦ C) by the studied composites after immersion in water for 30 days [means
(S.D.)]* , n = 4.
Composite Sorption on Desorption on Sorption on Sorption on
composite (%) composite (%) polymer composite
matrix (%) (␮g/mm3 )
TEC 1.10 (0.02)A 1.13 (0.02)A 6.29 (0.11)a 23.00 (0.40)
GR 0.68 (0.01)B 0.72 (0.02)B 5.21 (0.11) 14.65 (0.38)
PR 1.30 (0.02)C 1.28 (0.02)C 7.17 (0.08) 24.90 (0.99)
FSB 1.59 (0.01)D 1.63 (0.04)D 7.41 (0.03) 31.13 (0.44)
FST 1.66 (0.04)E 1.68 (0.04)E 6.05 (0.16)a 29.00 (1.51)
∗
Common corresponding uppercase letters in a given row and lowercase letters in a given column indicate no significant difference (p ≤ 0.05).

Table 4 – Solubility and volume increase of the studied composites after immersion in water for 30 days [means (S.D.)]* ,
n = 4.
Composite Solubility (%) Solubility (␮g/mm3 ) % Volume increase
a d
TEC 0.09 (0.02) 1.84 (0.31) 0.41 (0.62)g,h
GR 0.09 (0.02)a 2.03 (0.38)d 0.00 (0.00)h
PR 0.28 (0.03)b 5.43 (0.63)e 1.12 (0.64)g
FSB 0.25 (0.05)b,c 4.90 (0.82)e,f 0.82 (0.17)g
FST 0.22 (0.02)c 3.78 (0.32)f 1.00 (0.12)g
∗
Common corresponding lowercase letters in a given column indicate no significant difference (p ≤ 0.05).

The solubility in water and the volume increase is shown in a 2,0

Table 4. water
1,8 artificial saliva
Analogously, the results obtained for the sorption of artifi-
1,6
cial saliva (37 ± 1 ◦ C) are shown in Tables 5 and 6.
In Fig. 2a the sorption (%) is compared, in Fig. 2b the solu- 1,4
bility (%) is compared and finally in Fig. 3 the volume increase 1,2
% sorption

(%) of studied composites after immersion in water or artificial 1,0

saliva (37 ± 1 ◦ C) is compared. 0,8
The results obtained for the flexural strength and flexural
0,6
modulus of the studied composites after immersion in water
0,4
37 ± 1 ◦ C for 1 day or 30 days are shown in Table 7. Correspond-
ingly the results obtained after immersion of composites in 0,2

artificial saliva 37 ± 1 ◦ C for 1 day or 30 days are shown in 0,0

TEC GR PR FSB FST
Table 8.
The effect of the aging in liquid medium on flexural
strength of the studied composites is shown in Fig. 4. Cor- b 0,45
respondingly the effect of the aging in liquid medium on the 0,40 water
flexural modulus is shown in Fig. 5. artificial saliva
0,35
0,30
Solubility (%)

FST 0,25
0,20
FSB 0,15
0,10
PR
0,05
0,00
GR TEC GR PR FSB FST

TEC Fig. 2 – (a) Sorption of water or artificial saliva 37 ◦ C by the

studied composites after immersion in the liquid for 30
0,0 0,5 1,0 1,5 2,0 2,5 days. (b) Effect of the liquid medium aging on solubility of
volumetric shrinkage (%) studied composites after immersion in water or artificial
saliva for 30 days.
Fig. 1 – Means values and standard deviations of the
percentage of volumetric shrinkage of the studied
composites.
 d e n t a l m a t e r i a l s 2 7 ( 2 0 1 1 ) 598–607 603

Table 5 – Sorption of artificial saliva (37 ± 1 ◦ C) by the studied composites after immersion in artificial saliva for 30 days
[means (S.D.)]* , n = 4.
Composite Sorption on Desorption on Sorption on Sorption on
composite (%) composite (%) polymer composite
matrix (%) (␮g/mm3 )
TEC 1.11 (0.02)A 1.08 (0.01)A 6.37 (0.10) 23.30 (0.80)a
GR 0.63 (0.01)B 0.63 (0.03)B 4.82 (0.06) 13.60 (0.69)
PR 1.29 (0.02)C 1.26 (0.01)C 7.15 (0.11) 24.58 (0.85)a
FSB 1.58 (0.02)D 1.55 (0.02)D 7.33 (0.09) 30.84 (0.63)
FST 1.67 (0.03)E 1.64 (0.03)E 6.07 (0.12) 29.42 (0.09)
∗
Common corresponding uppercase letters in a given row and lowercase letters in a given column indicate no significant difference (p ≤ 0.05).

Table 6 – Solubility and volume increase of the studied composites after immersion in artificial saliva for 30 days [means
(S.D.)]* , n = 4.
Composite Solubility (%) Solubility (␮g/mm3 ) % Volume increase
TEC 0.09 (0.01)a 1.98 (0.11)b 1.26 (0.40)c
GR 0.06 (0.02)a 1.25 (0.40)b −0.22 (0.67)d
PR 0.36 (0.04) 6.24 (0.42) 0.71 (0.38)c,d
FSB 0.28 (0.01) 5.48 (0.15) 0.75 (0.74)c,d
FST 0.22 (0.04) 3.33 (0.74) 0.92 (0.71)c,d
*
Common corresponding lowercase letters in a given column indicate no significant difference (p ≤ 0.05).

Table 7 – Flexural strength, , and flexural modulus, E, of studied composites after immersion in water (37 ± 1 ◦ C) for 1
day or 30 days [means (S.D.)]* , n = 5.
Composite Flexural strength [MPa] Flexural modulus [GPa]

1 day 30 days 1 day 30 days

TEC 98.88 (5.94)a 79.49 (8.11) 7.72 (0.20) 6.94 (0.33)
GR 116.37 (3.70)b,A 116.13 (5.28)A 14.81 (0.07)B 14.44 (0.76)B
PR 107.47 (7.47)a,b 98.04 (2.69)c 8.36 (0.24)d,C 8.24 (0.33)C
FSB 144.36 (9.84) 95.57 (4.87)c 10.14 (0.21) 9.21 (0.26)
FST 103.69 (11.14)a,b 94.23 (11.19)c 8.42 (0.22)d 7.58 (0.12)
*
Common corresponding lowercase letters in a given column and uppercase letters in a given row indicate no significant difference (p ≤ 0.05).

Table 8 – Flexural strength, , and flexural modulus, E, of studied composites after immersion in artificial saliva
(37 ± 1 ◦ C) for 1 day or 30 days [means (S.D.)]* , n = 5.
Composite Flexural strength [MPa] Flexural modulus [GPa]

1 day 30 days 1 day 30 days

TEC 105.39 (3.20)a 76.94 (6.55)c 8.03 (0.14) 7.33 (0.23)
GR 112.24 (0.86)b 101.49 (3.91) 14.92 (0.32)A 14.91 (0.32)A
PR 115.97 (10.39)a,b 79.91 (6.08)c 8.76 (0.10)e,C 8.46 (0.17)C
FSB 147.93 (5.65) 86.36 (8.20)c 10.49 (0.20) 9.75 (0.24)
FST 127.19 (26.45)a,b 80.46 (12.81)c 8.54 (0.22)e 8.03 (0.22)
*
Common corresponding lowercase letters in a given column and uppercase letters in a given row indicate no significant difference (p ≤ 0.05).

Table 9 – Temperatures (◦ C) with the maximum degradation rate of each step of thermal degradation of studied
composites.
Composite 1st weight loss 2nd weight loss Weight loss at Organic Weight loss at
800 ◦ C (%) matrixa 2 steps (%)

T1 (◦ C) Weight loss (%) T2 (◦ C) Weight loss (%)

TEC 340.1 4.43 425.4 19.06 28.52 17.50 23.49
GR — — 424.3 12.23 14.54 13.00 12.23
PR 322.8 11.0 415.2 10.87 25.40 18.10 21.83
FSB 319.4 3.57 412.9 16.64 26.20 21.50 20.21
FST 344.8 6.66 419.9 16.92 29.79 27.50 23.59
a
These are the data provided by the manufacturers.
604 d e n t a l m a t e r i a l s 2 7 ( 2 0 1 1 ) 598–607

2,0 immersion for 1 day water

water a 16 saliva
saliva
14
1,6
Volume Increase (%)

Flexural modulus [GPa]

12

1,2 10

8
0,8
6

4
0,4
2

0
0,0
TEC GR PR FSB FST
TEC GR PR FSB FST

Fig. 3 – Volume increase (%) of studied composites after immersion for 30 days water
immersion in water or artificial saliva for 30 days. b 16 saliva
14

Flexural modulus [GPa]

12

10
In Fig. 6 the thermograms of the TGA and the thermograms 8
of the first derivative (dTGA) are shown. In Table 9 the temper-
6
atures with the maximum degradation rate of each step of
thermal degradation of the studied composites and the corre- 4
sponding weight loss are shown. 2

0
TEC GR PR FSB FST

Fig. 5 – Effect of the liquid medium aging on flexural

immersion for 1 day
water modulus of studied composites after storage in water or
a 180 saliva
artificial saliva for (a) 1 day and (b) 30 days.
150
Flexural strength [MPa]

120

90 4. Discussion

60 The volumetric shrinkage (%) of studied composites follows

the order Grandio (GR) < Tetric EvoCeram (TEC) < Protofill-nano
30 (PR) < Filtek Supreme Body (FSB) < Filtek Supreme Translucent
(FST) (Fig. 1). This order seems to depend on the total content
0
TEC GR PR FSB FST of organic matrix of composites. GR contains the least amount
of organic matrix (13.0 wt-%) and FST the most (30.0 wt-%)
immersion for 30 days (Table 1). However, PR showed higher shrinkage than TEC,
water
b 140 saliva although they both contain about the same amount of organic
matrix (∼18.0 wt-%). This is attributed to the different chem-
120
istry of their organic matrix. The organic matrix of PR consists
Flexural strength [MPa]

100 of Bis-GMA, UDMA and TEGDMA, while that of TEC consists

of Bis-GMA and UDMA. It is known that the polymerization
80
shrinkage of composites depends on the degree of conversion
60 of monomers during polymerization; the greater the degree
of polymerization the greater the shrinkage. It is well known
40
also from literature [23] that TEGDMA shows a much greater
20 degree of conversion than both Bis-GMA and UDMA.
After polymerization the composites were immersed in
0
water or artificial saliva. Water or artificial saliva uptake in
TEC GR PR FSB FST
the polymeric phase of polymer composites causes generally
Fig. 4 – Effect of the liquid medium aging on flexural two opposing processes. The solvent will extract unreacted
strength of studied composites after storage in water or components, mainly monomer resulting in shrinkage, loss of
artificial saliva for (a) 1 day and (b) 30 days. weight and reduction in mechanical properties. Conversely
 d e n t a l m a t e r i a l s 2 7 ( 2 0 1 1 ) 598–607 605

TEC 0,0
FSB 0,0
100 100
-0,5

deri. weight loss (%/min)

der. weight loss (%/min)

95
weight loss (%)

95 -0,5
-1,0

weight loss (%)

90 90
-1,5 -1,0
85 85
-2,0
-1,5
80 80
-2,5
-2,0
75 -3,0 75

70 -3,5 70 -2,5
100 200 300 400 500 600 700 800 100 200 300 400 500 600 700 800
o o
Temperature (C) Temperature (C)

GR 0,0
FST
100 100 0,0
-0,2
98
95

der.weight loss (%/min)

-0,5

der. weight loss (%/min)

-0,4
96
-0,6 90
weight loss (%)

weight loss (%)

94 -1,0
-0,8
85
92 -1,0
-1,5
80
90 -1,2

88 -1,4 75 -2,0
-1,6
86 70
-1,8 -2,5
84 65
100 200 300 400 500 600 700 800 100 200 300 400 500 600 700 800
o o
Temperature ( C) Temperature ( C)

PR
0,0
100
-0,2
95
der. weiht loss (%/min)

-0,4
weight loss (%)

90 -0,6

-0,8
85
-1,0
80 -1,2

75 -1,4

-1,6
70
100 200 300 400 500 600 700 800
o
Temperature ( C)

Fig. 6 – TGA and dTGA curves of studied composites in nitrogen.

solvent uptake leads to a swelling of the composite and an showed statistically higher water sorption. This shows that
increase in weight. The solvent diffuses into the polymer net- the water sorption of composites depends also on the matrix
work and separates the chains creating expansion. However chemistry. PR contains TEGDMA, which is known to be of
since the polymer network contains microvoids created dur- greater hydrophilicity than Bis-GMA and UDMA [12]. When
ing polymerization and free volume between chains, a part the amount of sorbed water was calculated on the basis of
of the solvent is accommodated without creating a change the content of composite in polymer matrix (Table 3) then the
in volume. Thus the dimensional change of a polymer com- order was different GR < FST≤TEC < PR < FSB.
posite in a solvent is complex and difficult to predict and The GR and TEC with lower polymer matrix content showed
depends on the chemical structure of the polymer matrix. also lower solubility than that of PR, FSB and FST (Table 4).
The hydrophilicity of the polymer needs to be of sufficient Analogous behavior was observed in artificial saliva (Table 6).
magnitude to distend the polymer. In all the composites stud- The amount of sorbed water (Fig. 2a), the solubility (Fig. 2b)
ied the amount of water sorbed is not statistically different and the volume increase (Fig. 3) is not statistically different
to the amount of water which is desorbed (Table 3) and fol- from the corresponding quantities observed in the case of
lows the order: GR < TEC < PR < FSB < FST. This order shows that artificial saliva.
water sorption seems to depend on the polymer matrix con- After immersion in water for 1 day FSB (79 wt% filler
tent. However PR, which has the same matrix content as TEC, content) showed the greatest flexural strength and TEC
606 d e n t a l m a t e r i a l s 2 7 ( 2 0 1 1 ) 598–607
(82–83 wt%) the lowest. GR (87 wt%), PR (81.9 wt%) and FST
(70 wt%) showed no statistically different flexural strength
(Table 3). This result shows that the flexural strength
depends not only on the filler content but also on the filler
chemistry.
After immersion in water for 30 days the flexural strength
of TEC remained constant while that of all other composites
decreased. It is worthy of note that after immersion in water
for 30 days GR showed the greatest flexural strength and TEC
the lowest. FSB, FST and PR showed no statistically different
flexural strength, which was less than that of GR but higher
than that of TEC.
The flexural modulus of composites after immersion for
one day follows the order TEC < PR≤FST < FSB < GR and after
immersion for 30 days the order TEC < FST < PR < FSB < GR
(Table 3). It is interesting to note that the flexural mod-
ulus of GR and PR remained constant after immersion
in water for 30 days, while that of FSB, PR and TEC
decreased.
Comparison of flexural strength after immersion for 1 day
in water or artificial saliva showed the values obtained are
comparable. When the composites remained in water or arti-
ficial saliva for 30 days, the saliva had a stronger effect on
the flexural strength for GR and PR and no significant differ-
ence was observed for the other composites. Comparison of
flexural modulus after immersion in water or artificial saliva
did not show any significant difference ( p < 0.05) for 1 day or
30 days.
Thermogravimetric analysis of dental composites gave
good information about the structure and the amount of the
organic matrix. In the authors’ previous work [24] the ther-
mal degradation mechanism of neat dental resins Bis-GMA,
Bis-EMA, UDMA and TEGDMA was studied. Differences in
the chemical structure of the resins considerably influence
the degradation behavior of the resins. Bis-GMA and Bis-EMA
showed one-step degradation mechanism with a maximum
rate corresponding to 415 and 424 ◦ C respectively [24]. On
the contrary TEGDMA and UDMA showed two degradation
steps with maximum rate at 306 and 403 ◦ C for TEGDMA and
357 and 444 ◦ C for UDMA. GR showed only a strong peak
at 424 ◦ C (19.06%, wt/wt) revealing that the organic matrix
consists mainly of Bis-GMA rather than TEGDMA (Table 1).
FSB showed a shoulder at 319 ◦ C (3.6%, wt/wt) and a strong
peak at 413 ◦ C (16.6%, wt/wt). Also FST showed a shoulder
at 345 ◦ C (6.7%, wt/wt) and a strong peak at 420 ◦ C (16.9%,
wt/wt). These results confirm that these composites contain
both aromatic and aliphatic dimethacrylate resins, and show
that the aromatic content (Bis-GMA and Bis-EMA) is higher
than that of the aliphatic (TEGDMA and UDMA). They also
confirm that FST contains more organic matrix than FSB. TEC
showed a small peak at 340 ◦ C (4.4%, wt/wt) which must be
attributed to the UDMA it contains, and a strong peak at 424 ◦ C
(19.06%, wt/wt) due to the Bis-GMA content. PR showed two
strong peaks at 323 ◦ C (11.0%, wt/wt) and at 415 ◦ C (10.9%,
wt/wt) which show that this composite contains about equal
quantities of aromatic (Bis-GMA) and aliphatic (TEGDMA and
UDMA) resins. All composites showed a weight loss higher
than their organic matrix content at 800 ◦ C, which must be due
to the condensation reactions of surface hydroxyl groups of
the filler.
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