Free corrosion potential

Equation (2-38) is valid for every region of the surface. In this case only weight loss corrosion is possible and not localized corrosion. Figure 2-5 shows total and partial current densities of a mixed electrode. In free corrosion 7 = 0. The free corrosion potential lies between the equilibrium potentials of the partial reactions and U Q, and corresponds in this case to the rest potential. Deviations from the rest potential are called polarization voltage or polarization. At the rest potential = ly l, which is the corrosion rate in free corrosion. With anodic polarization resulting from positive total current densities, the potential becomes more positive and the corrosion rate greater. This effect is known as anodic enhancement of corrosion. For a quantitative view, it is unfortunately often overlooked that neither the corrosion rate nor its increase corresponds to anodic total current density unless the cathodic partial current is negligibly small. Quantitative forecasts are possible only if the Jq U) curve is known. 

This criterion is derived from the fact that the free corrosion potential in soil is generally I/cu Cuso4 -0-55 V. Ohmic voltage drop and protective surface films are not taken into consideration. According to the information in Chapter 4, a maximum corrosion rate for uniform corrosion in soil of 0.1 mm a can be assumed. This corresponds to a current density of 0.1 A m l In Fig. 2-9, the corrosion current density for steel without surface film changes by a factor of 10 with a reduction in potential of about 70 mV. To reduce it to 1 jum a (0.14 V would be necessary. The same level would be available for an ohmic voltage drop. With surfaces covered with films, corrosion at the rest potential and the potential dependence of corrosion in comparison with act contrary to each other so that qualitatively the situation remains the same. More relevant is... 

Fig. 12-2 Local cathodic protection in a power station. deep anodes O horizontal anodes Potential readings Ccu-cuso4 volts (A) free corrosion potential before commissioning the cathodic protection (B) 4 months after switching on...

The free corrosion potential of t/cu-cuso4 = lowered to -0.9 V with... 

Further cell currents flow between the wells as a result of electrical connections established between them by the flow lines and of the different free corrosion potentials, thereby allowing them to behave as anode or cathode. The currents can amount to a few amps so that considerable corrosion damage can arise. The action of these cells can be prevented by building in insulators between the drilling and the field cable. 

An interesting field of application is the protection of tantalum against hydrogen embrittlement by electrical connection to platinum metals. The reduction in hydrogen overvoltage and the shift of the free corrosion potential to more positive values apparently leads to a reduced coverage by adsorbed hydrogen and thereby lower absorption [43] (see Sections 2.1 and 2.3.4). 

Bignold has postulated that increasing flow increases both mass transfer and by lowering the free corrosion potential the oxide solubility. This would lead to a higher dependency on mass transfer than expected. 

Edwards e/a/. carried out controlled potential, slow strain-rate tests on Zimaloy (a cobalt-chromium-molybdenum implant alloy) in Ringer s solution at 37°C and showed that hydrogen absorption may degrade the mechanical properties of the alloy. Potentials were controlled so that the tensile sample was either cathodic or anodic with respect to the metal s free corrosion potential. Hydrogen was generated on the sample surface when the specimen was cathodic, and dissolution of the sample was encouraged when the sample was anodic. The results of these controlled potential tests showed no susceptibility of this alloy to SCC at anodic potentials. 

The sometimes contradictory results from different workers in relation to the elements mentioned above extends to other elements . Some of these differences probably arise from variations in test methods, differences in the amounts of alloying additions made, variations in the amounts of other elements in the steel and the differing structural conditions of the latter. Moreover, the tests were mostly conducted at the free corrosion potential, and that can introduce further variability between apparently similar experiments. In an attempt to overcome some of these difficulties, slow strain-rate tests were conducted on some 45 annealed steels at various controlled potentials in three very different cracking environments since, if macroscopic... 

It is often difficult to conduct laboratory tests in which both the environmental and stressing conditions approximate to those encountered in service. This applies particularly to the corrosive conditions, since it is necessary to find a means of applying cyclic stresses that will also permit maintenance around the stressed areas of a corrosive environment in which the factors that influence the initiation and growth of corrosion fatigue cracks may be controlled. Among these factors are electrolyte species and concentration, temperature, pressure, pH, flow rate, dissolved oxygen content and potential (free corrosion potential or applied). 

With the noise techniques, both analogue and digital, no externally applied signal is required, and measurement of the fluctuations around the free corrosion potential provides all the information. Hie noise technique is useful in that it allows a fairly rapid estimation of the electrochemical impedance of the system being studied, whereas, with for instance, a.c. lnpedance techniques, very often the minimum frequency studied is still not low enough to provide sufficient information to allow an accurate estimation of the impedance. 

Results. The presence of Pt reduces the corrosion rate of Ti by shifting the free corrosion potential to more noble values (Fig. 6) where the Ti dissolution rate is slower. This shift is produced by the catalytic effect of Pt on hydrogen recombination which alters the cathodic reactions at the alloy surface. At the corrosion potential, the cathodic and anodic currents are equal. Although the shift in corrosion potential reduces the anodic current, anodic dissolution of Ti still occurs. The long-term corrosion rate of a surface alloy depends upon what happens to the Pt as the Ti is being dissolved. If Pt is removed from the surface, the corrosion rate will increase as the implanted volume of the alloy is dissolved. If Pt builds up on the surface, the corrosion rate should remain low. 

The surface charge on the metal is defined by the position of free corrosion potential /icon °f the metal with respect to its potential of zero charge Ev/( . When Econ-EPZC is negative, cations are adsorbed and when it is positive, negative ions are adsorbed and this adsorption is electrostatic in nature. Physical adsorption forces are relatively weak and have low activation energy. Some data on the values of zero charge potentials of metals are given in Table 1.22. 

The free corrosion potential, breakdown potential and corrosion rate of 316L stainless steel are chloride concentration dependent. As the chloride concentration increased, the free corrosion potential and the breakdown potential became less noble. The corrosion rate increased as the chloride concentration increased as expected. 

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