The present invention is directed to the preparation of in-situ formation of a series of glass-ceramic composites by the Self-propagating High temperature Synthesis (SHS) technique with advantages of processing simplicity as well as the potential of cost savings. The materials produced by the technique contain crystalline TiB2 phase and have either a pure glassy matrix or a glass matrix with partial devitrification based on the Al2O3—CaO system. The materials can potentially be used for infrared light transmission and for other high temperature applications. These materials can also be produced with relatively high porosity.