Lead, passivity

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. 

Anodes. Lead—antimony (6—10 wt %) alloys containing 0.5—1.0 wt % arsenic have been used widely as anodes in copper, nickel, and chromium electrowinning and metal plating processes. Lead—antimony anodes have high strength and develop a corrosion-resistant protective layer of lead dioxide during use. Lead—antimony anodes are resistant to passivation when the current is frequendy intermpted. 

Silver reduces the oxygen evolution potential at the anode, which reduces the rate of corrosion and decreases lead contamination of the cathode. Lead—antimony—silver alloy anodes are used for the production of thin copper foil for use in electronics. Lead—silver (2 wt %), lead—silver (1 wt %)—tin (1 wt %), and lead—antimony (6 wt %)—silver (1—2 wt %) alloys ate used as anodes in cathodic protection of steel pipes and stmctures in fresh, brackish, or seawater. The lead dioxide layer is not only conductive, but also resists decomposition in chloride environments. Silver-free alloys rapidly become passivated and scale badly in seawater. Silver is also added to the positive grids of lead—acid batteries in small amounts (0.005—0.05 wt %) to reduce the rate of corrosion. 

Lead and many of its ahoys exhibit excehent corrosion resistance owing to the rapid formation of a passive, impermeable, insoluble protective film when the lead is exposed to the corrosive solution (see Corrosion and corrosion control). 

Sometimes the formation of oxide films on the metal surface binders efficient ECM, and leads to poor surface finish. Eor example, the ECM of titanium is rendered difficult in chloride and nitrate electrolytes because the oxide film formed is so passive. Even when higher (eg, ca 50 V) voltage is apphed, to break the oxide film, its dismption is so nonuniform that deep grain boundary attack of the metal surface occurs. 

The second class of anodic inhibitors contains ions which need oxygen to passivate a metal. Tungstate and molybdate, for example, requke the presence of oxygen to passivate a steel. The concentration of the anodic inhibitor is critical for corrosion protection. Insufficient concentrations can lead to pitting corrosion or an increase in the corrosion rate. The use of anodic inhibitors is more difficult at higher salt concentrations, higher temperatures, lower pH values, and in some cases, at lower oxygen concentrations (37). 

Plating T anks. An electroless plating line consists of a series of lead-lined (for plastics etching) or plastic-lined tanks equipped with filters and heaters, separated by rinse tanks (24). Most metal tanks, except for passivated stainless steel used for electroless nickel, cannot be used to hold electroless plating baths because the metal initiates electroless plating onto itself. Tank linings must be stripped of metal deposits using acid at periodic intervals. 

APPLICATION OF SURFACE ELECTROCHEMICAL PASSIVATION OF LEAD-ANTIMONY ALLOY FOR A SIMPLE AND RAPID ELECTROCHEMICAL DETERMINATION OF ANTIMONY CONTENT OF ITS ALLOYS... 

The anodes are generally not of pure metals but of alloys. Certain alloying elements serve to give a fine-grained structure, leading to a relatively uniform metal loss from the surface. Others serve to reduce the self-corrosion and raise the current yield. Finally, alloying elements can prevent or reduce the tendency to surface film formation or passivation. Such activating additions are necessary with aluminum. 

Since the object to be protected represents a cell consisting of active and passive steel, considerable IR errors in the cell current must be expected in measuring the off potential. The considerations in Section 3.3.1 with reference to Eqs. (3-27) and (3-28) are relevant here. Since upon switching off the protection current, 7, the nearby cathodes lead to anodic polarization of a region at risk from corrosion, the cell currents and 7, have opposite signs. It follows from Eqs. (3-27) and (3-28) that the 77 -free potential must be more negative than the off potential. Therefore, there is greater certainty of the potential criterion in Eq. (2-39). 

Pits occur as small areas of localized corrosion and vary in size, frequency of occurrence, and depth. Rapid penetration of the metal may occur, leading to metal perforation. Pits are often initiated because of inhomogeneity of the metal surface, deposits on the surface, or breaks in a passive film. The intensity of attack is related to the ratio of cathode area to anode ai ea (pit site), as well as the effect of the environment. Halide ions such as chlorides often stimulate pitting corrosion. Once a pit starts, a concentration-cell is developed since the base of the pit is less accessible to oxygen. 

Exposure in a solution that is passivating and yet not far removed from the passive-activity boundary may lead to coiTosion if the exposure involves a strong abrasive condition as well. Pitting of pump shafts under packing handling sea water is an example of this abrasive effect. 

For those applications where high efficiency is important, synchronous rectification may be used on the higher current (power) outputs. Synchronous rectifier circuits are much more complicated than the passive 2-leaded rectifier circuits. These are power MOSFE B, which are utilized in the reverse conduction direction where the anti-parallel intrinsic diode conducts. The MOSFET is turned on whenever the rectifier is required to conduct, thus reducing the forward voltage drop to less than O.f V. Synchronous rectifiers can be used only when the diode current flows in the forward direction, that is in continuousmode forward converters. 

A passive lead network (using two resistors and one eapaeitor) has a transfer fune-tion of the form... 

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