The setting reaction of different dental glues, i.e. conventional glassionomer cement (GIC), resin modified glassionomer cement (RMGIC) and composite adhesive were investigated with the thermal activity monitor (TAM). The water content of the materials and the water activity in the specimens were determined with isopiestic measurements after different setting periods. The information extracted from the thermochemical analysis for the setting reaction at different time intervals were further correlated with the material balance of the setting biomaterial. In respect to the practical application of the materials in dentistry we discussed the formation and the mechanical strength of the interfacial layer formed between enamel and orthodontic attachments. The study clearly revealed that the use of the aforementioned techniques, namely calorimetric, adsorption measurements, and the combination with microscopy and spectroscopic techniques is a suitable tool in examining the setting process of dental material. The study further elucidate information on several aspects of bonding orthodontic attachments with GIC to enamel surfaces, evaluation of material properties, future developments of biomaterials and related dental materials for orthodontic, conservative and restoring strategies.