High-temperature corrosion can occur in numerous environments and is affected by various parameters such as temperature, alloy and protective coating compositions, stress, time, and gas composition. This article discusses the primary mechanisms of high-temperature corrosion, namely oxidation, carburization, metal dusting, nitridation, carbonitridation, sulfidation, and chloridation. Several other potential degradation processes, namely hot corrosion, hydrogen interactions, molten salts, aging, molten sand, erosion-corrosion, and environmental cracking, are discussed under boiler tube failures, molten salts for energy storage, and degradation and failures in gas turbines. The article describes the effects of environment on aero gas turbine engines and provides an overview of aging, diffusion, and interdiffusion phenomena. It also discusses the processes involved in high-temperature coatings that improve performance of superalloy.

High temperature corrosion may occur in numerous environments and is affected by factors such as temperature, alloy or protective coating composition, time, and gas composition. This article explains a number of potential degradation processes, namely, oxidation, carburization and metal dusting, sulfidation, hot corrosion, chloridation, hydrogen interactions, molten metals, molten salts, and aging reactions including sensitization, stress-corrosion cracking, and corrosion fatigue. It concludes with a discussion on various protective coatings, such as aluminide coatings, overlay coatings, thermal barrier coatings, and ceramic coatings.

The failure of T12 reheater tubes that had been in service for only 3000 h was investigated. The thickness of the tubes was visibly reduced by heavy oxidation corrosion on the inner and outer walls. The original pearlite substrate completely decomposed. Uniform oxide scale observed on the inner wall showed obvious vapor oxidation corrosion characteristics. Corrosion originated in the grain boundary, and selective oxidation occurred due to ion diffusion in the substrate. The layered oxide scale on the inner wall is related to the different diffusion rates for different cations. Exposure to high temperature corrosive flux accelerated the corrosion on the outer wall. Microstructure degradation and the corrosion characteristics observed indicate that the tubes failed primarily because of overheating, which is confirmed by calculations.

A microstructural analysis has been made of a burner nozzle removed from service in a coal gasification plant. The nozzle was a casting of a Co-29wt%Cr-19wt%Fe alloy. Extensive hot corrosion had occurred on the surface. There was penetration along grain boundaries, and corrosion products in these regions were particularly rich in S, and also contained Al, Si, O, and Cl. The grain boundaries contained Cr-rich particles which were probably Cr23-C6 type carbides. In the matrix, corrosion occurred between the Widmanstatten plates. Particles were found between these plates, most of which were rich in Cr and O, and probably were Cr2-O3 oxides. Other matrix particles were found which were rich in Al, O, and S. The corrosion was related to these grain boundary and matrix particles, which either produced a Cr-depleted zone around them or were themselves attacked.

After four months at a temperature of 400 to 5000 C, pipes at a gas generating plant were so heavily eroded they had to be replaced. Three sections of pipe, from different locations, were analyzed to determine whether mechanical wear or corrosion caused the damage. Samples of corrosion product from each pipe section were analyzed for carbon, sulfur, and iron and were found to consist mainly of iron sulfide mixed with soot and rust. The damage resulted from a high content of hydrogen sulfide in the gas (6% CO2, 20% CO, 8 to 12% H2, 0.5 to 1.5% CH4, remainder N2). To process the coal in question, the pipes material should be a heat-resistant steel that contains more chromium and has greater resistance to hydrogen sulfide.

Aluminide-coated and uncoated IN-713 turbine blades were returned for evaluation after service in a marine environment because of severe corrosion. Based on service time, failure of these blades by corrosive deterioration was considered to be premature. Analysis (visual inspection, 2.7x micrographic examination on sections etched with ferric chloride and hydrochloric acid in methanol) supported the conclusions that the blades failed by hot-corrosion attack. Variation in rate of attack on coated blades was attributed to variation in integrity of the aluminide coating, which had been applied in 1966, when these coatings were relatively new. It is evident that maintaining the integrity of a protective coating could significantly increase the life of a nickel-base alloy blade operating in a hot and corrosive environment.

Three radiant tubes, made of three different high-temperature alloys, were removed from a carburizing furnace after approximately eight months of service when they showed evidence of failure by collapsing (telescoping) in a region 30 cm (12 in.) from the tube bottoms in the vicinity of the burners. The tubes had an original wall thickness of 3.0 mm (0.120 in.) and were made of three different alloys: the first was Hastelloy X; the second alloy was RA 333, a wrought nickel-base heat-resistant alloy; and the third was experimental alloy 634, which contained 72% Ni, 4% Cr, and 3.5% Si. The three radiant tubes had been operated at a temperature of about 1040 deg C (1900 deg F) to maintain furnace temperatures of 900 to 925 deg C (1650 to 1700 deg F). Analysis (visual inspection and micrographic examination) supported the conclusion that all three tubes failed by corrosion. Recommendations included replacing the material with an alloy, such as RA 333, with a higher chromium content and with an additional element, like silicon, resistant to carburization-oxidation.

An Incoloy 800H (UNS N08810) transfer line on the outlet of an ethane-cracking furnace failed during decoking of the furnace tubes after nine years in service. A metallographic examination using optical and scanning electron microscopy as well as energy-dispersive x-ray spectroscopy revealed that the failure was due to sulfidation. The source of the sulfur in the furnace effluent was either dimethyl disulfide, injected into the furnace feed to prevent coke formation and carburization of the furnace tubes, or contamination of the feed with sulfur bearing oil.

Some examples of equipment failures involving high temperature operation are presented. They include some steam generator superheater components and a pump shaft that should not have been at high temperature. Metallographic analysis is used to determine the causes of failure in each case.

Gas turbines and other types of combustion turbomachinery are susceptible to hot corrosion at elevated temperatures. Two such cases resulting in the failure of a gas turbine component were investigated to learn more about the hot corrosion process and the underlying failure mechanisms. Each component was analyzed using optical and scanning electron microscopy, energy dispersive spectroscopy, mechanical testing, and nondestructive techniques. The results of the investigation provide insights on the influence of temperature, composition, and microstructure and the contributing effects of high-temperature oxidation on the hot corrosion process. Preventative measures are also discussed.

Three samples from a ruptured 316 stainless steel tube were examined. The tube, 114 mm OD, wall thickness 8.00 mm, with 13 mm thick 321 stainless steel fins welded to the outer surface of the tube, was part of a heater through which sour gas, containing methane plus H2S and CO, passed at 1150 psig. The sour gas was heated to 600 deg F by burners playing on the outside of the tube burning “sweet” gas plus air. The inner and outer surfaces of all samples showed evidence of corrosive attack. Electron probe microanalysis showed the corrosion products contained sulfur with iron, together with nickel to a lesser extent. Local thinning, cavitation, and ductile deformation markings associated with the unmatched sample taken from the center of the fire showed the tube ruptured as a result of overheating. Overheating while the temperature recorder was off the chart caused severe loss of tube strength, resulting in ductile rupture. The minimum overheating temperature could be deduced at around 1200 deg F due to the presence of a eutectic observed metallographically within the surface corrosion products.

The top tube of a horizontal superheater bank in the reheat furnace of a steam generator ruptured after seven years in service. The rupture was found to have occurred in the ferritic steel tubing (2.25Cr-1Mo steel (ASME SA-213, grade T-22)) near the joint where it was welded to austenitic stainless steel tubing (type 321 stainless steel (ASME SA-213, grade TP321H)). The surface temperature of the tube was found to be higher than operating temperature in use earlier. The ferritic steel portion of the tube was found to be longitudinally split and heavily corroded in the region of the rupture. A red and white deposit was found on the sides and bottom of the tube in the rupture area. The deposit was produced by attack of the steel by the alkali acid sulfate and had thinned the tube wall. It was concluded that rupture of the tube had occurred due to thinning of the wall by coal-ash corrosion. The thinned tubes were reinforced by pad welding. Type 304 stainless steel shields were welded to the stainless steel portions of the top reheater tubes and were held in place about the chromium-molybdenum steel portions of the tubes by steel bands.

A coil made of a nickel-chromium alloy (Material No. 2.4869) with approx. 80Ni and 20Cr had burned through after a brief period of operation as a heating element in a brazing furnace. The protective atmosphere consisted of an incompletely combusted coal gas. Furnace temperature reached 1150 deg C. This type of selective oxidation at which the easily oxidized chromium burns, while the nickel is not attacked, is caused by mildly oxidizing gases and is sometimes designated as green rot. Under these conditions, chromium-containing steels and alloys whose oxidation resistance is based upon formation of tight oxide layers are not stable.

An experimental high-temperature rotary valve was found stuck due to growth and distortion after approximately 100 h. Gas temperatures were suspected to have been high due to overfueled conditions. Both the rotor and housing in which it was stuck were annealed ferritic ductile iron similar to ASTM A395. Visual examination of the rotor revealed unusually heavy oxidation and thermal fatigue cracking along the edge of the gas passage. Material properties, including microstructure, composition, and hardness, of both the rotor and housing were evaluated to determine the cause of failure. The microstructure of the rotor was examined in three regions. The shaft material, the heavy section next to the gas passage and the thin edge of the rotor adjacent to the gas passage. The excessive gas temperatures were responsible for the expansion and distortion that prevented rotation of the rotor. Actual operating temperatures exceeded those intended for this application. The presence of transformation products in the brake-rotor edge indicated that the lower critical temperature had been exceeded during operation.

Over a period of about one year, three RA 330 alloy salt pots from a single heat-treating plant were submitted to failure analysis. All of the pots, which had 9.5 mm thick walls, were used primarily to contain neutral salts at temperatures from about 815 to 900 deg C (1500 to 1650 deg F). However, some cyaniding was also performed in these pots, which, when not in use, were idled at 760 deg C (1400 deg F). It was reported that sludge was removed from the bottom of the pots once a day. Normal pot life varied from about 6 to 20 months. The pots were removed from the furnace, visually inspected, and rotated 120 deg every three weeks to ensure that no single location was overheated for a prolonged period of time. Analysis (visual inspection, chemical analysis, metallographic examination, and x-ray analysis, 60x micrograph etched with 10% oxalic acid) supported the conclusion that the cause of failure of each of the three salt pots was severe intergranular corrosion accompanied by substantial chromium depletion. No recommendations were made.

High-chromium steel pipes 42.25 x 3.25 mm from a blast furnace gas fired recuperator for the preheating of air were heavily oxidized and perforated in places. It was found that the blast furnace gas had a high sulfur content. Both the carburization and the formation of sulfide proved that in addition, from time to time at least, combustion was incomplete and the operation was carried out in a reducing atmosphere, with the result that oxygen deficiency prevented the formation or maintenance of a protective surface layer on the external surface of the pipes. The sulfur would probably not have damaged the nickel-free steel used here at the given temperatures if it had been present as sulfur dioxide in an oxidizing atmosphere. The damage was therefore caused primarily by an incorrectly conducted combustion process.

During disassembly of an engine that was to be modified, a fractured turbine blade was found. When the fracture was examined at low magnification, it was observed that a fatigue fracture had originated on the concave side of the leading edge and had progressed slightly more than halfway from the leading edge to the trailing edge on the concave surface before ultimate failure occurred in dynamic tension. Analysis (including visual inspection, SEM, and 250x/500x micrographic examination) supported the conclusions that the blades failed due to thermal fatigue. Recommendations included application of a protective coating to the blades, provided the coating was sufficiently ductile to avoid cracking during operation to prevent surface oxidation. Such a coating would also alleviate thermal differentials, provided the thermal conductivity of the coating exceeded that of the base metal. It was also determined that directionally solidified blades could minimize thermal fatigue cracking by eliminating intersection of grain boundaries with the surface. However, this improvement would be more costly than applying a protective coating.

Heating elements, consisting of strips, 40 mm x 2 mm, of the widely used 80Ni-20Cr resistance heating alloy, and designed to withstand a temperature of 1175 deg C, were rendered unusable by scaling after a few months service in a through-type annealing furnace, Although the temperature supposedly did not exceed 1050 deg C. Structural observations indicated a special case of internal oxidation. The required conditions for this were apparently provided by the moist hydrogen atmosphere of the annealing furnace, in which the chromium was oxidized, while the oxides of iron and nickel were reduced. Even the carbon suffered incomplete combustion and was enriched in the core. Thus, no protective layer could form or be maintained. The intergranular advancement of the oxidation may have been favored by the precipitation of chromium-rich carbides on the austenite grain boundaries. This form of internal oxidation is, in the case of Ni-Cr alloys, known as green rot. Alloys containing iron should be more resistant. As a preventive measure it was recommended to reduce the operating temperature of the strip sufficiently to allow the use of Fe-Ni-Cr alloys.

The first-stage nozzles of a high-pressure turbine section of an industrial gas turbine exhibited leading and trailing-edge deterioration. The nozzles were made of X-40, a cobalt-base alloy, and were aluminide coated. Failure analysis determined that the deterioration was the result of hot corrosion caused by a combination of contaminants, cooling-hole blockage, and coating loss.

Severely reduced wall thickness was encountered at the liquid line of a lead-bath pan that was used in a continuous strip or wire oil-tempering unit. Replacement of the pan was necessary after six months of service. The pan, 6.9 m (22.5 ft) long, 0.6 m (2 ft) wide, and 38 cm (15 in.) deep with a 2.5-cm (1-in.) wall thickness, was a type 309 stainless steel weldment. Operating temperatures of the lead bath in the pan ranged from 805 deg C (1480 deg F) at the entry end to 845 deg C (1550 deg F) at the exit end. Analysis (visual inspection. metallographic analysis, moisture testing, and etched micrographs using Murakami's reagent) supported the conclusions that thinning of the pan walls at the surface of the molten lead resulted from using coke of high moisture content and from the low fluctuating coke level. Recommendations included reducing the supply of oxygen attacking the grain boundaries and the hydrogen that readily promoted decarburization with the use of dry (2 to 3% moisture content) coke. Maintaining a thick layer of coke over the entire surface of molten lead in the pan would exclude atmospheric oxygen from the grain boundaries.