Non-Invasive Rayleigh, Raman, and Chromium-Fluorescence Study of Phase Transitions: β-Alumina into γ-Alumina ‘Single’ Crystal and Then to α-Alumina

In many advanced materials production processes, the analysis must be non-invasive, rapid, and, if possible, <i>operando</i>. The Raman signal of the various forms of alumina, especially transition alumina, is very weak due to the highly ionic nature of the Al-O bond, which requires long exposure times that are incompatible with monitoring transitions. Here, we explore the use of the fluorescence signal of chromium, a natural impurity in alumina, and the Rayleigh wing to follow the crystallization process up to alpha alumina. To clarify the assignment of the fluorescence components, we compare the transformation of beta alumina single crystals into transition (gamma and theta) alumina and then into alpha alumina with the transformation of optically transparent alumina xerogel and glass, obtained by very slow hydrolysis-polycondensation of aluminum sec-butoxide, into alpha alumina. Vibrational modes are better resolved in thermally treated single crystals than in thermally treated xerogels. Measurements of the Rayleigh wing, the Boson peak, and the fluorescence signal are easier than those of vibrational modes for studying the evolution from amorphous to alpha alumina phases. The fluorescence spectra allow almost instantaneous (<1 s) quantitative control of the phases present.