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.

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.

A transition duct was part of a 100-MW power-generation gas turbine. The duct was fabricated from several panels of a modified nickel alloy, IN-617. After six years of operation, two such ducts failed during the next two years, causing outages. Failure was in the form of a total collapse of the duct. Carbides and carbonitrides were found in all of the transitions examined. Investigation supported the conclusion that failure was caused by oxidation, oxide penetration, and oxide spallation which caused thinning of the duct wall. It was felt that the high oxygen and nitrogen partial pressures of the gases within the duct, combined with the high temperatures, facilitated nitrogen pickup. No recommendations were made.

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.

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.

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.

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.

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.

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.

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.

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.

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.

An alloy IN-690 (N06690) incinerator liner approximately 0.8 mm (0.031 in.) thick failed after only 250 h of service burning solid waste. Investigation supported the conclusion that the root cause of the failure was overfiring during startup and sulfidation of the nickel-base alloy. No recommendations were made.

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.

Three radiant heating element tubes from an aluminum holding furnace failed after a few months of service. One side of each of the tubes had disintegrated, leaving large holes and thinned cross sections. Microstructural analysis showed that the surface of the tube had been oxidized along the grain boundaries and had extensive precipitation inside the grains. Chemical analysis indicated that the steel used for the tubes was AISI type 316 stainless steel Specifications for the tubes had called for AISI type 310S to be used. It was recommended that other tubes made from the same batch of steel sheet be checked.

The first-stage blades in a model 501D5 gas turbine had 16 cooling holes. After 32,000 h of service, the blades exhibited cracking at the cooling holes. The blade material was wrought Udimet 520 alloy, with nominal composition of 57Ni-19Cr-12Co-6Mo-1W-2Al-3Ti-0.05C-0.005B. The cooling holes' surface was not coated. Investigation supported the conclusions that the cracking at the cooling holes was due to grain-boundary oxidation and nitridation at the cooling hole surface, embrittlement and loss of local ductility of the base alloy, temperature gradient from the airfoil surface to the cooling holes, which led to relatively high thermal stresses at the holes located at the thicker sections of the airfoil, and stress concentration of 2.5 at the cooling hole and the presence of relatively high total strain (an inelastic strain of 1.2%) at the cooling hole surface. Recommendations include applying the specially designed methods given in this case study to estimate the metal temperature and stresses in order to predict the life of turbine blades under similar operating conditions.

Turbine buckets in a 37.5-MW gas turbine made of Udimet 500 superalloy failed in service. The power plant was located 1 km (0.6 miles) from the Pacific Ocean and operated on No. 2 diesel fuel, which was supplied by tanker ship. Turbine bucket failures occurred on three units after 2500 to 6400 h of operation. Investigation (visual inspection, metallographic examination, and stress analysis) supported the conclusion that the differing microstructure of the airfoil resulted in changes in mechanical properties. Because normal operation includes cycling of loads and temperatures, the shroud tip fractured due to thermomechanical fatigue in its degraded state. Recommendations included special chromium or silicon-rich coating to minimize corrosion in gas turbines operating in a marine environment with operating temperatures in the range of type 2 corrosion (650 to 750 deg C, or 1200 to 1380 deg F). Additionally, it was suggested that fuel delivery, handling, and treatment be high quality, to maintain fuel contamination within design limits, and inlet air filtration must be designed for the coastal site. Also, changing the bucket tip by increasing its thickness and changing the casting technique would reduce the stress and make the design more tolerant of corrosion.

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.

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.