Nickel alloys forms

Fluorine cannot be prepared directly by chemical methods. It is prepared in the laboratory and on an industrial scale by electrolysis. Two methods are employed (a) using fused potassium hydrogen-fluoride, KHFj, ill a cell heated electrically to 520-570 K or (b) using fused electrolyte, of composition KF HF = 1 2, in a cell at 340-370 K which can be electrically or steam heated. Moissan, who first isolated fluorine in 1886, used a method very similar to (b) and it is this process which is commonly used in the laboratory and on an industrial scale today. There have been many cell designs but the cell is usually made from steel, or a copper-nickel alloy ( Monel metal). Steel or copper cathodes and specially made amorphous carbon anodes (to minimise attack by fluorine) are used. Hydrogen is formed at the cathode and fluorine at the anode, and the hydrogen fluoride content of the fused electrolyte is maintained by passing in... 

From 760 to 960°C, circulating fans, normally without baffles, are used to improve temperature uniformity and overall heat transfer by adding some convection heat transfer. They create a directional movement of the air or atmosphere but not the positive flow past the heating elements to the work as in a convection furnace. Heating elements ate commonly chrome—nickel alloys in the forms described previously. Sheathed elements are limited to the very low end of the temperature range, whereas at the upper end silicon carbide resistors may be used. In this temperature range the selection of heating element materials, based on the combination of temperature and atmosphere, becomes critical (1). 

Eabrication techniques must take into account the metallurgical properties of the metals to be joined and the possibiUty of undesirable diffusion at the interface during hot forming, heat treating, and welding. Compatible alloys, ie, those that do not form intermetaUic compounds upon alloying, eg, nickel and nickel alloys (qv), copper and copper alloys (qv), and stainless steel alloys clad to steel, may be treated by the traditional techniques developed for clads produced by other processes. On the other hand, incompatible combinations, eg, titanium, zirconium, or aluminum to steel, require special techniques designed to limit the production at the interface of undesirable intermetaUics which would jeopardize bond ductihty. 

In atomization, a stream of molten metal is stmck with air or water jets. The particles formed are collected, sieved, and aimealed. This is the most common commercial method in use for all powders. Reduction of iron oxides or other compounds in soHd or gaseous media gives sponge iron or hydrogen-reduced mill scale. Decomposition of Hquid or gaseous metal carbonyls (qv) (iron or nickel) yields a fine powder (see Nickel and nickel alloys). Electrolytic deposition from molten salts or solutions either gives powder direcdy, or an adherent mass that has to be mechanically comminuted. 

Hard plating is noted for its excellent hardness, wear resistance, and low coefficient of friction. Decorative plating retains its brilliance because air exposure immediately forms a thin, invisible protective oxide film. The chromium is not appHed directiy to the surface of the base metal but rather over a nickel (see Nickel and nickel alloys) plate, which in turn is laid over a copper (qv) plate. Because the chromium plate is not free of cracks, pores, and similar imperfections, the intermediate nickel layer must provide the basic protection. Indeed, optimum performance is obtained when a controlled but high density (40—80 microcrack intersections per linear millimeter) of microcracks is achieved in the chromium lea ding to reduced local galvanic current density at the imperfections and increased cathode polarization. A duplex nickel layer containing small amounts of sulfur is generally used. In addition to... 

Copper—Nickels. The copper—nickel alloy system is essentially single phase across its entire range. Alloys made from this system are easily fabricated by casting, forming, and welding. They are noted for excellent tarnishing and corrosion resistance. Commercial copper alloys extend from 5 to 40 wt % nickel. Monel is a nickel—copper alloy that is outside of this range and contains 29—53 wt % of copper. 

Nickel and its alloys form another important class of non-ferrous metals (Table 1.3). The superb creep resistance of the nickel-based superalloys is a key factor in designing the modern gas-turbine aero-engine. But nickel alloys even appear in a model steam engine. The flat plates in the firebox must be stayed together to resist the internal steam pressure (see Fig. 1.3). Some model-builders make these stays from pieces of monel rod because it is much stronger than copper, takes threads much better and is very corrosion resistant. 

Two different sets of experimental conditions have been used. Buu-Hoi et al. and Hansen have employed the method introduced by Papa et using Raney nickel alloy directly for the desulfurization in an alkaline medium. Under these conditions most functional groups are removed and this method is most convenient for the preparation of aliphatic acids. The other method uses Raney nickel catalysts of different reactivity in various solvents such as aqueous ammonia, alcohol, ether, or acetone. The solvent and activity of the catalyst can have an appreciable influence on yields and types of compounds formed, but have not yet been investigated in detail. In acetic anhydride, for instance, desulfurization of thiophenes does not occur and these reaction conditions have been employed for reductive acetylation of nitrothiophenes. Even under the mildest conditions, all double bonds are hydrogenated and all halogens removed. Nitro and oxime groups are reduced to amines. 

Sulfidation is analogous, but catastrophic sulfidation is common because of the generally lower melting points of sulfides than corresponding oxide. This is especially true in the case of nickel alloys, when a nickel/nickel sulfide eutectic is formed. 

Steel is the most common constructional material, and is used wherever corrosion rates are acceptable and product contamination by iron pick-up is not important. For processes at low or high pH, where iron pick-up must be avoided or where corrosive species such as dissolved gases are present, stainless steels are often employed. Stainless steels suffer various forms of corrosion, as described in Section 53.5.2. As the corrosivity of the environment increases, the more alloyed grades of stainless steel can be selected. At temperatures in excess of 60°C, in the presence of chloride ions, stress corrosion cracking presents the most serious threat to austenitic stainless steels. Duplex stainless steels, ferritic stainless steels and nickel alloys are very resistant to this form of attack. For more corrosive environments, titanium and ultimately nickel-molybdenum alloys are used. 

In addition to nickel alloys, nickel also forms an important alloying element in stainless steels and in cast irons, in both of which it confers additional corrosion resistance and improved mechanical and engineering properties, and in Fe-Ni alloys for obtaining controlled physical and magnetic properties (see Chapter 3). With non-ferrous metals nickel also forms important types of alloys, especially with copper, i.e. cupro-nickels and nickel silvers these are dealt with in Section 4.2. 

During recent years a considerable amount of information has been published on the anodic behaviour of nickel alloys. The data include studies both of binary alloy systems in which nickel forms the major alloying component and of more complex commercially produced nickel alloys. The data are sufficiently numerous to permit a rational and fairly complete interpretation of many of the corrosion-resistant properties of nickel alloys on the basis of their anodic behaviour. 

Nickel alloys which rely on nobility for their corrosion resistance, viz. Ni-Cu and Ni-Mo alloys in acidic solution, do not usually pit in these circumstances. It should be noted, however, that the Ni-Cu alloy Monel 400 normally forms a protective oxide film in neutral and alkaline solutions, and this is of particular significance with regard to its corrosion resistance to... 

Another type of nickel alloy with which problems of intergranular corrosion may be encountered is that based on Ni-Cr-Mo containing about 15% Cr and 15% Mo. In this type of alloy the nature of the grain boundary precipitation responsible for the phenomenon is more complex than in Ni-Cr-Fe alloys, and the precipitates that may form during unfavourable heat treatment are not confined to carbides but include at least one inter-metallic phase in addition. The phenomenon has been extensively studied in recent years . The grain boundary precipitates responsible are molybdenum-rich M C carbide and non-stoichiometric intermetallic ix... 

Nickel and nickel alloys do not form thick layers of corrosion products when freely exposed to outdoor atmospheres in circumstances where the surface is periodically washed by rain, but such deposits may form on sheltered surfaces. Quantitative data on the rate of loss of metal and of pitting of nickel and nickel alloys exposed to outdoor atmospheres are avail-able . Figure 4.38 shows results obtained at three sites in the USA over a 7 year period and Fig. 4.39 gives results from a 10 year test at Birmingham. In both series of tests, Ni-Cr-Fe alloys gave lower weight losses than nickel itself or Ni-Cu alloys and the American results bring out the... 

Nickel and nickel alloys possess good resistance to sea-water in conditions where the protective properties of the passive film are fully maintained. As pointed out above, Ni-30 Cu Alloy 400, in contrast to its behaviour in acidic solution, normally forms a protective film in neutral and alkaline environments, including sea-water this alloy and its age hardening variant... 

There are no significant high-temperature applications for alloys of nickel with iron. The scales formed in air consist of nickel oxide and iron oxide and the latter is usually present in the form of the spinel, NiO-FejOj . In the case of the more dilute nickel alloys, internal oxidation of nickel was Observed S. Substitution of a substantial proportion of nickel by iron results in a deterioration in the oxidation resistance of nickel-chromium... 

In general, greatly reduced rates of attack are observed for impure or dilute nickel alloys compared with pure nickel when exposed to SO2 + O2 atmospheres. Haflan et al. have attributed this to the segregation of impurities at the sulphide/oxide interface causing breakup of the sulphide network. For example in the case of silicon additions, it has been shown that silicates form and it has been proposed that these alter the wetting characteristics of the sulphide and prevent the establishment of an interconnected sulphide network. 

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