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With Angle Resolved XRF (AR-XRF) the sample is investigated at different angles of detection and irradiation. The geometry of analysis indeed affects the intensity of the characteristic elemental fluorescence signal of the sample, which depends on the element distribution inside the sample. This technique has already proved to be very useful in analyzing metallic bilayer samples. In this paper, we applied AR-XRF to study a real case in the field of Cultural Heritage, with the analysis of a glazed ceramic coming from Puebla, Mexico. The analysis of the decorations, which present different thicknesses and compositions, has shown the limits of the technique, especially in the case of thick and diffused layers, and the importance of a priori knowledge to retrieve structural information in the case of a complex system with a great number of variables.
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