Quantification of the toxic hexavalent chromium content in an organic matrix by X-ray photoelectron spectroscopy (XPS) and ultra-low-angle microtomy (ULAM)

Highlights: • Common methods are not suitable for a reliable determination of Cr(VI) in organic coatings on steel. • Our proposed method is a combination of XPS and ultra-low-angle microtomy (ULAM). • The results allow referring to legal regulations of the Cr(VI) concentration. • For this method no accurate sample parameters are required. - Abstract: Cr(VI) is known for its corrosion inhibitive properties and is, despite legal regulations, still a potential candidate to be added to thin (1–3 μm) protective coatings applied on, e.g., electrical steel as used for transformers, etc. However, Cr(VI) is harmful to the environment and to the human health. Hence, a reliable quantification of it is of decisive interest. Commonly, an alkaline extraction with a photometric endpoint detection of Cr(VI) is used for such material systems. However, this procedure requires an accurate knowledge on sample parameters such as dry film thickness and coating density that are occasionally associated with significant experimental errors. We present a comprehensive study of a coating system with a defined Cr(VI) pigment concentration applied on electrical steel. X-ray photoelectron spectroscopy (XPS) was employed to resolve the elemental chromium concentration and the chemical state. Turning to the fact that XPS is extremely surface sensitive (<10 nm) and that the lowest commonly achievable lateral resolution is a number of times higher than the coating thickness (∼2 μm), a bulk analysis was achieved with XPS line scans on extended wedge-shaped tapers through the coating. For that purpose a special sample preparation step performed on an ultra-microtome was required prior to analysis. Since a temperature increase leads to a reduction of Cr(VI) we extend our method on samples, which were subjected to different curing temperatures. We show that our proposed approach now allows to determine the elemental and Cr(VI) concentration and distribution inside the coating.