Oxidation hot corrosion

Alloys, used at high temperatures, obtain their protection from a dense and adherent oxide layer formed on the metal surface. The corrosive attack of metals and alloys in molten salts is due to the solubility of oxide scales by basic and acidic dissolution. This breakdown of the passive film gives rise to accelerated metal consumption by enhanced oxidation (Hot Corrosion). The phenomenon is closely related to pitting corrosion of metals and alloys in aqueous solutions. 

The very high temperatures that it is possible to reach in a plasma are utilized in nuclear fusion processes (Chapter 52 Radioactive Elements) but also for solving more normal technical problems. This can be exemplified by the material situation in aero engines. Nickel alloys are utilized to withstand the high working temperatures, but special materials problems arise in those parts of the engine which are exposed to thermal shock or to extreme wear due to oxidation, hot corrosion (salt and sulfur)... 

Steel reheating furnace Recuperators Up to 870 X Oxidation/hot corrosion... 

Industrial materials without sufficient scaling resistance frequendy fail after a short period of time as a result of rapid oxidation or hot corrosion, in conjunction with severe spalling owing to poor adherence of the scale to the metallic component. As a result, the permissible limits of metal loss often are exceeded and expensive, and premature replacement of parts is requited. Extensive efforts are made to develop alloys which are not simply strong at elevated temperatures but which also possess the adequate surface stabiUty. 

Hot Corrosion. Hot corrosion is an accelerated form of oxidation that arises from the presence not only of an oxidizing gas, but also of a molten salt on the component surface. The molten salt interacts with the protective oxide so as to render the oxide nonprotective. Most commonly, hot corrosion is associated with the condensation of a thin molten film of sodium sulfate [7757-82-6], Na2S04, on superaHoys commonly used in components for gas turbines, particularly first-stage turbine blades and vanes. Other examples of hot corrosion have been identified in energy conversion systems, particularly coal gasifiers and direct coal combustors. In these cases the salt originates from alkali impurities in the coal which condense on the internal... 

The reaction of metals with gas mixtures such as CO/CO2 and SO2/O2 can lead to products in which the reaction of the oxygen potential in the gas mixture to form tire metal oxides is accompanied by the formation of carbon solutions or carbides in tire hrst case, and sulphide or sulphates in the second mixture. Since the most importairt aspects of this subject relate to tire performairce of materials in high temperature service, tire reactions are refeiTed to as hot corrosion reactions. These reactions frequendy result in the formation of a liquid as an intermediate phase, but are included here because dre solid products are usually rate-determining in dre coiTosion reactions. 

Corrosion is described as hot corrosion and sulfidation processes. Hot corrosion is an accelerated oxidation of alloys caused by the deposition of Na2S04. Oxidation results from the ingestion of salts in the engine and sulfur from the combustion of fuel. Sulfidation corrosion is considered a form of hot corrosion in which the residue that contains alkaline sulfates. Corrosion causes deterioration of blade materials and reduces component life. 

High-temperature hot corrosion has been known since the 1950s. It is an extremely rapid form of oxidation that takes place at temperatures between 1500°F/816°C and 1700°F/927°C in the presence of sodium sulfate (Na2S04). Sodium sulfate is generated in the combustion process as a result of the reaction between sodium, sulfur, and oxygen. Sulfur is present as a natural contaminant in the fuel. 

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. 

The terms hot corrosion or dry corrosion are normally taken to apply to the reactions taking place between metals and gases at temperatures above 100 C i.e. temperatures at which the presence of liquid water is unusual. The obvious cases of wet corrosion at temperatures above 100 C, i.e. in pressurised boilers or autoclaves, are not considered here. In practice, of course, common metals and alloys used at temperatures above normal do not suffer appreciable attack in the atmosphere until the temperature is considerably above 100 C. Thus iron and low-alloy steels form only the thinnest of interference oxide films at about 200 C, copper shows the first evidence of tarnishing at about 180 C, and while aluminium forms a thin oxide film at room temperature, the rate of growth is extremely slow even near the melting point. 

Calorised Coatings The nickel- and cobalt-base superalloys of gas turbine blades, which operate at high temperatures, have been protected by coatings produced by cementation. Without such protection, the presence of sulphur and vanadium from the fuel and chloride from flying over the sea promotes conditions that remove the protective oxides from these superalloys. Pack cementation with powdered aluminium produces nickel or cobalt aluminides on the surfaces of the blade aerofoils. The need for overlay coatings containing yttrium have been necessary in recent times to deal with more aggressive hot corrosion conditions. 

NaCl, interact with the sulphur and vanadium oxides emitted from the combustion of technical grade hydrocarbons and the salt spray to form Na2S04 and NaVCh. These corrosive agents function in two modes, either the acidic mode in which for example, the sulphate has a high SO3 thermodynamic activity, of in the basic mode when the S03 partial pressure is low in the combustion products. The mechanism of corrosion is similar to the hot corrosion of materials by gases with the added effects due to the penetration of the oxide coating by the molten salt. 

Let us now include an additional component to the Fe-0 system considered above, for instance S, which is of relevance for oxidation of FeS and for hot corrosion of Fe. In the Fe-S-0 system iron sulfides and sulfates must be taken into consideration in addition to the iron oxides and pure iron. The number of components C is now 3 and the Gibbs phase rule reads Ph + F = C + 2 = 5, and we may have a maximum of four condensed phases in equilibrium with the gas phase. A two-dimensional illustration of the heterogeneous phase equilibria between the pure condensed phases and the gas phase thus requires that we remove one degree of... 

---