Infrared spectroscopy attenuated total reflection technique

Infrared spectroscopy, including Fourier-transform infrared (FTIR) spectroscopy, is one of the oldest and most widely used analytical techniques in adhesion-related research. Transmission infrared spectroscopy has been used to identify compounds used in formulating adhesives and to follow curing reactions. Attenuated total reflection (ATR) (see Infrared spectroscopy attenuated total reflection) has been used to probe the surface composition of polymers that have been surface modified by an etching process or by deposition of a film. More recently, reflection-absorption infrared spectroscopy (see Infrared spectroscopy RAIR) has been used to characterize thin films on the surfaces of reflecting substrates. 

Spectroscopic methods are mainly useful to identify the elements, functional groups, and chemical structures close to the biomaterial surface. Techniques like X-ray photoelectron spectroscopy, attenuated total reflection fourier transform infrared spectroscopy, and secondary ion mass spectrometry have been used widely in determining the elemental composition and charged species at biomaterial surface. Other important characteristics obtained from the biomaterial surface are surface energy and relative wettability using thermodynamic method such as contact angle experiments. 

Infrared-based techniques are used to identify molecules on the surface. IR radiation is used to excite vibrational modes in molecules in the gas phase or adsorbed on a surface. The transmitted or reflected IR spectrum can be analyzed in a spectrometer. Considerable improvement in the sensitivity can be achieved by use of Fourier transform infrared (FTIR) spectroscopy. Attenuated total reflection (the ATR-FTIR method) inside a crystal (germanium) of high refractive index can be used to further enhance the surface sensitivity (using the evanescent field). 

Zhu Y, Uchida H, Watanabe M. Oxidation of carbon monoxide at a platinum film electrode studied by Fourier transform infrared spectroscopy with attenuated total reflection technique. Langmuir 1999 15 8757-64. 

Fourier transform infrared spectroscopy (FTIR) was conducted with a Spectmm 100 FTIR Spectrometer Perkin Elmer (Japan). FTIR spectra were recorded in range of 4000 to 550 cm with 4 cm resolution by using an attenuated total reflectance technique (Chittur, 1998). 

The development of repellent finishing is benefiting from recent progress in surface analyses by electron spectroscopy for chemical analyses, scanning electron microscopy, and the attenuated total reflection technique of infrared spectroscopy. 

Surface analysis has made enormous contributions to the field of adhesion science. It enabled investigators to probe fundamental aspects of adhesion such as the composition of anodic oxides on metals, the surface composition of polymers that have been pretreated by etching, the nature of reactions occurring at the interface between a primer and a substrate or between a primer and an adhesive, and the orientation of molecules adsorbed onto substrates. Surface analysis has also enabled adhesion scientists to determine the mechanisms responsible for failure of adhesive bonds, especially after exposure to aggressive environments. The objective of this chapter is to review the principals of surface analysis techniques including attenuated total reflection (ATR) and reflection-absorption (RAIR) infrared spectroscopy. X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), and secondary ion mass spectrometry (SIMS) and to present examples of the application of each technique to important problems in adhesion science. 

A number of techniques have been employed that are capable of giving information about amorphous phases. These include infrared spectroscopy, especially the use of the attenuated total reflection (ATR) or Fourier transform (FT) techniques. They also include electron probe microanalysis, scanning electron microscopy, and nuclear magnetic resonance (NMR) spectroscopy. Nor are wet chemical methods to be neglected for they, too, form part of the armoury of methods that have been used to elucidate the chemistry and microstructure of these materials. 

It is generally assumed the fluorescence and Fourier transform mid-infrared (FT-IR) spectroscopies do not suffer from the above-mentioned inconveniences and may be applied to turbid samples. Front-face (fluorescence) and attenuated total reflection (FT-IR) techniques may provide information on the structure of adsorbed proteins. 

In materials investigations surface-sensitive techniques are of special interest. The major contribution of infrared spectroscopy to this field is internal reflection spectroscopy (IRS), often called the "attenuated total reflection" (ATR) technique. To describe theory and principle, electromagnetic wave theory must be apphed [33]. 

Fourier transform-infrared (FT-IR) spectroscopic studies on SO-SA complexation provides information that may be complementary to that of NMR and other techniques, namely, in particular, on the involvement of functional groups in intermolecular and intramolecular interactions. Attenuated total reflectance (ATR) IR spectroscopy has been used for the study of binding modes of cinchona alkaloid selectors either in solution [95] or in solid state [94], or directly on the CSP [96]. 

A fiber-optic device has been described that can monitor chlorinated hydrocarbons in water (Gobel et al. 1994). The sensor is based on the diffusion of chlorinated hydrocarbons into a polymeric layer surrounding a silver halide optical fiber through which is passed broad-band mid-infrared radiation. The chlorinated compounds concentrated in the polymer absorb some of the radiation that escapes the liber (evanescent wave) this technique is a variant of attenuated total reflection (ATR) spectroscopy. A LOD for chloroform was stated to be 5 mg/L (5 ppm). This sensor does not have a high degree of selectivity for chloroform over other chlorinated aliphatic hydrocarbons, but appears to be useful for continuous monitoring purposes. 

An infrared spectrum is a plot of percent radiation absorbed versus the frequency of the incident radiation given in wavenumbers (cm ) or in wave length ( xm). A variation of this method, diffuse reflectance spectroscopy, is used for samples with poor transmittance, e.g. cubic hematite crystals. Increased resolution and sensitivity as well as more rapid collection of data is provided by Fourier-transform-IR (FTIR), which averages a large number of spectra. Another IR technique makes use of attenuated total reflectance FTIR (ATR-FTIR) often using a cylindrical internal reflectance cell (CIR) (e.g. Tejedor-Tejedor Anderson, 1986). ATR enables wet systems and adsorbing species to be studied in situ. 

Many important heterogeneous catalytic reactions occur at the interface between a solid catalyst and liquid or liquid-gas reactants. Notwithstanding the importance of solid-catalyzed reactions in the presence of liquid reactants, relatively little attention has been paid to spectroscopic methods that allow researchers to follow the processes occurring at the solid-liquid interface during reaction. This lack can be explained in part by the fact that there are only a few techniques that give access to information about solid-liquid interfaces, the most prominent of them being attenuated total reflection infrared spectroscopy (ATR-IR) and X-ray absorption fine structure (XAFS) spectroscopy. 

One other in situ technique can be used to determine fractional acidity in atmospheric aerosols by means of Fourier transform infrared (FTIR) spectroscopy (46). Originally, impactor samples were collected and were pressed into a KBr matrix, and then the IR spectrum was taken by attenuated total reflectance (ATR) FTIR spectroscopy to determine relative acidity, based on differences in absorption bands for sulfate and bisulfate species. Aerosols with [H+]/[S042 ] ratios greater than 1 could also be qualitatively identified. More recent innovations in the FTIR technique (47, 48) have made possible... 

X-ray photoelectron spectroscopy (XPS) was used for elemental analysis of plasma-deposited polymer films. The photoelectron spectrometer (Physical Electronics, Model 548) was used with an X-ray source of Mg Ka (1253.6 eV). Fourier transform infrared (FTIR) spectra of plasma polymers deposited on the steel substrate were recorded on a Perkin-Elmer Model 1750 spectrophotometer using the attenuated total reflection (ATR) technique. The silane plasma-deposited steel sample was cut to match precisely the surface of the reflection element, which was a high refractive index KRS-5 crystal. 

The primary techniques used in this study include X-ray photoelectron spectroscopy (XPS), reflection-absorption infrared spectroscopy (RAIR), and attenuated total reflectance infrared spectroscopy (ATR). XPS is the most surface-sensitive technique of the three. It provides quantitative information about the elemental composition of near-surface regions (< ca. 50 A sampling depth), but gives the least specific information about chemical structure. RAIR is restricted to the study of thin films on reflective substrates and is ideal for film thicknesses of the order of a few tens of angstroms. As a vibrational spectroscopy, it provides the type of structure-specific information that is difficult to obtain from XPS. The... 

Potts, R. O., Guzek, D. B., Harris, R. R. and McKie, J. E. (1985) A noninvasive, in vivo technique to quantitatively, measure water concentration of the stratum corneum using attenuated total-reflectance infrared spectroscopy. Arch. Dermatol. Res. 277, 489-95. 

Sampling in surface-enhanced Raman and infrared spectroscopy is intimately linked to the optical enhancement induced by arrays and fractals of hot metal particles, primarily of silver and gold. The key to both techniques is preparation of the metal particles either in a suspension or as architectures on the surface of substrates. We will therefore detail the preparation and self-assembly methods used to obtain films, sols, and arrayed architectures coupled with the methods of adsorbing the species of interest on them to obtain optimal enhancement of the Raman and infrared signatures. Surface-enhanced Raman spectroscopy (SERS) has been more widely used and studied because of the relative ease of the sampling process and the ready availability of lasers in the visible range of the optical spectrum. Surface-enhanced infrared spectroscopy (SEIRA) using attenuated total reflection coupled to Fourier transform infrared spectroscopy, on the other hand, is an attractive alternative to SERS but has yet to be widely applied in analytical chemistry. 

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