Reaction corrosion

In corrosion, adsorbates react directly with the substrate atoms to fomi new chemical species. The products may desorb from the surface (volatilization reaction) or may remain adsorbed in fonning a corrosion layer. Corrosion reactions have many industrial applications, such as dry etching of semiconductor surfaces. An example of a volatilization reaction is the etching of Si by fluorine [43]. In this case, fluorine reacts with the Si surface to fonn SiF gas. Note that the crystallinity of the remaining surface is also severely disrupted by this reaction. An example of corrosion layer fonnation is the oxidation of Fe metal to fonn mst. In this case, none of the products are volatile, but the crystallinity of the surface is dismpted as the bulk oxide fonns. Corrosion and etching reactions are discussed in more detail in section A3.10 and section C2.9. 

This chapter will explore surface reactions at the atomic level. A brief discussion of corrosion reactions is followed by a more detailed look at growth and etchmg reactions. Finally, catalytic reactions will be considered, with a strong emphasis on the surface science approach to catalysis. 

Since metals have very high conductivities, metal corrosion is usually electrochemical in nature. The tenn electrochemical is meant to imply the presence of an electrode process, i.e. a reaction in which free electrons participate. For metals, electrochemical corrosion can occur by loss of metal atoms tluough anodic dissolution, one of the fiindamental corrosion reactions. As an example, consider a piece of zinc, hereafter referred to as an electrode, inunersed in water. Zinc tends to dissolve in water, setting up a concentration of Zn ions very near the electrode... 

Surface science studies of corrosion phenomena are excellent examples of in situ characterization of surface reactions. In particular, the investigation of corrosion reactions with STM is promising because not only can it be used to study solid-gas interfaces, but also solid-liquid interfaces. 

The characterization of surfaces undergoing corrosion phenomena at liquid-solid and gas-solid interfaces remains a challenging task. The use of STM for in situ studies of corrosion reactions will continue to shape the atomic-level understanding of such surface reactions. 

For many practically relevant material/environment combinations, thennodynamic stability is not provided, since E > E. Hence, a key consideration is how fast the corrosion reaction proceeds. As for other electrochemical reactions, a variety of factors can influence the rate detennining step. In the most straightforward case the reaction is activation energy controlled i.e. the ion transfer tlrrough the surface Helmholtz double layer involving migration and the adjustment of the hydration sphere to electron uptake or donation is rate detennining. The transition state is... 

Based on the polarization curves of figure C2.8.4 tliere are several possibilities for reducing or suppressing tire corrosion reaction. The main idea behind every case is to shift tire corroding anode potential away from E. This can be done in tire following ways. 

A process resulting in a decrease in touglmess or ductility of a metal due to absorjDtion of hydrogen. This atomic hydrogen can result, for instance, in the cathodic corrosion reaction or from cathodic protection. 

This is essentially a corrosion reaction involving anodic metal dissolution where the conjugate reaction is the hydrogen (qv) evolution process. Hence, the rate depends on temperature, concentration of acid, inhibiting agents, nature of the surface oxide film, etc. Unless the metal chloride is insoluble in aqueous solution eg, Ag or Hg ", the reaction products are removed from the metal or alloy surface by dissolution. The extent of removal is controUed by the local hydrodynamic conditions. 

Corrosion occurs when the metallic iron in DRI is wetted with fresh or salt water and reacts with oxygen from air to form mst, Ee(OH)2- The corrosion reactions continue as long as water is present. Because water evaporates at approximately 100°C, corrosion reactions have a low temperature limit even though the reactions are exothermic. Small amounts of hydrogen may be generated when DRI reacts with water. However, this poses no safety problem as long as proper ventilation is provided. 

Allowing DRI to become wet does not necessatily cause it to overheat. When large pdes of DRI are wetted with rain, the corrosion reactions are limited to the outer surface area of the pde and the resultant heat from the corrosion reactions is dissipated into the atmosphere. However, if water penetrates into the pde from the bottom, or if wet DRI is covered with dry DRI, the heat from corrosion reactions can budd up inside the pde to the point where rapid reoxidation begins. Corrosion occurs significantly faster with salt water than with fresh water. DRI saturated with water can cause steam explosions if it is batch charged into an electric arc furnace. 

These oxazolines have cationic surface-active properties and are emulsifying agents of the water-in-oil type. They ate acid acceptors and, in some cases, corrosion inhibitors (see Corrosion). Reaction to oxazoline also is useful as a tool for determination of double-bond location in fatty acids (2), or for use as a protective group in synthesis (3). The oxazolines from AEPD and TRIS AMINO contain hydroxyl groups that can be esterified easily, giving waxes (qv) with saturated acids and drying oils (qv) with unsaturated acids. 

Many of the by-products of microbial metaboHsm, including organic acids and hydrogen sulfide, are corrosive. These materials can concentrate in the biofilm, causing accelerated metal attack. Corrosion tends to be self-limiting due to the buildup of corrosion reaction products. However, microbes can absorb some of these materials in their metaboHsm, thereby removing them from the anodic or cathodic site. The removal of reaction products, termed depolari tion stimulates further corrosion. Figure 10 shows a typical result of microbial corrosion. The surface exhibits scattered areas of localized corrosion, unrelated to flow pattern. The corrosion appears to spread in a somewhat circular pattern from the site of initial colonization. 

Biofilms can promote corrosion of fouled metal surfaces in a variety of ways. This is referred to as microbiaHy influenced corrosion. Microbes act as biological catalysts promoting conventional corrosion mechanisms the simple, passive presence of the biological deposit prevents corrosion inhibitors from reaching and passivating the fouled surface microbial reactions can accelerate ongoing corrosion reactions and microbial by-products can be directly aggressive to the metal. 

Anode Corrosion Reaction. Ziac might at first appear to be an unusual choice for battery anode material, because the metal is thermodynamically unstable ia contact with water... 

These two reactions then add up to the overall 2iac corrosion reaction (eq. 11). 

In a battery, the anode and cathode reactions occur ia different compartments, kept apart by a separator that allows only ionic, not electronic conduction. The only way for the cell reactions to occur is to mn the electrons through an external circuit so that electrons travel from the anode to the cathode. But ia the corrosion reaction the anode and cathode reactions, equations 8 and 12 respectively, occur at different locations within the anode. Because the anode is a single, electrically conductive mass, the electrons produced ia the anode reaction travel easily to the site of the cathode reaction and the 2iac acts like a battery where the positive and negative terminals are shorted together. 

The rate at which the corrosion of the 2iac proceeds depends on the rates of the two half reactions (eqs. 8 and 12). Equation 8, a necessary part of the desired battery reaction, fortunately represents a reaction that proceeds rather rapidly, whereas the reaction represented by equation 12 is slow. le, the generation of hydrogen on pure 2iac is a sluggish reaction and thus limits the overall corrosion reaction rate. 

In most aqueous systems, the corrosion reaction is divided into an anodic portion and a cathodic portion, occurring simultaneously at discrete points on metallic surfaces. Flow of electricity from the anodic to the cathodic areas may be generated by local cells set up either on a single metallic surface (because of local point-to-point differences on the surface) or between dissimilar met s. 

The electrical-resistance measurement has nothing to do with the electrochemistry of the corrosion reaction. It merely measures a bulk property that is dependent upon the specimens cross-section area. Commercial instruments are available (Fig. 28-5). 

Electrochemical techniques have been used for years to study fundamental phenomenological corrosion reactions of metals in corrosive environments. Unfortunately, the learning curve in the reduction of these elec trochemical theories to practice has been painfully slow. However, a recent survey has shown that many organizations in the... 

The primaiy use of this laboratoiy technique today is as a quick check to determine the order of magnitude of a corrosion reaction. Sometimes the calculated rate from an immersion test does not look correct when compared to the visual appearance of the metal coupon. 

With many natural substances also, the exact nature of the corrosive is uncertain and is subject to changes not readily controlled in the laboratory. In other cases, the corrosiveness of the solution may be influenced greatly by or even may be due principally to a constituent present in such minute proportions that the mass available in the hm-ited volume of corrosive solution that could be used in a laboratory setup would be exhausted by the corrosion reaction early in the test, and consequently the results over a longer period of time woiild be misleading. 

Multiinformational Prohes Corrosion probes can provide more information than just corrosion rate. The next three types of probes yield information about the type of corrosion, the kinetics of the corrosion reaction, as well as the local corrosion rate. 

In EIS, a potential is applied across a corroding metal in solution, causing current to flow The amount of current depends upon the corrosion reaction on the metal surface and the flow of ions in solution. If the potential is apphed as a sine wave, it will cause harmonics of the current output. The relationship between the apphed potential and current output is the impedance, which is analogous to resistance in a DC circiiit. 

Other Useful Information Obtained by Probes Both EIS and electrochemical noise probes can be used to determine information about the reactions that affect corrosion. Equivalent circuit analysis, when properly applied by an experienced engineer, can often give insight into the specifics of the corrosion reactions. Information such as corrosion product layer buildup, or inhibitor effectiveness, or coating breakdown can be obtained directly from analysis of the data from EIS or indirectly from electrochemical noise data. In most cases, this is merely making use of methodology developed in the corrosion laboratory. 

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