Amorphous alloys corrosion resistance

In neutral and alkaline environments, the magnesium hydroxide product can form a surface film which offers considerable protection to the pure metal or its common alloys. Electron diffraction studies of the film formed ia humid air iadicate that it is amorphous, with the oxidation rate reported to be less than 0.01 /rni/yr. If the humidity level is sufficiently high, so that condensation occurs on the surface of the sample, the amorphous film is found to contain at least some crystalline magnesium hydroxide (bmcite). The crystalline magnesium hydroxide is also protective ia deionized water at room temperature. The aeration of the water has Httie or no measurable effect on the corrosion resistance. However, as the water temperature is iacreased to 100°C, the protective capacity of the film begias to erode, particularly ia the presence of certain cathodic contaminants ia either the metal or the water (121,122). 

Nonferrous alloys account for only about 2 wt % of the total chromium used ia the United States. Nonetheless, some of these appHcations are unique and constitute a vital role for chromium. Eor example, ia high temperature materials, chromium ia amounts of 15—30 wt % confers corrosion and oxidation resistance on the nickel-base and cobalt-base superaHoys used ia jet engines the familiar electrical resistance heating elements are made of Ni-Cr alloy and a variety of Ee-Ni and Ni-based alloys used ia a diverse array of appHcations, especially for nuclear reactors, depend on chromium for oxidation and corrosion resistance. Evaporated, amorphous, thin-film resistors based on Ni-Cr with A1 additions have the advantageous property of a near-2ero temperature coefficient of resistance (58). 

The corrosion behaviour of amorphous alloys has received particular attention since the extraordinarily high corrosion resistance of amorphous iron-chromium-metalloid alloys was reported. The majority of amorphous ferrous alloys contain large amounts of metalloids. The corrosion rate of amorphous iron-metalloid alloys decreases with the addition of most second metallic elements such as titanium, zirconium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, cobalt, nickel, copper, ruthenium, rhodium, palladium, iridium and platinum . The addition of chromium is particularly effective. For instance amorphous Fe-8Cr-13P-7C alloy passivates spontaneously even in 2 N HCl at ambient temperature ". (The number denoting the concentration of an alloy element in the amorphous alloy formulae is the atomic percent unless otherwise stated.)... 

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 ... 

The high corrosion resistance of amorphous alloys disappears on heat treatment that produces crystallisation . Figure 3.71 shows an example of the... 

As can be seen in Fig. 3.67, the corrosion resistance of amorphous alloys changes with the addition of metalloids, and the beneficial effect of a metaU loid in enhancing corrosion resistance based on passivation decreases in the order phosphorus, carbon, silicon, boron (Fig. 3.72). This is attributed partly to the difference in the speed of accumulation of passivating elements due to active dissolution prior to passivation... 

Stress-corrosion cracking based on active-path corrosion of amorphous alloys has so far only been found when alloys of very low corrosion resistance are corroded under very high applied stresses . However, when the corrosion resistance is sufficiently high, plastic deformation does not affect the passive current density or the pitting potential , and hence amorphous alloys are immune from stress-corrosion cracking. 

Ion implantation and ion mixing produce amorphous alloys as thin as only several tens of nanometres. Implantation of metalloids such as phosphorus in austenitic stainless steel has been known to produce amorphous surface alloys having high corrosion resistance" ". 

Metastable amorphous materials can be produced by the rapid quenching of melts in the form of metallic alloys with glassy structures [149]. These materials have attracted the attention of metallurgists, physicists, and, recently, chemists because of their exceptional properties (easy magnetisation, superior corrosion resistance, high mechanical toughness, interesting electronic properties) [150]. The use of these materials in catalysis was reported some years ago [151]. 

A completely novel approach to technical electrolysis for anodic oxygen evolution from alkaline solution is the use of amorphous metals, i.e. chilled melts of nickel/cobalt mixtures whose crystallization is prevented by the addition of refractory metals like Ti, Zr, B, Mo, Hf, and P (46-51). For this type of material, enhanced catalytic activity in heterogeneous catalysis of gas-phase reactions has been observed (51). These amorphous metals are shown to be more corrosion resistant than the respective crystallized alloys, and the oxides being formed at their surfaces often exhibit a higher catalytic activity than those formed on ordered alloys, as shown by Kreysa (52-54). 

Mo are single phase, supersaturated solid solutions having an fee structure very similar to that of pure Al. Broad reflection indicative of an amorphous phase appears in deposits containing more than 6.5 atom% Mo. As the Mo content of the deposits is increased, the amount of fee phase in the alloy decreases whereas that of the amorphous phase increases. When the Mo content is more than 10 atom%, the deposits are completely amorphous. As the Mo atom has a smaller lattice volume than Al, the lattice parameter for the deposits decreases with increasing Mo content. Potentiodynamic anodic polarization experiments in deaerated aqueous NaCl revealed that increasing the Mo content for the Al-Mo alloy increases the pitting potential. It appears that the Al-Mo deposits show better corrosion resistance than most other aluminum-transition metal alloys prepared from chloroaluminate ionic liquids. 

Hydrogen is an excellent candidate as an efficient and inexpensive energy carrier in the future because it is recyclable, nonpolluting, and available in practically unlimited supply. Since hydrogen can be produced by the electrolysis of water, the search for suitable electrodes is important. Because amorphous alloys possess high mechanical strength and superior corrosion resistance, as well as a defect-free homogeneous structure, they are attractive as electrode materials. 

In this respect palladium is superior to all other platinum group metals, but it cannot be used because of its fast dissolution under working conditions. On the other hand, it has been known that certain amorphous alloys have extremely high corrosion resistance (S). These facts led to the studies of amorphous palladium-based alloys as anode materials in the electrolysis of soda. 

Beside the beneficial effect of the addition alloying metallic elements that contribute to the increased corrosion resistance, the amorphous structure itself is also responsible for the very low corrosion. For example, crystalline alloys with the same composition exhibit high rates of dissolution. The chemically homogeneous, single-phase nature of amorphous alloys is believed to account for their corrosion resistance (8, 100, 101). This also allows for the formation of a uniform, protective film on the surface of amorphous alloy electrodes. 

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