Objective: While many studies have examined depth of cure in
composites, no information is available on real-time reaction kinetics, including
dynamic temperature change, as a function of depth during composite
photopolymerization.
Methods: A 1 cm vertical column of Bis-GMA/TEGDMA-barium
glass composite between masked glass slides was positioned in a near-infrared (NIR)
spectrometer beam used to assess real-time reaction kinetics and conversion.
An aperture restricted the NIR signal to a 1 mm horizontal slice at
predetermined depths of 1, 3, 5, 7 and 9 mm within the composite. An embedded
thermocouple positioned just below the NIR sampling level provided dynamic localized
temperature sensing. Photopolymerization was triggered by a 90-120 s exposure of
the open upper composite surface with a dental curing light at either 50 or 500
mW/cm2 incident irradiance (n=3).
Results: The dynamic conversion data analyzed at 30, 60 and
90 s time-points showed progressive exponential declines in conversion with
increasing depth: r2 values >0.96. At all depths, the lower
irradiance exposure produced significantly lower conversion (p < 0.05) which
decreased more rapidly with respect to depth compared with the higher
irradiance. The rate of polymerization assessed at 10% conversion also showed
exponential declines with depth in the composite: r2 values
>0.92. The coupled conversion and temperature data demonstrate that
internal temperature and reaction rate both decrease with increasing depth
within the specimen but the thermal front consistently precedes the reaction
front. At the 9 mm sampling depth, delays of >10 s and >40 s were observed
between the initial light exposure and the localized onset of polymerization at
the high and low light intensities, respectively.
Conclusions: This novel analytical approach provides comprehensive,
site-specific kinetic data and clearly shows the significant effects of
attenuated light transmission on photopolymerization in composite materials.
Supported by NIH/NIDCR U24DE016502/2R01DE14227 and a gift
from Septodont.
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