Grain boundaries characterized

These are depicted schematically in Figure 18.4 in the case of metal A deposited on metal B. Bulk diffusion, as noted above, is the transfer of B into A or A into B through the crystal lattice. This is characterized by the coefficient D in the figure. Defect path diffusion is the migration along lattice defects such as grain boundaries, characterized by the coefficient D in the figure. Ordered A B, possible phases are indicated between the metals. Finally, Kirkendall void porosity is indicated and will be expected to be present if the interdiffusion rates from one metal to the other are not equal in both directions. 

Extended defects range from well characterized dislocations to grain boundaries, interfaces, stacking faults, etch pits, D-defects, misfit dislocations (common in epitaxial growth), blisters induced by H or He implantation etc. Microscopic studies of such defects are very difficult, and crystal growers use years of experience and trial-and-error teclmiques to avoid or control them. Some extended defects can change in unpredictable ways upon heat treatments. Others become gettering centres for transition metals, a phenomenon which can be desirable or not, but is always difficult to control. Extended defects are sometimes cleverly used. For example, the smart-cut process relies on the controlled implantation of H followed by heat treatments to create blisters. This allows a thin layer of clean material to be lifted from a bulk wafer [261. 

The principal applications of REELS are thin-film growth studies and gas-surface reactions in the few-monolayer regime when chemical state information is required. In its high spatial resolution mode it has been used to detect submicron metal hydride phases and to characterize surface segregation and difRision as a function of grain boundary orientation. REELS is not nearly as commonly used as AES orXPS. 

Stress in crystalline solids produces small shifts, typically a few wavenumbers, in the Raman lines that sometimes are accompanied by a small amount of line broadening. Measurement of a series of Raman spectra in high-pressure equipment under static or uniaxial pressure allows the line shifts to be calibrated in terms of stress level. This information can be used to characterize built-in stress in thin films, along grain boundaries, and in thermally stressed materials. Microfocus spectra can be obtained from crack tips in ceramic material and by a careful spatial mapping along and across the crack estimates can be obtained of the stress fields around the crack. ... 

The sputtering process is frequendy used in both the processing (e.g., ion etching) and characterization of materials. Many materials develop nonuniformities, such as cones and ridges, under ion bombardment. Polycrystalline materials, in particular, have grains and grain boundaries that can sputter at different rates. Impurities can also influence the formation of surface topography. ... 

To further characterize the event it is first necessary to identify critical features of the initial configuration that will strongly influence the process. For powder compacts, the most obvious features are the morphological characteristics of the powders, their microstructures, and the porosity of the compact. For solid density samples, the grain structure, grain boundaries, defect level, impurities, and inclusions are critical features. 

Palladium hydride is a unique model system for fundamental studies of electrochemical intercalation. It is precisely in work on cold fusion that a balanced materials science approach based on the concepts of crystal chemistry, crystallography, and solid-state chemistry was developed in order to characterize the intercalation products. Very striking examples were obtained in attempts to understand the nature of the sporadic manifestations of nuclear reactions, true or imaginary. In the case of palladium, the elfects of intercalation on the state of grain boundaries, the orientation of the crystals, reversible and irreversible deformations of the lattice, and the like have been demonstrated. 

Another type of model electrode uses multilayer electrolytic deposits, which attracted the interest of electrochemists long before physical methods for their structural characterization were introduced. These electrodes were usually characterized by their roughness factors rather than particle size, the former being of the order of 10 -10 (for original references, see the review [Petrii and Tsirhna, 2001]). Multilayer electrolytic deposits have very complex stmctures [Plyasova et al., 2006] consisting of nanometer-sized crystallites joined together via grain boundaries, and hence have very pecuhar electrocatalytic properties [Cherstiouk et al., 2008] they will not be considered further in this chapter. 

A typical ceramic sample contains contributions from the bulk, the grain boundaries, and the electrode. Each of these is characterized by a semicircular arc with a maximum at RCu> = 1, where the values of resistance, capacitance, and frequency refer directly to the bulk, grain boundaries, or electrodes (Fig. 6.7c). The separation of resistance due to the bulk from that of the grain boundaries is thus easily achieved using impedance spectroscopy. 

The surface of a solid sample interacts with its environment and can be changed, for instance by oxidation or due to corrosion, but surface changes can occur due to ion implantation, deposition of thick or thin films or epitaxially grown layers.91 There has been a tremendous growth in the application of surface analytical methods in the last decades. Powerful surface analysis procedures are required for the characterization of surface changes, of contamination of sample surfaces, characterization of layers and layered systems, grain boundaries, interfaces and diffusion processes, but also for process control and optimization of several film preparation procedures. 

In principle it is possible to verify these findings experimentally. Diffusion measurements characterizing single-crystal samples, free from defects and grain boundaries, should be able to demonstrate that smaller guests do not always diffuse faster. However, there are a number of problems in trying to find suitable experimental results with which to corroborate the claim of the theoretical simulations. One of these problems is the rather ideal distribution of cations that is assumed in the simulations of zeolites A and... 

Grain boundaries (and boundaries between phases) are elements of the microstructure of crystalline solids, being characterized by their number, shape, and topological arrangement. The microstructure is a non-equilibrium property. In the next section we discuss grain boundaries. 

Short-circuit diffusion along grain boundaries has been studied extensively via experiments and modeling. Because diffusion along dislocations and crystal surfaces is comparatively less well characterized, particular attention is paid to grainboundary transport in this chapter. However, briefer discussions of diffusion along dislocations and free surfaces are also presented. 

All real crystals have atoms which occupy external surface sites and which do not possess the correct number of nearest neighbors as a consequence, Thus, a surface is a scat of energy and is characterized by surface tension. Furthermore, internal surfaces exist, grain boundaries and twin boundaries across which atoms are incorrectly positioned. In a crystal of reasonable size—say 1 cubic centimeter, these two-dimensional defects, called surface defects, contain only about 1 atom in 106, a rather small fraction. Even so, surfaces are important attributes of solids. 

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