Fourier transform internal reflection studies

Holmen, B.A. Tejedor-Tejedor, M.S. Casey, WA. (1997) Hydroxymate complexes in solution at the goethite/water interface. A. Cylindrical internal reflectance Fourier transform infrared spectroscopic study. Langmuir 13 2197... 

Paik, C. S., Hu, C. B. Surface Chemical Analysis of Segmented Polyurethanes. Fourier Transform IR Internal Reflection Studies in Advances in Chemistry Series,Cooper, S., Estes, G. (Eds) 176, 69 (1979)... 

Surface Chemical Analysis of Segmented Polyurethanes. Fourier Transform IR Internal Reflection Studies... 

Holmen B. A., Tejedor-Tejedor M. I., and Casey W. H. (1997) Hydroxamate complexes in solution and at the goethite-water interface a cylindrical internal reflection Fourier transform infrared spectroscopy study. Langmuir 13, 2197-2206. 

A DIGILAB 14B/D Fourier Transform infrared spectrometer was utilized to obtain 1 cm resolution spectra over the 4000 to 600 cm region for copolyether-urethane-urea, polyether-urethane, polypropylene glycol. Urethane I, Urethane II and Urea I. The sample chamber was allowed to come to equilibrium with a continuous nitrogen purge prior to data collection of 250 scans per sample for transmission studies and 1000 scans per sample for internal reflectance studies. 

Titration calorimetry and cylindrical internal reflection-Fourier transform infrared (CIR-FTIR) spectroscopy are two techniques which have seldom been applied to study reactions at the solid-liquid interface. In this paper, we describe these two techniques and their application to the investigation of salicylate ion adsorption in aqueous goethite (a-FeOOH) suspensions from pH 4 to 7. Evidence suggests that salicylate adsorbs on goethite by forming a chelate structure in which each salicylate ion replaces two hydroxyls attached to a single iron atom at the surface. 

To put things into perspective, we. can broadly classify these analytical methods into bulk, dry surface, and in situ interfacial techniques. This chapter focuses on the last category, illustrating two in situ techniques used to study anion binding at the goethite (a-FeOOH)-water interface titration calorimetry and cylindrical internal reflection-Fourier transform infrared (CIR-FTIR) spectroscopy. In fact, CIR-FTIR could prove to be extremely powerful, since it allows direct spectroscopic observation of ions adsorbed at the mineral-water interface. 

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. 

Ellipsometry is probably the only easy-to-use surface analysis method which can be operated in situ and in real time. On the contrary, multiple internal reflection Fourier transform infrared spectroscopy is a very powerful technique [38] but it is rather tricky to implement. Ellipsometry allows real time studies of the surface modification during exposure to the plasma, and after the treatment. Figure 10 shows for example the variation of and A ellipsometry angles upon fluorination of Si in fluorine-based plasmas as a function of pressure and gas mixture [39], thus demonstrating the sensitivity of the technique. Infrared ellipsometry has also been used with success to investigate reaction layer composition and formation on Si in CF4-based plasmas [40,41], or to monitor patterning [42]. 

The use of infrared spectroscopy in the Earth and environmental sciences has been widespread for decades however, until development of the attenuated total reflectance (ATR) technique, the primary use was ex situ material characterization (Chen and Gardella, 1998 Tejedor-Tejedor et al., 1998 Degenhardt and McQuillan, 1999 Peak et al., 1999 Wijnja and Schulthess, 1999 Aral and Sparks, 2001 Kirwan et al., 2003). For the study of environmental systems, the strength of the ATR-Fourier transform infrared (FTIR) technique lies in its intrinsic surface sensitivity. Spectra are collected only from absorptions of an evanescent wave with a maximum penetration depth of several micrometers from the internal reflection element into the solution phase (Harrick, 1967). This short optical path length allows one to overcome any absorption due to an aqueous phase associated with the sample while maintaining a high sensitivity to species at the mineral-water interface (McQuillan, 2001). Therefore, ATR—FTIR represents a technique capable of performing in situ spectroscopic studies in real time. 

A technique which has proven useful for our studies is that of cylindrical internal reflectance (CIR), coupled with a Fourier transform infrared spectrometer. In this study, an IBM-85 FTIR equipped with either a DTGS (deuterated triglycine sulfate) or MCT (mercury-cadmium-tellurium) detector was used. The infrared radiation is focused by concave mirrors onto the 45° conical ends of a transmitting crystal (Figure 1). The crystal may be made of any material which is optically transparent, has a high mechanical strength and high index of refraction, and is resistant to thermal shock and chemical attack. Suitable materials include ZnS, ZnSe,... 

Additional techniques exist for measuring fluid absorption at adhesive interfaces. Fourier transform infrared spectroscopy in the multiple internal reflection mode (FTIR-MIR) is an available technique for studying diffusion at the interface. FTlR-MlR has provided direct evidence of water accumulation, and therefore adhesive debonding, at the interface [12,13]. The technique of neutron reflectivity has also shown that the concentration of absorbed fluid can be significantly greater at the interface than in the bulk adhesive [14-18]. 

Due to the fundamental importance of the adsorbed protein film, many methods have been used to characterize its nature. These methods include ellipsometry (3,A), Fourier transform infrared spectroscopy (FTIR) (5,6), multiple attenuated internal reflection spectroscopy (MAIR) (7,8) immunological labeling techniques (9), radioisotope labeled binding studies (j ), calorimetric adsorption studies (jj ), circular dichroism spectroscopy (CDS) (12), electrophoresis (j ), electron spectroscopy for chemical analysis (ESCA) (1 ), scanning electron microscopy (SEM) (15,16,9), and transmission electron microscopy (TEM) (17-19). 

Another variant of IR spectroscopic technique is known as Fourier Transform IR Attenuated Total Reflection Spectroscopy (ATR FT-IR) has been described by Poston et al. [123] to study adsorbates at the silica-solution interface. The authors reported the preparation of ZnSe internal-reflection elements coated with a porous silica layer of ca. 700 nm thick. They studied the adsorption of ethylacetate from n-heptane solutions. This technique allows the determination of IR spectra in-situ and its dependence on the solution concentration. They found a nonlinear adsorption isotherm of ethylacetate on... 

The use of cylindrical internal reflectance cells for HP-IR was pioneered by Moser and further modified by others.This method involves the use of an optically transparent internal reflectance crystal (typically ZnS, ZnSe, sapphire). Due to the inherently short path length, the method is not as sensitive as transmission-based IR, and a Fourier transform infrared (FTIR) spectrometer is therefore generally required. In addition, the type of crystal may need to be changed depending on the reaction of interest, as the optics may be corroded by some reagents or catalysts. However, as the path length is fixed regardless of conditions, it is much easier to quantify catalyst species, and unlike transmission systems the cells can also be used for the study of liquid-solid and gas-liquid-solid mixtures. ... 

Ever since the first reports of optical studies of electrochemical systems, efforts have been made to obtain infrared spectra of reaction intermediates and adsorbates. The earliest studies were based on total internal reflection using an n-type germanium electrode (transparent to IR radiation), and OTTLE systems using gold minigrids sandwiched between NaCl plates. These were not particularly successful, however, and it is only recently that these configurations have again been used, this time for Fourier Transform spectroscopy [29,30]. Undoubtedly the most successful technique has been potential modulated external reflectance IR spectroscopy [31]. 

Applying attenuated total reflection Fourier transform infrared and total internal reflection fluorescence spectroscopy, the same group studied the secondary structure and aggregation properties of different proteins that are adsorbed onto planar PAA brushes (Hollmann, Steitz, Czeslik, 2008 Reichhart Czeslik, 2008). They found... 

Multiple block copolymers form a domain-matrix morphology due to the chemical and steric incompatibilities of the two chemically different blocks. The surface molecular and morphological structures of a series of block copolyether-urethane-ureas have been studied in detail via Electron Spectroscopy for Chemical Analysis (ESCA) and Fourier Transform Infrared Spectroscopy (FTIR) coupled with internal reflectance techniques. ESCA provides elemental information concerning the very surface, while FTIR provides the molecular and secondary bonding Information of the surface and into the bulk. Bulk and surface chemical and morphological structures are shown to be quite different, and are affected by synthetic and fabrication variables. 

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