Composite films of nanosized TiO2 particles, which contained rutile as the only detected crystal modification, and poly(vinyl alcohol), poly(vinyl pyrrolidone) or poly(4-vinylpyridine) were prepared from aqueous dispersions. During exposure to UV irradiation the nanocomposites comprising poly(vinyl alcohol) or poly(vinyl pyrrolidone) turned blue as a consequence of a partial reduction of TiIV to TiIII. The color intensity increased with increasing TiO2 content and irradiation time. This color did not fade after removal of the UV source in spite of the sensitivity of TiIII to atmospheric oxygen. By contrast, exposure to water caused the nanocomposites to adopt their original colorless appearance. These colorization-decolorization cycles could be repeated more than 10 times without apparent loss of intensity. Due to the small size of the TiO2 nanoparticles (ca. 3 nm), patterned blue structures of high resolution could be created in the polymeric materials, for instance with simple masking methods.
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