Electrode corrosion

Haynie, F. H. and Ketcham, S. J., Electrochemical Behaviour of A1 Alloys Susceptible to Intergranular Corrosion. Electrode Kinetics of Oxide-covered Al , Corrosion, 19,403t (1963) Ketcham, S. J. and Haynie, F. H., Electrochemical Behaviour of Al Alloys Susceptible to Intergranular Corrosion. Effect of Cooling Rate on Structure and Electrochemical Behaviour in 202A Al Alloy , Corrosion, 19, 242t (1963)... 

On the negative side, materials problems related to corrosion, electrode degradation, electrocatalyst sintering and recrystalhzation, and electrolyte loss by evaporation are all accelerated at higher temperatures. 

Metal Alloy Corrosion electrode potential (mV, NHE) Potential following surface reduction in 10 N-HCl— reduced surface potential (mV, NHE) Rest potential in blood plasma (mV, NHE) Potential change following implantation in calf (mV, NHE) Thrombosis index (0-5) Test position d... 

On the basis of the performances of various types of ADAFCs, the most relevant observation is the mandatory presence of OH ions in the fuel stream. Up to date, in the absence of OH in the alcohol solution, the cell performance is very poor and far from a possible industrial application. The addition of MOH into alcohol supply, however, is not desirable for different reasons, such as corrosion, electrode weeping, mechanic electrode destruction by carbonate crystals, and catalyst decomposition [145]. Therefore, in addition to short-time tests, durability tests on ADAFCs fuelled with alcohol -I- MOH in the presence of CO2 have to be carried out, to find a MOH content, resulting in a good compromise between the positive effect on cell performance and the negative effect on the durability. 

Oxidation reaction (corrosion) Electrode potential ( volt)... 

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... 

Corrosion protection of metals can take many fonns, one of which is passivation. As mentioned above, passivation is the fonnation of a thin protective film (most commonly oxide or hydrated oxide) on a metallic surface. Certain metals that are prone to passivation will fonn a thin oxide film that displaces the electrode potential of the metal by +0.5-2.0 V. The film severely hinders the difflision rate of metal ions from the electrode to tire solid-gas or solid-liquid interface, thus providing corrosion resistance. This decreased corrosion rate is best illustrated by anodic polarization curves, which are constructed by measuring the net current from an electrode into solution (the corrosion current) under an applied voltage. For passivable metals, the current will increase steadily with increasing voltage in the so-called active region until the passivating film fonns, at which point the current will rapidly decrease. This behaviour is characteristic of metals that are susceptible to passivation. 

AC impedance spectroscopy is widely employed for the investigation of both solid- and liquid-phase phenomena. In particular, it has developed into a powerfiil tool m corrosion teclmology and in the study of porous electrodes for batteries [, and ]. Its usage has grown to include applications ranging from... 

Photoelectrochemistry may be used as an in situ teclmique for the characterization of surface films fonned on metal electrodes during corrosion. Analysis of the spectra allows the identification of semiconductor surface phases and the characterization of their thickness and electronic properties. 

For example, for iron in aqueous electrolytes, tlie tliennodynamic warning of tlie likelihood of corrosion is given by comparing tlie standard electrode potential of tlie metal oxidation, witli tlie potential of possible reduction reactions. 

As botli processes, reduction and oxidation, take place on tlie same electrode surface (a short-circuited system), it is not possible to directly measure tlie corrosion current. Experimentally, only tlie sum of tlie anodic and catliodic... 

The last example presented in this section deals with the pitting corrosion of Fe in CIO solutions. Perchlorate is less known as an aggressive ion but reveals some unique and remarkable characteristics with regard to pitting corrosion. For example, the critical pitting potential (1.46 V against a standard hydrogen electrode (SHE) for Fe/1 M NaClO ) can be measured with an accuracy of less than 4 mV [61] which is very unexpected if compared to... 

The electrode potential of aluminium would lead us to expect attack by water. The inertness to water is due to the formation of an unreactive layer of oxide on the metal surface. In the presence of mercury, aluminium readily forms an amalgam (destroying the original surface) which is. therefore, rapidly attacked by water. Since mercury can be readily displaced from its soluble salts by aluminium, contact with such salts must be avoided if rapid corrosion and weakening of aluminium structures is to be prevented. 

It is used in certain nickel-based alloys, such as the "Hastelloys(R)" which are heat-resistant and corrosion-resistant to chemical solutions. Molybdenum oxidizes at elevated temperatures. The metal has found recent application as electrodes for electrically heated glass furnaces and foreheaths. The metal is also used in nuclear energy applications and for missile and aircraft parts. Molybdenum is valuable as a catalyst in the refining of petroleum. It has found applications as a filament material in electronic and electrical applications. Molybdenum is an... 

Electromagnetic flow meters ate avadable with various liner and electrode materials. Liner and electrode selection is governed by the corrosion characteristics of the Hquid. Eor corrosive chemicals, fluoropolymer or ceramic liners and noble metal electrodes are commonly used polyurethane or mbber and stainless steel electrodes are often used for abrasive slurries. Some fluids tend to form an insulating coating on the electrodes introducing errors or loss of signal. To overcome this problem, specially shaped electrodes are avadable that extend into the flow stream and tend to self-clean. In another approach, the electrodes are periodically vibrated at ultrasonic frequencies. 

Ion implantation has also been used for the creation of novel catalyticaHy active materials. Ruthenium oxide is used as an electrode for chlorine production because of its superior corrosion resistance. Platinum was implanted in mthenium oxide and the performance of the catalyst tested with respect to the oxidation of formic acid and methanol (fuel ceU reactions) (131). The implantation of platinum produced of which a catalyticaHy active electrode, the performance of which is superior to both pure and smooth platinum. It also has good long-term stabiHty. The most interesting finding, however, is the complete inactivity of the electrode for the methanol oxidation. 

Although ceramic electrodes have received much attention (101), they have not been successful in channels operating with slag-laden flows, because of excessive electrochemical corrosion caused by the slag. Only weU-cooled metallic elements have been used successfully in slagging environments. 

Tips of platinum, platinum—nickel alloy, or iridium can be resistance-welded to spark-plug electrodes for improved reHabiHty and increased lifetime. These electrodes are exposed to extremely hostile environments involving spark erosion, high temperature corrosion, thermal shock, and thermal fatigue. 

Atmospheric corrosion is electrochemical ia nature and depends on the flow of current between anodic and cathodic areas. The resulting attack is generally localized to particular features of the metallurgical stmcture. Features that contribute to differences ia potential iaclude the iatermetaUic particles and the electrode potentials of the matrix. The electrode potentials of some soHd solutions and iatermetaUic particles are shown ia Table 26. Iron and sUicon impurities ia commercially pure aluminum form iatermetaUic coastitueat particles that are cathodic to alumiaum. Because the oxide film over these coastitueats may be weak, they can promote electrochemical attack of the surrounding aluminum matrix. The superior resistance to corrosion of high purity aluminum is attributed to the small number of these constituents. 

Magnetic flow meters are sometimes utilized in corrosive Hquid streams or slurries where a low unrecoverable pressure drop and high rangeabiHty is required. The fluid is required to be electrically conductive. Magnetic flow meters, which use Faraday s law to measure the velocity of the electrically conductive Hquid, are relatively expensive. Their use is therefore reserved for special situations where less expensive meters are not appropriate. Installation recommendations usually specify an upstream straight mn of five pipe diameters, keeping the electrodes in continuous contact with the Hquid. 

The titanium oxide film consists of mtile or anatase (31) and is typically 250-A thick. It is insoluble, repairable, and nonporous in many chemical media and provides excellent corrosion resistance. The oxide is fully stable in aqueous environments over a range of pH, from highly oxidizing to mildly reducing. However, when this oxide film is broken, the corrosion rate is very rapid. Usually the presence of a small amount of water is sufficient to repair the damaged oxide film. In a seawater solution, this film is maintained in the passive region from ca 0.2 to 10 V versus the saturated calomel electrode (32,33). 

Eor the negative electrolyte, cadmium nitrate solution (density 1.8 g/mL) is used in the procedure described above. Because a small (3 —4 g/L) amount of free nitric acid is desirable in the impregnation solution, the addition of a corrosion inhibitor prevents excessive contamination of the solution with nickel from the sintered mass (see Corrosion and corrosion inhibitorsCorrosion and corrosion control). In most appHcations for sintered nickel electrodes the optimum positive electrode performance is achieved when one-third to one-half of the pore volume is filled with active material. The negative electrode optimum has one-half of its pore volume filled with active material. 

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