Effects of curing time and filler concentration on curing and postcuring of urethane dimethacrylate composites: a microcalorimetric study. 
The isothermal enthalpy changes with time of a dental composite were examined by microcalorimetry to isolate the effects of different filler concentrations and curing times on chemical aging of these composites.  Urethane dimethacrylate (UDMA) monomer, zirconia-silica (ZS) powder, and 3-methacryloxypropyltrimethoxysilane (MAPM) were used as organic and inorganic matrices, and a coupling agent, respectively.  The composite was mixed in different ratios and cured by visible light.  The enthalpy changes with time for 0, 15, 45, 75% ZS-filled UDMA and 75% MAPM-silanated ZS-filled UDMA cured for 13, 30, 90, 150, and 300 s were measured at 37.0 degrees, 57.0 degrees, and 65.5 degrees C until equilibrium.  Increased curing time and filler concentration caused the excess enthalpy changes (dH) and their rate of change (dH/dt) to increase with annealing time and apparent equilibrium was reached faster.  In addition, dH showed nonlinear dependence with the increase in filler concentration by showing a maxima for samples containing 25 wt% filler.  Further, filler silanation caused dH/dt to increase and required shorter times to reach apparent equilibrium.  dH also reached a minimum when samples contained silanated filler, compared to composites containing unsilanated filler.  It was concluded that the shorter curing time caused the occurrence of spontaneous densification, which facilitated continual resin curing; and longer curing time caused higher crosslinking of the organic phase.  Moderate concentration of inorganic phase restricts the molecular motion of the surface layer of polymer onto filler particles, and the polymer is regarded as highly crosslinked, while a higher filler concentration forms aggregates that are covered by the polymer which causes a decrease in the molecular packing of the resin, and is reflected as low enthalpy values.  Finally, silanation of the filler showed a highly endothermic reaction that is probably due to breaking and forming of bonds at the interface between the organic and the inorganic phases in the composites.