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Article history:
Objectives. To investigate the movement of resin matrix with respect to the ller particles of
lled composites during their photo cure without or with polymerization contraction stress
(PCS).
7 January 2010
Methods. Two types of composites were prepared. Glass beads as macroscopic llers were
placed into the center of a bis-GMA/TEGDMA resin to make single bead-embedding composites and a variety of llers of different compositions, sizes, and shapes were mixed with
another bis-GMA/TEGDMA resin to make lightly lled composites. They were photo cured in
Keywords:
a cavity constructed with an acrylic or aluminum ring sitting on a polyester strip. Bonding to
Composite
the ring constrained the polymerization shrinkage and thus produced a PCS. The formation
Fillerresin interface
of gaps between the ller and the resin was detected by optical microscopy for the glass
Polymerization
beadresin systems, and by light attenuation and scanning electron microscopy (SEM) for
Shrinkage
Stress
Results. In general, for composites with untreated llers, the optical microscopy and
SEM revealed gaps at the llerresin interface only when they were cured under constrained shrinkage conditions. These composites attenuated more light when cured under
constrained shrinkage conditions than when under non-constrained conditions. For the
composites with silane-treated llers, no gaps were observed. Some did not show any signicant difference in light attenuation when cured under either constrained or non-constrained
conditions.
Conclusions. The resin tends to move away from the ller particles under the inuence of
PCS. Strengthening the llerresin interaction, such as by the use of silane-treated ller,
may help prevent the resin departure and thus the formation of gaps.
2010 Published by Elsevier Ltd on behalf of Academy of Dental Materials. All rights
reserved.
1.
Introduction
Corresponding author at: Bisco Inc., 1100 W Irving Park Road, Schaumburg, IL 60193, USA. Tel.: +1 847 534 6096; fax: +1 847 891 6705.
E-mail address: lfeng@bisco.com (L. Feng).
0109-5641/$ see front matter 2010 Published by Elsevier Ltd on behalf of Academy of Dental Materials. All rights reserved.
doi:10.1016/j.dental.2010.03.004
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d e n t a l m a t e r i a l s 2 6 ( 2 0 1 0 ) 719729
Attribute
Manufacturer
Borosilicate
Bis-GMAa /TEGDMAb (50:50 for beads and 60:40 for llers) plus 0.50%
CQc and 0.50% EDMABd
All Bond 2 One Step
316 Silicone Release Spray
2.
Table 1 lists the materials used in this study. The glass bead,
served as a macroscopic ller particle for direct visualization, was made from a glass ber (0.3 mm in diameter) by
aming one of its ends with a propane torch. The resin composition comprised of a typical dimethacrylate blend used for
commercial dental composites. The bonding agents created
a constrained shrinkage condition by bonding the composite
to the ring while the separating agent freed the shrinkage by
preventing the composite from adhering to the ring.
Table 2 shows the seven tested llers with varying compositions, shapes, and sizes. They were either used untreated
(as received) or silane treated to strengthen their interactions
with the resin. A composite slurry was made by thoroughly
blending each of the llers into the 60:40 bis-GMA/TEGDMA
resin by grind-mixing with a ceramic mortar and pestle. The
resin was only lightly lled (20 wt% for Spherical 1, 40 wt% for
Irregular 2, and 10 wt% for the rests) to allow enough light to
pass through so sufciently accurate irradiance readings could
be accomplished.
The constraint of polymerization shrinkage was provided
by a circular cavity, constructed by sitting either an acrylic
or aluminum ring (6.0 mm in inner diameter, 9.5 mm in outer
diameter, and 2.0 mm in height) on a clear polyester strip and
covered with another strip. Because of its high compliance,
the polyester strip deformed easily under PCS, contributing little constraint to the shrinkage of a curing resin or composite.
Therefore, the top and bottom of the ring can be approximately
treated as unbonded surfaces and the C-factor was 1.5 for
both types of rings. Acrylic rings were either sandblasted and
primed with bonding agent One Step to constrain shrinkage,
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d e n t a l m a t e r i a l s 2 6 ( 2 0 1 0 ) 719729
Trade name
Spherical 1
Spherical 2
Spherical 3
Zeeospheres W-210
TC3
SP25512
Irregular 1
Irregular 2
Irregular 3
Nano-ller
GM27884
Raysorb T-4000
EG2933
Aerosil OX-50
Composition
Aluminum silicate
Silica
Barium aluminum
borosilicate
Barium glass
Strontium glass
Strontium glass
Silica
Manufacturer
3M St. Paul, MN
Suzuki Yusu Industrial Osaka, Japan
Diameter
(m)
3
1
2
1
10
3
0.04
Loading
(wt%)
20
10
10
10
40
10
10
All the llers were used either as received (untreated), or silanized with -methacrxypropyltrimethoxy silane (silane treated).
For optical microscope observations, a specimen was prepared by pipetting the 50:50 bis-GMA/TEGDMA resin into a
cavity formed by an acrylic or aluminum ring and then carefully dropping one glass bead (0.51.0 mm in diameter) into
the resin near the center. No cover strip was applied for this
set of experiments. Three types of glass beads were fabricated: smooth, smooth but with a nick (cut with a scalpel
when the bead was still hot and pliable), and roughened
(by sandblasting with 50 m Al2 O3 ). They were used without
treatments, coated with the separating agent, or treated with
silane. Treatments for the last one included 9.5% hydrouoric acid etching (Porcelain Etchant, Bisco), water rinsing,
Fig. 1 Optical microscope images of smooth glass beads in the 50:50 bis-GMA/TEGDMA resin, cured with non-constrained
polymerization shrinkage (Scale bar = 0.5 mm): (A) untreated and uncured as the control, (B) untreated, (C) separating agent
treated, and (D) silane treated. Like the uncured (A), none of the cured (BD) showed the gap formation at the beadresin
interface.
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d e n t a l m a t e r i a l s 2 6 ( 2 0 1 0 ) 719729
the thickness of the material to that of the ring (2.0 mm). Aluminum rings were exclusively used here because they would
not interfere with the light measurements because of their
opacity. The composite was irradiated with a halogen curing
unit (VIP, Bisco) under 500 mW/cm2 for 2 20 s from both top
and bottom. After the strips were removed, the cured specimen was placed between the light guide of the VIP and a digital
radiometer (Cure Rite 8000, EFOS, Mississauga, ON). Acting as a
lter window, the cured composite attenuated the penetrating
light by scattering as well as absorbing. The way of measuring
the attenuated light was very similar to that used by Musanje
and Darvell [25]. The formation of gaps at the llerresin interface increased the mismatch of refractive indices, making the
material less transparent [26]. A chemical cured composite
Fig. 2 Optical microscope images of smooth glass beads in the 50:50 bis-GMA/TEGDMA resin, cured with constrained
polymerization shrinkage (Scale bar = 0.5 mm): (A) untreated and uncured as the control, (B) untreated (acrylic ring), (C)
separating agent treated (acrylic ring), (D) untreated (aluminum ring), and (E) silane treated (aluminum ring). After cure,
(BD) developed gaps while (E) did not.
d e n t a l m a t e r i a l s 2 6 ( 2 0 1 0 ) 719729
723
Fig. 3 Optical microscope images of smooth glass beads with a nick in the 50:50 bis-GMA/TEGDMA resin, cured with
non-constrained polymerization shrinkage (Scale bar = 0.5 mm): (A) untreated and uncured, (B) the same specimen as in (A)
but cured, (C) separating agent treated and uncured, and (D) the same specimen as in (C) but cured. The nicks not seen in
the uncured (A) and (C) were now visible after cure in (B) and (C), indicated by the arrows.
with 10 wt% TiO2 powder (P25, Degussa) was prepared for estimating light transmission around the peripheral of the cured
composite: there could be gaps along the margin between the
composite and the separating agent treated ring after the polymerization shrinkage. Four to ve specimens were measured
for each condition. The t-test was used to compare the means
of measured light irradiance of those without and with polymerization shrinkage constraint.
Specimens for SEM observations were similarly cured as
those above. But this time acrylic rings were used instead since
the cured composite inside the aluminum ring had a strong
tendency to debond from the ring during polishing. After cure
and removal of the strips, the top of the specimen was ground
into a at surface with a 320 grit SiC paper (3M). The surface
was then consecutively polished with a 1500 grit SiC paper
(3M), 1 m, and 0.3 m Al2 O3 papers (both from Buehler, Lake
Bluff, IL) in the absence of water. The polished specimens (two
for each experimental condition) were air cleaned, sputtercoated with gold, and observed with SEM SM-510 (Topcon,
Tokyo, Japan) under 15 kV.
3.
Results
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d e n t a l m a t e r i a l s 2 6 ( 2 0 1 0 ) 719729
Fig. 4 Optical microscope images of glass beads in the 50:50 bis-GMA/TEGDMA resin, cured with non-constrained
polymerization shrinkage (Scale bar = 0.5 mm): (A) smooth and uncured, (B) the same specimen as in (A) but cured, (C)
roughened and uncured, (D) the same specimen as in (C) but cured, (E) roughened, separating agent treated, and uncured,
and (F) the same specimen as in (E) but cured. After cure, while the transparency of (B) remained unchanged in comparison
with that of (A), the transparencies of (D) and (F) became lower than those in (C) and (E), respectively.
one (Fig. 4(D) vs. (C)). The change was more discernable for the
roughened and separating agent treated bead (Fig. 4(F) vs. (E)).
It is worth noting that we took a great effort to sure that these
reductions of transparencies were not an optical illusion, such
as defocusing, by ne tuning the focus as well as by using three
identically fabricated beads.
Fig. 5 presents the light irradiance attenuated by composites with various llers untreated and silane-treated, and
cured non-constrained and constrained. Also given were four
different controls in the caption: the irradiances for (I) a neat
resin only (with no ller), (II) a completely clear specimen (with
d e n t a l m a t e r i a l s 2 6 ( 2 0 1 0 ) 719729
4.
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Discussion
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d e n t a l m a t e r i a l s 2 6 ( 2 0 1 0 ) 719729
Fig. 6 SEM micrographs of composites with: (A) untreated Spherical 1 and cured with non-constrained shrinkage, (B)
untreated Spherical 1 and cured with constrained shrinkage, and (C) silane-treated Spherical 1 and cured with constrained
shrinkage. The arrows in (B) indicate gaps, which were about 10% of all the visible interfaces on the image. Also more gaps
appeared to be around bigger llers than smaller ones.
demonstrated by the use of non-bonded nano-ller to deliberately weaken the llerresin interactions [14]. Conversely, too
low a PCS is unable to overcome the attraction, no separation
would occur. Whether or not the PCS can actually separate the
resin from the ller and then expand the void will depend on
its magnitude with respect to other opposing forces. An analogous process of generating a porous structure in polymers
has been utilized in manufacturing breathable lms [32,33]. A
particulate (CaCO3 ) lled composite is stretched and its deformation causes debonding between the ller and the polymer
matrix, producing pores. The debonding stress is a function
of the thermal stress, the reversible work of adhesion, the
Youngs modulus of the matrix, and the radius of particles
[32].
The reversible work of adhesion is related to the magnitude of llerresin interactions in our systems. We observed
that the use of acrylic rings, which due to its low elastic modulus (3.3 GPa [34]) produced a PCS of 4 MPa, could always create
gaps around a smooth glass bead if the bead was coated with
the separating agent (Fig. 2(C)). With untreated beads, gaps
could still form but only at about 33% of the time (Fig. 2(B)).
Gaps appeared every time again when the shrinkage was constrained by aluminum rings, which produced a PCS of 20 MPa
owning to their much higher elastic modulus (69 GPa [35])
(Fig. 2(D)). Finally, no gaps were ever found around silanetreated beads even when aluminum rings were used (Fig. 2(E)).
The last observation, together with that from Fig. 5(B), suggests
that with a proper silane treatment, the llerresin interfacial
bonding can be strong enough to resist the high PCS created
by rigid aluminum rings. By the same token, however, the fact
that the composites using a silane-treated ller still resulted
in a lower attenuated irradiance, Fig. 5(B) implies that the efciency of silane treatment as well as mixing status may play
important roles, too.
The aforementioned processes are schematically summarized in Fig. 7 by using 2D illustrations. When the resin shrinks
during cure, the void also shrinks (Fig. 7(A)), which reduces its
surface area and is thus energetically favorable by reducing the
total surface free energy. The shrinkage of the void appears to
increase the resin volume as the total volume equals those of
the resin and the void. However, since the total volume also
shrinks, this compensates both reduced volumes of void and
resin. The system is stable. Therefore, we suggest that free
shrinkage and the reduction of surface area together are the
driving force for the resin to move toward the particle during
cure (Fig. 7(B)).
There are several scenarios that do not fulll the two
requirements and thus may see the resin being separated from
d e n t a l m a t e r i a l s 2 6 ( 2 0 1 0 ) 719729
727
Fig. 7 2D schematics showing effects of different scenarios on the shrinkage direction of the resin matrix with respect to
the ller particles. (A) Non-constrained shrinkage with an empty void, (B) non-constrained shrinkage with a global convex
surface (ller particle), (C) constrained shrinkage with a global convex surface, (D) non-constrained shrinkage with a global
convex surface but a local concave one, and (E) non-constrained shrinkage with resin ssures and a resin chamber.
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d e n t a l m a t e r i a l s 2 6 ( 2 0 1 0 ) 719729
dle, where the surface was slightly concave (Figs. 2(BD) and
3(B)).
The third scenario is not proven in our experiments
but worthy of some speculation based on what has been
discussed. In composites with highly agglomerated ller particles, their touching one another may create local chambers,
where the shrinkage of resin is constrained (Fig. 7(E)) and the
total resin shrinkage will have no effects. Also, local concavity
is not limited to individual particles. Resin dead-ends, such
as pockets, valleys, bits, and ssures may form from closely
packed ller particles as well (Fig. 7(E)). All of these can serve as
concave surfaces and the trapped resin will likely move away
from the interface under polymerization shrinkage regardless how the global composite shrinksdoing so will always
reduce the surface area as well as the PCS.
We only added a small fraction of ller in the composites
for light attenuation measurements in order to maintain a
high curing homogeneity as well as measuring accuracy. With
a ller loading around 6080 wt% in a regular composite, the
population of gaps may be different. From our limited experiments, we noticed that our model composites with higher
ller loading seemed to produce greater irradiance differences
between those with constrained shrinkage and those without,
even with silane-treated llers. It could have been the results
of the enhanced disparities due to the presence of a larger
interfacial area and thus more associated gaps. It is possible
that commercial composites could show a greater structural
and property disparity because they contain much more ller
than those used in this research.
Finally, as suggested by this work as well as the other
studies [12,1721], it is very plausible that the structure and
properties of a composite, when it is cured with the polymerization shrinkage constrained, may differ from those
non-constrained. In reality, almost all composites used in vivo
are cured under some kind of PCS, while the specimens prepared for the evaluation of mechanical properties are not. Yet,
the data of the latter are always unequivocally used to represent those of the former. It is an unfortunate fact. Hopefully
this paper will encourage research workers and manufacturers to address this issue.
5.
Conclusions
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