Differential scanning calorimetry studies on aqueous low-toxicity monomer-crosslinker gelcasting systems loaded with zirconia powder provided information on the onset and kinetics of the polymerization reaction. A simple procedure was developed to determine the relative importance of the individual components on the gelation process. It was found that the thermal stability and dissociation of the initiator control the gelation rate and that the zirconia particles accelerate the gelation.