Zinc polycarboxylate cements: a chemical study of erosion and its relationship to molecular structure

Experimental results show that the rate of elution of Zn2+ and Mg2+ ions from polycarboxylate cements decrease with the cement's age. This phenomenon is explained by the setting reaction in which these cations are liberated from the oxide powder by an exchange with protons from the polyacid and in this state are vulnerable to water leaching. Subsequently, these cations become bound to the polyanion chain and become more resistant to water leaching. Magnesium ions are more easily hydrolyzed than zinc ions because they are less strongly bound to the polyanion chain. Zinc ions are apparently more strongly bound to a polyacid which is a copolymer of acrylic and itaconic acids, than to the homopolymer of acrylic acid. The pattern of elution of ions differs between the different cements, so that measurements after 24 hours cannot be used to predict long-term durability on a comparative basis. This coupled with the slow but continuous loss of ions makes a 24-hour test of doubtful validity. Polycarboxylate cements absorb water that is present in the matrix in loosely bound and tightly bound forms. The ionization of the polyacid to a polyanion during the course of the reaction apparently creates a demand for water, and the cement where the COOH:C ratio in the polyacid is highest absorbs the most water.