Crevice

Highly localised wa.stage also does not occur very often. It is more representative of a crevice than mass wastage. 

Lin et al. [70, 71] have modeled the effect of surface roughness on the dependence of contact angles on drop size. Using two geometric models, concentric rings of cones and concentric conical crevices, they find that the effects of roughness may obscure the influence of line tension on the drop size variation of contact angle. Conversely, the presence of line tension may account for some of the drop size dependence of measured hysteresis. 

In the following, the most typical modes of corrosion—other than the above discussed unifonn dissolution (active corrosion) and localized pitting and crevice corrosion (local active dissolution)—are briefly presented. 

The rather low value obtained with the copper phthalocyanine, a low-energy solid (line (v)), is probably explicable by some reversible capillary condensation in the crevices of the aggregate, the effect of which would be to increase the uptake at a given relative pressure the plausibility of this explanation is supported by the fact that very low values of s, 1-47-1-77, were obtained with certain other phthalocyanines known to be meso-porous (cf. Chapter 3). 

Deviation from the standard isotherm in the high-pressure region offers a means of detecting the occurrence of capillary condensation in the crevices l>etween the particles of a solid and in any mesopores present within the particles themselves. A convenient device for detecting deviations from the standard is the t-plot . In the next section the nature and uses of t-plots will be discussed, together with a,-plots, a later development from them. As will l>e shown, both of these plots may l>e used not only for the detection of capillary condensation in mesopores, but also for showing up the presence of micropores and evaluating their volume. 

Increases in the appHed static pressure increase the acoustic intensity necessary for cavitation, but if equal number of cavitation events occur, the coUapse should be more intense. In contrast, as the ambient pressure is reduced, eventuaUy the gas-fiUed crevices of particulate matter which serve as nucleation sites for the formation of cavitation in even "pure" Hquids, wiU be deactivated, and therefore the observed sonochemistry wiU be diminished. 

Some nonhygroscopic materials such as metals, glass, and plastics, have the abiUty to capture water molecules within microscopic surface crevices, thus forming an invisible, noncontinuous surface film. The density of the film increases as the relative humidity increases. Thus, relative humidity must be held below the critical point at which metals may etch or at which the electrical resistance of insulating materials is significantly decreased. 

Surface Area. Surface area is the available area of fillers, be it on the surface or in cracks, crevices, and pores. The values obtained from different methods for measuring the surface area of a filler may vary significandy. These variations are because of the nature of the methods and in many instances yield information related to the heterogeneity of the surface. Understanding the surface area is important because many processing factors are dependent on the surface area, eg, ease of filler dispersion, rheology, and optimum filler loading. 

True Density or Specific Gravity. The average mass per unit volume of the individual particles is called the tme density or specific gravity. This property is most important when volume or mass of the filled composition is a key performance variable. The tme density of fillers composed of relatively large, nonporous, spherical particles is usually determined by a simple Hquid displacement method. Finely divided, porous, or irregular fillers should be measured using a gas pycnometer to assure that all pores, cracks, and crevices are penetrated. 

Another related term is smolder resistance. Smolder resistance implies resistance to ignition by a smoldering source, such as aUt cigarette, placed on the surface of a fabric or in the crevice formed between two butting fabrics. Smolder resistance does not necessarily imply flame resistance, although the material in question may well be flame resistant. A fabric can be smolder resistant and not flame resistant, or vice versa. 

Stalactites and stalagmites are conical, icicle-like shapes of pure CaCO that form on roofs and floors, respectively, of caverns. These are precipitated from cold groundwater that drips from limestone crevices. 

Ma.rine. In the presence of an electrolyte, eg, seawater, aluminum and steel form a galvanic cell and corrosion takes place at the interface. Because the aluminum superstmcture is bolted to the steel bulkhead in a lap joint, crevice corrosion is masked and may remain uimoticed until replacement is required. By using transition-joint strips cut from explosion-welded clads, the corrosion problem can be eliminated. Because the transition is metaHurgicaHy bonded, there is no crevice in which the electrolyte can act and galvanic action caimot take place. Steel corrosion is confined to external surfaces where it can be detected easily and corrected by simple wire bmshing and painting. 

For caustic crevice environment, a plant-specific chemical impurity molar ratio <0.5 is defined, eg, Na Cl molar ratio <0.5. ... 

Stress corrosion cracking, prevalent where boiling occurs, concentrates corrosion products and impurity chemicals, namely in the deep tubesheet crevices on the hot side of the steam generator and under deposits above the tubesheet. The cracking growth rates increase rapidly at both high and low pH. Either of these environments can exist depending on the type of chemical species present. 

Titanium is susceptible to pitting and crevice corrosion in aqueous chloride environments. The area of susceptibiUty for several alloys is shown in Figure 7 as a function of temperature and pH. The susceptibiUty depends on pH. The susceptibiUty temperature increases paraboHcaHy from 65°C as pH is increased from 2ero. After the incorporation of noble-metal additions such as in ASTM Grades 7 or 12, crevice corrosion attack is not observed above pH 2 until ca 270°C. Noble alloying elements shift the equiUbrium potential into the passive region where a protective film is formed and maintained. 

Fig. 7. Temperature—pH limits for crevice corrosion of titanium alloys in naturally aerated sodium chloride-rich brines. The shaded areas indicate regions...

This results in the prevention of caustic buildup beneath deposits or within a crevice where leakage is occurring. Caustic corrosion (and caustic embrittlement, discussed later) does not occur, because high caustic concentrations do not develop. 

Localized corrosion, which occurs when the anodic sites remain stationary, is a more serious industrial problem. Forms of localized corrosion include pitting, selective leaching (eg, dezincification), galvanic corrosion, crevice or underdeposit corrosion, intergranular corrosion, stress corrosion cracking, and microbiologicaHy influenced corrosion. Another form of corrosion, which caimot be accurately categorized as either uniform or localized, is erosion corrosion. 

Crevice Corrosion. Crevice corrosion is intense locali2ed corrosion that occurs within a crevice or any area that is shielded from the bulk environment. Solutions within a crevice are similar to solutions within a pit in that they are highly concentrated and acidic. Because the mechanisms of corrosion in the two processes are virtually identical, conditions that promote pitting also promote crevice corrosion. Alloys that depend on oxide films for protection (eg, stainless steel and aluminum) are highly susceptible to crevice attack because the films are destroyed by high chloride ion concentrations and low pH. This is also tme of protective films induced by anodic inhibitors. 

The best way to prevent crevice corrosion is to prevent crevices. From a cooling water standpoint, this requires the prevention of deposits on the metal surface. Deposits may be formed by suspended soHds (eg, silt, siUca) or by precipitating species, such as calcium salts. 

The most likely places for SCC to be initiated are crevices or areas where the flow of water is restricted. This is due to the buildup of corrodent concentrations in these areas. For example, chloride can concentrate from 100 ppm in the bulk water to as high as 10,000 ppm (1%) in a crevice. Deposits are initiating sites because of crevices formed beneath them. The low water velocities in shell-side cooling are also detrimental. 

Toxic chemical munitions have unique characteristics in comparison to other weapons systems, reaching personnel both widely dispersed and concentrated in fortifications, ie, gases and aerosols are not bound by corners. These materials can penetrate crevices reaching personnel physically protected from high explosives. In addition, toxic chemicals are minimum-destmction weapons as regards matHriel (5). 

Two types of localized corrosion are pitting and crevice corrosion. Pitting corrosion occurs on exposed metal surfaces, whereas crevice corrosion occurs within occluded areas on the surfaces of metals such as the areas under rivets or gaskets, or beneath silt or dirt deposits. Crevice corrosion is usually associated with stagnant conditions within the crevices. A common example of pitting corrosion is evident on household storm window frames made from aluminum alloys. 

The stainless steels contain appreciable amounts of Cr, Ni, or both. The straight chrome steels, types 410, 416, and 430, contain about 12, 13, and 16 wt % Cr respectively. The chrome—nickel steels include type 301 (18 wt % Cr and 9 wt % Ni), type 304 (19 wt % Cr and 10 wt % Ni), and type 316 (19 wt % Cr and 12 wt % Ni). Additionally, type 316 contains 2—3 wt % Mo which gready improves resistance to crevice corrosion in seawater as well as general corrosion resistance. AH of the stainless steels offer exceptional improvement in atmospheric conditions. The corrosion resistance results from the formation of a passive film and, for this reason, these materials are susceptible to pitting corrosion and to crevice corrosion. For example, type 304 stainless has very good resistance to moving seawater but does pit in stagnant seawater. 

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