During microscopic examination of a number of cases of caustic cracking, a certain feature has been recognized that appeared to be associated only with caustic cracking. This was a preferential attack on the carbide envelopes and lamellae of the pearlite grains. Evidence suggests that the intergranular path of caustic cracks in steam boilers may be due largely to the presence, probably on a submicroscopic scale, of carbides at the grain boundaries, thus rendering these regions susceptible to preferential attack. It is known that some steels are more liable to develop caustic cracks than others, although their microstructures may not show any significant differences, and it seems probable that this behavior may be related to the amount and continuity of the grain-boundary carbides.

Caustic cracking is the term used to describe one of the forms in which stress-corrosion cracking manifests itself in carbon steels. In the present study, persistent leakage occurred after ten weeks of service from tube expansions in the steam and mud drum of a two-drum D type boiler, which failed to respond to repeated expansion. The leakage was traced to circumferential cracking in the portion of Fe-0.11C-0.46Mn-0.018S-0.011P tubes within the expanded region. Microscopic examination indicated that all cracks started from the outer surface of the tubes in the expanded portion. The form of cracking which was mostly intergranular. Examination at higher magnification disclosed that a selective attack had taken place on the carbide constituents of the pearlite grains. An alkaline deposit on the fireside surface of the tube resulted from the evaporation of boiler water which had found its way past the tube expansions. This indicated that this operation had not resulted in a satisfactorily tight joint.

The onset of leakage adjacent to two butt welds in a 2 in. bore pipe was traced to the development of fine cracks. The pipe carried 40% sodium hydroxide solution. The actual temperature was not known, but the pipeline was steam traced at a pressure of 30 psi, equivalent to a temperature of 130 deg C (266 deg F). Magnetic crack detection revealed circumferential crack-like indications situated a short distance from the butt weld. Cracking originated on the bore surfaces of the tube and was of an intergranular nature reminiscent of caustic cracking in steam boilers. The strength of the solution of caustic soda and possibly the temperature also were in the range known to produce stress-corrosion cracking of mild steels in the presence of stresses of sufficient magnitude. In this instance the location of the cracking suggested that residual stresses from welding, which approach yield point magnitude, were responsible. As all other welds were suspect, the remedy was to remove the joints and to reweld followed by local stress relief.

Original carbon steel and subsequent replacement austenitic stainless steel superheater tube U-bend failures occurred in a waste heat boiler. The carbon steel tubes had experienced metal wastage in the form of caustic corrosion gouging, while the stainless steel tubes failed by caustic-induced stress-corrosion cracking. Sodium was detected by EDS in the internal deposits and the base of a gouge in a carbon steel tube and in the internal deposits of the stainless steel tube. The sodium probably formed sodium hydroxide with carryover moisture and caused the gouging, which was further aggravated by the presence of silicon and sulfur (silicates and sulfates). It was recommended that the tubes be replaced with Inconel 600 or 601, as a practical option until the carryover problem could be solved.

A type 430Ti stainless steel flue gas expansion joint cracked because of caustic-induced stress-corrosion cracking. Energy-dispersive X-ray spectroscope analysis of the fracture surface deposits revealed the presence of sodium and potassium—caustics in hydroxide form. Primary fracture surfaces were all similar in appearance, and a primary crack origin could not be identified. A secondary crack brought to fracture in the laboratory showed brittle, cleavage features rather than classic, tensile overload features. This suggested that the material was embrittled.

Several articulated bellows of 10 in. ID developed leakage from the convolutions after a service life of some 18 months. One of the units received from examination showed cracking at the crown of a convolution and at the attachment weld to the pipe. Sectioning of the bellows revealed many others cracks on the internal surface which did not penetrate to the outside. Microscopical examination showed multiple intergranular, tree-like cracking typical of stress-corrosion cracking. Concentration of sodium hydroxide occurred in the bellows unit and the stress-corrosion cracking which developed was of the form known as caustic cracking. It was recommended that water for de-superheater use should be taken after the deaerator and prior to the addition of salts which may deposit or concentrate in the desuperheater.

Rivets from the longitudinal seam of the terminal shell ring of a 12 year old Lancashire boiler broke off easily during examination. Cleavage fractures indicated a brittle material. Microstructure of a sectioned rivet head was typical of a normal rimming steel except the ferrite crystals contained numerous nitride needles. Their existence indicated an abnormally high nitrogen content. If such a steel is heated for a lengthy period to a temperature of that prevailing in a boiler, precipitation of the nitrides may be expected, with consequent embrittlement. In this case, embrittlement of this type was the primary cause of the breaking off of the type rivet heads. Nothing was observed in the course of the examination that suggested caustic cracking.

Cracking was discovered in an in-service, second-stage turbine impeller during a downtime inspection. The fabricated 4300 series low-alloy steel impeller was used in a compressor in an industrial petrochemical plant. It was also reported that a process upset had allowed a 10% NaOH solution to be ingested by the unit. Routine magnetic particle inspection revealed numerous cracks in the hub area and vane tips of the second-stage impeller Additionally, the outside surface of the backing plate showed a cyclic pattern of cracks. An overview of a conventional, systematic metallurgical approach to failure analysis to confirm that the cracking was caused by a caustic stress-corrosion cracking mechanism is presented.

Several 304H stainless steel superheater tubes fractured in stressed areas within hours of a severe caustic upset in the boiler feedwater system. Tests performed on a longitudinal weld joint, which connected two adjacent tubes in the tertiary superheater bank, confirmed caustic-induced stress-corrosion cracking, promoted by the presence of residual welding stresses. Improved maintenance of check valves and routine inspection of critical monitoring systems (conductivity alarms, sodium analyzers, etc.) were recommended to help avoid future occurrences of severe boiler feedwater contamination. Additional recommendations were to eliminate these short longitudinal weld joints by using a bracket assembly joint between the tubes, use a post-weld heat treatment to relieve residual welding stress or select a more stress-corrosion cracking resistant alloy for this particular application.

A water tube boiler with two headers and 15.5 atm working pressure became leaky in the lower part due to the formation of cracks in the rivet-hole edges. The boiler plate of 20 mm thickness was a rimming steel with 0.05% C, traces of Si, 0.38% Mn, 0.027% P, 0.035% S, and 0.08% Cu. The mean value of the yield point was 24 (24) kg/sq mm, the tensile strength 39 (38) kg/sq mm, the elongation at fracture, d10, 26 (24)%, the necking at fracture 71 (66)% and notch impact value 11.5 (9.4) kgm/sq cm (the values in brackets are for the transverse direction). The specimen from inside surface of the boiler was polished and etched with Fry-solution, which revealed parallel striations formed due to the cold bending of the plate. The zones of slip were concentrated around the rivet holes. The cracks were formed here. The structure examination proved that the cracks had taken an exactly intercrystalline path, which is characteristic for caustic corrosion cracks. It was recommended that the internal stresses be removed through annealing or alternatively lye-resistant steel should be used.

The presence of secondary, branching intergranular stress-corrosion cracking in a type 440C stainless bearing caused the analyst to overlook the real culprit, which was a mechanically-initiated, primary transgranular crack that propagated through the steel's hard chromium carbide. Failure was actually caused by overload. Had the original conclusion been accepted, a relatively exotic alloy would have been specified. In another case, brass heat exchanger tube failure was automatically attributed to attack by an acidic cleaner, and a decision was made to stop using the solution. A more thorough analysis showed failure was caused by tube vibration. In a third case, a type 304 stainless steel bellows in a test loop was thought to have failed because of chloride stress corrosion. The report concluded with a recommendation that carbon steel be used as an alternative bellows material. Caustic, not chloride, stress corrosion was the culprit. Had material substitutions been made on the original premise of countering chloride stress corrosion, most of the loop's highly stressed components would have eventually failed.

An A-470 steel rotor disk was removed from the high-pressure portion of a steam turbine-powered compressor after nondestructive testing revealed cracks in the shoulder of the disk during a scheduled outage. Samples containing cracks were examined using various methods. Multiple cracks, primarily intergranular were found on the inlet and outlet faces along prior-austenite grain boundaries. The cracks initiated at the surface and propagated inward. Multiple crack branching was observed. Many of the cracks were filled with iron oxide. X-ray photoelectron spectroscopy indicated the presence of sodium on crack surfaces, which is indicative of NaOH-induced stress-corrosion cracking. Failure was attributed to superheater problems that resulted in caustic carryover from the boiler. Two options for disk repair, installing a shrink-fit disk or applying weld buildup, were recommended. Weld repair was chosen, and the rotor was returned to service; it has performed for more than 1 year without further incident.

A steam jacketed autoclave of orthodox design was fabricated from mild steel for a working pressure of 320 psi. The only unusual feature in its construction was a protective layer of weld metal, which was deposited on the internal surface of the upper half of the 1 in. thick shell. The first indication of latent trouble was provided by the bolts which attached the stirring paddles to the shaft and the stationary scraper blades to the shell, either failing in service or breaking off when an attempt was made to remove them. It was the practice to renew them all annually. Microscopic examination of a failed bolt showed the path of the fracture and the secondary cracking associated with it were intergranular, suggesting that failure resulted from stress corrosion. A steel of the rimming type had been used to make the bar from which the bolt was forged. Cracks which originate at the root of threads generally result from fatigue but, in this instance, their intergranular mode of progression indicated that they were due to stress-corrosion. Examination of shell material showed that the cracks in the vessel were wholly intergranular. It was apparent from this evidence that this cracking was also due to stress-corrosion.

A bent Ni-Cu Monel 400 alloy tube, which operated as part of a pipeline in a petrochemical distillery, failed by through-thickness cracking. The pipeline was used to carry a stream of gaseous hydrocarbons containing hydrochloric acid (HCl) into a reaction tower. The tower provided a caustic solution (NaOH) to remove HCl from the stream, before the latter was directed to a burner. Metallographic examination showed that the cracks were intergranular and were frequently branched. Although nominal chemical composition of the component was found within the specified range, energy dispersive x-ray analysis (EDXA) indicated significant segregation of sulfur and chlorine along the grain boundaries. Failure was attributed to hypochlorous-acid (HClO)-induced stress-corrosion cracking (SCC). The HClO was formed by the reaction of HCl with atmospheric O 2 that entered the tube during shutdowns and startups. Residual stresses, originating from in situ bend forming of the tube during assembly of the line, provided a driving force for crack growth, and the segregation of sulfur on grain boundaries made the material more susceptible to cracking.

A large pressure vessel that had been in service as a hydrogen sulfide (H2S) absorber developed cracks and began leaking at a nozzle. The vessel contained a 20% aqueous solution of potassium hydroxide (KOH), potassium carbonate (K2CO3), and arsenic. The vessel wall was manufactured of ASTM A516, grade 70, low-carbon steel plate. A steel angle had been formed into a ring was continuously welded to the inside wall of the vessel. The groove formed by the junction of the lower tray-support weld and the top part of the weld around the nozzle was found to have a crack. Pits and scale near the crack origin were revealed by microscopic examination and cracking was found to be transgranular. Periods of corrosion alternated with sudden instances of cleavage, under a tensile load, along preferred slip planes were interpreted during examination with a microscope. It was concluded that the combination of the residual plus operating stresses and the amount of KOH present would have caused stress corrosion as a result of caustic embrittlement. It was recommended that the tray support should be installed higher on the vessel wall to prevent coincidence of the lower tray-support weld with the nozzle weld.

Numerous cracks observed on the surface of a forged A470 Class 4 alloy steel steam turbine rotor disc from an air compressor in a nitric acid plant were found to be the result of caustic induced stress-corrosion cracking (SCC). No material defects or anomalies were observed in the disc sample that could have contributed to crack initiation or propagation or secondary crack propagation. Chlorides detected in the fracture surface deposits were likely the primary cause for the pitting observed on the disc surfaces and within the turbine blade attachment area. It was recommended that the potential for water carryover or feedwater induction into the turbine be addressed via an engineering evaluation of the plant's water treatment procedures, steam separation equipment, and start-up procedures.

This article commences with a discussion on the characteristics of stress-corrosion cracking (SCC) and describes crack initiation and propagation during SCC. It reviews the various mechanisms of SCC and addresses electrochemical and stress-sorption theories. The article explains the SCC, which occurs due to welding, metalworking process, and stress concentration, including options for investigation and corrective measures. It describes the sources of stresses in service and the effect of composition and metal structure on the susceptibility of SCC. The article provides information on specific ions and substances, service environments, and preservice environments responsible for SCC. It details the analysis of SCC failures, which include on-site examination, sampling, observation of fracture surface characteristics, macroscopic examination, microscopic examination, chemical analysis, metallographic analysis, and simulated-service tests. It provides case studies for the analysis of SCC service failures and their occurrence in steels, stainless steels, and commercial alloys of aluminum, copper, magnesium, and titanium.

Gross wastage and embrittlement were observed in plain carbon steel desuperheaters in five new Naval power plants. The gross wastage could be duplicated in laboratory bomb tests using sodium hydroxide solutions and was concluded to be caused by free caustic concentrated by high heat flux. The embrittlement was shown to be caused by the flow of corrosion generated hydrogen which converted the cementite to methane which nucleated voids in the steel. A thermodynamic estimate indicated that a small amount of chromium would stabilize the carbides against decomposition by hydrogen in this temperature range, and laboratory tests with 2-14% Cr steel verified this.

A power plant using two steam generators (vertical U-tube and shell heat exchangers, approximately 21 m (68 ft) high with a steam drum diameter of 6 m (20 ft)) experienced a steam generator tube rupture. Each steam generator contained 11,012 Inconel alloy 600 (nickel-base alloy) tubes measuring 19 mm OD, nominal wall thickness of 1.0 mm (0.042 in.), and average length of 18 m (57.75 ft). The original operating temperature of the reactor coolant was 328 deg C (621 deg F). A tube removal effort was conducted following the tube rupture event. Investigation (visual inspection, SEM fractographs, and micrographs) showed evidence of IGSCC initiating at the OD and IGA under ridgelike deposits that were analyzed and found to be slightly alkaline to very alkaline (caustic) in nature. Crack oxide analysis indicated sulfate levels in excess of expected values. The analysis supported the conclusion that that the deposits formed at locations that experienced steam blanketing or dryout at the higher levels of the steam generators. Recommendations included steam generator water-chemistry controls, chemical cleaning, and reduction of the primary reactor coolant system temperature.

The phenomenon of on-load corrosion is directly associated with the production of magnetite on the water-side surface of boiler tubes. On-load corrosion may first be manifested by the sudden, violent rupture of a boiler tube, such failures being found to occur predominantly on the fire-side surface of tubes situated in zones exposed to radiant heat where high rates of heat transfer pertain. In most instances, a large number of adjacent tubes are found to have suffered, the affected zone frequently extending in a horizontal band across the boiler. In some instances, pronounced local attack has taken place at butt welds in water-wall tubes, particularly those situated in zones of high heat flux. To prevent on-load corrosion an adequate flow of water must occur within the tubes in the susceptible regions of a boiler. Corrosion products and suspended matter from the pre-boiler equipment should be prevented from entering the boiler itself. Also, it is good practice to reduce as far as possible the intrusion of weld flash and other impedances to smooth flow within the boiler tubes.