Multilayer ytterbium-hafnate/silicate coatings deposited by directed vapor deposition and designed to protect SiC-based ceramic matrix composites were assessed to determine their thermochemical stability and resistance to attack by molten silicate deposits (CMAS). The study revealed that reactions occurring at the interface between Yb2Si2O7 and Yb4Hf3O12 layers promote coating delamination following isothermal annealing for 100h/1500 degrees C while coating architectures involving Yb2SiO5 in contact with Yb4Hf3O12 do not experience similar degradation. The outer Yb4Hf3O12 layers, segmented for compliance, were only moderately effective in mitigating CMAS infiltration at 1300 degrees C and 1500 degrees C. The results indicate that the reaction between the melt and coating forms large volumes of a silicate garnet phase at 1300 degrees C, or a cuspidine-type aluminosilicate at 1500 degrees C, in addition to the apatite and reprecipitated fluorite phases observed in related systems.