**Pieter Samyn**

Applied and Analytical Chemistry, Institute for Materials Research (IMO-IMOMEC), University of Hasselt, B-3590 Diepenbeek, Belgium; pieter.samyn@uhasselt.be; Tel.: +32-11-26-8594

Received: 11 February 2018; Accepted: 20 March 2018; Published: 24 April 2018

**Abstract:** The creation of functional papers requires a specific deposition of chemical moieties at the surface. In particular, water-repellent barrier coatings can be formed by the deposition of (poly(styrene-co-maleimide) nanoparticles filled with different vegetable oils. The analysis of coated paper surfaces by dispersive Raman spectroscopy allows for statistical classification of different coating types and chemical mapping of the lateral surface distribution of the coating components. The Raman spectra were used to quantify the amount of free oil and imide content. The partial least squares model with three principal components (PC) could differentiate between the type of oil (degree of saturation in PC-1), coating thickness (cellulose bands of paper substrate in PC-2), and organic coating phase (styrene, imide in PC-3). The chemical surface maps with average intensities indicate coating inhomogeneities for thin coatings located near the organic coating components, while the presence of free oil acts as a natural binder in between the organic phase and provides a more homogeneous coating. Depending on the type of oil, a higher amount of free oil coincides with lower imide content at the surface. The surface coverage of polyunsaturated oils overlaps relatively well with the areas of organic coating components, as the oil is largely encapsulated. The surface coverage for mono- and unsaturated oils is rather complementary to the organic phase as there are larger amounts of free oil. The latter is confirmed by single wavenumber maps and image processing constructing composite chemical surface maps.

**Keywords:** paper; coating; surface; Raman; microscopy; mapping
