The glass transition temperature of anhydrous amorphous calcium carbonate

Abstract

Amorphous calcium carbonate (ACC) is the least stable polymorph of calcium carbonates. It has been identified to play an important role in nature (e.g., biomineralization and speleothem formation), where it acts as a precursor for the transformation to more stable polymorphs such as calcite. Furthermore, the use of ACC in technical applications requires a robust understanding of the material’s properties. We present the first study that reveals the existence of a glass transition for synthetic and anhydrous ACC. The glass transition occurs at 339 °C. Such measurements are impossible with conventional differential scanning calorimetry (DSC) due to the high tendency of ACC to crystallize. Fast scanning DSC with heating rates of 500 °C/s and higher, however, can be used to separate the endothermic glass transition signature from the exothermic crystallization event since crystallization is shifted to higher temperatures. This allows the detection and quantification of the glass transition for ACC. These observations indicate that ACC is a structural glass and are especially significant because the synthesis of ACC, precipitation from a solution followed by lyophilization, contrasts with the more conventional and well-known route of glass formation–the rapid cooling of a melt. Moreover, we prove that a structural glass can be produced from a simple single-component carbonate system.