We have recently synthetized piezoelectrically active oriented α-quartz thin films with controllable porosity directly on silicon (Science 340, 827−831 (2013)). Polycrystalline α-quartz films bear an epitaxial relationship with the underlying (100) face of the Si substrate. Columnar crystallites are all equally oriented and have a net piezo-electric effect. This mechanism of α-quartz formation needs the presence of Sr+2 or Ba2+ ions to take place and it is still not totally understood. We propose to study a model-system using structured amorphous silica monoliths to which we add Sr2+ (or Ba2+) that acts as heterogeneous catalyser for quartz crystallization. For disentangling the mechanism behind the devitrification-crystallization process of Sr2+-(or Ba2+)-doped amorphous silica monoliths, we intent to follow by in situ neutron thermodiffractometry the whole devitrification process. These studies should provide evidence of whether quartz formation is driven by the presence of intermediate silicate phases that will vanish after thermal treatment and assist the quartz crystallization at the interface during the oxidation process.