Surface techniques, applications minerals

Surface spectroscopic techniques must be separated carefully into those which require dehydration for sample presentation and those which do not. Among the former are electron microscopy and microprobe analysis, X-ray photoelectron spectroscopy, and infrared spectroscopy. These methods have been applied fruitfully to show the existence of either inner-sphere surface complexes or surface precipitates on minerals found in soils and sediments (13b,30,31-37), but the applicability of the results to natural systems is not without some ambiguity because of the dessication pretreatment involved. If independent experimental evidence for inner-sphere complexation or surface precipitation exists, these methods provide a powerful means of corroboration. 

Applications of Surface Techniques to Chemical Bonding Studies of Minerals... 

The spatial distribution of these mineral constituents was assessed by contouring and by trend surface analysis. One problem that must be addressed in a study such as this, is whether the density of data points is sufficient to justify the description of trends across the basin, or is local variability in the constituents too great. Application of trend surface analysis permitted a statistical assessment of basinal trends, and indicated the extent of local variation. In this paper, contour maps are presented to show important basinal trends trend surface analysis indicated that these trends were statistically significant. Details of the trend surface technique and complete data are described in Rimmer (12). 

The application of nuclear methods to studies of ceramic surfaces and interfaces is a well-developed methodology, although not as yet applied extensively to mineral surfaces. Relevant applications of RBS, PIXE, NRA, ERDA and high-resolution a-spectroscopy have been described in the review by Matzke [9.1]. Analyses by RBS, used in the channeling mode, and NRA have revealed structural defects in U Ov-y RBS is sensitive mainly to the metal atom sublattice. whereas NRA can be used selectively to study the nonmeial sublattice. It was shown that the U sublattice is nearly identical to that of UO2, whereas significant cluster formation occurs in the O sublattice these observations have implications for surface sites in the material. Investigations of surface reactions (e.g., leaching and dis.soIution) of titanates and UO2 by nuclear techniques have... 

Sorption processes are influenced not just by the natures of the absorbate ion(s) and the mineral surface, but also by the solution pH and the concentrations of the various components in the solution. Even apparently simple absorption reactions may involve a series of chemical equilibria, especially in natural systems. Thus in only a comparatively small number of cases has an understanding been achieved of either the precise chemical form(s) of the adsorbed species or of the exact nature of the adsorption sites. The difficulties of such characterization arise from (i) the number of sites for adsorption on the mineral surface that are present because of the isomorphous substitutions and structural defects that commonly occur in aluminosilicate minerals, and (ii) the difference in the chemistry of solutions in contact with a solid surface as compound to bulk solution. Much of our present understanding is derived from experiments using spectroscopic techniques which are able to produce information at the molecular level. Although individual methods may often be applicable to only special situations, significant advances in our knowledge have been made... 

The above techniques have a wide array of applications, including those that are both analytical and physicochemical (such as bonding) in nature. Typical examples of research include the surface chemistry of ferrite minerals (38) and the valence states of copper in a wide array of copper (39) minerals. Other areas of bonding that have been studied include the oxidation state of vanadium (40) in vanadium-bearing aegirities (also using x-ray photoelectron spectroscopy) and the. surface features of titanium perovskites (41). ... 

Present data illustrate the technique for an in situ determination of surface areas. Related methods had been applied primarily to the study of site distributions in clay minerals, particularly by Russian workers (66), and they were used by Bergmann and O Konski in a detailed investigation of the methylene blue-montmorillonite system (3). In fact, changes in electronic spectra arising from surface interactions received sufficient attention in the past to warrant their review by A. Terenin (65). Most of these investigations involved transmittance spectra but new techniques in reflection spectrophotometry and applications of the Kubelka-Munk relation have facilitated the quantitative evaluation of spectra in highly turbid media (35, 69, 77). Thus, in agreement with the work of Kortiim on powders and anhydrous dispersions (31, 32, 33), our results demonstrate the applicability of the Kubelka-Munk function... 

The next chapter is a review of current practice in lubrication of internal combustion engines and lubricant design. The role of individual lubricant components and their use in mineral and synthetic formulations is covered. This is followed by a discussion of the tribochemical effects of additive interactions. The heart of the manuscript is chapters, "Tribochemical nature of antiwear film , "Surface tribochemistry and activated processes", and "Analytical techniques in lubricating practices". Topics covered include tribofilm formation, organomolybdenum compounds in surface protection, catalytic activity of rubbing surfaces, introduction of some techniques for evaluation of tribofilms composition and analytical techniques for evaluation of lubricant degradation. Examples of the application of basic concepts are introduced, eg., acidity and basicity in the process of lubricant deterioration. 

In addition to practical applications, metal cluster-derived catalysts, particularly intrazeolite metal cluster compounds, may aid in the identification of catalytically important bonding and structural patterns and thereby further our molecular understanding of surface science and heterogeneous catalysis. The ship-in-bottle technique for the synthesis of bulky metal-mixed metal cluster compounds inside zeolites and/or interlayered minerals has gained growing attention for the purpose of obtaining catalytic precursors surrounded by the interior constraint, imposing molecular shape selectivity. Such approaches may pave the way to offer the molecular architecture of hybrid (multifunctional) tailored catalysts to achieve the desired selectivity and stability for industrial processes. 

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