Morphological changes in UO based on calcination temperature have been quantified enabling a morphological feature to serve as a signature of processing history in nuclear forensics. Five separate calcination temperatures were used to synthesize α-UO, and each sample was characterized using powder X-ray diffraction (p-XRD) and scanning electron microscopy (SEM). The p-XRD spectra were used to evaluate the purity of the synthesized U-oxide; the morphological analysis for materials (MAMA) software was utilized to quantitatively characterize the particle shape and size as indicated by the SEM images. Analysis comparing the particle attributes, such as particle area at each of the temperatures, was completed using the Kolmogorov-Smirnov two sample test (K-S test). These results illustrate a distinct statistical difference between each calcination temperature. To provide a framework for forensic analysis of an unknown sample, the sample distributions at each temperature were compared to randomly selected distributions (100, 250, 500, and 750 particles) from each synthesized temperature to determine if they were statistically different. It was found that 750 particles were required to differentiate between all of the synthesized temperatures with a confidence interval of 99.0%. Results from this study provide the first quantitative morphological study of U-oxides, and reveals the potential strength of morphological particle analysis in nuclear forensics by providing a framework for a more rapid characterization of interdicted uranium oxide samples.

The analytical techniques typically utilized in a nuclear forensic investigation often provide limited information regarding the process history and production conditions of interdicted nuclear material. In this study, scanning electron microscopy (SEM) analysis of the surface morphology of amorphous-UO samples calcined at 250, 300, 350, 400, and 450°C from uranyl peroxide was performed to determine if the morphology was indicative of the synthesis route and thermal history for the samples. Thermogravimetic analysis-mass spectrometry (TGA-MS) and differential scanning calorimetry (DSC) were used to correlate transitions in the calcined material to morphological transformations. The high-resolution SEM images were processed using the Morphological Analysis for Material Attribution (MAMA) software. Morphological attributes, particle area and circularity, indicated significant trends as a result of calcination temperature. The quantitative morphological analysis was able to track the process of particle fragmentation and subsequent sintering as calcination temperature was increased. At the 90% confidence interval, with 1000 segmented particles, the use of Kolmogorov-Smirnov statistical comparisons allowed discernment between all calcination temperatures for the uranyl peroxide route.

The hydration and morphological effects of amorphous (A)-UO 3 following storage under varying temperature and relative humidity have been investigated. This study provides valuable insight into U-oxide speciation following aging, the Uoxide quantitative morphological data set, and, overall, the characterization of nuclear material provenance. A-UO 3 was synthesized via the washed uranyl peroxide synthetic route and aged based on a 3-factor circumscribed central composite design of experiment. Target aging times include 2.57, 7.00, 14.0, 21.0, and 25.4 days, temperatures of 5.51, 15.0, 30.0, 45.0, and 54.5 °C, and relative humidities of 14.2, 30.0, 55.0, 80.0, and 95.8% were examined. Following aging, crystallographic changes were quantified via powder X-ray diffraction and an internal standard Rietveld refinement method was used to confirm the hydration of A-UO 3 to crystalline schoepite phases. The particle morphology from scanning electron microscopy images was quantified using both the Morphological Analysis of MAterials software and machine learning. Results from the machine learning were processed via agglomerative hierarchical clustering analysis to distinguish trends in morphological attributes from the aging study. Significantly hydrated samples were found to have a much larger, plate-like morphology in comparison to the unaged controls. Predictive modeling via a response surface methodology determined that while aging time, temperature, and relative humidity all have a quantifiable effect on A-UO 3 crystallographic and morphological changes, relative humidity has the most significant impact.

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The morphological changes that take place during the processing and storage of uranium oxides can provide valuable information on the processing history and storage conditions of an interdicted sample. In this study microstructural changes in two uranium oxides (UO2 and U3O8) due to changes in the aging conditions at elevated temperatures were quantified and modeled using a response surface methodology approach. This allowed the morphological changes to be used as a signature for the aging conditions for nuclear forensic analysis. A Box-Behnken design of experiment was developed using the independent variables: temperature from 100 to 400 °C, aging times from 2 to 48 h, and partial pressure of ${{\rm{O}}_2}({{\rm{P}}_{{{\rm{O}}_{\rm{2}}}}})$ between ~0.0 kPa and 21.3 kPa. The design of experiment consisted of 54 samples per uranium oxide. Each aged sample was characterized using scanning electron microscopy (SEM) for image analysis. Utilizing the Morphological Analysis for Materials (MAMA) software package, particle size and shape were quantified using the acquired SEM images. Analysis of the particle attributes was completed using the Kolmogorov–Smirnov two sample test (K–S test) to determine if the particle size and shape distributions were statistically distinct. This data was then used to create response surfaces of the quantitative morphological changes based on the developed design of experiment. The U3O8 samples showed no statistically quantifiable differences due to the aging conditions. However, the UO2 samples had distinct morphological changes due to the experimental aging conditions. Specifically, the temperature factor had an increasing effect on the particle area, and a decreasing effect on particle circularity.

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