Polymorphism of Tricalcium Silicate and Its Solid Solutions

In tricalcium silicate and its solid solutions six modifications were established: one rhombohedral ( R ), two monoclinic ( M _I, M _II), and three triclinic ( T _I, T _II, T _III). All these forms are rhombohedral or pseudorhombohedral and extremely similar; the variations in the X-ray diagrams and the transformation enthalpies are minute. Only three of the five transitions were observed by both X rays and DTA: T _I- T _II (600°), T _III– M _I (980°), and M _I– M _II (990°); one was established by DTA ( T _II– T _III, 920°) and one by X rays only ( M _II– R , 1050°C). This scheme of polymorphism is compared critically with results of other authors, and the nature of the various displacive transformations is discussed. X-ray and DTA investigations of solid solutions of Ca₃SiO₅ with Al₂O₃ and ZnO established the phase relations as functions of temperature and composition. With Al₂O₃, two modifications ( T _I and T _II) were stabilized; and with ZnO, five polymorphs ( T _I T _II, M_I, M _II, and R ). With both pure C₃S and the solid solutions, the results are consistent and have a close bearing on the constitution of alites in portland cement clinker.