Ni alloys

Raney nickel A special form of nickel prepared by treating an Al-Ni alloy with NaOH solution. The nickel is left in a spongy mass which is pyrophoric when dry. This form of nickel is a most powerful catalyst, especially for hydrogenations. 

Low Expansion Alloys. Binary Fe—Ni alloys as well as several alloys of the type Fe—Ni—X, where X = Cr or Co, are utilized for their low thermal expansion coefficients over a limited temperature range. Other elements also may be added to provide altered mechanical or physical properties. Common trade names include Invar (64%Fe—36%Ni), F.linvar (52%Fe—36%Ni—12%Cr) and super Invar (63%Fe—32%Ni—5%Co). These alloys, which have many commercial appHcations, are typically used at low (25—500°C) temperatures. Exceptions are automotive pistons and components of gas turbines. These alloys are useful to about 650°C while retaining low coefficients of thermal expansion. Alloys 903, 907, and 909, based on 42%Fe—38%Ni—13%Co and having varying amounts of niobium, titanium, and aluminum, are examples of such alloys (2). 

Ni alloys of 30—32 wt % are used as temperature-compensator alloys and are characterized by a steep decrease ia magnetic permeabiUty with temperature. These alloys are ideally suited ia electrical circuits as shunts which maintain constant magnetic strength ia devices such as electric meters, voltage regulators, and speedometers. 

The method of Cu determination in which ligand is monometal Tb-L complex was used in analysis of standard samples of Zn and Ni alloys. Experimental detection limit for copper is 0.01 pg/mL. 

Copper alloys include brasses (Cu-Zn alloys), bronzes (Cu-Sn alloys), cupronickels (Cu-Ni alloys) and nickel-silvers (Cu-Sn-Ni-Pb alloys). 

Stainless steels include ferritic stainless (Fe-Cr-Ni alloys with < 6% Ni) and austenitic stainless (Fe-Cr-Ni alloys with > 6.5% Ni). 

ASTM A297 Gr. HK or A 351 HK-40, a 26 Cr-20 Ni alloy with a carbon range of 0.35 to 0.45 percent, i.s the material almost always specified for catalyst tubes. A recent API Survey indicated that for most plants the tube wall was designed on the basis of stress to produce rupture in 100,000 hours. Other design bases were 50 percent of the stress to produce rupture in 10.000 hours or 40 to 50 percent of the stress to produce one percent creep in 10,000 hours. 

Extensive field experience has shown the 50 Cr/50 Ni and 60 Cr/40 Ni alloys to offer the best answer to controlling fuel oil ash corrosion. Type 446 stainless steel also shows acceptable corrosion rates but must be used judiciously due to its low strength at elevated temperatures and weldability. Since components of 50 Cr/50 Ni in contact with vanadium-sodium fuel ash melts still suffer high corrosion rates, they should be designed to minimize the amount of surface area available where ash may accumulate. 

Peak overlaps that totally obscure one of the elements in the spectrum have been shown to be separable. A Co—Ni alloy film under a Cu film is a combination that produces a spectrum where the Ni peaks are all overlapped by Cu or Co peaks, or... 

More effort has probably been devoted to study of the corrosion and passivation properties of Fe-Cr-Ni alloys, e.g. stainless steel and other transition-metal alloys, than to any other metallic system [2.42, 2.44, 2.55, 2.56]. The type of spectral information obtainable from an Fe-Cr alloy of technical origin, carrying an oxide and contaminant film after corrosion, is shown schematically in Fig. 2.13 [2.57]. 

The resulting stress-volume relations for the 28.5-at. % Ni alloys are shown in Figure 5.13. The cusp in the fee curve at 430 MPa (4.3 kbar) is the mean value observed for the Hugoniot elastic limit, whereas the dashed line shown for the fee alloy indicates the stress region for which some strain hardening is indicated from the stress profiles. It is readily apparent that below 2.5 GPa (25 kbar) the fee alloy shows a much larger compressibility than the bcc alloy. 

The well defined change in compressibility of the fee alloy at 2.5 GPa clearly indicates the expected behavior of a second-order phase transition. The anomalously high value of the compressibility for the pressure-sensitive fee alloy is demonstrated in the comparison of compressibilities of various ferromagnetic iron alloys in Table 5.1. The fee Ni alloy, as well as the Invar alloy, have compressibilities that are far in excess of the normal values for the... 

D. Y. Li, L. Q. Chen. Morphological evolution of coherent multivariant TiNi precipitates in Ti-Ni alloys under an applied stress-a computer simulation study. Acta Mater 46 639, 1998. 

The non-ferrous alloys include the misleadingly named nickel silver (or German silver) which contains 10-30% Ni, 55-65% Cu and the rest Zn when electroplated with silver (electroplated nickel silver) it is familiar as EPNS tableware. Monel (68% Ni, 32% Cu, traces of Mn and Fe) is used in apparatus for handling corrosive materials such as F2 cupro-nickels (up to 80% Cu) are used for silver coinage Nichrome (60% Ni, 40% Cr), which has a very small temperature coefficient of electrical resistance, and Invar, which has a very small coefficient of expansion are other well-known Ni alloys. Electroplated nickel is an ideal undercoat for electroplated chromium, and smaller amounts of nickel are used as catalysts in the hydrogenation of unsaturated vegetable oils and in storage batteries such as the Ni/Fe batteries. 

Experimentally it is found that the Fe-Co and Fe-Ni alloys undergo a structural transformation from the bee structure to the hep or fee structures, respectively, with increasing number of valence electrons, while the Fe-Cu alloy is unstable at most concentrations. In addition to this some of the alloy phases show a partial ordering of the constituting atoms. One may wonder if this structural behaviour can be simply understood from a filling of essentially common bands or if the alloying implies a modification of the electronic structure and as a consequence also the structural stability. In this paper we try to answer this question and reproduce the observed structural behaviour by means of accurate alloy theory and total energy calcul ions. 

To summarize we have reproduced the intricate structural properties of the Fe-Co, Fe-Ni and the Fe-Cu alloys by means of LMTO-ASA-CPA theory. We conclude that the phase diagram of especially the Fe-Ni alloys is heavily influenced by short range order effects. The general trend of a bcc-fcc phase transition at lower Fe concentrations is in accordance with simple band Ailing effects from canonical band theory. Due to this the structural stability of the Fe-Co alloys may be understood from VGA and canonical band calculations, since the common band model is appropriate below the Fermi energy for this system. However, for the Fe-Ni and the Fe-Cu system this simple picture breaks down. 

Sulfur compounds, whether organic or inorganic in nature, cause sulfidation in susceptible materials. The sulfide film, which forms on the surface of much con-stmction materials at low temperatures, becomes friable and melts at higher temperatures. The presence of molten sulfides (especially nickel sulfide) on a metal surface promotes the rapid conversion to metal sulfides at temperatures where these sulfides are thermodynamically stable. High-alloy materials such as 25% Cr, 20% Ni alloys are widely used, but these represent a compromise between sulfidation resistance and mechanical properties. Aluminum and similar diffusion coatings can be of use. 

Most cases of crevice corrosion take place in near-neutral solutions in which dissolved oxygen is the cathode reactant, but in the case of copper and copper alloys crevice corrosion can occur owing to differences in the concentration of Cu ions however, in the latter the mechanism appears to be different, since attack takes place at the exposed surface close to the crevice and not within the crevice in fact, the inside of the crevice may actually be cathodic and copper deposition is sometimes observed, particularly in the Cu-Ni alloys. Similar considerations apply in acid solutions in which the hydrogen ion is the cathode reactant, and again attack occurs at the exposed surface close to the crevice. 

Horvath, J. and Uhlig, H., Metallurgical Factors Affecting the Critical Potential for Pitting Corrosion of Cr-Fe-Ni Alloys , J. Electrochem. Soc., 114, 201c (1%7)... 

To examine the situation with alloys in a little more detail, the Cu-Ni alloys will first be considered. Here the mutual solubility of the two oxides NiO and CU2O can probably be neglected, and these are the only two possible oxidation products. Assume for simplicity that the alloy is thermodynamically ideal, and let and Xn be the mole fractions in the alloy. Consider the reactions... 

Couper reports cracking of an Fe-36 Ni alloy in 10-55 days in this medium. Radd eta . have noted cracking of Fe-36 Ni alloys at ambient temperatures in an unspecified environment, but this possibly may have been residual traces of acid copper chloride etching solution. 

Cid etal. studied the corrosion resistance of Ni, 5% Fe-Ni and 10% Fe-Ni alloys in the trans-passive region in sulphuric acid. For a given acid concentration the addition of iron reduced the corrosion rate. It was concluded that the addition of small percentages of Fe was doubly beneficial, decreasing both general and intergranular corrosion. 

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. 

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