Prediction of unknown uranyl oxide hydrate structure types: Comparison of calculated and measured XRD powder patterns

The accurate identification of uranium-bearing corrosion products from spent fuel leaching studies is often difficult because the XRD powder patterns for many U(VI) phases are closely similar. Standard pattern-matching techniques commonly used for phase identification (e.g., JCPDS) make confident phase identification difficult and can oversimplify complex mixtures of UOHs. Refinement methods that fit the full XRD powder pattern, such as Rietveld, may be the only methods for accurate UOH identification, especially for data from sample mixtures. Rietveld refinement of XRD powder data for uranium oxides can be accomplished for phases whose structures are well defined. Unfortunately, many of the uranyl oxide hydrates are still ill-defined, both structurally and compositionally. The uranyl oxide hydrates have large unit cells and relatively low symmetries, as well as close structural similarities, all of which complicates the simultaneous refinement of mixed UOH phases. Modeling peak shape profiles can also hamper refinements of mixed-UOH samples due to extreme peak overlap. Because of these difficulties, Rietveld structure determination for UOHs from sample mixtures remains intractable, although structure determination may be possible for fine-grained, single-phase samples. Nonetheless, Rietveld refinement is the most promising method for accurately identifying the component phases in a mixture, but the unknown UOH structures must be determined before this technique can be applied successfully