Anodic protection continued

It is possible to obtain conditions in which the anodic him continues to grow to form a blue or black layer, and this, although not exceptionally protective, has uses in the treatment of baking pans. A typical anodising solution contains 100g/1 Na2HP04 IZHjO and 20 ml/1 phosphoric acid, and is used at 350 A/m at 60-90°C for about 10 min. 

Galvanized steel is a common example of galvanic coupling where steel (Fe) with a standard electrode potential of—0.440 Vvs. SHE is cathodicaUy protected by a coating of zinc with a more active standard electrode potential of—0.763 V. Obviously, zinc is not a corrosion-resistant metal and cannot be classified as a barrier coating. It protects the steel from corrosion because of its sacrificial properties. Because zinc is less noble than steel, it acts as the anode. The sacrificial anode is continuously consumed by anodic dissolution and protects the more positive metal from corrosion. In practice, sacrificial anodes are... 

In general terms, the systems for protection of steel in concrete are generally full wave rectifiers with smoothing to minimize interference and any possible adverse effects on the anode. A continuously variable output is usually specified. Most cathodic protection systems are run under constant current control, although constant voltage (or an option for both methods) is sometimes specified. Control by constant half cell potential against an embedded reference electrode is rarely specified for steel in atmospherically exposed concrete but may be applied to buried or submerged parts of structures. 

Eventually, as the anodic process continues, a hard, dense, protective layer of Pb02 is formed on the anode surface. Once this protective film has been formed, cathode contamination decreases and the amount of sludge generated by the anode decreases as well. This process (called conditioning) may take 30-60 days or more depending on the anode composition and current density (1). Because of the difficulty in conditioning anodes, operators of zinc cellhouses are very reluctant to replace an entire cell of used, conditioned anodes with new, unconditioned anodes. Operators will normally replace only one or two anodes per cell or try to condition the anodes prior to use in the cells. 

Stainless steel or nickel-base alloy weld overlays have been used to extend the life of both continuous and batch digesters. Other corrosion protective measures for digesters include anodic protection and thermal spray coating [1161. 

Thin layer activation coupons have been used to continuously monitor corrosion rates in continuous digesters, and to verify the effectiveness of anodic protection systems [180], The surface of a thin layer activation coupon is irradiated to a shallow depth and monitoring is performed with a Geiger counter 6x>m outside the digester wall. Subtracting for effects of half-life decay, the corrosion rate can be estimated from the decreased activity of the coupon. 

Electrochemical protection is divided into cathodic and anodic protection. Cathodic protection based on the change of potential of a metal in the negative direction is realized in electrolytic environments, in most cases neutral, mainly of steel and reinforced concrete structures. A well-designed and correctly realized CP reduces the corrosion rate to almost zero. In practice it is realized with the use of an impressed current or protectors (galvanic anodes). The scope of application is enormous and continuously increases. With the use of this technology it is possible to protect vessels and ships, docks, berths, pipelines, deep wells, tanks, chemical apparatus, underground and underwater municipal and industrial infrastructure, reinforced concrete... 

The potential control in anodic protection installations has two functions. First, the potential must be measured and compared to a desired preset value. Second, a control signal must then be sent to the power supply to force the dc current between the cathode and vessel wall. In early systems, this control function was done in an ON-OFF method because of the high costs of electronic drcuitiy. The recent progress in power electronics has resulted in all systems having a continuous proportional-fype control. Packaging these electronic components occasionally involves special requirements because most of the installations are made in chemical plants. Explosion-proof enclosures are sometimes required, and chemically resistant enclosures are necessary in other installations. 

Figure 9.5 Acid cooler, courtesy Chemetics. Cool water flows through 1610 internal 2-cm diameter tubes, while warm acid flows cotmter currently (and turbulently) around the tubes. The tubes are 316-L stainless steel. They are resistant to water-side corrosion. They are electrochemically passivated against acid-side corrosion by an anodic protection system which continuously applies an electrical potential between the tubes and several electrically isolated metal rods ( anodic protection ). Details shell diameter 1.65 m shell material 304-L stainless steel acid flow 2000 m /h water flow 2900 m /h acid temperature drop 40 °C (green pipes=water metallic pipes = acid). Figure 24.7 gives an internal view.

The third widely used protection method is that of "cathodic protection", where a small negative potential is continuously applied to the metal surface to render it passive. Its counterpart, "anodic protection" can also be used to keep a metal in a permanently oxidized state, rendering it passive to corrosion. Quite evidently, this method is more cumbersome and expensive than most methods, although it does find niche uses where it is more practical, e.g. metal pipelines which have periodic control stations on the pipeline. 

In Fig. 15-9 two potentiostatically controlled protection rectifiers and an additional diode are included to drain peak currents. At pipeline crossings with an external rail network (e.g., in regions outside the urban area), the forced stray current drainage should be installed as close as possible to the rails that display negative potentials for the longest operation time. The currents absorbed from the positive rails continue to flow also in the region outside the rail crossings. Here the use of potentiostatically controlled rectifiers is recommended these should be connected not only to the rails but also to impressed current anodes. 

The distance between the structure and fixed impressed current anodes is an important factor. The number of anodes has to be small so the anodes need to be relatively large, which will result in too negative a potential if the distance is not sufficiently great. A minimum distance of 1.5 m is prescribed [1-3], but this involves considerable construction effort due to the effects of heavy seas. Besides the so-called restriction on impressed current installations, there is the requirement that the corrosion protection be switched off when diving work is being carried out [14]. This regulation is not justifiable. Work on the underwater region of production platforms takes place continuously, as far as the weather allows if the protection must be switched off each time, the impressed current protection becomes very limited. 

In addition, with high solid content of the cooling water and at high flow velocities, severe corrosive conditions exist which continuously destroy surface films. Cathodic protection alone is not sufficient. Additional measures must be undertaken to promote the formation of a surface film. This is possible with iron anodes because the anodically produced hydrated iron oxide promotes surface film formation on copper. 

The cost and economics of cathodic protection depend on a variety of parameters so that general statements on costs are not really possible. In particular, the protection current requirement and the specific electrical resistance of the electrolyte in the surroundings of the object to be protected and the anodes can vary considerably and thus affect the costs. Usually electrochemical protection is particularly economical if the structure can be ensured a long service life, maintained in continuous operation, and if repair costs are very high. As a rough estimate, the installation costs of cathodic protection of uncoated metal structures are about 1 to 2% of the construction costs of the structure, and are 0.1 to 0.2% for coated surfaces. 

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. 

Although iron pipes suffer from the same corrosion risk as steel pipelines, associated with the generation of a galvanic cell with a small anode and a large cathode, the risk is mitigated for iron pipelines because the electrical continuity is broken at every pipe joint. For this reason long-line currents are uncommon in iron lines and cathodic protection is rarely necessary. It also accounts for the ability to protect iron lines by the application of nonadherent polyethylene sleeving . 

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