Noble corrosion resistance

Copper possesses good corrosion resistance primarily because it is relatively noble (corrosion resistant by immunity), and it is most suitable for reducing environments. The potential range where the material is active in aqueous solutions (Figure 10.1) is so high that reduction of hydrogen ions is not a possible cafliodic reaction. Therefore, copper is immune for example in oxygen-free sulphuric acid. Corrosion can only occur if there is some other oxidizer present that causes a cathodic reaction. 

Because the corrosion resistance of lead and lead alloys is associated with the formation of the protective corrosion film, removal of the film in any way causes rapid attack. Thus the velocity of a solution passing over a surface can lead to significantly increased attack, particularly if the solution contains suspended particulate material. Lead is also attacked rapidly in the presence of high velocity deionised water. The lack of dissolved minerals in such water prevents the formation of an insoluble protective film. In most solutions, lead and lead alloys are resistant to galvanic corrosion because of the formation of a nonconductive corrosion film. In contact with more noble metals, however, lead can undergo galvanic attack which is accelerated by stray electrical currents. 

In the electromotive force series of the elements, silver is less noble than only Pd, Hg, Pt, and Au. AH provide high corrosion resistance. Silver caimot form oxides under ambient conditions. Its highly reactive character, however, results in the formation of black sulfides on exposure to sulfur-containing atmospheres. 

Zinc—Nickel. Steel has the best salt spray resistance when the nickel is 12—13% of the alloy. At increasing nickel contents, the deposit becomes more difficult to chromate and more noble, eventually becoming cathodic to steel. At those levels and above, corrosion resistance usually decreases and is dependent on a complete lack of porosity for protection of the steel. In efforts to replace cadmium and nickel—ca dmium diffused coatings in the aircraft industry, 2inc—nickel has insufficient wear properties for some appHcation, but is under study as an undercoat to various electroless nickel top coats (153). 

The addition of about 20% nickel to cast iron produces materials with a stable austenitic structure these materials are sometimes known as austenitic cast irons but are more often referred to commercially as Ni-Resist cast irons. The austenitic matrix of these irons gives rise to very different mechanical and physical properties to those obtained with the nickel-free grey cast irons. The austenitic matrix is more noble than the matrix of unalloyed grey irons and it was shown in the early work of Vanick and Merica that the corrosion resistance of cast iron increases with increasing nickel content up to about 20% (Fig. 3.42). 

In 3% sodium chloride solution at 60°C the austenitic irons again show superior characteristics to the ferritic. The breakdown potentials determined in this environment, which provide a relative measure of the resistance to attack in neutral chloride solutions, are generally more noble for the austenitic irons than for the ferritic (Table 3.47). This indicates that the austenitic irons should show better corrosion resistance in such environments. 

On the basis of these data, nickel is considered to be a slightly noble metal, although in practice, as will be seen below, it is considerably more corrosion resistant in both acidic and alkaline solutions than would be predicted from Fig. 4.19. 

Tantalum-Titanium Bishop examined the corrosion resistance of this alloy system in hydrochloric, sulphuric, phosphoric and oxalic acids and found that alloys containing up to about 50% titanium retained much of the superlative corrosion resistance of tantalum. Under more severe conditions, a titanium content of below 30% appears advisable from the standpoint of both corrosion resistance and hydrogen embrittlement, although contacting or alloying the material with noble metals greatly decreases the latter type of attack. Tantalum-titanium alloys cost less than tantalum because titanium is much cheaper than tantalum, and because the alloys are appreciably lower in density. These alloys are amenable to hot and cold work and appear to have sufficient ductility to allow fabrication. 

The outstanding characteristics of the noble metals are their exceptional resistance to corrosive attack by a wide range of liquid and gaseous substances, and their stability at high temperatures under conditions where base metals would be rapidly oxidised. This resistance to chemical and oxidative attack arises principally from the Inherently high thermodynamic stability of the noble metals, but in aqueous media under oxidising or anodic conditions a very thin film of adsorbed oxygen or oxide may be formed which can contribute to their corrosion resistance. An exception to this rule, however, is the passivation of silver and silver alloys in hydrochloric or hydrobromic acids by the formation of relatively thick halide films. 

The factors leading to the high resistance of the noble metals to chemical attack, i.e. their thermodynamic stability over a wide range of conditions and the possibility of the formation of very thin protective films under oxidising conditions, have already been mentioned. A factor tending to reduce corrosion resistance in aqueous solutions is the tendency of these metals to form complexes with some anions. 

Some investigatorshave advocated a type of accelerated test in which the specimens are coupled in turn to a noble metal such as platinum in the corrosive environment and the currents generated in these galvanic couples are used as a measure of the relative corrosion resistance of the metals studied. This method has the defects of other electrolytic means of stimulating anodic corrosion, and, in addition, there is a further distortion of the normal corrosion reactions and processes by reason of the differences between the cathodic polarisation characteristics of the noble metal used as an artificial cathode and those of the cathodic surfaces of the metal in question when it is corroding normally. 

Stern, eta obtained potentiostatic polarisation curves for titanium alloys in various solutions of sulphuric acid and showed that the mixed potentials of titanium-noble metal alloys are more positive than the critical potential for the passivity of titanium. This explains the basis for the beneficial effects of small amounts of noble metals on the corrosion resistance of titanium in reducing-type acids. Hoar s review of the work on the effect of noble metals on including anodic protection should also be consulted... 

Glassy carbon (vitreous carbon) is a further modification. It is a smooth and tight material of high corrosion resistance and for many reactions it may be a suitable alternative of platinum. It is relatively expensive, but much cheaper than noble metals. It is very hard and brittle and allows only limited possibilities for... 

High nitrile photocured coatings on B40 coated steel panels exhibit corrosion resistance when their open circuit potentials are either more noble or less noble than the B40 coated steel panel (Figure 3). At first, we assumed that enhanced nobility should give rise to enhanced corrosion resistance, i.e. the galvanic series. 

Our electrochemical work differed drastically from the Groseclose work in that polymer coated metal samples were employed. Furthermore, we found that coatings can have corrosion resistance when their rest potentials are either more noble (B210/NVP) or less noble (B210/GBL) than the uncoated substrate. Leidheiser (22,23) examin zinc phosphate pretreated panels with automotive primer after 10 days exposure to the salt spray. The start and finish rest potentials of the samples with good paint performance were consistently more negative than those samples with poor paint performance ... 

Noble metal connections can reduce the corrosion to an "acceptable" level. This assumption is not true for leads which enter the package from sensors such as micro-electrodes which are characterized by relatively high impedances. The trend for neuroprosthe-tio devices is towards closed-loop control in which the use of high impedance bioelectric sensors will be common. In addition, differing potentials within multi-circuit cables can result in corrosion even when the conductors are fabricated from highly corrosion resistant materials such as MP35N. 

Most other metals in the cooling system are subject to similar corrosive influences, although of reduced intensity, as they will have been selected in part due to their more corrosion-resistant (or noble) properties, albeit at a higher purchasing cost. Although some of these metals and alloys may be quite exotic (and therefore more expensive), they will be used because of a particular suitability for heat exchangers or as components for special types of pumps or valves they may also tend to be inherently noble. 

For this study by Thompson et al (42), ion implantation and RBS were combined with more traditional electrochemical measurements to help establish the corrosion mechanisms of alloys in which a noble metal (Pt) was combined with an active/passive base metal (Ti). The alloys were created by ion implantation of Pt into pure Ti and were not of uniform bulk composition. Such surface alloys offer the possibilities of using a very small amount of a noble material to create a corrosion resistant coating on an otherwise chemically unstable but inexpensive metal or alloy. 

Corrosion rates of atomized, rapidly solidified alloy cast and chill cast alloys are given in Table 4.73. The data show that atomized rapidly solidified alloy is comparable in corrosion resistance to the cast AZ ID alloys. Rapid solidification improves the corrosion resistance of the alloys since the homogeneous microstructures tend to disperse the elements and particles, which otherwise act as cathodic sites. Extended solubility of various elements may also shift the electrode potentials to more noble values. 

Steel phases have an influence on the rate of corrosion. Ferrite has a weak resistance to pitting. The presence of martensite can increase the hydrogen fragilization of steel. Intermetallic phases as Fe2Mo in high Ni content alloys can influence the corrosion resistance. The precipitate CuA12 in aluminum alloys the series 2000 is more noble than the matrix, with corrosion around the precipitate. The majority of case histories reported in the literature have involved austenitic stainless steels, aluminum alloys, and to a lesser degree, some ferritic stainless steels and nickel-based alloys.31... 

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