The presented study focuses on photoluminescent pigments applied on cotton fabric by a screen-printed procedure using polydimethylsiloxane (PDMS) as a binder. Microscopic data depicts irregular shapes and relatively wide size distribution (3–80 µm) of pigments. Regarding composition, the Energy-Dispersive X-ray (EDX) and Fourier Transform Infrared (FTIR) spectroscopy data complement findings suggesting the presence of Eu-doped strontium aluminate in the yellow-green, calcium aluminate in the violet pigment, and metal oxides in the blue pigment. The optical properties of pigment-enriched PDMS-coated cotton fabric were assessed and reflectance intensity was found to be concentration-dependent only in the blue pigment. The luminescence decay data show that luminescence intensity decreased with the reduction of pigment concentration in the following order, yellow-green > blue > violet pigments. Relying on absorption and emission data of powdered pigments, the confocal microscopy enables visualization of the pigments’ distribution within a 3D image projection. This identifies the most homogeneous distribution in the case of the blue pigment, as well as the presence of a continuous fluorescing signal in the z projection when 5% pigment was used. This was, for the first time, presented as a powerful tool for non-destructive visualization of photoluminescent pigments’ spatial distribution when printed on textile (cotton) fabric. Finally, the photoluminescent PDMS coating demonstrates high washing and abrasion resistance, contributing to overall functionality of printed cotton fabrics when commercial types of pigments are applied.
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