Oxide layers nickel

The tlrermodynamic activity of nickel in the nickel oxide layer varies from unity in contact with tire metal phase, to 10 in contact with the gaseous atmosphere at 950 K. The sulphur partial pressure as S2(g) is of the order of 10 ° in the gas phase, and about 10 in nickel sulphide in contact with nickel. It therefore appears that the process involves tire uphill pumping of sulphur across this potential gradient. This cannot occur by the counter-migration of oxygen and sulphur since the mobile species in tire oxide is the nickel ion, and the diffusion coefficient aird solubility of sulphur in the oxide are both vety low. 

Using the unique four-electrode STM described above, Bard and coworkers (Lev, 0. Fan, F-R.F. Bard, A.J. J. Electroanal. Chem.. submitted) have obtained the first images of electrode surfaces under potentiostatic control. The current-bias relationships obtained for reduced and anodically passivated nickel surfaces revealed that the exponential current-distance relationship expected for a tunneling-dominated current was not observed at the oxide-covered surfaces. On this basis, the authors concluded that the nickel oxide layer was electrically insulating, and was greater than ca. 10 A in thickness. Because accurate potential control of the substrate surface is difficult in a conventional, two-electrode STM configuration, the ability to decouple the tip-substrate bias from... 

It is, of course, well known that metal-semiconductor interfaces frequently have rectifier characteristics. It is significant, however, that this characteristic has been confirmed specifically for systems that have been used as inverse supported catalysts, including the system NiO on Ag described above as catalyst for CO-oxidation. In the experimental approach taken, nickel was evaporated onto a silver electrode and then oxidized in oxygen. A space charge-free counter-electrode was then evaporated onto the nickel oxide layer, and the resulting sandwich structure was annealed. The electrical characteristic of this structure is represented in Fig. 8. The abscissa (U) is the applied potential the ordi-... 

Sulfide SPCE modified with electrochemically generated nickel oxide layer 20 pM 80 pM... 

Recent investigations (9, 11, 83, 92, 178, 272) of regeneration by 02 have resulted in modest success. Table XXII lists studies made of Ni (11, 178), Cu (92), Pt (83), and Mo (272). These studies indicate that sulfur can be removed as S02 by low-pressure (PQl = 3 x 10 9 7 x 10 kPa) oxidation at temperatures ranging from ambient to nearly 1600 K. Significant differences in the kinetics of sulfur removal observed in these studies are attributed to different reaction mechanisms being predominant at different temperatures. On the other hand, attempts to remove sulfur from polycrystalline Ni surface by atmospheric pressure oxidation (P0l = 10-760 Torr) at temperatures from 300 to 800 K were unsuccessful (9). Instead, nickel oxide layers were formed on top of the sulfur layer. Treatment of the oxidized catalyst with H2 at 700 K for 2 hr reduced the Ni oxide completely to the metal at the same time it caused the return of the sulfur layer to the surface. 

These MIM diodes can be used as mixing elements at optical frequencies. When illuminating the contact point with a focused CO2 laser, a response time of 10 s or better has been demonstrated by the measurement of the 88-THz emission from the third harmonic of the CO2 laser. If the beams of two lasers with the frequencies f and /2 are focused onto the junction between the nickel oxide layer and the sharp tip of a tungsten wire, the MIM diode acts as a rectifier and the wire as an antenna, and a signal with the difference frequency f — f2 is generated. Difference frequencies up into the terahertz range can be monitored [4.111] (see Sect. 5.8.7). The basic processes in these MIM diodes represent very interesting phenomena of solid-state physics. They could be clarified only recently [4.111]. 

The addition of tetraethyl orthosilicate, TEDS, to the alcdiol solutions of anhydrous halide was proved to be a suitable method to prepare electrochromic Ni-based thin films (Moser, 1989). Coatings obtained from such sols exhibited a higher hardness and better adhesion to the substrate and a reversible transmittance change of 53% at 550 nm. Mild et al. used a mixture of nickel nitrate hexahydrate with ethylene glycole and tetraethyl orthosilicate (TEDS) for the fabrication of nickel oxide layers (Miki, 1995). Ni(Si)oxide layers (Ni/Si = 2.5-10) were studied by Surcaet al. They added 3-aminopropyltrimethoxysilane (3-APMS) to the nickel sulfate sol (see above) (Surca, 1997). The electrochromic changes were about 50% (500 nm, 100th cycle). 

Once a corrosion product layer is formed, the corrosion process may continue through the diffusion of at least one of the reactants through the corrosion product layer. Let us consider, for example, the case of nickel exposed to air at high temperature. Corrosion can theoretically continue through the nickel oxide layer by means of diffusion in either direction, alone or by counter-current diffusion, as illustrated in Fig. 15.9. 

Nickel is a key component in the electronics industry, where it is utilized in diodes, wires and switches and as an important alloying constituent in many biomaterials. In spite of the spontaneous formation of a nickel oxide layer under ambient conditions, the use of nickel can cause corrosion-related issnes. 

The BLM layer uses a glue layer of chromium or titanium. These metals stick well to other metals and most dielectrics, but they are not solderable. Copper, nickel, and silver have been used as the solder-wetting layer for BLM in appHcations involving 95% lead—5% tin solders. Gold is commonly used as the oxidation layer on account of its resistance to oxidation and its excellent solderabiUty. 

The oxidation of nickel-copper alloys provides an example of die dependence of the composition of the oxide layer on the composition of the alloy. Nickel-copper alloys depart from Raoult s law, but as a first approximation can be taken as ideal. The Gibbs energy change for the reaction... 

Because oxides are usually quite brittle at the temperatures encountered on a turbine blade surface, they can crack, especially when the temperature of the blade changes and differential thermal contraction and expansion stresses are set up between alloy and oxide. These can act as ideal nucleation centres for thermal fatigue cracks and, because oxide layers in nickel alloys are stuck well to the underlying alloy (they would be useless if they were not), the crack can spread into the alloy itself (Fig. 22.3). The properties of the oxide film are thus very important in affecting the fatigue properties of the whole component. 

To fully understand the formation of the N13S2 scale under certain gas conditions, a brief description needs to be given on the chemical aspects of the protective (chromium oxide) Ci 203/(nickel oxide) NiO scales that form at elevated temperatures. Under ideal oxidizing conditions, the alloy Waspaloy preferentially forms a protective oxide layer of NiO and Ci 203 The partial pressure of oxygen is such that these scales are thermodynamically stable and a condition of equilibrium is observed between the oxidizing atmosphere and the scale. Even if the scale surface is damaged or removed, the oxidizing condition of the atmosphere would preferentially reform the oxide scales. 

Certainly a thermodynamically stable oxide layer is more likely to generate passivity. However, the existence of the metastable passive state implies that an oxide him may (and in many cases does) still form in solutions in which the oxides are very soluble. This occurs for example, on nickel, aluminium and stainless steel, although the passive corrosion rate in some systems can be quite high. What is required for passivity is the rapid formation of the oxide him and its slow dissolution, or at least the slow dissolution of metal ions through the him. The potential must, of course be high enough for oxide formation to be thermodynamically possible. With these criteria, it is easily understood that a low passive current density requires a low conductivity of ions (but not necessarily of electrons) within the oxide. 

Barrett and his colleagues , and Kosakhave summarised existing information on the scales formed on nickel-chromium alloys. Up to about 10% Cr, the thick black scale is composed of a double layer, the outer layer being nickel oxide and the inner porous layer a mixture of nickel oxide with small amounts of the spinel NiO CrjOj. Internal oxidation causes the formation of a subscale consisting of chromium oxide particles embedded in the nickel-rich matrix. At 10-20% Cr the scale is thinner and grey coloured and consists of chromium oxide and spinel with the possible presence of some nickel oxide. At about 25-30% Cr a predominantly chromium oxide scale is... 

The transition from non-protective internal oxidation to the formation of a protective external alumina layer on nickel aluminium alloys at 1 000-1 300°C was studied by Hindam and Smeltzer . Addition of 2% A1 led to an increase in the oxidation rate compared with pure nickel, and the development of a duplex scale of aluminium-doped nickel oxide and the nickel aluminate spinel with rod-like internal oxide of alumina. During the early stages of oxidation of a 6% A1 alloy somewhat irreproducible behaviour was observed while the a-alumina layer developed by the coalescence of the rodlike internal precipitates and lateral diffusion of aluminium. At a lower temperature (800°C) Stott and Wood observed that the rate of oxidation was reduced by the addition of 0-5-4% A1 which they attributed to the blocking action of internal precipitates accumulating at the scale/alloy interface. At higher temperatures up to 1 200°C, however, an increase in the oxidation rate was observed due to aluminium doping of the nickel oxide and the inability to establish a healing layer of alumina. 

Another factor that determines the long-term stability of the protective oxide layer is its ability to prevent sulphur penetration which would lead to the eventual formation of chromium sulphide beneath the external oxide layer. With most commercial nickel chromium alloys internal sulphidation... 

The second stage in the carburisation process, that of carbon ingress through the protective oxide layer, is suppressed by the development of alumina or silica layers as already discussed and in some cases protective chromia scales can also form. Diffusion and solubility of carbon in the matrix has been shown by Schnaas et to be a minimum for binary Fe-Ni alloys with a nickel content of about 80<7o, and Hall has shown that increasing the nickel content for the nickel-iron-2S<7o-chromium system resulted in lower rates of carburisation (Fig. 7.54). 

The main characteristic of attack by halogens at elevated temperatures is that most reaction products are volatile compared with the solid products that form in all cases considered hitherto in this chapter. Thus, in cases where metals are exposed to pure halogen gases large mass losses are usually reported with very little external scale formation. Li and Rapp " showed that internal chloridation occurred when nickel-chromium alloys were exposed to Ni + NiClj powders at 700-900°C. However, where oxide scales can also form, as in combustion gases, the oxide layer was usually highly... 

Foreign cations can increasingly lower the yield in the order Fe, Co " < Ca " < Mn < Pb " [22]. This is possibly due to the formation of oxide layers at the anode [42], Alkali and alkaline earth metal ions, alkylammonium ions and also zinc or nickel cations do not effect the Kolbe reaction [40] and are therefore the counterions of choice in preparative applications. Methanol is the best suited solvent for Kolbe electrolysis [7, 43]. Its oxidation is extensively inhibited by the formation of the carboxylate layer. The following electrolytes with methanol as solvent have been used MeOH-sodium carboxylate [44], MeOH—MeONa [45, 46], MeOH—NaOH [47], MeOH—EtsN-pyridine [48]. The yield of the Kolbe dimer decreases in media that contain more than 4% water. 

Another way to protect a metal uses an impervious metal oxide layer. This process is known as passivation, hi some cases, passivation is a natural process. Aluminum oxidizes readily in air, but the result of oxidation is a thin protective layer of AI2 O3 through which O2 cannot readily penetrate. Aluminum oxide adheres to the surface of unoxidized aluminum, protecting the metal from further reaction with O2. Passivation is not effective for iron, because iron oxide is porous and does not adhere well to the metal. Rust continually flakes off the surface of the metal, exposing fresh iron to the atmosphere. Alloying iron with nickel or chromium, whose oxides adhere well to metal surfaces, can be used to prevent corrosion. For example, stainless steel contains as much as 17% chromium and 10% nickel, whose oxides adhere to the metal surface and prevent corrosion. 

Unlike the cathodic reaction, anodic oxidation (ionization) of molecular hydrogen can be studied for only a few electrode materials, which include the platinum group metals, tungsten carbide, and in alkaline solutions nickel. Other metals either are not sufficiently stable in the appropriate range of potentials or prove to be inactive toward this reaction. For the materials mentioned, it can be realized only over a relatively narrow range of potentials. Adsorbed or phase oxide layers interfering with the reaction form on the surface at positive potentials. Hence, as the polarization is raised, the anodic current will first increase, then decrease (i.e., the electrode becomes passive see Fig. 16.3 in Chapter 16). In the case of nickel and tungsten... 

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