Mg.sub.x Al.sub.2-2x Ti.sub.1+x O.sub.5 (x.ltoreq.0.2) protective coatings have been developed for both dense and porous substrates, such as SiC and Si.sub.3 N.sub.4, using a chemical solution processing method involving the hydrolysis and condensation of magnesium, aluminum and titanium precursors. The solution viscosities, pH values, H.sub.2 O/alkoxide molar ratios, and dip coating withdrawal rates which are optimum for crack-free Mg.sub.x Al.sub.2-2x Ti.sub.1+x O.sub.5 (x.ltoreq.0.2) are 1.0 to 6.2 cP, pH 1-4.5, molar ratio 1.5-10, and withdrawal rate of 2.2-8.0 cm/min, respectively. Conversion of the amorphous coating to crystalline Mg.sub.x Al.sub.2-2x Ti.sub.1+x O.sub.5 (x.ltoreq.0.2) is achieved by a succession of calcination below 450.degree. C. and a final heat treatment above 1000.degree. C. for ten hours with controlled heating and cooling rates.