XRF, μ-XRD and μ-spectroscopic techniques for revealing the composition and structure of paint layers on polychrome sculptures after multiple restorations

► Novel combined application of recently developed analytical techniques. ► New analytical methodology for the study of complex polychrome structures. ► First article devoted to the study of sculpture cross-sections using laboratory-made micro-XRD systems. ► Study of paint layers on sculptures restored/repainted several times across centuries. ► Identification of pigments used in ancient and recent times on a Gothic polychromed wood sculpture.