Photo‐chemistry of pigments. Studies on the mechanism of chalking

Studies are presented which demonstrate that: (1) irradiation of titanium and zinc oxide pigments produces singlet oxygen; (2) irradiation of titanium dioxide pigments in water yields, hydrogen peroxide; and (3) the formation of singlet oxygen and hydrogen peroxide correlates with chalking tendencies of the pigments. These findings, together with the results of quenching studies, are interpreted in terms of a working hypothesis, for the generation of reactive oxidants, which ties together previous work into a unified scheme. The relative chalking rates of anatase and rutile titanium dioxide as well as the improvement of chalk resistance by surface treatment, are discussed within the framework of this scheme. The role of singlet oxygen in the chalking process, the importance of its presence with regard to the control of chalking, and possible mechanisms for its formation are also discussed.