Aluminum passivity

Korlach, J., Marks, P.J., Cicero, R.L., Gray, J.J., Murphy, D.L., Roitman, D.B., Pham, T.T., Otto, G.A., Foquet, M., and Turner, S.W (2008). Selective aluminum passivation for targeted immobilization of single DNA polymerase molecules in zero-mode waveguide nanostructures. Proc. Natl Acad. Sci. USA 105 1176-1181. 

Magnesium and zinc are the predominantly used galvanic anodes for the cathodic protection of pipelines [13—16]. The corrosion potential difference of magnesium with respect to steel is 1 V, which Umits the length of the pipeline that can be protected by one anode. Economic considerations have led to the use of aluminum and its alloys as anodes. However, aluminum passivates easily, decreasing current output. To avoid passivation, aluminum is alloyed with tin, indium, mercury, or gallium. The electrochemical properties of these alloys, such as theoretical and actual output, consumption rate, efficiency, and open circuit (corrosion) potential, are given in Table 15.1. 

This same reaction of the liquid salt and liquid sodium is relevant for the high safety standard of ZEBRA batteries In case of mechanical damage of the ceramic separator due to a crash of the car the two liquids react in the same way, and the salt and aluminum passivates the NiCb cathode. The energy released is reduced by about 1/3 compared to the normal discharge reaction of sodium with nickel chloride. 

Fluorine can be handled using a variety of materials (100—103). Table 4 shows the corrosion rates of some of these as a function of temperature. System cleanliness and passivation ate critical to success. Materials such as nickel, Monel, aluminum, magnesium, copper, brass, stainless steel, and carbon steel ate commonly used. Mote information is available in the Hterature (20,104). 

Nitric acid reacts with all metals except gold, iridium, platinum, rhodium, tantalum, titanium, and certain alloys. It reacts violentiy with sodium and potassium to produce nitrogen. Most metals are converted iato nitrates arsenic, antimony, and tin form oxides. Chrome, iron, and aluminum readily dissolve ia dilute nitric acid but with concentrated acid form a metal oxide layer that passivates the metal, ie, prevents further reaction. 

Zirconium is a highly active metal which, like aluminum, seems quite passive because of its stable, cohesive, protective oxide film which is always present in air or water. Massive zirconium does not bum in air, but oxidizes rapidly above 600°C in air. Clean zirconium plate ignites spontaneously in oxygen of ca 2 MPa (300 psi) the autoignition pressure drops as the metal thickness decreases. Zirconium powder ignites quite easily. Powder (<44 fim or—325 mesh) prepared in an inert atmosphere by the hydride—dehydride process ignites spontaneously upon contact with air unless its surface has been conditioned, ie, preoxidized by slow addition of air to the inert atmosphere. Heated zirconium is readily oxidized by carbon dioxide, sulfur dioxide, or water vapor. 

A critical issue is the stabiUty of the hydride electrode in the cell environment. A number of hydride formulations have been developed. Table 5 shows hydride materials that are now the focus of attention. Most of these are Misch metal hydrides containing additions of cobalt, aluminum, or manganese. The hydrides are prepared by making melts of the formulations and then grinding to fine powers. The electrodes are prepared by pasting and or pressing the powders into metal screens or felt. The additives are reported to retard the formation of passive oxide films on the hydrides. 

An especially insidious type of corrosion is localized corrosion (1—3,5) which occurs at distinct sites on the surface of a metal while the remainder of the metal is either not attacked or attacked much more slowly. Localized corrosion is usually seen on metals that are passivated, ie, protected from corrosion by oxide films, and occurs as a result of the breakdown of the oxide film. Generally the oxide film breakdown requires the presence of an aggressive anion, the most common of which is chloride. Localized corrosion can cause considerable damage to a metal stmcture without the metal exhibiting any appreciable loss in weight. Localized corrosion occurs on a number of technologically important materials such as stainless steels, nickel-base alloys, aluminum, titanium, and copper (see Aluminumand ALUMINUM ALLOYS Nickel AND nickel alloys Steel and Titaniumand titanium alloys). 

For example, chloride and duoride ions, even in trace amounts (ppm), could cause the dissolution of aluminum metallization of complimentary metal oxide semiconductor (CMOS) devices. CMOS is likely to be the trend of VLSI technology and sodium chloride is a common contaminant. The protection of these devices from the effects of these mobile ions is an absolute requirement. The use of an ultrahigh purity encapsulant to encapsulate the passivated IC is the answer to some mobile ion contaminant problems. 

Yellow brass Admiralty brass Aluminum bronze Red brass Copper Silicon bronze 70-30 cupronickel Nickel (passive)... 

Pitting is also promoted by low pH. Thus, acidic deposits contribute to attack on stainless steels. Amphoteric alloys such as aluminum are harmed by both acidic and alkaline deposits (Fig. 4.4). Other passive metals (those that form protective corrosion product layers spontaneously) are similarly affected. 

Silt, sand, concrete chips, shells, and so on, foul many cooling water systems. These siliceous materials produce indirect attack by establishing oxygen concentration cells. Attack is usually general on steel, cast iron, and most copper alloys. Localized attack is almost always confined to strongly passivating metals such as stainless steels and aluminum alloys. 

Figure 2-11 shows weight loss rate-potential curves for aluminum in neutral saline solution under cathodic protection [36,39]. Aluminum and its alloys are passive in neutral waters but can suffer pitting corrosion in the presence of chloride ions which can be prevented by cathodic protection [10, 40-42]. In alkaline media which arise by cathodic polarization according to Eq. (2-19), the passivating oxide films are soluble ... 

Other passivating materials suffer pitting corrosion by chloride ions [62] in a way similar to stainless steels (e.g., Ti [63] and Cu [64]). The pitting potential for aluminum and its alloys lies between = -0.6 and -0.3 V, depending on the material and concentration of chloride ions [10,40-42]. 

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. 

Oxide, hydroxide and basic salts of aluminum are less soluble at pH values of about 7 than those of zinc [17], which explains the easy passivatability. Galvanic anodes of aluminum alloys are primarily employed in the area of offshore technology. The anodes work in relatively pure seawater flowing with a high velocity so that by using suitable alloys, passivation phenomena are rare. Their low weight is particularly favorable in view of a service time of 20 to 30 years. 

Pure aluminum is used in the electrolysis protection process, which does not passivate in the presence of chloride and sulfate ions. In water very low in salt with a conductivity of x < 40 yUS cm" the polarization can increase greatly, so that the necessary protection current density can no longer be reached. Further limits to its application exist at pH values < 6.0 and >8.5 because there the solubility of Al(OH)3 becomes too high and its film-forming action is lost [19]. The aluminum anodes are designed for a life of 2 to 3 years. After that they must be renewed. The protection currents are indicated by means of an ammeter and/or a current-operated light diode. In addition to the normal monitoring by service personnel, a qualified firm should inspect the rectifier equipment annually. 

Today for this kind of object, the aluminum anodes are usually insulated and connected via cables outside the tank. By this means it is possible to purify and activate the anodes by applying anodic current pulses from an external voltage source. This is necessary during the course of operation since the anode surfaces can be easily passivated by oil films [7]. 

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