We report on picosecond time resolved spectroscopy of photogenerated infrared active vibrations in thin films of 2,5-dioctyloxy poly(phenylene vinylene). We excited the films by ?4 ps long pulses of 565 nm laser light with 2×1013 photons/cm2 per pulse and repetition rate of 76 MHz. We then followed the temporal evolution of the infrared active vibrational (IRAV) spectrum using a subsequent, variably delayed, weak tunable IR probe pulses of similar temporal duration. Under these conditions, we show clear spectroscopic evidence for photogenerated infrared active vibrations at times which are shorter than our temporal resolution (<4 ps). We suggest that the transient IRAV absorption is due to secondary polarons formation following exciton dissociation. 相似文献
TeMxMo1.7O mixed oxides (M = V and/or Nb; x = 0-1.7) have been prepared by calcination of the corresponding salts at 600 °C in an atmosphere of N2. A new crystalline phase, with a Te/V/Mo atomic ratio of 1/0.2-1.5/1.7, has been isolated and characterised by XRD and IR spectroscopy. This phase is observed in the TeVMo or TeVNbMo mixed oxide but not in the TeNbMo mixed oxide. The new crystalline phase shows an XRD pattern similar to Sb4Mo10O31 and probably corresponds to the M1 phase recently proposed by Aouine et al. (Chem. Commun. 1180, 2001) to be present in the active and selective MoVTeNbO catalysts. Although these catalysts present a very low activity in the propane oxidation, they are active and selective in the oxidation of propene to acrolein and/or acrylic acid. However, the product distribution depends on the catalyst composition. Acrolein or acrylic acid can be selectively obtained from propene on Nb-free or Nb-containing TeVMo catalysts, respectively. The presence of both V and Nb, in addition to Mo and Te, appears to be important in the formation of acrylic acid from propene. 相似文献
Filiform corrosion is mainly considered as a cosmetic attack and is undesirable in most applications. The initiation and propagation of the filaments are related to different parameters such as the presence of defects, the permeability of the coating to water and oxygen, the adherence of the paint system and the presence of salts.
The aim of this work is to study the behaviour of painted aluminium samples towards filiform corrosion or delamination. The 6082 Aluminium alloy was selected and the samples were covered with a cataphoretic epoxy primer without lead (PPG Industries France). Prior to the application of the electrocoat, the samples were pre-treated by a commercial Zr/Ti or chromate conversion treatment or simply etched with a commercial acid etching product.
Filiform corrosion was studied by the normalized test (ISO/DIS 4623): painted and scratched samples were inoculated in HCl and exposed in a constant humidity chamber at 40 °C and 82% RH for 3 weeks. After exposure the samples were subjected to a visual and optical microscopic examination.
Electrochemical impedance spectroscopy was used to study the sensitivity to filiform corrosion. The operating mode of this test is similar to the normalized one. The samples were scratched before inoculation for 1 h in HCl and then exposed to the humidity chamber for a maximum of 4 days. The samples were tested by EIS in an acidified 0.1 M Na2SO4 electrolyte solution. The resulting impedance spectra were analyzed with an appropriate equivalent electrical circuit which allows the evaluation of the exposed metallic surface area, directly related to the extent of filiform corrosion or delamination. Different parameters were varied: the exposure time in the humidity chamber; the immersion time in the electrolyte sulphate solution as well as its pH and the coating thickness. 相似文献
Mg-Al hydrotalcites intercalated with five different interlayer anions—CO32−, SO42−, Cl−, HPO42− or terephthalate—were synthesized by either the coprecipitation or ion-exchange method. The structure of the as-synthesized samples and the presence of intended anions in the interlayer gallery of hydrotalcites were determined by X-ray diffraction and FTIR spectroscopy. On calcination at 600 °C the materials were transformed into mixed metal oxides. The kind of the counterbalancing anions present in the parent hydrotalcite influences strongly textural parameters of the obtained Mg-Al oxides. Both temperature-programmed desorption of NH3 and CO2, and test reaction of 2-methyl-3-butyn-2-ol (MBOH) conversion were used to determine the acidity and basicity of the samples. The hydrotalcite derived mixed Mg-Al oxides showed the presence of Brønsted and Lewis acid and base sites. However, the strong basic character of the solids caused that acetone and acetylene were observed as the major products of MBOH conversion. 相似文献
Cure reactions of the stoichiometric mixtures of diglycidyl ether of bisphenol A (DGEBA) and two very low molecular weight aliphatic polyether diamines (PED) were studied by using fluorescence and mid- and near-IR spectroscopic techniques. As the cure proceeded, the primary amine groups in PED are converted to the secondary and the tertiary amines. Near-IR spectral analysis was used to calculate the concentration of the three amine groups as a function of cure time. The decrease in the fluorescence intensity of DGEBA at about 307 nm was observed due to more effective quenching of the tertiary amine groups in PED, in comparison to the primary and the secondary amine groups. A large decrease in fluorescence intensity at 75 and 95 °C cure was observed. The amount of all the amine species was estimated from NIR spectra to shed light on the cure kinetics of PPO (polypropylene oxide) in comparison with PEO (polyethylene oxide) epoxy, as well as to explain their fluorescence behavior.The fluorescence intensity changes were correlated to the extent of epoxy reaction obtained by mid- and near-IR spectroscopy. 相似文献
The structural properties and hydrogen bonding of undoped and phosphorous doped polycrystalline silicon produced by step-by-step laser dehydrogenation and crystallization technique were investigated using Raman spectroscopy and hydrogen effusion measurements. At low laser fluences, EL, a two-layer system is created. This is accompanied by the change in hydrogen bonding. The intensity of the Si–H vibration mode at 2000 decreases faster than the one at 2100 cm−1. This is even more pronounced in phosphorous-doped specimens. The laser crystallization results in an increase of the hydrogen binding energy by approximately 0.2–0.3 eV compared to the amorphous starting materials. 相似文献