Fourier transform infrared-reflectance transmission measurement

Cabioc h et al. developed a method based on carbon ion implantation into a metal matrix (Ag, Cu), resulting in onions with typical diameters in the 3-15 nm range. Snfficient quantities could be produced for investigation of their optical, electronic, and tribological properties. Fourier transform infrared (FTIR) spectroscopy measurements on these carbon onions demonstrated that the most stable state for the onions consists of concentric spheres of fnllerenes. The electronic properties of the onions were characterized by spatially resolved electron energy loss spectroscopy (EELS) in transmission, and reflection mode. ... 

Fourier transform infrared microscopes are equipped with a reflection capability that can be used under these circumstances. External reflection spectroscopy (ERS) requires a flat, reflective surface, and the results are sensitive to the polarization of the incident beam as well as the angle of incidence. Additionally, the orientations of the electric dipoles in the films are important to the selection rules and the intensities of the reflected beam. In reflectance measurements, the spectra are a function of the dispersion in the refractive index and the spectra obtained are completely different from that obtained through a transmission measurement that is strongly influenced by the absorption index, k. However, a complex refractive index, n + ik can be determined through a well-known mathematical route, namely, the Kramers-Kronig analysis. 

In order to actually cover 19 decades in frequency, dielectric spectroscopy makes use of different measurement techniques each working at its optimum in a particular frequency range. The techniques most commonly applied include time-domain spectroscopy, frequency response analysis, coaxial reflection and transmission methods, and at the highest frequencies quasi-optical and Fourier transform infrared spectroscopy (cf. Fig. 2). A detailed review of these techniques can be found in Kremer and Schonhals [37] and in Lunkenheimer [45], so that in the present context only a few aspects will be summarized. 

The apparatus used for IR microscopy is a Fourier-transform infrared (FTIR) spectrometer coupled on-line with an optical microscope. The microscope serves to observe the sample in white light at significant magnification for the purpose of determining its morphology, as well as to select the area for analysis. The spectrometer, on the other hand, enables study of the sample by transmission or reflection measurement for the purpose of determining the chemical composition. It also provides information about the microstructure and optical properties (orientation) of the sample. It is possible to apply polarised light both in the observation of the sample and in spectrometric measurements. 

Altered surfaces have been inferred from solution chemistry measurements (e.g., Chou and Wollast, 1984, 1985) and from spectroscopic measurements of altered surfaces, using such techniques as secondary ion mass spectrometry (for altered layers that are several tens of nm thick (e.g., Schweda et al, 1997), Auger electron spectroscopy (layers <10 nm thick (e.g., Hochella, 1988), XPS (layers <10 nm thick (e.g., Hochella, 1988 Muir et al, 1990), transmission electron microscopy (TEM, e.g., Casey et al, 1989b), Raman spectroscopy (e.g.. Gout et al, 1997), Fourier transform infrared spectroscopy (e.g., Hamilton et al, 2001), in situ high-resolution X-ray reflectivity (Farquhar et al, 1999b Fenter et al, 2003), nuclear magnetic resonance (Tsomaia et al, 2003), and other spectroscopies (e.g., Hellmann et al, 1997). 

Deposition of analytes in solvent-elimination LC-FTIR is performed on powdered substrates, mirrors, or IR-transparent windows. Correspondingly, diffuse reflection Fourier-transform infrared (DRIFT) detection, reflection-absorption (R-A) spectroscopy, or transmission measurements are applied to investigate the analyte deposits. 

Among these, some of the most frequently used are attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy. X-ray photoelectron spectroscopy (XPS), static secondary ion mass spectrometry (SSIMS), energy dispersive X-ray spectroscopy (EDS), optical microscopy, laser confocal scanning microscopy (LCSM), scanning electron microscopy (SEM), enviromnental scanning electron microscopy (ESEM), transmission electron microscopy (TEM), atomic force microscopy (AFM), contact angle measurement, and some evaluation methods for the biocompatibility of membrane surfaces. 

In the case of reflection measurements, the sample replaces one of the mirrors in the Michelson interferometer (see Fig. 32). The reference mirror is assumed to be 100% reflecting in the far-infrared, and in the sample interferogram the power reflectance R of the sample and the phase shift y> at the reflection (usually n for nonabsorbing media with w > 1) take over the role of T and q> in transmission measurements. The interferogram obtained in this case is also somewhat shifted and as3nmnetiic (see Fig. 33, KBr sample). By means of the cosine and sine Fourier transforms, R and y>, and finally n and x, are evaluated from the experimental data. 

IR spectroscopy is one of the few analytical techniques that can be used for the characterization of solid, liquid, and gas samples. The choice of sampling technique depends upon the goal of the analysis, qualitative identification or quantitative measurement of specific analytes, upon the sample size available, and upon sample composition. Water content of the sample is a major concern, since the most common IR-transparent materials are soluble in water. Samples in different phases must be treated differently. Sampling techniques are available for transmission (absorption) measurements and, since the advent of FTIR, for several types of reflectance (reflection) measurements. The common reflectance measurements are attenuated total reflectance (ATR), diffuse reflectance or diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and specular reflectance. The term reflection may be used in place of reflectance and may be more accurate specular reflection is actually what occurs in that measurement, for example. However, the term reflectance is widely used in the literature and will be used here. 

While diffraction grating based spectrophotometers are a powerful tool to collect transmission and reflection spectra in the UV to near infra-red range of the spectrum, they are not the best choice for measurements in the mid and far infrared range. For measurements in the IR, dispersive instruments are not as efficient or convenient as the Fourier transform (FT) spectrometers. Generally, FT instruments have a higher throughput, better accuracy and precision, compared to grating based instruments. 

Infrared spectroscopy is predominantly performed in the Fourier-transform mode and then commonly abbreviated as FTIR. The great advantage of FTIR spectroscopy is the great number of measurement options (and accessories), that allow spectra to be taken conveniently from just about any kind of sample. Polymeric powders can be characterized by pressing them into the conventional KBr pellets, but also, without any sample preparation, by diffuse reflectance (DRIFT). Very thin films of polymers can be measured in the conventional transmission mode, but any kind of film (thick or thin), as well as large polymeric objects, can be measured by ATR. ATR probes can also be used to characterize solutions... 

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