Fuel oxide layers

Sodium and potassium are restricted because they react with sulfur at elevated temperatures to corrode metals by hot corrosion or sulfurization. The hot-corrision mechanism is not fully understood however, it can be discussed in general terms. It is believed that the deposition of alkali sulfates (Na2S04) on the blade reduces the protective oxide layer. Corrosion results from the continual forming and removing of the oxide layer. Also, oxidation of the blades occurs when liquid vanadium is deposited on the blade. Fortunately, lead is not encountered very often. Its presence is primarily from contamination by leaded fuel or as a result of some refinery practice. Presently, there is no fuel treatment to counteract the presence of lead. 

There is a third real reason for deviations from Eq. (5.18) in the case that a non-conductive insulating product layer is built via a catalytic reaction on the catalyst electrode surface (e.g. an insulating carbonaceous or oxidic layer). This is manifest by the fact that C2H4 oxidation under fuel-rich conditions has been found to cause deviations from Eq. (5.18) while H2 oxidation does not. A non-conducting layer can store electric charge and thus the basic Eq. 5.29 (which is equivalent to Eq. (5.18)) breaks down. 

It is presumed that the global-quenching criteria of premixed flames can be characterized by turbulent shaining (effect of Ka), equivalence ratio (effect of 4>), and heat-loss effects. Based on these aforemenhoned data, it is obvious that the lean methane flames (Le < 1) are much more difficult to be quenched globally by turbulence than the rich methane flames (Le > 1). This may be explained by the premixed flame shucture proposed by Peters [13], for which the premixed flame consisted of a chemically inert preheat zone, a chemically reacting inner layer, and an oxidation layer. Rich methane flames have only the inert preheat layer and the inner layer without the oxidation layers, while the lean methane flames have all the three layers. Since the behavior of the inner layer is responsible for the fuel consumption that... 

Outside of the double-layer region, water itself may be oxidized or reduced, leaving stable hydride, hydroxyl, or oxide layers on the electrode surface. These species may adsorb strongly and block sites from participating in electrocatalysis, as for example, hydroxyl species present at the polymer electrolyte membrane fuel cell... 

Figure 25.3 The reaction zone configuration used in the present analysis. On the left side solid lines for T, T02, and YcH.4 represent the outer solution, and the dashed lines show profiles resulting from finite reaction rates in the oxygen-consumption layer. The right side corresponds to an expanded view of the regions around in the left sketch, represented by a single fine there, showing the structure of the radical-equilibrium and fuel-consumption layers A — location of fuel and radical layers, B — oxidation layer, C — radical-equilibration layer, and D — fuel-consumption layer...

The heat produced by the reaction of a pyrolant is dependent on various physicochemical properties, such as the chemical nature of the fuel and oxidizer, the fractions in which they are mixed, and their physical shapes and sizes. Metal particles are commonly used as fuel components of pyrolants. When a metal particle is oxidized by gaseous oxidizer fragments, an oxide layer is formed that coats the particle. If the melting point of the oxide layer is higher than that of the metal particle, the metal oxide layer prevents further supply of the oxidizer fragments to the metal, and so the oxidation remains incomplete. If, however, the melting point of the oxide layer is lower than that of the metal particle, the oxide layer is easily removed and the oxidation reaction can continue. 

It is usual to operate an aqueous-medium fuel cell under pressure at temperatures well in excess of the normal boiling point, as this gives higher reactant activities and lower kinetic barriers (overpotential and reactant diffusion rates). An alternative to reliance on catalytic reduction of overpotential is use of molten salt or solid electrolytes that can operate at much higher temperatures than can be reached with aqueous cells. The ultimate limitations of any fuel cell are the thermal and electrochemical stabilities of the electrode materials. Metals tend to dissolve in the electrolyte or to form electrically insulating oxide layers on the anode. Platinum is a good choice for aqueous acidic media, but it is expensive and subject to poisoning. 

Depth profiles of matrix elements on Mn- and Co-perovskite layers of fuel cathodes have been measured by LA-ICP-MS in comparison to other well established surface analytical techniques (e.g., SEM-EDX).118 On perovskite layers at a spatial resolution of 100p.m a depth resolution of 100-200 nm was obtained by LA-ICP-MS. The advantages of LA-ICP-MS in comparison to other surface analytical techniques (such as XPS, AES, SIMS, SNMS, GD-OES, GDMS and SEM-EDX) are the speed, flexibility and relatively low detection limits with an easy calibration procedure. In addition, thick oxide layers can be analyzed directly and no charging effects are observed in the analysis of non-conducting thick layers. 

Can failures occur from time to time. The release of fission products from them depends on the temperature and type of fuel. If the fuel is uranium metal, as in the Windscale and Magnox reactors, and the can fails, the uranium will oxidise in air or C02. In laboratory experiments, the mass median aerodynamic equivalent diameter (MMAD) of the particles produced by oxidation of uranium increased from about 40 ptm when the temperature of oxidation was 600°C to 500 jum at 1000°C (Megaw et al., 1961). At high temperature, a coherent sintered oxide layer formed on the uranium and this hindered the formation of particles. 

Metallic membranes for hydrogen separation can be of many types, such as pure metals Pd, V, Ta, Nb, and Ti binary alloys of Pd, with Cu, Ag, and Y Pd alloyed with Ni, Au, Ce, and Fe and complex alloys of Pd alloyed with more than one metal [3], Body-centered cubic metals, for example, Nb and V, have higher permeability than face-centered cubic metals, for instance, Pd and Ni [26-29], Even though Nb, V, and Ta possess a permeability greater than that of Pd, these metals develop oxide layers and are complicated to be used as hydrogen separation membranes [29], Especially, the Pd and Pd-based membranes have in recent times obtained renovated consideration on account of the prospects of a generalized use of hydrogen as a fuel in the future [26], We emphasize on these types of membranes in this chapter. 

Chapters I to III introduce the reader to the general problems of fuel cells. The nature and role of the electrode material which acts as a solid electrocatalyst for a specific reaction is considered in chapters IV to VI. Mechanisms of the anodic oxidation of different fuels and of the reduction of molecular oxygen are discussed in chapters VII to XII for the low-temperature fuel cells and the strong influence of chemisorhed species or oxide layers on the electrode reaction is outlined. Processes in molten carbonate fuel cells and solid electrolyte fuel cells are covered in chapters XIII and XIV. The important properties of porous electrodes and structures and models used in the mathematical analysis of the operation of these electrodes are discussed in chapters XV and XVI. 

In thermites using aluminum metal as the fuel, the passivation of the metal surface with oxide must be taken into account. For micrometer sized particles of aluminum, the oxide passivation layer is negligible, but on the nano-scale this passivation layer of alumina begins to account for a significant mass portion of the nanoparticles. In addition, the precise nature of the oxide layer is not the same for all manufacturers of aluminum nanoparticles, so the researcher must use TEM to measure oxide thickness to allow calculation of active aluminum content before stoichiometric calculations are carried out for the mixing of thermites. Table 13.3 shows details of some of the percentages of aluminum in aluminum nanoparticles and shows just how significant and inconsistent the oxide layer can be. 

Reactions I-IV are global steps for gaseous fuel oxidation. Reactions V-VII, are for char oxidation. The single film model is used here, where the particle is consumed via reactions with oxygen (or carbon dioxide) and no reaction occurs in the boundary layer. CO and CO2 are the two products formed at the particle surface. The first four reactions are treated based on the eddy-dissipation concept [8], which assumes that chemical reactions in the gaseous phase occur rapidly and the mean consumption rate of fuel is limited by the mixing rate of fuel and oxidant. The char reactions are treated using kinetic Arrhenius expression. 

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