The specific aim of this paper is to measure the optical constants of fresh varnish layers up to a thickness of 10 μm by spectroscopic ellipsometry. It is the first time that this technique has been used in artwork conservation and it may prove very promising due to its nondestructive character. Samples of fresh dammar varnish (natural resin) and Paraloid B72 (synthetic resin) applied on glass and carbon black acrylic paint were analyzed. Both varnishes were considered as perfect dielectrics, and the real part of their refractive index was described by the Cauchy model: <i>n</i> (λ) = <i>A</i> + <i>B</i>/λ<sup>2</sup> + C/λ<sup>4</sup>. The Cauchy coefficients for dammar varnish and Paraloid B72 were then determined for layers of known thickness. The ellipsometric data were fitted to a model, which includes a mixed varnish–air layer. The optical properties of this layer were calculated by the Bruggeman effective medium approximation. In the case of carbon black acrylic paint, another mixed layer (paint–varnish) was added to the model. The results are very close to the values given in the literature. Given the measurement reproducibility, the results show that ellipsometry can discriminate between dammar varnish and Paraloid B72. This is very important in artwork conservation studies, because it has been done by time-consuming, destructive techniques up to now. Future work includes measurements of other types of natural and synthetic varnishes, in an attempt to introduce a nondestructive method for picture varnish identification and aging studies.

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