Hybrid optical films of TiO2‐triethoxysilane‐capped polythiourethane (TCPTU) with high refractive indices have been prepared via an in situ sol‐gel method. The high refractive index triethoxysilane‐capped polythiourethane (TCPTU) was synthesized by polyaddition of the triethoxysilane‐modified trimercaptothioethylamine (TMTEA) and 2,2′‐dimercaptoethylsulfide (MES) with 2,4‐tolylene diisocyanate (TDI). The titania content in the hybrid films can be adjusted from 0 to 80 wt.‐% by the feed ratio of titania precursor [Ti(OBu)4] to polymer (TCPTU). Both FTIR and DSC analyses indicate that there is chemical bonding between the titania domain and the polymer chain. TGA results suggest that the titania of high content was successfully incorporated into polymer matrices and this series of hybrid films have good thermal properties. AFM measurements indicate that in the hybrid films the titania domains are of nanosize scale and the domain size averagely decreases from 60–80 nm to 5–20 nm with increasing content of titania, and the variation of surface roughness for the hybrid films has the same trend. These may be relative to the content of TCPTU and the interaction between titania and polymer (TCPTU). The refractive indices of the hybrid films at 632.8 nm increased from 1 632 to 1 879 as the titania content varied from 0 to 80 wt.‐%.
Colloids of TiO2, where rutile was the only crystal modification which could be detected, with ca. 2.5 nm average particle diameter were synthesized by hydrolysis of TiCl4 in acidic solutions. The as‐prepared particles were incorporated in polymers such as poly(vinyl alcohol) (PVAL), partially hydrolyzed poly(vinyl acetate) (PVAC88), polyvinylpyrrolidone, and poly(4‐vinylpyridine). Nanocomposites transparent in the visible range were obtained. The highest TiO2 contents in such materials were achieved with PVAL and PVAC88, with TiO2 contents of ca. 35 wt.‐% (i.e. 10.5 vol.‐%). In particular, the nanocomposites with TiO2 contents above 24 wt.‐% acted as efficient UV filters for radiation up to ca. 360 nm. At very low TiO2 contents, an absorption maximum of the embedded TiO2 particles was observed at 225 nm with an extinction coefficient of 140 000 cm?1 and a full width at half maximum of 45 nm, i.e. not only the absorption at the maximum at 225 nm but also at the flank of this band contributed significantly to the broadband UV absorption in the nanocomposites at higher TiO2 fractions. The incorporation of TiO2 enhanced the refractive index of the nanocomposites: for instance a refractive index of 1.609 was measured for a nanocomposite comprising 10.5 vol.‐% TiO2 in PVAL, compared with 1.521 for the pristine polymer.
TEM image of a section of a nanocomposite of poly(vinyl alcohol) and 11 wt.‐% TiO2 (appearing dark). 相似文献
A novel method was developed for the preparation of GRIN plastic rods containing inorganic nanoparticles. Silver nanoparticles were prepared by using W/O (water in oil) reversed micelle technique in the presence of bis(2-ethylhexyl) sulpho-succinate (AOT) surfactant. The effects of w values (w=[H2O]/[AOT]), silver nitrate concentration, AOT/isooctane/H2O ratio, and initiator concentration on the nanoparticle size were investigated. Optical absorption spectra of the micellar samples were recorded on a spectrophotometer at room temperature in the range of 200–900 nm. The nanoparticle size was confirmed by TEM technique. To introduce the nanoparticles into the GRIN plastic rods, methyl methacrylate (MMA) was used instead of isooctane in the organic phase. Nanoparticles were found to increase the refractive index of plastic rods effectively. However, the existence of surfactant may cause the aggregation of nanoparticles leading to the occurrence of light scattering and becoming opaque. We estimated both real image transmission and the three dimensional refractive index distributions of the GRIN plastic rods prepared in this investigation. The results in this investigation suggest that nanoparticles could be used as a dopant to fabricate GRIN plastic rods and increase its refractive index effectively. 相似文献
