The setting behavior of calcium alginate impression materials was investigated by monitoring the viscosity, calcium ion activity, and shear modulus during the reaction. Structural information was also obtained from the dependence of viscosity and compressive modulus on the calcium concentration in model systems. The gelation time is primarily controlled by the concentration of Na4P2O7 in solution acting as a retarder, while the level and particle size of the alginate and CaSO4 · 2H2O also affect the kinetics through the dissolution rates and concentration effects. The Ca2+ crosslinks bridging the alginate chains in the network appear to be labile. Although this process of bond interchange and that of continued polymerization during deformation may be contributory mechanisms to permanent set, bond rupture appears to be the primary mechanism. Bond rupture can be reduced by increasing the alginate content in the system which also raises the tear energy. Both the permanent set and tear energy are affected by the filler particle morphology.