Corrosion anodic

Copper-containing lead alloys undergo less corrosion in sulfuric acid or sulfate solutions than pure lead or other lead alloys. The uniformly dispersed copper particles give rise to local cells in which lead forms the anode and copper forms the cathode. Through this anodic corrosion of the lead, an insoluble film of lead sulfate forms on the surface of the lead, passivating it and preventing further corrosion. The film, if damaged, rapidly reforms. 

The main cause of anode wear is electrochemical oxidation or sulfur attack of anodic surfaces. As copper is not sufficiently resistant to this type of attack, thin caps of oxidation and sulfur-resistant material, such as platinum, are bra2ed to the surface, as shown in Eigure 15a. The thick platinum reinforcement at the upstream corner protects against excessive erosion where Hall effect-induced current concentrations occur, and the interelectrode cap protects the upstream edge from anodic corrosion caused by interelectrode current leakage. The tungsten undedayment protects the copper substrate in case the platinum cladding fails. 

Purification actually starts with the precipitation of the hydrous oxides of iron, alumina, siUca, and tin which carry along arsenic, antimony, and, to some extent, germanium. Lead and silver sulfates coprecipitate but lead is reintroduced into the electrolyte by anode corrosion, as is aluminum from the cathodes and copper by bus-bar corrosion. 

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... 

Area effects in galvanic corrosion are very important. An unfavorable area ratio is a large cathode and a small anode. Corrosion of the anode may be 100 to 1,000 times greater than if the two areas were the same. This is the reason why stainless steels are susceptible to rapid pitting in some environments. Steel rivets in a copper plate will corrode much more severely than a steel plate with copper rivets. 

A note of caution about roof fasteners. A common mistake is to fix a galvanised or aluminium roof in place with nails or screws of a different metal copper or brass, for instance. The copper acts as cathode, and the zinc or aluminium corrodes away rapidly near to the fastening. A similar sort of goof has been known to occur when copper roofing sheet has been secured with steel nails. As Fig. 24.6 shows, this sort of situation leads to catastrophically rapid corrosion not only because the iron is anodic, but because it is so easy for the electrons generated by the anodic corrosion to get away to the large copper cathode. 

Enhancement of Anodic Corrosion by Cell Formation or Stray Currents from dc Installations... 

Even with the superposition of the ac with a cathodic protection current, a large part of the anodic half wave persists for anodic corrosion. This process cannot be detected by the normal method (Section 3.3.2.1) of measuring the pipe/soil potential. The IR-free measurable voltage between an external probe and the reference electrode can be used as evidence of more positive potentials than the protection potential during the anodic phase. Investigations have shown, however, that the corrosion danger is considerably reduced, since only about 0.1 to 0.2% contributes to corrosion. 

There are two types of impressed current anodes either they consist of anodically stable noble metals (e.g., platinum) or anodically passivatable materials that form conducting oxide films on their surfaces. In both cases, the anodic redox reaction occurs at much lower potentials than those of theoretically possible anodic corrosion. 

Rectifiers working according to the control diagram in Fig. 8-6 are used for anodic corrosion protection in passivatable systems that go spontaneously from the passive to the active state when the protection current is switched off [12]. The predetermined nominal voltage between reference electrode and protected object is compared with the actual voltage f/j in a differential display unit D. The difference AU = is amplified in a voltage amplifier SV to VqAU. This... 

With underground installations in the soil, it must be ensured that no water can penetrate in gaps between cathodically protected and unprotected parts since the cathodically unprotected side of the coupling can be destroyed by anodic corrosion. Sections of pipe behind the insulator must be particularly well coated. 

Fig. 10-9 Internal cathodic protection to avoid the danger of anodic corrosion behind an insulating joint in a brine pipeline.

Bus bars of a transformer substation must not be directly grounded. They must be connected with rails by at least two insulated cables. Metal sheathing of feeder and return current cables must only then be connected with the rails or bus bar if an increase in anodic corrosion on other buried installations is absolutely excluded. The insulation of all return cables must therefore be monitored regularly. 

From these two examples, which as will be seen subsequently, present a very oversimplified picture of the actual situation, it is evident that macroheterogeneities can lead to localised attack by forming a large cathode/small anode corrosion cell. For localised attack to proceed, an ample and continuous supply of the electron acceptor (dissolved oxygen in the example, but other species such as the ion and Cu can act in a similar manner) must be present at the cathode surface, and the anodic reaction must not be stifled by the formation of protective films of corrosion products. In general, localised attack is more prevalent in near-neutral solutions in which dissolved oxygen is the cathode reactant thus in a strongly acid solution the millscale would be removed by reductive dissolution see Section 11.2) and attack would become uniform. 

Lead is characterised by a series of anodic corrosion products which give a film or coating that effectively insulates the metal mechanically from the electrolyte (e.g. PbS04, PbClj, PbjO, PbCrO<. PbO, PbO, 2PbC03.Pb<0H)z), of which PbS04 and Pb02 are the most important, since they play a part in batteries and anodes. Lead sulphate is important also in atmospheric passivation and chemical industry applications. 

Pavlov, D. and Rogachev, T. Dependence of the Phase Composition of The Anodic Layer on Oxygen Evolution and Anodic Corrosion of Lead Electrode in Lead Dioxide Potential Region , Electrochim. Acta., 23, 1237 (1978)... 

Rhodium and iridium have a resistance to anodic corrosion comparable with that of platinum, and are more resistant to the influence of alternating currents. A platinum-iridium alloy, in the form of a coating on titanium, is preferred to pure platinum for the production of chlorine from brine , due to its improved corrosion resistance and lower overvoltage. 

Palladium is considerably less resistant to anodic corrosion than platinum, though it may be used for evolution of oxygen from alkaline solutions. It is attacked rapidly when used as an anode in sea-water, and dissolves quantitatively in acid chloride solutions. 

One advantage of steel as an anode is the low gassing at the electrode during operation, since the predominant reaction is the corrosion of iron. Thus, the problem of resistive polarisation due to gas blocking, as may be the case with more inert materials, does not occur. Iron compounds do, of course, form but these do not appreciably affect the anode/soil resistivity. Furthermore, the introduction of metallic ions, by anode corrosion, into the adjacent high resistivity soil is beneficial in lowering the resistivity. 

Sacrificial anodes are of limited application due to accumulation of anode corrosion product and also in many cases, to high water resistivity. 

The overall process is metal transfer from anode to cathode via the solution. The form of anode corrosion is important, and materials may be added both to the anode metal and to the electrolyte, to influence it. There are important instances where an insoluble anode is used, and the anode reaction becomes the oxidation of water or hydroxyl ions ... 

The anode is usually soluble, and is made from a high purity form of the metal being deposited, or occasionally from an alloy. A soluble anode is often the cheapest and most convenient means of replacing the metal reduced at the cathode. Effective anode corrosion is important, and different examples present a variety of types of dissolution. 

Plating bath Anodes Corrosion process Current Potential density (V) (A/m ) (vj.S.H.E.) ... 

Degradation of wood is also observed adjacent to anodic corrosion sites. Some metal ions, notably Fe, catalytically decompose the cellulose components of wood. This significantly reduces the wood s fastener-holding ability. 

Some investigatorshave advocated a type of accelerated test in which the specimens are coupled in turn to a noble metal such as platinum in the corrosive environment and the currents generated in these galvanic couples are used as a measure of the relative corrosion resistance of the metals studied. This method has the defects of other electrolytic means of stimulating anodic corrosion, and, in addition, there is a further distortion of the normal corrosion reactions and processes by reason of the differences between the cathodic polarisation characteristics of the noble metal used as an artificial cathode and those of the cathodic surfaces of the metal in question when it is corroding normally. 

Anode Corrosion Efficiency the ratio of the actual corrosion rate of the anode to the theoretical rate according to Faraday s Law, expressed as a percentage. 

The periodic development and use of new steel alloys can improve ferrous corrosion resistance however, where economizer units are constructed of copper alloys, under certain conditions serious copper corrosion problems may result. This occurs when FW having a pH over 8.3 also contains small amounts of ammonia and dissolved oxygen (DO). The ammonia may be present, for example, as a result of the overuse or inappropriate application of certain amines. Further damage may occur from the plating-out of the copper-ammonia ion then created as a cathode on boiler tubes. This promotes anodic corrosion of the immediate surrounding anodic areas. 

Anodic polarization also may occur. Typically, this begins with the formation of a thin, impervious oxide film, chemisorbed at the anode (as on the surface of stainless steels). However, for most metals used in boiler plant systems this chemisorption process must be aided by anodic corrosion inhibitors to reduce corrosion rates to tolerable levels. An example is the application of nitrite-based inhibitors, widely used in HW heating systems. 

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