The effects of different additives on the dielectric relaxation and the dynamic mechanical properties of urethane dimethacrylate.

The polymer-filler interaction of a dental composite was examined by dielectric measurements to determine how a non-compatible inorganic phase modifies the molecular behaviour of the polymer chains and how modification of this phase by silanation can affect these molecular behaviours. Urethane dimethacrylate (UDMA) monomer and zirconia-silica (ZS) powder were used as organic and inorganic phases, respectively. 3-Acryloxypropyltrimethoxysilane (MAPM) and 4-aminobutyltriethoxysilane (ABTE) were used as silanating coupling agents. The components of the composite were mixed in different ratios after treating the filler with from 0 to 30 times the minimum uniform coverage with the silane, then the composite was made into thin films. The dielectric spectra of five replicas for each filler-monomer ratio were measured, and three replicas were measured for each silane and for each amount of silane used to treat the filler. Increasing the filler concentration in the composites decreased the intensity of Tan(delta)epsilon for the alpha- and beta-relaxations, where the beta-relaxations also became broader and the alpha-relaxations were totally obstructed. The alpha-relaxations were shifted to higher temperatures, while the beta-relaxations were shifted to lower temperatures. Filler treatment with small amounts of MAPM shifted the alpha-relaxations to higher temperatures; they were shifted back to lower temperatures when the filler was treated with large amounts of silane. Filler treatment with large amounts of ABTE (30-fold) caused an extra peak to emerge in the high-temperature region. It can be concluded that increasing filler concentration restricts the mobility of the main chains and decreases the thickness of the surface layer, while allowing more movement of the local chains. Filler treatment with MAPM was shown to be a compatible coupling agent with the ZS and the UDMA systems. Such compatibility was observed through the effectiveness of the chemical linkage of the silane to the filler and the polymer without forming a separate inter-phase. Filler treatment with ABTE was shown to be an incompatible coupling agent for the ZS-filled UDMA system. The incompatibility was observed by the occurrence of a new peak that characterizes an inter-phase.