Bulk solid analysis techniques

Through the combined use of catalytic probe reactions, Mossbauer, EXAFS, XPS, XRD, it has been demonstrated that the anticipated particle structures for the half-SMAD and full SMAD procedures are close to reality.(40-42) Thus, 119Sn Mossbauer, a bulk solid analysis technique, revealed the relative amounts of Sn, Pt-Sn alloy, SnO, and Sn02 present in the catalysts. It was possible to differentiate Sn° from Pt-Sn alloy through supporting evidence of XPS and selective oxidation, since it was found that ultra-fine Sn° particles were much more susceptible to oxidation than Pt-Sn alloy particles. Also, since the full SMAD Pt°-Sn°/Al203 catalysts behaved much differently than Pt°/Al203, it is clear that the SMAD catalysts are not made up of separate Pt° and Sn particles. 

Some of the techniques included apply more broadly than just to surfaces, interfaces, or thin films for example X-Ray Diffraction and Infrared Spectroscopy, which have been used for half a century in bulk solid and liquid analysis, respectively. They are included here because they have by now been developed to also apply to surfaces. A few techniques that are applied almost entirely to bulk materials (e.g.. Neutron Diffraction) are included because they give complementary information to other methods or because they are referred to significantly in the 10 materials volumes in the Series. Some techniques were left out because they were considered to be too restricted to specific applications or materials. 

In spite of the large success of XRD in routine structural analysis of solids, this technique does present some limitations when applied to catalysis [1,9]. First, it can only detect crystalline phases, and fails to provide useful information on the amorphous or highly dispersed solid phases so common in catalysts [22], Second, due to its low sensitivity, the concentration of the crystalline phase in the sample needs to be reasonably high in order to be detected. Third, XRD probes bulk phases,... 

Very often, techniques for direct solid analysis are classified into two groups according to whether they provide bulk information (of interest for homogeneous samples) or analytical information with lateral and/or depth resolution. 

The chemical, physical and technical properties of catalysts and many other porous technical materials are to a very great degree determined by both their texture and their structure, but the analytical composition of the surface also plays a role. Modern surface analysis techniques, like auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS) have revealed that in many cases the atomic composition of the surface of a solid material deviates strongly from the composition of the bulk material. 

Photoelectron spectroscopy of valence and core electrons in solids has been useful in the study of the surface properties of transition metals and other solid-phase materials. When photoelectron spectroscopy is performed on a solid sample, an additional step that must be considered is the escape of the resultant photoelectron from the bulk. The analysis can only be performed as deep as the electrons can escape from the bulk and then be detected. The escape depth is dependent upon the inelastic mean free path of the electrons, determined by electron-electron and electron-phonon collisions, which varies with photoelectron kinetic energy. The depth that can be probed is on the order of about 5-50 A, which makes this spectroscopy actually a surface-sensitive technique rather than a probe of the bulk properties of a material. Because photoelectron spectroscopy only probes such a thin layer, analysis of bulk materials, absorbed molecules, or thin films must be performed in ultrahigh vacuum (<10 torr) to prevent interference from contaminants that may adhere to the surface. 

If the sample is a bulk solid sample and is an electrical conductor, it is possible to use it as the cathode of a kind of spectral lamp whose functioning principle is identical to that described for a hollow cathode lamp (cf. Section 13.5.1 and Figure 14.5). The atoms sputtered and removed from the surface of the sample are excited by the plasma. This GD-OES technique provides a rapid and accurate surface analysis, less susceptible to matrix effects and sample homogeneity. It has the advantage of yielding spectra with low background levels whose emission lines are narrow since atomization takes place at lower temperatures than that of the previous techniques. 

Microscopy. Characterization of particulate from suspensions using microscopic methods is an effective method for establishing the size distribution of the particles and also their composition. Using properly prepared samples, automated image analysis techniques can be used that significantly reduce data collection times. Although the size distribution and composition of the suspended particles are important, the real strength of microscopic methods is the ability to observe particles in suspension and to determine how they interact and associate. There is little difference in microscopic methods applied to solids in suspension or to oil droplets in suspension (emulsions). As a result, the bulk of this discussion is borrowed from a similar chapter on emulsion characterization found in reference 19. 

The term surface analysis is used to mean the characterization of the chemical and physical properties of the surface layer of solid materials. The surface layer of a solid usually differs in chemical composition and in physical properties from the bulk solid material. A common example is the thin layer of oxide that forms on the surface of many metals such as aluminum upon contact of the surface with oxygen in air. The thickness of the surface layer that can be studied depends on the instrumental method. This layer may vary from one atom deep, an atomic monolayer, to 100-1000 nm deep, depending on the technique used. Surface analysis has become increasingly important because our understanding of the behavior of materials has grown. The nature of the surface layer often controls important material behavior, such as resistance to corrosion. The various surface analysis methods reveal the elements present, the distribution of the elements, and sometimes the chemical forms of the elements in a surface layer. Chemical speciation is possible when multiple siuface techniques are used to study a sample. 

Laser ablation Laser ablation (LA) in combination with the ICP atomiser has become a powerful and flexible techniqvie for solid sample introduction [47]. LA-AES has found its niche primarily as a bulk sampling technique for the analysis of bulk solid materials with a large focal spot (500—1000 pm). It offers comparable detection capability to spark ablation/emission but is not dependent on the sample being conductive. The experimental set-up, revealed in Fig. 12.32, consists in its simplest form of a pulsed laser (excimer- or Nd YAG-laser) with a defined pulse energy, some focusing optics, and a sample cell with a continuous Ar flow con-... 

Diffusion is the mass transfer caused by molecular movement, while convection is the mass transfer caused by bulk movement of mass. Large diffusion rates often cause convection. Because mass transfer can become intricate, at least five different analysis techniques have been developed to analyze it. Since they all look at the same phenomena, their ultimate predictions of the mass-transfer rates and the concentration profiles should be similar. However, each of the five has its place they are useful in different situations and for different purposes. We start in Section 15.1 with a nonmathematical molecular picture of mass transfer (the first model) that is useful to understand the basic concepts, and a more detailed model based on the kinetic theory of gases is presented in Section 15.7.1. For robust correlation of mass-transfer rates with different materials, we need a parameter, the diffusivity that is a fundamental measure of the ability of solutes to transfer in different fluids or solids. To define and measure this parameter, we need a model for mass transfer. In Section 15.2. we discuss the second model, the Fickian model, which is the most common diffusion model. This is the diffusivity model usually discussed in chemical engineering courses. Typical values and correlations for the Fickian diffusivity are discussed in Section 15.3. Fickian diffusivity is convenient for binary mass transfer but has limitations for nonideal systems and for multicomponent mass transfer. 

Both solid and liquid samples can be analyzed by XRF as described earlier in the chapter. With the exception of micro-XRF, XRF is considered to be a bulk analysis technique. This means that the analysis represents the elemental composition of the entire sample, assuming the sample is homogeneous. The term bulk analysis is used to distinguish such techniques from surface analysis techniques (Chapter 14), which look at only a very thin layer at the sample surface. But there are conditions that must be considered in XRF in order to obtain accurate results. The limiting factor for direct XRF analysis or the analysis of prepared samples is that the signal of the characteristic radiation from the sample originates from different layers within the sample. 

It is also common for pol3rmeric compoimds to form surface regions with compositions different from the bulk material, by selective diffusion of components. This process is termed blooming when the surface component is solid, and bleeding if it is liquid. Sulfur and fatty acid blooms can inhibit adhesion in rubber laminates (3). Laser desorption mass spectroscopy has been employed to identify surface species on vulcanized rubber (4). X-ray scattering methods for the study of polymer surfaces and interfaces have been reviewed (5). Other surface analysis techniques commonly used with polymers include attenuated total reflectance (6-8), electron microprobe (9), Auger electron spectroscopy (10), x-ray photoelectron spectroscopy (11), and scanning probe microscopic methods (12). Overviews on polymer surface analysis have been published (13,14). 

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