Optical and Structural Properties of Composites Based on Poly(urethane) and TiO2 Nanowires

Abstract

This article’s objective is the synthesis of new composites based on thermoplastic polyurethane (TPU) and TiO2 nanowires (NWs) as free-standing films, highlighting their structural and optical properties. The free-standing TPU–TiO2 NW films were prepared by a wet chemical method accompanied by a thermal treatment at 100 °C for 1 h, followed by air-drying for 2 h. X-ray diffraction (XRD) studies indicated that the starting commercial TiO2 NW sample contains TiO2 tetragonal anatase (A), cubic Ti0.91O (C), and orthorhombic Ti2O3 (OR), as well as monoclinic H2Ti3O7 (M). In the presence of TPU, an increase in the ratio between the intensities of the diffraction peaks at 43.4° and 48° belonging to the C and A phases of titanium dioxide, respectively, is reported. The increase in the intensity of the peak at 43.4° is explained to be a consequence of the interaction of TiO2 NWs with PTU, which occurs when the formation of suboxides takes place. The variation in the ratio of the absorbance of the IR bands peaked at 765–771 cm−1 and 3304–3315 cm−1 from 4.68 to 4.21 and 3.83 for TPU and the TPU–TiO2 NW composites, respectively, with TiO2 NW concentration equal to 2 wt.% and 17 wt.%, indicated a decrease in the higher-order aggregates of TPU with a simultaneous increase in the hydrogen bonds established between the amide groups of TPU and the oxygen atoms of TiO2 NWs. The decrease in the ratio of the intensity of the Raman lines peaked at 658 cm−1 and 635 cm−1, which were assigned to the vibrational modes Eg in TiO2 A and Eg in H2Ti3O7 (ITiO2-A/IH2Ti3O7), respectively, from 3.45 in TiO2 NWs to 0.94–0.96 in the TPU–TiO2 NW composites, which indicates that the adsorption of TPU onto TiO2 NWs involves an exchange reaction of TPU in the presence of TiO2 NWs, followed by the formation of new hydrogen bonds between the -NH- of the amide group and the oxygen atoms of TixO2x-mn, Ti2O3, and Ti0.91O. Photoluminescence (PL) studies highlighted a gradual decrease in the intensity of the TPU emission band, which is situated in the spectral range 380–650 nm, in the presence of TiO2 NW. After increasing the TiO2 NW concentration in the TPU–TiO2 NW composite mass from 0 wt.% to 2 wt.% and 17 wt.%, respectively, a change in the binding angle of the TPU onto the TiO2 NW surface from 12.6° to 32° and 45.9°, respectively, took place.