Diffraction methods, surface analysis

Surfiice order and cleanliness. The most common use of LEED is in association with other surface analysis or surfiice research methods, to check surfiice structural order and cleanliness. A visual display of the diffraction pattern is used. An expected pattern, with sharp diffracted beams, is an indication that the surfiice is clean and well ordered. 

In this chapter, we have chosen from the scientific literature accounts of symposia published at intervals during the period 1920 1990. They are personal choices illustrating what we believe reflect significant developments in experimental techniques and concepts during this time. Initially there was a dependence on gas-phase pressure measurements and the construction of adsorption isotherms, followed by the development of mass spectrometry for gas analysis, surface spectroscopies with infrared spectroscopy dominant, but soon to be followed by Auger and photoelectron spectroscopy, field emission, field ionisation and diffraction methods. 

In one of the earliest reports of the use of clean evaporated alloy films in surface studies, Stephens described the preparation and characterization of Pd-Au films and presented some results for the adsorption of oxygen on them 46). Films of pure Pd and 60% Au were evaporated directly from wires, while films of 80% Au and pure Au were evaporated from a pre-outgassed tungsten support wire. The films were evaporated in a UHV system and the pressure was kept below PC8 Torr during evaporation. After evaporation, the films were stabilized by cycling between —195° and 30°C four times. They w ere characterized by X-ray diffraction and chemical analysis surface areas were measured by the BET method using krypton adsorption. 

Four samples of faujasite were synthesized at Si/Al ratios of 2.61, 2.80, 2.97 and 3.03 using published methods from seeded slurries (8-9) and using proprietary methods. One additional sample of Si/Al ratio 2.58 was purchased from Union Carbide. The samples were characterized by X-ray powder diffraction, by surface area measurements, and by wet chemical analysis. The results of these measurements are contained in Table I. 

The simplest method of XRD analysis, used in early studies and described by Tite (1972 286), is the powder diffraction method. A small sample, typically 5-10 mg, is removed from the artifact, either by scraping the surface, cutting... 

In 1966, a catalyst based on a complex uranium antimonate system was developed and brought into commercial use (4, 87). Several physical methods of analysis were used in an attempt to clarify relationships between the structure and properties of the uranium antimonate system and its catalytic properties (20, 88, 89). X-Ray diffraction and infrared analysis demonstrated that the optimum selectivity for acrylonitrile formation coincided with the maximum concentration of the USb3O10 compound. The crystal structure of USb3O10 was shown to consist of layers of heavy atoms and oxygen ions alternated by layers of oxygen ions. Measurements by ESCA indicated that the surface layers contained U5+ and Sb5+ with intensities corresponding to the USb3O10 formula. 

As with all surface analytical methods, surface preparation is critical to obtaining reproducible SHG from metallic surfaces and single crystals in particular. For surfaces prepared in UHV and then transferred to an electrochemical cell, sputtering and heating or annealing followed by Auger analysis of impurities should proceed inert transfer. Low energy electron diffraction (LEED) can also be used to check surface order. Metal electrode surfaces, particularly for the rotational anisotropy ex-... 

In addition to diffraction methods, also spectroscopic techniques, especially NMR spectroscopy, are extensively used to study the complex interaction of water and the clay mineral surfaces. NMR spectroscopy has become a valuable tool to investigate the dynamics of water [41, 48-54]. The study of interaction of water with clays using NMR techniques has primarily involved measurements of H and 2H spin-lattice relaxation and lineship analysis of H and 2H in water molecules adsorbed on clays [32, 41, 51-54], Based upon the results of such studies, it is possible to calculate the distribution, orientation, and diffusion rates of water molecules bound to clays. It was found that water molecules have a preferential orientation on clays with low water contents at temperatures near 298K [52, 54]. 

The failure analysis can be done using a judicious combination of several methods such as visual examination, metallography, microscopy, electron microprobe, energy dispersive X-ray analysis, X-ray diffraction methods for determining residual stress in the sample, surface analytical techniques to determine the nature and composition of surface deposits and finite element analysis modeling. 

Surface analytical methods — Important ex situ methods for surface analysis are X-Ray Photoelectron Spectroscopy (XPS) UV-Photoelectron Spectroscopy (UPS), Auger Electron Spectroscopy (AES), Ion Scattering Spectroscopy (ISS), Rutherford Backscattering (RBS), Secondary Ion Mass Spectroscopy (SIMS), Scanning Electron Microscopy (SEM), Electron Microprobe Analysis (EMA), Low Energy Electron Diffraction (LEED), and High Energy Electron Diffraction (RHEED). 

The chemical composition can be measured by traditional wet and instrumental methods of analysis. Physical surface area is measured using the N2 adsorption method at liquid nitrogen temperature (BET method). Pore size is measured by Hg porosimetry for pores with diameters larger than about 3.0 nm (30 A) or for smaller pores by N2 adsorp-tion/desorption. Active catalytic surface area is measured by selective chemisorption techniques or by x-ray diffraction (XRD) line broadening. The morphology of the carrier is viewed by electron microscopy or its crystal structure by XRD. The active component can also be measured by XRD but there are certain limitations once its particle size is smaller than about 3.5 nm (35 A). For small crystallites transmission electron microscopy (TEM) is most often used. The location of active components or poisons within the catalyst is determined by electron microprobe. Surface contamination is observed directly by x-ray photoelectron spectroscopy (XPS). 

It is evident from the above discussion that catalyst characterization is an activity important for scientific understanding, design, and troubleshooting of catalyzed processes. There is no universal recipe as to which characterization methods are more expedient than others. In the opinion of the writer, we will see continued good use of diffraction methods and electron microscopy, surface analysis, IR spectroscopy, and chemisorption methods, increased use of combined EM and ESCA analyses for determining the dopant dispersion, increased use of MAS-NMR and Raman spectroscopies for understanding of solid state chemistry of catalysts, and perhaps an increased use of methods that probe into the electronic structure of catalysts, including theory. 

In this expression, the subscripts 1 and 2 refer to inclusion and surface sorption, respectively. Other techniques for characterizing complexes include desorption methods, elemental analysis, X-ray diffraction, spectroscopic methods, thermogravimetry, and others. 

Layer charges can be calculated from mineral and chemical composition. Mineral composition can be determined by the comparison of x-ray diffraction and thermal analytical and surface area studies. Chemical composition is determined by a total chemical analysis of the sample. In the classical method, chemical analysis is made after acidic dissolution (Ross and Hendricks 1945). Nowadays, nondestructive analytical methods (e.g., electron microscopy, prompt gamma activation analysis, etc.) are also applied. Chemical composition is usually given as oxides (e.g., Si02, A1203, etc.). The cations are divided into three groups ... 

For supported metal catalysts, no simple calculation is possible. A direct measurement of the metal crystallite size or a titration of surface metal atoms is required (see Example 1.3.1). TWo common methods to estimate the size of supported crystallites are transmission electron microscopy and X-ray diffraction line broadening analysis. Transmission electron microscopy is excellent for imaging the crystallites, as illustrated in Figure 5.1.5. However, depending on the contrast difference with the support, very small crystallites may not be detected. X-ray diffraction is usually ineffective for estimating the size of very small particles, smaller than about 2 nm. Perhaps the most common method for measuring the number density of exposed metal atoms is selective chemisorption of a probe molecule like H2, CO, or O2. 

Among the ex situ methods that can be employed in surface analysis, low-energy electron diffraction (LEED) and x-ray photoelectron spectroscopy (XPS) can give the crystal structure and the nature of the surface ad-layers after the electrochemical and adsorption experiments as explained in this chapter [31,32]. Among the in situ non-electrochemical techniques, the radiotracer method [33] gives information about the adsorbed quantities however, infrared spectroscopy in FTIR mode [34] allows the identity of the bonding of the adsorbed molecules, and finally ellipsometry [35] makes possible the study of extremely thin films. Recently, some optical methods such as reflectance, x-ray diffraction, and second harmonic generation (SHG) [36] have been added to this list. 

G.L. Price. Reflection High Energy Electron Diffraction. In D.J. O Conner, B.A. Sexton, and R. St. C. Smart, editors, Surface Analysis Methods in Materials Science. Springer Series in Surface Sciences, Volume 23. Springer-Verlag, Berlin, 1992. 

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