FOURIER TRANSFORM INFRARED STUDIES OF POLY (ETHYLENE TEREPHTHALATE) FILM IN THE GLASS TRANSITION REGION

Three specimens from a solution-cast poly (ethylene terephthalate) (PET) film, one being liquid-N_2 quenched from 92℃(Q), one being slowly cooled from 92℃(SC) and one being quenched and sub-T_g annealed at 67℃(AN), have been studied by specimen difference spectra Q-SC and AN-Q and temperature difference spectra T-70 and T_2-T_1 for every 2℃steps on heating to 90℃at 2℃/min. SC and AN showed more gauche conformers than Q. That means that the PET chain has more trans conformers at higher temperatures and some of these are frozen during quenching through T_g. A band at 1340 cm~(-1) has been found to be complex containing overlapping bands reflecting trans in crystalline regions and trans in amorphous regions. The temperature difference spectra on heating through T_g showed that the spectral changes in Q are gradual while a rather abrupt change occurs in AN at 80—82℃for the bands at 1340, 1042 and 1020 cm~(-1). No new conformational structure or new vibrational mode is involved. A kind of locking mechanism is suggested which hinders the molecular vibrational changes in AN below T_g until a sudden release occurs at T_g. These locking sites can be nothing else than sites of tighter local packing of chain segments. Consequently it is believed that inter-chain van der Waals attraction energy plays a dominating role in the volume relaxation and sub-T_g annealing of quenched amorphous polymers.     

TiO2 and SnO2@TiO2 hollow spheres assembled from anatase TiO2 nanosheets with enhanced lithium storage properties

TiO(2) and SnO(2)@TiO(2) hollow spheres assembled from anatase TiO(2) nanosheets with exposed (001) high-energy facets are constructed via a templating approach, and the as-prepared samples exhibit enhanced lithium storage properties.     

Engineering nonspherical hollow structures with complex interiors by template-engaged redox etching

Despite the significant advancement in making hollow structures, one unsolved challenge in the field is how to engineer hollow structures with specific shapes, tunable compositions, and desirable interior structures. In particular, top-down engineering the interiors inside preformed hollow structures is still a daunting task. In this work, we demonstrate a facile approach for the preparation of a variety of uniform hollow structures, including Cu(2)O@Fe(OH)(x) nanorattles and Fe(OH)(x) cages with various shapes and dimensions by template-engaged redox etching of shape-controlled Cu(2)O crystals. The composition can be readily modulated at different structural levels to generate other interesting structures such as Cu(2)O@Fe(2)O(3) and Cu@Fe(3)O(4) rattles, as well as Fe(2)O(3) and Fe(3)O(4) cages. More remarkably, this strategy enables top-down engineering the interiors of hollow structures as demonstrated by the fabrication of double-walled nanorattles and nanoboxes, and even box-in-box structures. In addition, this approach is also applied to form Au and MnO(x) based hollow structures.     

Polycrystalline silicon thin films prepared by Ni silicide induced crystallization and the dopant effects on the crystallization

Intrinsic and doped polycrystalline silicon thin films were grown by the Ni silicide seeds induced crystallization. The Ni first reacted to Si forming a silicide seeds, then these seeds act as nuclei, from which the grains start to grow laterally. Compared with traditional Ni induced lateral crystallization, polycrystalline silicon thin film was grown by Ni silicide induced crystallization with low Ni contamination and large grain sizes. It can be found that the Ni silicide induced crystallization rate is accelerated by p-type doping and is decelerated by n-type doping. And the slightly and strongly phosphorous-doped polycrystalline silicon can be obtained with different grain shapes. Also, the sheet resistance of doped polycrystalline silicon decreases with the increasing of the doping atoms. A reasonable explanation is presented for the dopant effects on the growth rate, microstructure and electronic properties of the samples.     

In‐situ stress suppression of hydrogenated a‐CNx film prepared via Ar gas introduction

Evolution of hydrogenated amorphous carbon nitride films was investigated with an introduction of Ar gas in the deposition. The results showed that compressive stress of the films decreased versus an increase of Ar flow rate. Especially, at an Ar flow rate of 5 sccm the film exhibited lower compressive stress, higher hardness and lower root‐mean‐square (rms) roughness than the films deposited without Ar gas introduction. Structural analysis showed that the films with higher hardness, low compressive stress and lower rms roughness had relatively high sp² and nitrogen content. It was attributed to the assistance of Ar plasma, which can cause N atom to enter graphite ring easily and form curved graphite microstructure. Copyright © 2016 John Wiley & Sons, Ltd.     

Fabrication of Heterostructured Fe2TiO5–TiO2 Nanocages with Enhanced Photoelectrochemical Performance for Solar Energy Conversion

Photocatalysts with well-designed compositions and structures are desirable for achieving highly efficient solar-to-chemical energy conversion. Heterostructured semiconductor photocatalysts with advanced hollow structures possess beneficial features for promoting the activity towards photocatalytic reactions. Here we develop a facile synthetic strategy for the fabrication of Fe₂TiO₅–TiO₂ nanocages (NCs) as anode materials in photoelectrochemical (PEC) water splitting cells. A hydrothermal reaction is performed to transform MIL-125(Ti) nanodisks (NDs) to Ti–Fe–O NCs, which are further converted to Fe₂TiO₅–TiO₂ NCs through a post annealing process. Owing to the compositional and structural advantages, the heterostructured Fe₂TiO₅–TiO₂ NCs show enhanced performance for PEC water oxidation compared with TiO₂ NDs, Fe₂TiO₅ nanoparticles (NPs) and Fe₂TiO₅–TiO₂ NPs.     

Reflection–absorption infrared spectroscopy investigation of the crystallization kinetics of poly(ethylene terephthalate) ultrathin films

Reflection–absorption infrared spectroscopy was used to study the crystallization behavior of poly(ethylene terephthalate) (PET) ultrathin films. The crystallinity of ultrathin films was estimated by the fraction of trans conformers of PET. The isothermal and nonisothermal crystallization kinetics of ultrathin films with different thicknesses were investigated. The thinner PET film showed slower kinetics during isothermal crystallization than the thicker film. Moreover, the final crystallinity of films with various thicknesses were reduced with decreasing thickness. An Avrami equation was used to fit the acquired results. The Avrami exponents decreased with the film thickness. As for the nonisothermal crystallization, the cold‐crystallization starting temperature shifted to a lower temperature as the film thickness increased. The influence of the substrate on the crystallization kinetics of the films was also studied. The half‐crystallization times and final crystallinities of ultrathin films adsorbed onto a self‐assembled‐monolayer‐treated surface and an untreated substrate were clearly different, although their thickness dependence was similar. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4440–4447, 2004     

Luminescence functionalization of SBA-15 by YVO4:Eu3+ as a novel drug delivery system

Luminescence functionalization of the ordered mesoporous SBA-15 silica was realized by depositing a YVO4:Eu3+ phosphor layer on its surface via the Pechini sol-gel process, resulting in the formation of the YVO4:Eu3+@SBA-15 composite material. This material, which combines the mesoporous structure of SBA-15 and the strong red luminescence property of YVO4:Eu3+, can be used as a novel functional drug delivery system. The structure, morphology, porosity, and optical properties of the materials were well characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, N2 adsorption, and photoluminescence spectra. As expected, the pore volume, surface area, and pore size of SBA-15 decrease in sequence after deposition of the YVO4:Eu3+ layer and the adsorption of ibuprofen (IBU, drug). The IBU-loaded YVO4:Eu3+@SBA-15 system still shows the red emission of Eu3+ (617 nm, 5D0-7F2) under UV irradiation and the controlled drug release property. Additionally, the emission intensity of Eu3+ increases with an increase in the cumulative released amount of IBU in the system, making the extent of drug release easily identifiable, trackable, and monitorable by the change of luminescence. The system has great potential in the drug delivery and disease therapy fields.