受抑全内反射的偏振分光器

概述了薄膜偏振分光器的研究现状及其主要特点,对不同于MacNeille设计原理的受抑全内反射偏振分光器进行了研究,这种偏振分光器基于受抑全内反射和薄膜干涉原理,当入射角大于临界角时,在宽波段宽角度范围内反射P偏振光,透射S偏振光。重点分析这种偏振分光器的设计原理,设计了波长范围为420￣680 nm、空气中的入射角范围为±10°、膜系的消光比为TS/TP≥1000的用于背投系统的薄膜偏振分光器。     

DAC/FTIR和GC/FTIR联用技术鉴定爆炸残留物

来自爆炸现场的爆炸残留物样品一般呈微粒状。利用配置高压金刚石池(AC)的傅里叶变换红外光谱仪(DAC/FTIR)可以检验小至1微克重的炸药微粒,测试样品在高压条件下,其红外吸收频率会向高波数位移。利用大口径熔融石英毛细管柱气相色谱与傅里叶变换红外光谱联用技术(GC/FTIR)可以分离、鉴定炸药混合物和现场提取的爆炸残留物。     

Deposition characteristics of low dielectric constant siof films prepared by ECR PECVD

SiOF film has attracted significant attention as a new interlayer dielectric material since it exhibits a lower dielectric constant than SiO₂. In this study, we prepared SiOF films by using the electron cyclotron resonance plasma-enhanced chemical vapor deposition (ECR PECVD) method and observed the dependence of the film properties on such various deposition parameters as the SiF₄/O₂ flow rate ratio, substrate temperature, microwave power and pressure. The increase in the film’s fluorine content led to a decrease in the dielectric constants. This was due to a decrease in ionic polarization rather than to a decrease in electronic polarization. The film properties have not exhibited a large dependence on the substrate temperature, in the range of 25~200°C. When the plasma was not activated, i. e. when the microwave power was as low as 300 W or the pressure was higher than 5 mTorr, the dielectric constants of the films were lower than 3.0 because of the high fluorine content, but the films contained silicon difluoride (Si-F₂) bonds. Since Si-F₂ bonds play a critical role in the absorption of water molecules which causes an increase in the dielectric constants of the films, the deposition conditions where the Si-F₂ bonds are formed should be avoided.     

Stability and excitation of potassium promoter in iron catalysts – the role of KFeO2 and KAlO2 phases

The kinetics of the NO SCR with propane has been studied on a low‐exchanged Cu‐ZSM‐5 catalyst. The study of the kinetics of individual reaction stages (2‐nitrosopropane isomerization to acetone oxime and reaction of adsorbed acetone oxime with gaseous NO) has shown that the NO reaction with acetone oxime is the rate‐determining stage in the whole chain of transformations leading to the formation of molecular nitrogen in the low‐temperature region below 300 °C. The kinetic analysis of the reaction has revealed that at the temperatures above 300 °C propane plays a more important role. This revised version was published online in July 2006 with corrections to the Cover Date.     

Analysis of oxidation states of vanadium in vanadia–titania catalysts by the IR spectra of adsorbed NO

Adsorption of NO on vanadia–titania samples pre-subjected to different reduction treatments has been studied by FTIR spectroscopy. When the NO adsorption is performed at 85 K on oxidized samples, antisymmetric NONO species, typical for V⁵⁺ sites, are detected and characterized by bands at 1779 and 1686 cm⁻¹. At ambient temperature, however, adsorption is negligible and only with time reactive adsorption occurs producing NO⁺ (2120 cm⁻¹), nitro/nitrato species (bands in the 1650–1100 cm⁻¹ region) and weakly adsorbed NO (broad band at 1915 cm⁻¹). Adsorption of NO at ambient temperature on reduced samples results in the formation of two types of species: (i) V⁴⁺(NO)₂ dinitrosyls characterized by ν_s(NO) and ν_as(NO) at 1903–1880 and 1769–1753 cm⁻¹, respectively, and (ii) V³⁺(NO)₂ complexes, which give rise to ν_s(NO) at 1834–1822 cm⁻¹ and ν_as(NO) at 1697–1685 cm⁻¹. At low temperature the dinitrosyls are transformed into species in which more than one (NO)₂ dimer is attached to one cationic site. Addition of O₂ to NO, preadsorbed on reduced vanadia–titania samples, results in a fast oxidation of the V³⁺(NO)₂ species, whereas the V⁴⁺(NO)₂ complexes are more stable and do not disappear completely in the presence of oxygen. The results obtained suggest that NO is a convenient probe molecule for the analysis of the oxidation state of vanadium in vanadia–titania catalysts. To prevent oxidation of reduced vanadium sites, low equilibrium pressures of NO and registration of the IR spectrum soon after the NO admission are recommended. This revised version was published online in August 2006 with corrections to the Cover Date.     

Thermal oxidative process in extra-virgin olive oils studied by FTIR,rheology and time-resolved luminescence

With the aim to characterise the antioxidant properties of different extra-virgin olive oils and to understand in more detail the mechanisms of oil degradation, we have made an experimental study on thermal induced oxidative processes of extra-virgin olive oils by using different techniques: Fourier Transform Infrared (FTIR) spectroscopy, rheology and time-resolved luminescence. The oxidation process was followed at three different heating temperatures (30, 60 and 90 °C) as a function of time up to 35 days. Thermal treatment induced changes in the FTIR spectra in the wavenumbers region 3100–3600 cm⁻¹: in particular, the absorption profiles show an initial formation of hydroperoxides and a subsequent increase of alcohols and secondary oxidation products. In agreement with the FTIR data, rheology measurements show that after thermal treatment all examined samples exhibit an increase in the viscosity values with respect to pristine ones, indicating that the heat treatment induces the formation of polar molecules with propensity to form hydrogen bonds, which has as a consequence a viscosity increase. Finally, a lifetime increase of luminescence of chlorophyll is observed in agreement with the viscosity rise. Indeed, the viscosity increase reduces the frequency of collisions between the chromophore and its environment, consequently lowering the non-radiative contribution to the luminescence decay.     

The use of spectroscopic measurements from full scale industrial production to achieve stable end product quality

The present study was conducted to investigate different approaches to improve product quality in an industrial setting, by utilizing spectroscopic measurements for process optimization where data are obtained directly from full scale production. The approach taken is to utilise spectroscopic techniques as a fingerprint of uncontrollable raw material variation. The FTIR spectra were used to predict the end product characteristics along with the process parameters instead of predicting previously defined characteristics of the raw material. The present case under study is from cheese production aiming for reduced variation in the dry matter content of the final product. Fourier transform infrared spectra (FTIR) are available at the plant, but not fully utilized. The results from the study showed that the FTIR spectra do contain significant information relevant for the end product characteristics which is not yet utilized, suggesting that FTIR spectra can be used for process optimisation to improve the stability of the quality. Different strategies to incorporate the spectral data are presented, and the usefulness of full scale production for process optimisation is discussed. The present study also contains optimisation of the production based on data modelling of the raw material variation, the process settings and the product quality over a long time period.     

Thermal decomposition behavior of tobacco stem Part I: TGA–FTIR–MS analysis

In the present study, the thermal degradation behavior of tobacco stem was examined by means of a thermogravimetric analyzer (TGA) under nitrogen atmosphere at temperature range of 25–1,000°C. The TG curve indicated that the pyrolysis process of tobacco included three zones, and main pyrolysis occurred in the second zone by means of the decomposition of hemicellulose, cellulose, and lignin in a temperature range of 180–540°C. Furthermore, the gases evolved during the degradation were analyzed simultaneously via TGA coupled with a Fourier transform infrared spectrometer (FTIR) and mass spectrometer (MS). Carbon dioxide, methane, water, formaldehyde, and propanal were the main volatiles detected via MS and confirmed by FTIR.     

超细粉碎对煤表面性质及超净煤分选的影响

为探讨超细粉碎对煤表面性质及絮团和超净煤分选的影响，选取淮南气煤(HN)和太西无烟煤(TX)2种不同变质程度的煤样，利用傅里叶红外光谱仪（FTIR）、ζ电位仪、比表面分析仪、微量热仪分析了不同超细粉碎时间后煤颗粒表面官能团、电位以及润湿性的变化，分别研究了粒度、表面电位和润湿性对絮团形成的影响，结合超净煤的分选结果，综合探讨了超细粉碎、表面性质变化、絮团形成以及超净煤分选的关系。结果表明：超细粉碎改变了煤粒表面的亲水基和疏水基的比例；随着粒度的减小，太西煤的电动电位绝对值先减小后增大，在粒度8.30 μm时电负性最弱，润湿热出现小的峰值，搅拌过程中形成的大尺度絮团较多，在乳化柴油用量67.62 kg/t时，分选出的超净煤灰分0.68%，产率高达97.26%；而淮南煤随着粒度的减小，电负性逐渐增强，润湿热单调递减，润湿性逐渐减弱，在相同搅拌强度下，细颗粒形成的大尺度絮团减少，分选出的超净煤产率降低；分散剂的加入有效地降低了淮南气煤分选出超净煤的灰分，粒度越小，灰分减小愈明显。     

Simultaneous monitoring of the transport of anions and cations across polypyrrole based composite membranes

A mechanism for the macroscopic charge balance during the transport of anions and cations across polypyrrole based composite membranes is proposed. For the mechanism to be studied, anions and cations were monitored simultaneously across PPy based composite membranes, which are known to have cation exchange (PPy(PSS)), anion exchange (PPy(ClO₄)) and mixed ion exchange properties (PPy(pTS)). Even though none of the membranes were found to be completely permselective, the flux of cations was higher than that of anions across the PPy(PSS) composite membrane, while the flux of anions was higher than that of cations across the PPy(ClO₄) composite membrane. Distinct changes in pH of the receiving solution were also observed. These were a decrease in pH when a predominantly anion exchanging polypyrrole composite membrane was used, and an increase in pH when a membrane that maintains charge balance principally by cation exchange was used. When membranes which display approximately equal permeability towards anions and cations were used the pH of the receiving solution was ca. 6–8. There was only a negligible flux of Ca²⁺ across the PPy(PSS) membrane in the transport experiments carried out with the source solution consisting of either Ca(NO₃)₂ or an equimolar mixture of KNO₃ and Ca(NO₃)₂. The PPy(PSS) composite membrane was impermeable towards NO₃⁻ ions when the source solution was Ca(NO₃)₂ but permeability towards NO₃⁻ was observed when the source solution was either KNO₃ or an equimolar mixture of KNO₃ and Ca(NO₃)₂.