Corrosion phase boundary reactions

This handbook deals only with systems involving metallic materials and electrolytes. Both partners to the reaction are conductors. In corrosion reactions a partial electrochemical step occurs that is influenced by electrical variables. These include the electric current I flowing through the metal/electrolyte phase boundary, and the potential difference A( = 0, - arising at the interface. and represent the electric potentials of the partners to the reaction immediately at the interface. The potential difference A0 is not directly measurable. Therefore, instead the voltage U of the cell Me /metal/electrolyte/reference electrode/Me is measured as the conventional electrode potential of the metal. The connection to the voltmeter is made of the same conductor metal Me. The potential difference - 0 is negligibly small then since A0g = 0b - 0ei ... 

If the corrosive medium is an electrolyte solution, the resulting corrosion reactions are electrochemical. This means that material transport in the form of metal ions and charge exchange in the form of electrons take place at the metal-solution phase boundary because of the conductivity caused in the liquid phase by mobile anions and cations and the electron conductivity of the metals. 

Electrochemical inhibitors retard or prevent the anodic and/or cathodic partial reactions (i.e they influence the reaction at the metal/corrosive medium interface). Chemical inhibitors can react both with the material and form protective coatings and with the medium itself or its constituents and thus diminish its aggressiveness. Physical inhibitors form adsorption layers on the metal surface, which block the corrosion reaction. Inhibitors that influence the electrochemical electrode reactions are subdivided according to their mode of action and site of action in the area of the metal/ medium phase boundary, with the subdivision being between interface inhibitors, electrolyte film inhibitors, membrane inhibitors, and passivators. 

Although there is no external current, anodic and cathodic processes can still occur at sites on the interface between solid and aqueous solution because of the electrolytic conductance of the corrosive medium. At electrochemical equilibrium, this leads to a definite jump in the electrical potential at the phase boundary. Kinetic barriers to certain partial reaction steps of the electrochemical process can cause the potential to be displaced from its equilibrium value. Thus, for example, instead of a dissolution of metal ... 

If the product layer is nearly free of pores, then the anodic dissolution of metal will practically cease. The metal is then said to be passivated . The thickness of the compact product layer will reach a stationary value. For oxide products which are essentially electronic conductors, this stationary thickness will be determined by the very low ionic conductivity in the oxide on the one hand, and by the rate of dissolution of the oxide in the electrolyte on the other. However, in many cases the oxide layers are porous, so that the electrolyte can continue to attack the metal, independently of the transport of ions and electrons in the oxide. From the above discussion it can be seen that corrosion reactions in aqueous ionic solutions in which a solid product layer is formed on a metal are among the most complicated of all heterogeneous solid state reactions. The reasons for this are the electrochemical nature of these reactions, the great number of possible elementary steps which can occur at the various phase boundaries, and electrical space charge phenomena which occur in the reaction product. 

In [56], microprobe studies on the distribution of the elements in the surface layers of the pipes in the experiments [55] demonstrated areas of chloride and sulphate concentration at the metal/surface layer phase boundary. This gives the surface layers semi-conductor properties, leading to partial separation of regions at vhich anodic and cathodic part reactions proceed. As the concentration of copper ions increases, the cathodic part current is increased, so that pitting corrosion is intensified at the anodic regions. 

Chemical reaction This involves the formation of distinct compounds by reaction between the solid metal and the fused metal or salt. If such compounds form an adherent, continuous layer at the interface they tend to inhibit continuation of the reaction. If, however, they are non-adherent or soluble in the molten phase, no protection will be offered. In some instances, the compounds form in the matrix of the alloy, for example as grain-boundary intermetallic compound, and result in harmful liquid metal embrittlement (LME) although no corrosion loss can be observed. 

Equations (18-20) are discretized by the control volume method53 and solved numerically to obtain distributions of species (H2, 02, and N2) concentration, phase potential (solid and electrolyte), and the current resulting from each electrode reaction, in particular, carbon corrosion and oxygen evolution currents at the cathode catalyst layer, with the following initial and boundary conditions ... 

Table 1 of a paper by Murr (2) lists problems and/or concerns related to specific interface materials and specific components of SECS. In Table 2 of the same work, he related topical study areas and/or research problems to S/S, S/L, S/G, L/L, and L/G interfaces. It is also useful to divide interface science into specific topical areas of study and consider how these will apply to interfaces in solar materials. These study areas are thin films grain, phase, and interfacial boundaries oxidation and corrosion adhesion semiconductors surface processes, chemisorption, and catalysis abrasion and erosion photon-assisted surface reactions and photoelectrochemistry and interface characterization methods. The actual or potential solar applications, research issues and/or concerns, and needs and opportunities are presented in the proceedings of a recent Workshop (4) and summarized in a recent review (3). 

The FACTSage thermochemical database was used to identify the thermodynamically stable phases that could exist in a system comprised of a pure metal, oxygen, HC1 and Cl2 at 500°C (Suppiah, 2008). The predominant Fe, Ni, Cu and Cr phases in an 02/HCl/Cl2 environment were determined. The equilibrium reaction boundary was plotted as a function of the partial pressures of 02 and HC1, for a constant Cl2 partial pressure. The resulting predominance diagrams were plotted over an 02 and HC1 partial pressure range of 10-20 to 1 atm for Cl2 partial pressures between 10-6 and 1 atm. The predominant Ni and Cr species are solids, suggesting that a corrosion resistant protective layer could be formed on the metal. 

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