Corrosive potential

In the case of a neutral solution (e.g. pH = 7), depending on the corrosion potential all these tliree ranges (stability, dissolution or oxide fonnation) may be involved. 

Other techniques to detennine the corrosion rate use instead of DC biasing, an AC approach (electrochemical impedance spectroscopy). From the impedance spectra, the polarization resistance (R ) of the system can be detennined. The polarization resistance is indirectly proportional to j. An advantage of an AC method is given by the fact that a small AC amplitude applied to a sample at the corrosion potential essentially does not remove the system from equilibrium. 

Extended stabiUty testing is a necessity for emulsion systems in metal containers because of the corrosion potential of water. In most cases where a stable emulsion exists, there is less corrosion potential in a w/o system because the water is the internal phase. 

The following mechanisms in corrosion behavior have been affected by implantation and have been reviewed (119) (/) expansion of the passive range of potential, (2) enhancement of resistance to localized breakdown of passive film, (J) formation of amorphous surface alloy to eliminate grain boundaries and stabilize an amorphous passive film, (4) shift open circuit (corrosion) potential into passive range of potential, (5) reduce/eliminate attack at second-phase particles, and (6) inhibit cathodic kinetics. 

Both molybdate and orthophosphate are excellent passivators in the presence of oxygen. Molybdate can be an effective inhibitor, especially when combined with other chemicals. Orthophosphate is not really an oxidizer per se but becomes one ia the presence of oxygen. If iron is put iato a phosphate solution without oxygen present, the corrosion potential remains active and the corrosion rate is not reduced. However, if oxygen is present, the corrosion potential iacreases ia the noble direction and the corrosion rate decreases significantly. 

Internal Reports Skin Corrosion Potential ofEiquid Citric Acid S0%,Jan. 19, 1979, Dermal Irritation of Citric Acid in the Rabbit, Dec. 20, 1990, Ocular Irritation of Citric Acid in the Rabbit, May 14, 1991, Miles Inc., Elkhart, Ind. 

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). 

Anodic Inhibitors. Passivating or anodic inhibitors produce a large positive shift in the corrosion potential of a metal. There are two classes of anodic inhibitors which are used for metals and alloys where the anodic shift in potential promotes passivation, ie, anodic protection. The fkst class includes oxidking anions that can passivate a metal in the absence of oxygen. Chromate is a classical example of an oxidking anodic inhibitor for the passivation of steels. 

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. 

It is now well established that the activity of pitting, crevice corrosion, and stress-corrosion cracking is strongly dependent upon the corrosion potential (i.e., the potential difference between the corrod-... 

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... 

The corrosion potential is not near the oxidation/reduction potential for either reaction. 

Generai description. Galvanic corrosion refers to the preferential corrosion of the more reactive member of a two-metal pair when the metals are in electrical contact in the presence of a conductive fluid (see Chap. 16, Galvanic Corrosion ). The corrosion potential difference, the magnitude of which depends on the metal-pair combination and the nature of the fluid, drives a corrosion reaction that simultaneously causes the less-noble pair member to corrode and the more-noble pair member to become even more noble. The galvanic series for various metals in sea water is shown in Chap. 16, Table 16.1. Galvanic potentials may vary with temperature, time, flow velocity, and composition of the fluid. 

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. 

Evaluation of the corrosion potential from Eq. (2-53) is inadmissible when the metal ion, for example, reacts further in strongly complexing solutions ... 

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. 

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