Corrosive current

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. 

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 corrosion current can be converted into material loss (m ) using Faraday s law according to equation C2.8.14) ... 

C, the corrosion current density, /, at the open-circuit corrosion potential, E. See also discussion in text. 

The sohd line in Figure 3 represents the potential vs the measured (or the appHed) current density. Measured or appHed current is the current actually measured in an external circuit ie, the amount of external current that must be appHed to the electrode in order to move the potential to each desired point. The corrosion potential and corrosion current density can also be deterrnined from the potential vs measured current behavior, which is referred to as polarization curve rather than an Evans diagram, by extrapolation of either or both the anodic or cathodic portion of the curve. This latter procedure does not require specific knowledge of the equiHbrium potentials, exchange current densities, and Tafel slope values of the specific reactions involved. Thus Evans diagrams, constmcted from information contained in the Hterature, and polarization curves, generated by experimentation, can be used to predict and analyze uniform and other forms of corrosion. Further treatment of these subjects can be found elsewhere (1—3,6,18). 

The amount of externally applied current needed to change the corrosion potential of a freely corroding specimen by a few millivolts (usually 10 mV) is measured. This current is related to the corrosion current, and therefore the corrosion rate, of the sample. If the metal is corroding rapidly, a large external current is needed to change its potential, and vice versa. 

Corrosion Rate by CBD Somewhat similarly to the Tafel extrapolation method, the corrosion rate is found by intersecting the extrapolation of the linear poi tion of the second cathodic curve with the equihbrium stable corrosion potential. The intersection corrosion current is converted to a corrosion rate (mils penetration per year [mpy], 0.001 in/y) by use of a conversion factor (based upon Faraday s law, the electrochemical equivalent of the metal, its valence and gram atomic weight). For 13 alloys, this conversion factor ranges from 0.42 for nickel to 0.67 for Hastelloy B or C. For a qmck determination, 0.5 is used for most Fe, Cr, Ni, Mo, and Co alloy studies. Generally, the accuracy of the corrosion rate calculation is dependent upon the degree of linearity of the second cathodic curve when it is less than... 

There are several methods for relating the corrosion current, the apphed potential, and the polarization resistance. These methods involve various ways of stepping or ramping either the potential or current. Also, a constant value of potential or current can be applied. 

To obtain the corrosion current from Rp, values for the anodic and cathodic slopes must be known or estimated. ASTM G59 provides an experimental procedure for measuring Rp. A discussion or the factors which may lead to errors in the values for Rp, and cases where Rp technique cannot be used, are covered by Mansfeld in Polarization Resistance Measurements—Today s Status, Electrochemical Techniques for Corrosion Engineers (NACE International, 1992). 

Galvanic corrosion typically involves two or more dissimilar metals. It should be recognized, however, that sufficient variation in environmental and physical parameters such as fluid chemistry, temperature (see Case History 16.3), flow velocity, and even variations in degrees of metal cold work can induce a flow of corrosion current even within the same metal. 

Under aggressive corrosion conditions it is estimated that the maximum corrosion current density in a galvanised steel sheet will be 6 X 10 A m . Estimate the thickness of the galvanised layer needed to give a rust-free life of at least 5 years. The density of zinc is 7.13 Mg m , and its atomic weight is 65.4. Assume that the zinc corrodes to give Zn " ions. 

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... 

Before a drainage test is carried out, a so-called zero profile is measured. This involves the indication of corrosion currents, which, according to whether AU values are increasing or decreasing, locate the anodic or cathodic regions (see Fig. 18-3). 

The oil enmeshes in the tail, as shown in Figure 4-480, and provides a mechanical barrier to attack of the aqueous corrodents on the base metal. The oily film also increases the resistance to corrosion current flow and, thus, stifles the rate of corrosion. An advantage of using organic film-forming inhibitors... 

To avoid galvanic problems, different materials of con-stmction may have to be electrically isolated or at least the electrical resistance between them increased to a level sufficient to reduce the corrosion current to an acceptable value. In some instances it is more practical to paint or otherwise coat the more cathodic of the two parts of the couple. The anodic material should not be coated, since even more rapid penetration would occur at any breaks in the coating. 

When the anodic and cathodic sites are inseparable the corrosion current cannot be determined directly by an ammeter, but it can be evaluated electro-chemically by the linear polarisation technique see Sections 19.1-19.3). 

Chlorides have probably received the most study in relation to their effect on corrosion. Like other ions, they increase the electrical conductivity of the water so that the flow of corrosion currents will be facilitated. They also reduce the effectiveness of natural protective films, which may be permeable to small ions the effect of chloride on stainless steel is an extreme example but a similar effect is noted to a lesser degree with other metals. Turner" has observed that the meringue dezincification of duplex brasses is affected by the chloride/bicarbonate hardness ratio. 

Although Table 2.16 shows which metal of a couple will be the anode and will thus corrode more rapidly, little information regarding the corrosion current, and hence the corrosion rate, can be obtained from the e.m.f. of the cell. The kinetics of the corrosion reaction will be determined by the rates of the electrode processes and the corrosion rates of the anode of the couple will depend on the rate of reduction of hydrogen ions or dissolved oxygen at the cathode metal (Section 1.4). 

The general form of the anodic polarisation curve of the stainless steels in acid solutions as determined potentiostaticaiiy or potentiodynamically is shown in Fig. 3.14, curve ABCDE. If the cathodic curve of the system PQ intersects this curve at P between B and C only, the steel is passive and the film should heal even if damaged. This, then, represents a condition in which the steel can be used with safety. If, however, the cathodic curve P Q also intersects ED the passivity is unstable and any break in the film would lead to rapid metal solution, since the potential is now in the active region and the intersection at Q gives the stable corrosion potential and corrosion current. 

It should be noted that it is extremely difficult to predict service lives of buried pipelines from the results of controlled trials with small specimens, whether in the laboratory or in the field. For example a study on the comparative corrosion resistances of ductile and grey iron pipes carried out jointly by European pipemakers in 1964-1973 indicated a mean pitting rate of 0 -35 mm/y for uncoated ductile iron pipe exposed in a typical heavy Essex clay of 500-900 ohm cm resistivity for 9 years. This is clearly at odds with the rate of 1 mm/y normally found on a corroded service pipe from such a soil. The discrepancy appears to be due to the use of specimens that were only a third of a pipe length each and were buried separately. It may reflect the contribution of the total surface area of the pipe as a cathode to the corrosion current at the anodic area at the pitting site. 

A method of representing the behaviour of copper in dilute aqueous solutions by means of corrosion-current/pH diagrams has been given by Rubinic and Markovic. ... 

Patches of conductive lead sulphide can be formed on lead in the presence of sewage. This can result in the flow of a large corrosion current . Sulphate-reducing bacteria in soils can produce metal sulphides and H2S, which results in the formation of deep pits containing a black mass of lead sulphide . Other micro-organisms may also be involved in the corrosion of lead in soil . 

Figure 4.35 illustrates the effect of temperature on the rate of development of pitting, measured as a corrosion current in an acidic solution containing Cl it is seen that quite small increments in temperature have large effects. The influence of temperature is of considerable significance when metals and alloys act as heat transfer surfaces and are hotter than the corrosive environment with which they are in contact. In these circumstances. 

Some of the investigations involving electrochemical measurements have been concerned with relating easily determined quanities such as corrosion potential and corrosion current with the behaviour of a material in corrosion fatigue, so that this behaviour can be rapidly assessed without the necessity of the laborious collection of data which was the feature of McAdam s approach. Endo and Komai have derived an expression relating the increase... 

Fig. 8.75 Relation between (k — l)/n) and tj in 1% NaCl, where k is the ratio of fatigue strength in air to that in a corrosive environment, the notch sensitivity factor on fatigue strength, the corrosion current density at start of fatigue cycling, and jy the total life in...

Fig. 12.4 Corrosion diagram for a zinc diecasting in a nickel plating bath, pH 2-2. There are two possible cathodic reactions, hydrogen evolution (H) and nickel ion reduction (AO. The corrosion current is the sum of the partial cathode currents. Even with live entry the potential is still too high to suppress corrosion, though the rate is reduced to...

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