Journal of Dental Research

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Impact of Curing Protocol on Conversion and Shrinkage Stress

H. Lu, J.W. Stansbury and C.N. Bowman
J DENT RES 2005 84: 822
DOI: 10.1177/154405910508400908

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 RESEARCH REPORTS
Biomaterials & Bioengineering
H. Lu1, J.W. Stansbury1,2,
and C.N. Bowman1,2*
1 Department of Chemical & Biological Engineering,
Engineering Center, ECCH 111, University of Colorado at
Boulder, Boulder, CO 80309-0424, USA; and 2Department
of Restorative Dentistry, University of Colorado Health
Sciences Center, Denver, CO 80262, USA; *corresponding
author, Christopher.Bowman@colorado.edu
J Dent Res 84(9):822-826, 2005
ABSTRACT
Since considerable shrinkage stress develops
during the curing of dental composites, various
soft-start photocuring protocols, aiming to lower
stress but not compromise conversion, have been
proposed. We hypothesized that utilizing soft-start
photocuring will result in not only reduced stress,
but also decreased conversion. We evaluated the
impact of 3 protocols (soft-start, pulse, and
standard) on the stress development and
polymerization extent of an experimental
composite. A novel set-up capable of
simultaneous shrinkage stress, conversion, and
temperature measurements on the same specimen
was utilized. Analysis of the data shows that stress
rises dramatically as a function of conversion in
the vitrified state, and the utilization of soft-start
or pulse curing results in specimens with reduced
final conversion and shrinkage stress, compared
with specimens cured according to the standard
full-intensity protocol. Finally, this study
demonstrates that the predominant reason for the
reduced shrinkage stress attained with soft-start or
pulse curing is a modest decrease in final
conversion.
KEY WORDS: shrinkage stress, conversion, curing
protocol, dental composite.
Received December 15, 2003; Last revision May 17, 2005;
Accepted June 1, 2005
A supplemental appendix to this article is published
electronically only at http://www.dentalresearch.org.
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International and American Associations for Dental Research
Impact of Curing Protocol on
Conversion and Shrinkage Stress
INTRODUCTION
D imethacrylate-based dental restorative composites have become
increasingly popular with the support of facile photopolymerization
techniques. Highly crosslinked polymeric restorations with excellent tooth-
like appearance are formed on command under ambient conditions.
However, constrained shrinkage during polymerization densification
generates polymerization shrinkage stress, which is one of the most
significant concerns during the highly technique-sensitive clinical placement
of composite restorations (Carvalho et al., 1996; Davidson and Feilzer,
1997). Although polymerization shrinkage has been significantly reduced in
modern dental composite formulations, largely through the addition of
inorganic filler, the induced shrinkage stress remains too high to allow direct
filling to be applied in some large posterior restorations (Dietschi and
Krejci, 2001).
Since the detrimental shrinkage stress tremendously weakens the
performance and longevity of dental composites, numerous approaches have
been proposed to decrease and minimize the shrinkage stress through
manipulation of curing protocols and placement techniques. Among these
approaches, soft-start curing (irradiation begins with a low-intensity,
followed by a full-light intensity) and pulse curing (similar to soft-start
curing except that a dark interval is included between the initial low-
intensity and the following full-intensity curing) have attracted extensive
investigations. One hypothesis for advocating these types of curing
protocols is that the initial low-light intensity could facilitate a certain
degree of polymer chain relaxation, such that a portion of the shrinkage
stress relaxes while the system has not yet reached the vitrification stage. It
has been claimed that the soft-start curing method partially relieves
shrinkage stress, and achieves improved integrity of the composite/tooth
interface, without compromising the final double-bond conversion or
mechanical properties of the cured dental composite (Uno and Asmussen,
1991; Feilzer et al., 1995; Mehl et al., 1997; Lim et al., 2002). However,
whether this approach significantly reduces shrinkage stress without
decreasing the final conversion and mechanical properties is still under
extensive debate, and the real benefit of soft-start curing has not being
confirmed clinically (Friedl et al., 2000; Asmussen and Peutzfeldt, 2003;
Soh and Yap, 2004).
One reason leading to this perplexity is that the interrelationships among
double-bond conversion, polymerization rate, and polymerization shrinkage
stress in composite dental restoratives are not well-understood. Since the
double-bond conversion is related directly to the amount of polymerization
shrinkage (Patel et al., 1987) and the material's mechanical properties
(Lovell et al., 2003; Steeman et al., 2004), it is crucial that one follow the
real-time conversion while monitoring the shrinkage stress development of
the same specimen. In evaluations of the effects of various curing protocols
on conversion and shrinkage stress development, it can be misleading if the
J Dent Res 84(9) 2005 Effect of Curing on Shrinkage Stress
conversion measurement and shrinkage stress measurement are
performed on different specimens, or the two measurements are
performed at different times, since slight differences in sample
size, configuration, or irradiation conditions can significantly
diminish the validity of a direct correlation of the data from
these two distinct experiments. Unfortunately, this aspect has
been overlooked in most studies associated with curing
protocol and shrinkage stress, not to mention in numerous other
studies where the assessment of double-bond conversion was
not performed at all.
In this investigation, we hypothesized that utilizing soft-
start curing would result in not only reduced shrinkage stress,
but also decreased double-bond conversion. The impact of
three photocuring protocols (soft-start, pulse, and standard) on
simultaneous stress and conversion development was examined
with a novel experimental technique that is capable of
measuring the real-time stress and conversion concurrently on
the same specimen. The results were further elucidated
regarding fundamental relationships among polymerization
kinetics, network evolution, temperature change, and shrinkage
stress development.
MATERIALS & METHODS
Materials
An experimental composite containing 70 wt% resin and 30 wt%
silanized filler was used in this study. Since stress is predicated on
the shrinkage of the resin component, the filler used was
minimized for a clear indication of how various clinically used
photo-curing protocols may affect the development of stress. The
resin was composed of 2,2-bis[4-(2-hydroxy-3-methacryloxyprop-
1-oxy)phenyl]propane (Bis-GMA, Esstech, Essington, PA, USA)
and the reactive diluent triethyleneglycol dimethacrylate
(TEGDMA, Polysciences, Warrington, PA, USA) at 70:30 weight
ratio, along with 0.3 wt% camphorquinone (CQ, Aldrich Chemical,
Milwaukee, WI, USA) as the visible-light initiator and 0.8 wt%
ethyl 4-dimethylaminobenzoate (EDAB, Aldrich Chemical) as the
co-initiator. A nanofiller (OX-50, Degussa AM, Frankfurt,
Germany) was selected to maintain a relatively high degree of
translucency in the uncured and cured composite materials. The
filler was treated with 5 wt% silane coupling agent ␥ -
methacryloxypropyl trimethoxysilane (Aldrich Chemical), before
being blended with the Bis-GMA/TEGDMA resin. All chemicals
were used as received.
Simultaneous Shrinkage Stress
and Conversion Measurement
The shrinkage stress measurement device, referred to as a
tensometer, was designed and fabricated at the Paffenbarger
Research Center of the American Dental Association Health
Foundation. This device is based on the cantilever beam theory
that tensile force generated by a shrinking sample causes the
cantilever of known beam constant to deflect. The shrinkage stress
is then obtained by dividing the shrinkage force by the cross-
sectional area of the disk-shaped sample (6.0 mm in diameter and
2.5 mm in thickness). The detailed description, experimental
procedure, and characterization of the tensometer have been
discussed in previous papers (Lu et al., 2004a,b).
In situ, real-time monitoring of the polymerization kinetics is
enabled by means of near-infrared (NIR) spectroscopy, coupled
with a fiber optic remote sensing technique. We obtained serial
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International and American Associations for Dental Research
823
NIR spectra by configuring 2 optical fibers (wavelength from 350
to 2400 nm) to a Fourier transform-infrared spectrophotometer
(Nexus 670, Nicolet Instrument, Madison, WI, USA) through a
NIR fiberport. During the dynamic measurement of stress
evolution, NIR signal was transmitted via fiber optic cables (1 mm
diameter) through the diameter aspect of the specimen mounted in
the tensometer. Conversion was monitored by real-time NIR in
series collection mode, with a temporal resolution of 0.46 sec
between spectrum collections. The series run collects peak area
data from the region of 6232 to 6101 cm-1, so that the decay of the
methacrylate double-bond concentration during polymerization can
be monitored. A detailed description of this simultaneous
measurement technique has been discussed previously (Lu et al.,
2004b), and illustrations are also available online as Appendices.
Curing Protocols
We used a halogen dental lamp, variable intensity polymerizer
(VIP, BISCO, Schaumburg, IL, USA), to introduce the different
curing protocols. The quartz rod ends were treated with silane
bonding agent to ensure stable adhesion to the composite specimen
during photopolymerization. Light intensity at the specimen
interface of the lower quartz rod, which is used to conduct the
curing light, was measured with a radiometer (Model 100,
Demetron Research, Danbury, CT, USA). Three different curing
protocols were investigated: STAN_irradiate at a constant light
intensity of 450 mW/cm2 for 60 sec; SOFT_start at 100 mW/cm2
for the first 5 sec, followed immediately by another 60 sec of
irradiation at 450 mW/cm2; and PULSE_start at 100 mW/cm2 for
the first 5 sec, wait for 2 min, then irradiate for another 60 sec at
450 mW/cm 2 . All experiments were performed at ambient
temperature (23 ± 1°C). The internal temperature of the composite
during polymerization was monitored with an embedded K-type
miniature thermocouple (diameter 0.127 mm; Omega Engineering,
Stamford, CT, USA). For each set of experiments, 3 replicate runs
were conducted. Results were analyzed by one-way analysis of
variance (ANOVA) and Tukey's HSD post hoc test, with a
significance level of 0.05.
RESULTS
As revealed in conversion vs. time plots for specimens cured
with the three protocols—STAN, SOFT, and PULSE (Fig.
1a)—polymerization proceeds rapidly, and specimens cured in
STAN mode reached the highest final conversion (at 20 min
from the start of irradiation), with an average of 67.5 ± 2.4%.
Specimens cured with the SOFT protocol achieved an average
of 61.9 ± 0.4% final conversion, while specimens cured in
PULSE mode reached an average of 60.4 ± 0.7% final
conversion. Between SOFT and PULSE curing protocols, no
statistically significant difference for final conversion was
found (Table).
Shrinkage stress development as a function of time is
presented in Fig. 1b. The final shrinkage stress values obtained
with the STAN, SOFT, and PULSE curing protocols were 2.18
± 0.04 MPa, 1.87 ± 0.03 MPa, and 1.77 ± 0.08 MPa,
respectively (Table). Compared with the final shrinkage stress
of specimens cured with STAN mode, the final shrinkage stress
of SOFT and PULSE specimens decreased significantly, by
14% and 19%, respectively. However, as noted, their final
conversions are also significantly lower than the final
conversion obtained in STAN mode.
As shown in real-time temperature vs. time profiles (Fig.
824 Lu et al. J Dent Res 84(9) 2005

Figure 2. Sample temperature vs. time for Bis-GMA/TEGDMA/OX-50

(49/21/30 by wt; Initiator, CQ 0.21 wt %; EDAB, 0.56 wt%) cured with
3 different curing protocols at T0 = 23°C: STAN, 450 mW/cm2 for 60
sec (—); SOFT, 100 mW/cm2 for 5 sec, followed by 450 mW/cm2 for
60 sec (– –); PULSE, 100 mW/cm2 for 5 sec, wait for 2 min, followed by
450 mW/cm 2 for 60 sec (...). Vertical bar represents standard
deviation. Estimate of variability is shown in the Table (n = 3).

(approximately 10°C). Polymerization rate and shrinkage stress

Figure 1. Double-bond conversion vs. time (a) and shrinkage stress vs.
time (b) for Bis-GMA/TEGDMA/OX-50 (49/21/30 by wt; Initiator,
CQ 0.21 wt%; EDAB, 0.56 wt%) cured with 3 different curing protocols
at T 0 = 23°C: STAN, 450 mW/cm 2 for 60 sec (—); SOFT, 100
mW/cm2 for 5 sec, followed by 450 mW/cm2 for 60 sec (– –); PULSE,
100 mW/cm2 for 5 sec, wait for 2 min, followed by 450 mW/cm2 for
60 sec (...). Vertical bar represents standard deviation. Estimate of
variability is shown in the Table (n = 3).
development rate have also been analyzed based on the
derivative of double-bond conversion and shrinkage stress with
respect to time. Specimens cured with STAN mode achieve not
only the highest final conversion and shrinkage stress, but also
the highest polymerization rate and shrinkage stress
development rate (Table).
To elucidate further the effects of curing protocols on
polymerization progress and shrinkage stress development, we
examined shrinkage stress as a function of conversion on the
same specimen (Fig. 3; graphs represent the average values of
stress and conversion obtained for each of the curing
protocols). It can be seen that, for all 3 curing protocols, the
stress evolution is concentrated in the latter stages (i.e., high
double-bond conversion) of polymerization, with its dramatic
increase linked to the asymptotic approach of conversion to its
limiting value.

2), the STAN curing mode generates a significantly higher DISCUSSION

temperature increase (approximately 15°C), while the other 2 During free-radical photopolymerization of dimethacrylate
curing modes reach similar maximum temperature increases dental resins, the rapid development of a highly crosslinked
network drastically restricts the mobility of
Table. Summary of Real-time Polymerization, Stress Development, and Temperature reacting species, and instigates such
Measurement Results* (mean ± SD; n = 3) phenomena as auto-acceleration, reaction-
diffusion-controlled termination, and
Maximum Maximum Stress Maximum incomplete conversion (Bowman and
Curing Final Final Shrinkage Polymerization Development Rate Temperature Anseth, 1995; Decker, 1996; Stansbury and
Protocols Conversion (%) Stress (MPa) Rate (1/min) (MPa/min) Increase (°C) Dickens, 2001a). For dental resins cured
under clinical conditions, final conversion
STAN 67.5 ± 2.4a 2.18 ± 0.04a 6.5 ± 2.1a 3.9 ± 0.2a 14.5 ± 1.7a is typically between ca. 55 and 75%
SOFT 61.9 ± 0.4b 1.87 ± 0.03b 2.9 ± 0.3b 3.3 ± 0.1b 9.9 ± 1.6b (Ferracane, 1995; Stansbury and Dickens,
PULSE 60.4 ± 0.7b 1.77 ± 0.08b 2.6 ± 0.3b 2.2 ± 0.2c 9.2 ± 2.7b 2001b), which also agrees with the ultimate
conversions observed in this study.
* Polymerization rate and shrinkage stress development rate were analyzed with use of the The significantly higher final
derivation of double-bond conversion and shrinkage stress with respect to time.
a Within each column, groups depicted by the same superscript are not statistically different, conversion for specimens cured with STAN
P = 0.05. mode is attributed to the complex nature of
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J Dent Res 84(9) 2005 Effect of Curing on Shrinkage Stress
photopolymerization behavior and the kinetics of
dimethacrylate resins. One particularly important phenomenon
is excess free volume (Kloosterboer, 1988; Anseth et al.,
1995a). During photopolymerization of multi(meth)acrylate
systems, the development of a crosslinked network is rapid, and
gel point conversion is well below 10% (Macosko and Miller,
1976; Odian, 1991). For the microscopic free volume generated
by chemical reaction to be converted into macroscopic volume
shrinkage, the crosslinked polymer network must move
cooperatively. However, when macroscopic volumetric
shrinkage cannot keep up with the chemical reaction, a
temporary excess of free volume is created which effectively
increases the mobility of radicals and unreacted double-bonds.
Therefore, higher degrees of conversion can be achieved, in
comparison with those achieved in equilibrium volume systems
(Anseth et al., 1995b). This phenomenon becomes more
pronounced as the polymerization rate dramatically increases,
and further enhanced conversion can be achieved. Other
researchers have also observed that systems cured with higher
incident light intensity achieve higher polymerization rates and
final conversion (Maffezzoli and Terzi, 1998; Lovell et al.,
1999).
Another aspect which affects conversion is the elevated
temperature due to the exothermic polymerization as well as
energy absorbed from the curing lamp. As shown in Fig. 2 and
the Table, specimens cured with the STAN mode have greater
temperature increases compared with specimens irradiated with
the SOFT or PULSE mode. The higher temperature not only
increases polymerization kinetics, but also enhances mobility
of reacting species and postpones vitrification (Lange, 1999);
hence, this non-isothermal process contributes to the increased
polymerization rate and higher extent of polymerization.
We found that the predominant portion of the shrinkage
stress did not start to develop until a much higher extent of
polymerization was reached (Fig. 3). In these studies, more
than 70% of the overall shrinkage stress was observed to
develop over the last 15% of conversion. The significant
increase of stress over conversion in the latter regime of
polymerization is predominantly associated with the several-
orders-of-magnitude increase of polymeric elastic modulus
during the vitrification stage (Lange, 1999; Sakaguchi et al.,
2002; Steeman et al., 2004).
Moreover, the direct correlation of real-time shrinkage
stress and conversion from the same specimen clearly shows
that, in the latter stage of polymerization, where shrinkage
stress was concentrated, a small increase in conversion leads to
a very significant increase of shrinkage stress. Not only will
this small increase in conversion affect the final magnitude of
stress developed in the forming network, but it is also critical
when the effects of different curing protocols on stress
evolution are investigated. It is therefore not surprising to
observe that soft-start or pulse curing led to decreased
shrinkage stress; however, significantly decreased final
conversion was also produced. This finding is in contrast to
other results, which indicated that reduced shrinkage stress can
be achieved with soft-start curing, while the same final
conversion can still be achieved (Uno and Asmussen, 1991;
Lim et al., 2002). Furthermore, it should be noted that, in these
previous studies, conversion values were obtained either from
specimens different from those used for shrinkage stress
evaluation, or from the same specimen (or a portion of it), but
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825
Figure 3. Shrinkage stress as a function of double-bond conversion for
Bis-GMA/TEGDMA/OX-50 (49/21/30 by wt; Initiator, CQ 0.21 wt%;
EDAB, 0.56 wt%) cured with 3 different curing protocols at T0 = 23°C:
STAN, 450 mW/cm2 for 60 sec (—); SOFT, 100 mW/cm2 for 5 sec,
followed by 450 mW/cm2 for 60 sec (– –); PULSE, 100 mW/cm2 for 5
sec, wait for 2 min, followed by 450 mW/cm2 for 60 sec (...). Each
curve represents the average of 3 replicate runs (n = 3).
at a different time than the stress determination (Uno and
Asmussen, 1991; Lim et al., 2002).
One major hypothesis supporting soft-start or pulse curing
is that the initial lower light intensity would allow for polymer
chain relaxation, so that shrinkage stress can be partly relaxed
before the vitrification stage is reached. However, as illustrated
in Fig. 3, for highly crosslinked, glassy Bis-GMA/TEGDMA
systems, the majority of shrinkage stress develops during and
after the vitrification stage, where viscosity approaches infinity,
and elastic modulus is so high that stress relaxation is hardly
observable. Consequently, any stress relaxation prior to the
vitrification stage does not provide as much benefit to overall
shrinkage stress reduction as expected. This finding was also
supported by a separate investigation, where shrinkage stress
relaxation phenomena were observed only prior to vitrification
(Lu et al., 2004c). However, for this limited relaxation to be
achieved, a much longer relaxation time is required, as
compared with clinically practical time scales (Lu et al.,
2004c).
In conclusion, the results from the simultaneous, in situ
shrinkage stress ~ conversion measurements have confirmed
our initial hypotheses, that utilizing low initial light intensity
curing protocols resulted in specimens with both decreased
double-bond conversion and shrinkage stress, compared with
specimens cured with standard, full-intensity protocols.
Specimens cured according to the conventional protocol also
achieve the highest polymerization rate, shrinkage stress
development rate, and temperature increase.
ACKNOWLEDGMENTS
This research was financially supported by the NIH through
grant #DE10959. The authors thank Esstech for providing Bis-
GMA resin and Dr. Sheldon Newman for providing the curing
lamp and radiometer.
826
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