光声位相理论及其在化学中的应用研究进展

光声位相作为光声光谱重要的一部分, 包含着很多有价值的信息, 对它的研究可以获得其它光谱甚至光声振幅谱都不能得到的信息。光声位相在测定样品的光学和热学性质、样品无辐射弛豫过程的研究以及深度剖面分析等方面显示了特有的能力。本文结合本实验室近几年的工作, 在光声光谱理论的基础上,对光声位相理论及其在化学中的应用作一综述。     

Surface and depth-profile analysis using FTIR spectroscopy

Summary The introduction of Fourier Transform techniques and the increasing use of computers in infrared spectroscopy has made new techniques of investigation available to the spectroscopist, such as photoacoustic spectroscopy (PAS) and IR microscopy. These methods now complement the techniques of specular reflectance and attenuated total reflectance. Thin films on metals, sometimes with a thickness of much less than a micron, can be studied by various specular reflectance methods. The physical basis of the attenuated total reflectance technique (ATR) leads to a penetration of the radiation in the order of a few microns. It is, therefore, especially suitable for the investigation of surfaces and of layers close to the surface. By changing the modulation frequency of the IR radiation, i.e. the mirror velocity of the FTIR spectrometer, photoacoustic spectroscopy (PAS) can be employed to study layers at various depths below the surface of a sample. Therefore, this technique allows depth-profile analysis, so that PAS reveals itself as a complementary method to attenuated total reflectance spectroscopy. Samples with inhomogeneous profiles, e.g. laminated polymer films, can often be prepared as microtome slices perpendicular to the layered structure. Using infrared microscopy it is now possible to investigate different regions of the cross-section easily. The size of the regions that can be studied in this way may be as small as a few microns.

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Oberflächen- und Tiefenprofilanalyse mit Hilfe der FTIR-Spektroskopie

     

Polarized FT-IR photoacoustic spectroscopy on polymer fibers

The orientation of macromolecular chains in two melt-spun polymer fibers (segmented polyurethane elastomer and melt-modified polyolefine fibers) was studied by photoacoustic spectroscopy (PAS) with polarized light in the mid-infrared range. The PAS orientation functions calculated from the photoacoustic signal intensities of orientation sensitive bands describe the orientation of the different chain segments with respect to the fiber axis. Thus, the orientation of hard and soft segments in the unstressed polyurethane fiber is different and both are similiar to that of the corresponding injection molded bars. With increased spinning velocity an improved orientation of the polyolefine chains along the fiber axis, but only in the amorphous regions of the polymer, were detected. Only a slight reduction of orientation was measured as a result of the subsequent chemical crosslinking in the polyolefines.     

Frequency-domain photopyroelectric spectroscopy of condensed phases (PPES): A new,simple and powerful spectroscopic technique

A new, powerful, and experimentally very convenient spectroscopic technique is described. The technique uses pyroelectric polyvinylidene difluoride (PVDF) thin film detectors in contact with solid or liquid samples. The instrumental and spectral characteristics of photopyroelectric spectroscopy (PPES) are presented, and its advantages over conventional photoacoustic spectroscopy (PAS) are discussed.     

Applications of photoacoustic step-scan FT-IR spectroscopy to polymeric materials

Thin coatings technology demands that characterization tools are readily available to distinguish between the composition and physical state of the coated layers versus the substrate. In principle, infrared photoacoustic spectroscopy (PAS) possesses all the appropriate features to become a mainstream technique for these types of characterizations. These features include the ability to characterize coatings of a variety of thickness (monolayers to tens of microns) and the fact that the technique requires virtually no sample preparation. One category of such samples involves systems having few micron thin layered structures coated on relatively thick polyester substrates. The phase delay of the photoacoustic signal can be used in conjunction with the knowledge of the thermal properties of the coated fluids in the calculation of the relative as well as the absolute depths of these multi-layered coatings. The phase delay is calculated at wavelengths that are characteristic of the various components of the different layers in the system. The technique is applied to the characterization of a coated system having a submicron layer as the top layer. Step-scan FT-IR photoacoustic data are presented that prove the ability of the technique to successfully isolate the infrared signature of the top layer from the infrared spectrum of the bulk material, proving the sub-micron resolution capability of the method. In addition, results will be shown that underline the fact that the most serious problem in PAS is saturation at high absorptivities.     

小波变换与分析化学信号处理

介绍了小波变换的基本理论并对小波变换的常用算法和应用进行了评述。由于小波变换的时2频局部化性质, 使其成为信号处理的强有力工具。在分析化学领域中, 小波变换在流动注射分析、伏安分析、高效液相色谱、红外光谱、质谱、核磁共振谱、可见-紫外光谱、光声光谱、扩展X-射线吸收精细结构(EXAFS) 谱等分析化学信号的平滑滤噪、数据压缩、重叠信号解析等方面都有成功的应用。     

Multi-frequency S2FTIR PA spectral depth profiling by use of sinusoidal phase modulation and harmonic demodulation up to 2250 Hz (10th harmonic)

Multi-frequency phase modulation for step-scan Fourier transform infrared photoacoustic spectroscopy (S²FTIR PAS) is demonstrated using a single frequency sinusoidal modulation of the interferometer movable mirror with modulation amplitude 5.2 λ_He-Ne. A digital signal processing (DSP) lock-in amplifier is used to demodulate the photoacoustic response at the fundamental phase modulation frequency and its harmonic frequencies. Because the phase modulation is sinusoidal and of the appropriate amplitude, all the even and odd harmonics (up to the 10th harmonic) can be detected with good signal-to-noise ratio (SNR). Applications of this multi-frequency phase modulation approach for photoacoustic depth profiling are demonstrated by the study of a simple two-layered polymer sample. The sampling depth multiplexing advantage (as compared to that obtained with other types of phase modulation) is clearly demonstrated with the analysis of the phase and magnitude of signals at the fundamental frequency and all the harmonic frequencies. This is the first report of using the sinusoidal phase modulation method to easily obtain multi-frequency and high-frequency light modulation for FTIR PAS depth profiling. Although these data have been obtained sequentially, it would be possible (with considerable economy of time) to obtain them simultaneously by use of the internal digital signal processing capability of the instrument.     

Investigation of fungal deterioration of synthetic paint binders using vibrational spectroscopic techniques

The deterioration of synthetic polymers caused by biological process is usually evaluated by visual inspection and measuring physical effects. In contrast to this approach, we have applied vibrational spectroscopies to study the biodegradation of the synthetic resins. 29 synthetic resins used as paint binding media, including acrylic, alkyd and poly(vinyl acetate) polymers, were examined for potential susceptibility to fungal degradation using the standard method ASTM G21-96(2002). In addition, the degraded resins were analysed by Raman spectroscopy, FT-IR and FT-IR photoacoustic spectroscopy. Almost all the acrylic resins studied proved to be resistant to microbial attack, while all alkyd resins and some poly(vinyl acetates) turned out to be biodegradable. Within a few days of inoculation Aspergillus niger was the most copious fungus on the biodegraded resins. A comparison of the IR and Raman spectra of control and biodegraded resins did not show any differences, but photoacoustic spectroscopy revealed additional bands for the fungal-degraded resins, consistent with the presence of fungal-derived substances. The additional bands in the photoacoustic spectra were due to the presence of Aspergillus niger and melanin, a fungal pigment. Since IR photoacoustic spectroscopy can be also a suitable technique for the chemical characterisation of binding media, the same spectroscopic analysis can be employed to both characterise the material and obtain evidence for fungal colonization. Microbial growth on Sobral 1241ML (alkyd resin) after 28 d (growth rating 4) compared with the non-inoculated resin.     

Multi-frequency S2FTIR PA spectral depth profiling by use of sinusoidal phase modulation and harmonic demodulation up to 2250 Hz (10th harmonic)

Multi-frequency phase modulation for step-scan Fourier transform infrared photoacoustic spectroscopy (S²FTIR PAS) is demonstrated using a single frequency sinusoidal modulation of the interferometer movable mirror with modulation amplitude 5.2 λ_He-Ne. A digital signal processing (DSP) lock-in amplifier is used to demodulate the photoacoustic response at the fundamental phase modulation frequency and its harmonic frequencies. Because the phase modulation is sinusoidal and of the appropriate amplitude, all the even and odd harmonics (up to the 10th harmonic) can be detected with good signal-to-noise ratio (SNR). Applications of this multi-frequency phase modulation approach for photoacoustic depth profiling are demonstrated by the study of a simple two-layered polymer sample. The sampling depth multiplexing advantage (as compared to that obtained with other types of phase modulation) is clearly demonstrated with the analysis of the phase and magnitude of signals at the fundamental frequency and all the harmonic frequencies. This is the first report of using the sinusoidal phase modulation method to easily obtain multi-frequency and high-frequency light modulation for FTIR PAS depth profiling. Although these data have been obtained sequentially, it would be possible (with considerable economy of time) to obtain them simultaneously by use of the internal digital signal processing capability of the instrument. Received: 8 January 1998 / Accepted: 22 February 1998     

The electronic absorption spectra of nine substituted phenols

A new technique—photoacoustic spectroscopy (PAS)—is used for the first time to record the u.v.-vis spectra of nine substituted phenols. The π-π* electronic transitions analogous to benzene first primary and secondary transitions could be detected from the PAS spectra in comparison with the u.v. solution and vapour phase spectra recorded by conventional methods. Detection of singlet → triplet absorptions from the PAS spectra, with significant intensity, is considered to be an important feature which transitions are in general either not observed or observed with weak intensity, by conventional methods. The analyses show that a few excited state combinations observed in the u.v.-vis PAS spectra compare well with such combinations in the ground state observed in the near i.r. PAS spectra of the molecules.     

Microwave-assisted polyol synthesis of CuInTe2 and CuInSe2 nanoparticles

Nanoparticles of the CuInTe(2) (CIT) and CuInSe(2) (CIS) alloys have been prepared using the microwave-assisted polyol method. In this simple and quick reaction the polyol is both the solvent and the reducing agent. XRD studies show that nanoparticles of CIT and CIS are formed in the body-centered tetragonal structure and their average diameters are approximately 94 and approximately 83 nm, respectively. Electron microscopy studies show that these formed particles are poorly aggregated with a mean diameter of 100 and 85 nm, respectively. The products have been characterized by different analytical techniques, and the electronic properties have been measured using photoacoustic spectroscopy (PAS).     

Photoacoustic determination of the band gaps of Ca2MnO4 and Ca3Mn2O7

Black powders of the magnetically layered semiconductors Ca₂MnO₄ and Ca₃Mn₂O₇ prepared by a carbonate-precursor technique have been investigated by photoacoustic spectroscopy (PAS) over the energy range 1.25–4 eV. The band-gap energies of these two compounds have been evaluated to be 1.6 and 1.4 (± 0.1) eV, respectively. It is concluded that PAS is a most useful method for determining the variation of the band gap with composition in large band-gap polycrystalline semiconductors.     

Study on structural variation of silica gel using Nd3+ as a probe by photoacoustic spectroscopy

The structural variations of silica gels heated at different temperatures have been firstly studied using Nd(3+) as a probe by photoacoustic spectroscopy (PAS), together with IR spectroscopy and thermal analysis. With increasing temperature, the f-f transitions of Nd(3+) show a red shift and the PA intensities increase. The PA branching vector of the transitions from ground state to 4G(5/2)+(2)G(7/2), which are hypersensitive transitions, increase and the others decrease or change little. These indicate that the covalency of the bond that Nd(3+) forms increases and the symmetry around Nd(3+) decreases, which reflects the structural variations of silica gels.     

The photoacoustic spectra of substituted benzenes in the near infrared region—I

The photoacoustic spectra of three benzonitriles, five acetophenones and three benylbromides were recorded using the commercial EDT OAS 400 photoacoustic spectrometer in the near i.r. region, i.e. 3850–10000 cm⁻¹ (2.6−1.0 μm). A combined study of the mid and far i.r. absorption spectra with the near i.r. PAS spectra led to a provisional assignment of the observed PAS peaks as combinations of fundamentals and overtone bands.     

Comparison of portable devices for sub-ambient concentration measurements of methane (CH4) and nitrous oxide (N2O) in soil research

ABSTRACT

Production and consumption of methane (CH₄) and nitrous oxide (N₂O) in soils have a strong influence on global greenhouse gases (GHG) budgets. Therefore, it is crucial to precisely measure GHG fluxes at the soil–atmosphere interface. In upland soils, CH₄ and N₂O can be consumed by microbiological processes, and the respective concentrations can be lower than in the atmosphere, demanding highly sensitive gas analysing systems. Traditionally, soil air is sampled in vials and analysed in the laboratory by gas chromatography (GC). During the last decade, different technologies have been developed that allowed to build portable gas analysers that are able to measure sub-ambient gas concentration directly in the field. Here, we compared sub-ambient to ambient CH₄ and N₂O concentration values from four portable devices using different measurement technologies (a portable GHG analyser based on laser absorption spectroscopy [LAS], two portable Fourier transform infrared spectroscopy [FTIR] devices and a field gas analyser using photoacoustic spectroscopy [PAS]) to traditional GC analysis in the laboratory (a GC system equipped with a flame ionisation detector [GC-FID] and an electron capture detector [GC-ECD]). The accuracy and precision of photoacoustic spectroscopy measurements are strongly influenced by the water vapour content and non-target gases in the sampling air. We used an advanced set-up for a widely used PAS analyser enabling N₂O measurements at sub-ambient concentrations with similar precision and accuracy as the GC-ECD system. Measurements of CH₄ and N₂O by FTIR and LAS devices were in good agreement with the GC systems. We conclude that the portable devices are suitable for studies of GHG fluxes in the field. Thanks to their universal and portable character, LAS, PAS and FTIR devices represent useful alternatives to currently used technologies for field studies.     

Effects of sampling methodologies on FT-IR data base searching

The sampling methodologies employed in Fourier Transform Infrared (FT-IR) spectroscopy tend to distort to a degree the data obtained relative to that which would be obtained via transmittance. This distortion complicates data base searching. A standard sample of polystyrene was investigated using the techniques of transmittance, attenuated total reflectance (ATR), diffuse reflectance (DRIFT) and photoacoustic spectroscopy (PAS). Several types of corrections are employed to minimize the distortions due to sampling methodologies.These corrections are evaluated with respect to four distinct search algorithms. The results obtained indicate that proper mathematical treatment of the data prior to data base searching enhances the discrimination value of a data base search.     

Direct photothermal techniques for rapid quantification of total anthocyanin content in sour cherry cultivars

The analytical performance of the newly proposed laser-based photoacoustic spectroscopy (PAS) and of optothermal window (OW) method for quantification of total anthocyanin concentration (TAC) in five sour cherry varieties is compared to that of the spectrophotometry (SP). High performance liquid chromatography (HPLC) was used to identify and quantify specific anthocyanins. Both, PAS and OW are direct methods that unlike SP and HPLC obviate the need for the extraction of analyte. The outcome of the study leads to the conclusion that PAS and OW are both suitable for quick screening of TAC in sour cherries. The correlation between the two methods and SP is linear with R² = 0.9887 for PAS and R² = 0.9918 for OW, respectively. Both methods are capable of the rapid determination of TAC in sour cherries without a need for a laborious sample pretreatment.