Nickel-molybdenum alloys, anodic

Fie. 5.29 Anodic polarization curves for nickel-molybdenum alloys in 1 N H2S04. Redrawn from Ref 26... 

Amorphous Fe-3Cr-13P-7C alloys containing 2 at% molybdenum, tungsten or other metallic elements are passivated by anodic polarisation in 1 N HCl at ambient temperature". Chromium addition is also effective in improving the corrosion resistance of amorphous cobalt-metalloid and nickel-metalloid alloys (Fig. 3.67). The combined addition of chromium and molybdenum is further effective. Some amorphous Fe-Cr-Mo-metalloid alloys passivate spontaneously even in 12 N HCl at 60° C. Critical concentrations of chromium and molybdenum necessary for spontaneous passivation of amorphous Fe-Cr-Mo-13P-7C and Fe-Cr-Mo-18C alloys in hydrochloric acids of various concentrations and different temperatures are shown in Fig. 3.68 ... 

Examples of metals that are passive under Definition 1, on the other hand, include chromium, nickel, molybdenum, titanium, zirconium, the stainless steels, 70%Ni-30% Cu alloys (Monel), and several other metals and alloys. Also included are metals that become passive in passivator solutions, such as iron in dissolved chromates. Metals and alloys in this category show a marked tendency to polarize anodicaUy. Pronounced anodic polarization reduces observed reaction rates, so that metals passive under Definition 1 usually conform as well to Definition 2 based on low corrosion rates. The corrosion potentials of metals passive by Definition 1 approach the open-circuit cathode potentials (e.g., the oxygen electrode) hence, as components of galvanic cells, they exhibit potentials near those of the noble metals. 

Anodic protection of high alloy steels (chromium-nickel and chromium-nickel-molybdenum) is possible in all sulfuric acid concentrations and necessary especially at elevated temperatures (up to approx. 120 °C). For example, the protection of steel containing 18% Cr, 10% Ni, and 2% Mo in sulfuric acid of 20-60% concentration (at 47 °C) causes a decrease of the corrosion rate of over 1000 times. For a given acid concentration, the dissolution rate during anodic protection depends on the composition of the steel and the temperature of the solution. 

The alloying elements molybdenum and copper do not, by themselves, enhance passivity of nickel in acid solutions, but instead ennoble the metal. This means that, in practice, these alloying elements confer benefit in precisely those circumstances where chromium does not, viz. hydrogen-evolving acidic solutions, by reducing the rate of anodic dissolution. In more oxidising media the anodic activity increases, and, since binary Ni-Mo and Ni-Cu alloys do not passivate in acidic solutions, they are generally unsuitable in such media. 

Because these variables have a very pronounced effect on the current density required to produce and also maintain passivity, it is necessary to know the exact operating conditions of the electrolyte before designing a system of anodic protection. In the paper and pulp industry a current of 4(KX) A was required for 3 min to passivate the steel surfaces after passivation with thiosulphates etc. in the black liquor the current was reduced to 2 7(X) A for 12 min and then only 600 A was necessary for the remainder of the process . From an economic aspect, it is normal, in the first instance, to consider anodically protecting a cheap metal or alloy, such as mild steel. If this is not satisfactory, the alloying of mild steel with a small percentage of a more passive metal, such as chromium, molybdenum or nickel, may decrease both the critical and passivation current densities to a sufficiently low value. It is fortunate that the effect of these alloying additions can be determined by laboratory experiments before application on an industrial scale is undertaken. 

During investigations, we chose the following two regimes of preparing molybdenum and nickel alloys electrolysis at a cathodic current density of 5 mA-cm in the NaCl-KCl-NiCl2-Ni melt (anode is metallic nickel), at a temperature of 1123 K, process time of 1 hour, and currentless transfer in the NaCl-KCl-NiCl2-Ni melt at the same temperature and time. 

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