Surface imperfection

Actual crystal planes tend to be incomplete and imperfect in many ways. Nonequilibrium surface stresses may be relieved by surface imperfections such as overgrowths, incomplete planes, steps, and dislocations (see below) as illustrated in Fig. VII-5 [98, 99]. The distribution of such features depends on the past history of the material, including the presence of adsorbing impurities [100]. Finally, for sufficiently small crystals (1-10 nm in dimension), quantum-mechanical effects may alter various physical (e.g., optical) properties [101]. 

Dislocation theory as a portion of the subject of solid-state physics is somewhat beyond the scope of this book, but it is desirable to examine the subject briefly in terms of its implications in surface chemistry. Perhaps the most elementary type of defect is that of an extra or interstitial atom—Frenkel defect [110]—or a missing atom or vacancy—Schottky defect [111]. Such point defects play an important role in the treatment of diffusion and electrical conductivities in solids and the solubility of a salt in the host lattice of another or different valence type [112]. Point defects have a thermodynamic basis for their existence in terms of the energy and entropy of their formation, the situation is similar to the formation of isolated holes and erratic atoms on a surface. Dislocations, on the other hand, may be viewed as an organized concentration of point defects they are lattice defects and play an important role in the mechanism of the plastic deformation of solids. Lattice defects or dislocations are not thermodynamic in the sense of the point defects their formation is intimately connected with the mechanism of nucleation and crystal growth (see Section IX-4), and they constitute an important source of surface imperfection. 

Most solid surfaces are marred by small cracks, and it appears clear that it is often because of the presence of such surface imperfections that observed tensile strengths fall below the theoretical ones. For sodium chloride, the theoretical tensile strength is about 200 kg/mm [136], while that calculated from the work of cohesion would be 40 kg/mm [137], and actual breaking stresses are a hundreth or a thousandth of this, depending on the surface condition and crystal size. Coating the salt crystals with a saturated solution, causing surface deposition of small crystals to occur, resulted in a much lower tensile strength but not if the solution contained some urea. 

We have considered briefly the important macroscopic description of a solid adsorbent, namely, its speciflc surface area, its possible fractal nature, and if porous, its pore size distribution. In addition, it is important to know as much as possible about the microscopic structure of the surface, and contemporary surface spectroscopic and diffraction techniques, discussed in Chapter VIII, provide a good deal of such information (see also Refs. 55 and 56 for short general reviews, and the monograph by Somoijai [57]). Scanning tunneling microscopy (STM) and atomic force microscopy (AFT) are now widely used to obtain the structure of surfaces and of adsorbed layers on a molecular scale (see Chapter VIII, Section XVIII-2B, and Ref. 58). On a less informative and more statistical basis are site energy distributions (Section XVII-14) there is also the somewhat laige-scale type of structure due to surface imperfections and dislocations (Section VII-4D and Fig. XVIII-14). 

Metal Preparation. Preparation of the metal surfaces to be bonded usually is required because most metals contain surface imperfections or contaminants that undesirably affect bond properties. The cladding faces usually are surface ground, using an abrasive machine, and then are degreased with a solvent to ensure consistent bond strength (26). In general, a surface finish that is >3.8 fim deep is needed to produce consistent, high quaUty bonds. 

To obtain satisfactory moldings with good surface appearance, contamination, including that by moisture, must be avoided. For good molding practice, particularly with the more polar styrene copolymers, drying must be part of the molding operation. A maximum of 0.1 wt % moisture can be tolerated before surface imperfections appear. 

If an E-E core is used (which is a common choice), there should be no air-gap and the mating surfaces of the cores must be polished. Any surface imperfections would lower the permeability. 

Some polymers, although transparent, may have a cloudy or milky appearance, generally known as haze. It is often measured quantitatively as the amount of light deviating by more than 2.5 degrees from the transmitted beam direction. Haze is often the result of surface imperfections, particularly with thin films of low-density polyethylene. 

The preceding analysis is premised on having continuous fibers of equal strength all of which fracture at the same longitudinal position. However, fibers under tension do not all have the same fracture strength nor do they fracture in the same place. Rather, because surface imperfections vary from fiber to fiber, the individual fibers have different fracture strengths. A statistical analysis is then necessary to rationally define the strength of a composite material. 

Fig. 1.1 Surface imperfections in a crystal (after Erlich and Turnbull )...

Electropolishing appears to be helpful in reducing the tendency of pits to develop at surface imperfections, but not necessarily at sites associated with structural features of the metal. 

Since fatigue cracks often start at a random surface imperfection, considerable scatter occurs in fatigue data, increasing with the increasing lifetime wherever crack initiation occupies most of the fatigue life of a specimen. When a line of the best fit is drawn from the available data points on an S-N curve, this represents the mean life expected at any given stress level or the stress that would cause, say, 50% of the product failures in a given number of cycles. 

The interpretation of voltammetry curve for the Pt(100) surface poses some problems, e.g. the origin of the peak at E=—0.15 V (Fig. 1). Markovifi et al. (12) ascribed this peak to hydrogen adsorption on particular surface imperfections, the (111)-oriented step sites. The height of this peak varies from one set of data to another, indicating a lack of control of the surface structure. Further support of this view will be shown below with the data for stepped surfaces. 

The curve for Pt(100) shows some features which could be due to the presence of the surface imperfections. Defect formation on the Pt(100) surface by an H /O flame or by electrochemical... 

Because the penetrator is applied to the surface of the material, the surface must be prepared such that it is representative of the structure of the material. The surface should be free from surface imperfections, such as scales and pits, and the surface should be flat. Some tests may require the surface to be highly polished. 

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