Solid state NMR and X-ray studies of the structural evolution of nanocrystalline zirconia

A combination of X-ray techniques [diffraction and Zr K-edge absorption (EXAFS and XANES)] and multinuclear (H-1, C-13, O-17) solid-state NMR spectroscopy is employed to follow in detail the structural development of nanocrystalline zirconia. O-17 magic-angle spinning NMR spectroscopy of sol-gel produced undoped ZrO2 shows unequivocally that oxygen sites in the initial gel are monoclinic-like. This result is consistent with X-ray absorption measurements, which also suggest that the structures of the initial amorphous phases of doped and undoped samples produced by the hydroxide-precipitation and sol-gel methods are very similar. On crystallization, the local structure of the crystalline component is tetragonal, but a significant fraction of the sample remains disordered. Heating to higher temperatures results in conversion to monoclinic zirconia in undoped samples at room temperature. For sol-gel-produced ZrO2, C-13 NMR shows that loss of all of the organic fragments occurs prior to crystallization. The H-1 NMR experiments determined that the proton content remains significant until well above the crystallization temperature, so that the composition is not accurately described as ZrO2 until > 500 degreesC.