Reflection-Absorption Spectrometry with Metal Substrates

INFRARED REFLECTION-ABSORPTION SPECTROMETRY WITH METAL SUBSTRATES... 

In solvent-elimination LC-FTIR, basically three types of substrates and corresponding IR modes can be discerned, namely, powder substrates for diffuse reflectance (DRIFT) detection, metallic mirrors for reflection-absorption (R-A) spectrometry, and IR-transparent windows for transmission measurements [500]. The most favourable solvent-elimination LC-FTIR results have been obtained with IR-transparent deposition substrates that allow straightforward transmission measurements. Analyte morphology and/or transformation should always be taken into consideration during the interpretation of spectra obtained by solvent-elimination LC-FTIR. Dependent on the type of substrate and/or size of the deposited spots, often special optics such as a (diffuse) reflectance unit, a beam condenser or an FITR microscope are used to scan the deposited substances (typical diameter of the FITR beam, 20 pm). 

Nowadays, the use of the reflection electron microscope (REM) or, recently, the tunnel electron microscope, as well as secondary ion mass spectrometry (SIMS), AES, electron-dispersive X-ray spectrometry, impedance spectroscopy, and so on, are yielding substantial increases in the knowledge of corrosion reactions in coatings and at their interface with metal or other substrates. As far as zinc or zinc-coated surfaces are concerned, problems of interfacial and intercoat adhesion, differential diffusion phenomena and electrolytic cell behavior on the substrate, and interreactions of zinc with conversion coatings (chromates, phosphates, silanes, silanols, etc.) have been analyzed, leading toward spectacular improvements in, for example, paint adhesion, absorption of conversion coatings and, in general, the protective action inside films as well as on their substrates. 

The first commercially successful off-line DD-HPLC/FT-IR interface was the LC Transform, made by Lab Connections [41]. With this device, nebulization is initiated ultrasonicaUy and the solvent is evaporated with either a thermospray or a concentric flow nebulizer. The solutes are first deposited on a rotating germanium disk on the underside of which a thick layer of aluminum has been deposited. After the deposition step, the disk is then moved to a specular reflection accessory that is mounted in the sample compartment of a standard FT-IR spectrometer. The developers of the LC Transform recognized that it is more convenient to measure the spectra of the components that had been deposited on the disk by reflection spectrometry than by transmission. However, the deposition of a very thin film of each eluate on a metal substrate would not allow its reflection-absorption spectrum to be measured with adequate efficiency without resorting to grazing incidence measurements, for which the disadvantages were discussed in Section 23.3.3. 

In this chapter, a sensitive method for measurement by continuous-scan Fourier-transform infrared (FT-IR) spectrometry called polarization-modulation spectrometry is introduced this is a useful method for measuring, with high signal-to-noise ratio, not only the reflection-absorption spectra of thin films adsorbed onto metal substrates but also other spectra such as vibrational circular dichroism (VCD) spectra. Polarization-modulation spectrometry is a type of double-modulation FT-IR spectrometry [1], In this chapter, descriptions of double-modulation spectrometry are given first, then polarization-modulation spectrometry is discussed, and then its application to the measurement of reflection-absorption spectra of thin films on metal substrates is discussed. 

In a similar manner to that developed with Equations (11.1a) and (11.1 b) for the intensity of the beam of infrared radiation that has passed through the target and reference samples in double-modulation spectrometry, when polarization-modulation spectrometry is applied to a reflection-absorption measurement of a thin film adsorbed onto a metal substrate, the intensity of reflection B (v, f) is expressed in the following form as a function of wavenumber V and time f. 

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