Three separate corrosion mechanisms were involved in the failure of an AISI type 304 stainless steel pipe elbow. The major cracks, including the one that penetrated the wall, tend to be wide-mouthed, tapering to a blunt tip, with corrosion products filling much of the crack space. This was characteristic of corrosion fatigue. The second type of cracking originated at some of the major cracks. These cracks were branched and transgranular, which is characteristic of stress-corrosion caused by chlorides. The third crack mode, an intergranular network, was most probably the result of hydrogen sulphide attack. The 13-year service life of the elbow made it difficult, if not impossible, to determine the order of the corrosion mechanisms or the length of time it took to reach the present state of degradation after the initiation of corrosion. Based on the long service life the present material has given, it was recommended that it be used again.

Some of the admiralty brass tubes were failing in a heat exchanger. The heat exchanger cooled air by passing river water through the inside of the tubes. The wall thickness of all tubes ranged between 1.19 to 1.27 mm (0.047 to 0.050 in.). General intergranular corrosion occurred at the inside surfaces of the tubes. Transgranular stress-corrosion cracking, probably the result of sulphates under basic conditions, and dezincification occurred also as the result of galvanic corrosion under the deposits in the tubes. Recommendations were to use a closed-loop water system to eliminate sulphates, ammonia, etc., and to run trials on one unit with tubes of other alloys such as 80-20 Cu-Ni or 70-30 Cu-Ni to evaluate their performance prior to any large scale retubing operations.

Nineteen out of 26 bolts in a multistage water pump corroded and cracked after a short time in a severe working environment containing saline water, CO 2 , and H 2 S. The failed bolts and intact nuts were to be made from a special type of stainless steel as per ASTM A 193 B8S and A 194. However, the investigation (which included visual, macroscopic, metallographic, SEM, and chemical analysis) showed that austenitic stainless steel and a nickel-base alloy were used instead. The unspecified materials are more prone to corrosion, particularly galvanic corrosion, which proved to be the primary failure mechanism in the areas of the bolts directly exposed to the working environment. Corrosion damage on surfaces facing away from the work environment was caused primarily by chloride stress-corrosion cracking, aided by loose fitting threads. Thread gaps constitute a crevice where an aggressive chemistry is allowed to develop and attack local surfaces.

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.

Failed ferrous components were analyzed from a crane that operated on an offshore platform. The crane failed during operation and fell into the sea. The brake spring on the boom hoist was found to have fractured in four places. The spring contained a line defect (seam) that was the source of each crack. The fracture of the oil quenched and tempered (HRC 50 ASTM A229) spring was by stress-corrosion cracking after the crane fell into the sea because fatigue cannot account for the fractures observed. The crane failure was caused by an overload created by the operator catching a free-falling load.

A type 321 stainless steel (AMS 5570) pressure-tube assembly that contained a brazed reinforcing liner leaked during a pressure test. Fluorescent liquid-penetrant inspection revealed a circumferential crack extended approximately 180 deg around the tube parallel to the fillet of the brazed joint. The presence of multiple origin cracks was indicated on the inside surface of a fractured portion of the crack surface. The cracks had originated adjacent to the braze joining the tube and the reinforcing liner and propagated through the wall to the outer surface. The residues on the inner surface of the tube were identified as fluorides from the brazing flux by chemical analysis. The nature of the crack, potential for corrosion due to residual fluorides and residual swaging stress in the tube prior to brazing, confirmed that failure of the tube end was due to stress-corrosion cracking. Stress relief treatment of tube before brazing and immediate cleaning of brazing residual fluorides was recommended to avoid failure.

Following the discovery numerous cracks at many of the welded seams of a mild steel CO2 absorber vessel, a sample for examination was removed from the worst affected area where repairs had been effected. A 12 in. long circumferential crack was visible. Specimens were taken to cover the several locations of cracking which, in all cases, were found to be similar and of the intergranular type filled with oxide or corrosion product. The association of the cracks with the weld seams indicated that contraction stresses from welding were primarily responsible. Failure of the absorber vessel was found to be due to stress corrosion. Although the active agent present was not positively identified, the aqueous solution of monoethanolamine was thought to be the most probable. The origin of the stresses was not elucidated but the association of the cracks with the welded seams indicated inherent residual stresses as being primarily responsible. Tests carried out tend to suggest that stress relief was not carried out. For the replacement plant, consideration of stress relieving or the use of an alternative material was advised.

Banding wires of the rotor of an 1800 hp motor were renewed following replacement of the banding rings. After about six months of service, a breakdown occurred due to bursting of the banding wires in several places. The 0.064 in. diam wire was nonmagnetic and of the 18/8 Cr-Ni type of austenitic stainless steel. The fractures were short and partially crystalline, with no evidence of slowly developing cracks of the fatigue type. Microscopical examination of sections taken through the fractures showed the cracking to be of the multiple branching type. Because the material was in the heavily cold-worked condition, it was not possible to determine with certainty if the cracks were of the inter- or trans-granular type. It was concluded that failure was due to stress-corrosion cracking in a chloride environment. Failure of the wires was likely due to the use of a chloride-containing flux during the soldering operation.

Small paddles used to mix pulp had experienced a high incidence of breakage through the shafts. In some of the shanks, shrinkage was found relatively close to the surface where threads had been cut all the length of the shaft. Chemistries were within normal CF-8M ranges. Metallography showed the parts to be correctly heat treated. Cross sections of several of the parts showed pitting corrosion, and beneath the pits, stress-corrosion cracks in areas where the shafts had been bent during use. All the samples showed deep SCC in the areas where bending had occurred. In several cases, centerline shrinkage from inadequate risering had decreased life by reducing the cross-sectional area. Type CF-8M is not resistant to chloride SCC where the chloride concentration is considerable. The biggest problem was the bending of these parts. Deformed material with high residual stresses would always be susceptible to SCC. Redesign to lower stresses was essential. In addition, change to a high-strength duplex stainless steel with its higher strength and greater resistance to chlorides was recommended. Finally, the part must be adequately risered to produce solid shanks free from shrinkage.

A CF-8M (cast type 316) neck liner or manway was removed from the top of a digester vessel. Repeated attempts to repair the part in the field during its life cycle of many years had failed to keep the unit from leaking. The casting was a CF-8M modified with the molybdenum level at the top end of the range. The plate was standard 317L material. The filler metal was type 316, although marginal in molybdenum content. Investigation (visual inspection, chemical analysis, micrographs, and metallographic examination) supported the conclusion that the damage to the neck liner was due to Cl-SCC in an area of debris buildup. It appeared the original casting suffered SCC in a low-oxygen area high in chlorides from repeated wet/dry cycles where there was a buildup of debris. Recommendations included redesigning the neck liner to eliminate the abrupt change where there was debris buildup. If redesign was impossible, an alloy more resistant to Cl-SCC, such as a duplex stainless steel or a high-molybdenum (4 to 6%) austenitic stainless steel, should be used.

Several air heat exchangers failed in service in a pulp and paper operation. The tubes were made from AISI 316 stainless steel with an extruded aluminum fin mechanically bonded to the outside. Originally, the failures were blamed on poor tube to header welds. The units were sent back to the manufacturer for repair. Some of the units failed the hydrostatic test after they were repaired. Microscopic examination revealed the presence of branched transgranular cracks characteristic of stress-corrosion cracking. Only some of the tubes failed and these did so by stress-corrosion cracking. The most probable primary cause of the stress-corrosion cracking was local high residual stresses indicated by the areas of high hardness in the tubes. Low halogens in the water and airborne corrodents found normally in a pulp and paper mill were all that were required in the presence of high residual stresses in the tubes to initiate stress-corrosion cracking. Use of a low-carbon grade of stainless steel such as 316L was recommended to facilitate formation of the tube without producing excessive residual stresses. It was recommended also that failed units be segregated until it can be determined if the failure was related to operating pressure or some other unique cause.

The Pandia digester is a long cylindrical vessel which uses alkaline sulfite liquor to cook sawdust for pulping. The inlet cone was fabricated from AISI 304L stainless steel with E308 welds. Typical liquor concentration was approximately 80% NaOH, 20% Na2SO3 with chloride concentrations at 2 grams per liter. The operating pressures in the inlet cone were up to 1.2 MN/sq m (170 psig). The inlet cone had developed leaks within a year of service. Liquid penetrant inspection showed significant through-wall cracking near the fillet welds joining the bottom flange and side wall and the butt welds. Metallographic specimens were prepared from the welds to examine the microstructure and nature of the cracks. The cooking liquor at the inlet cone contained over ppm chlorides and was aggressive to 304 stainless steel. The cracking was identified as chloride-induced SCC. The inlet cone was replaced with an Inconel clad carbon steel inlet cone to combat the SCC.

A falling film black liquor evaporator consisted of flat twin plate heat exchangers and was used to increase black liquor solids content prior to its burning in the recovery boiler. Several plate heat exchangers were fabricated of AISI type 316L stainless steel by electric resistance welding. Cracks initiated at the inside surface of the welded areas and penetrated through the wall thickness. In several locations, the weld fractured and the plates separated with significant spring back, indicative of high residual stresses attributed to fabrication and weld procedures. The cracks had extended radially from the electric resistant weld into the base metal. Metallographic examination revealed the cracks were transgranular and branching, characteristic of SCC in austenitic stainless steels. The fracture surfaces had a brittle cleavage-like appearance, typical of SCC in austenitic stainless steels. Chlorides in the service environment were a contributory factor. The primary factor causing SCC localized at the electric resistant welds was substantial residual stresses as a result of fabrication procedures. It was recommended that the heat exchanger plates be subjected to stress-relief heat treatment following fabrication and welding.

Eddy-current inspection was performed on a leaking absorber bundle in an absorption air-conditioning unit. The inspection revealed crack-like indications in approximately 50% of the tubes. The tube material was phosphorus-deoxidized copper. Investigation (visual inspection, chemical analysis, 0.75x images, 2x macrographs after light acid cleaning to remove corrosion product, and 75x micrographs) supported the conclusion that the absorber tubes failed by SCC initiated by ammonia contamination in the lithium bromide solution. No recommendations were made.

A tubular heat exchanger in a refinery reformer unit leaked after one month of service. The exchanger contained 167 type 304 stainless steel U-bent integral-finned tubes. Cracks in the tube wall were revealed during examination. Hardness of the tube was found to be 30 HRC at the inside surface and up to 40 HRC at the base of the fin midway between the roots which indicated that the fins were cold formed and not subsequently annealed thus susceptible to SCC because of a high residual stress level. It was revealed by metallographic examination that the fracture was predominantly by transgranular branched cracking and had originated from the inside surface. It was concluded that the tubes failed in SCC caused by chlorides in the presence of high residual stresses. The finned tubes were ordered in the annealed condition as a corrective measure.

Several fuses made of nickel silver (57 to 61% Cu, 11 to 13% Ni, bal Zn) exposed to air containing ammonium and nitrate ions failed by SCC. Test solutions of 1 N ammonium nitrate (NH4NO3) and a 1:1 mixture of 1 N sodium nitrate (NaNO3) and 1 N calcium nitrate (Ca(NO3) 2) were prepared. In addition, stressed fuses made of nickel silver and of cupro-nickel (80Cu-20Ni) were exposed to a drop of corrosive solution in the stressed area. All nickel silver specimens failed after two days of exposure to NH4NO3 solution. However, 17% of them failed and 67% showed crack initiation but no failure after 42 days of exposure to NaNO3 + Ca(NO3)2 solution. None of the cupro-nickel specimens failed, but among those exposed to NH4NO3, 17% displayed crack initiation and 83% showed partial dealloying after 42 days. Based on the test results, the fuse material was changed from nickel silver to cupro-nickel, solving the SCC problem.

Electrical contact-finger retainers blanked and formed from annealed copper alloy C65500 (high-silicon bronze A) failed prematurely by cracking while in service in switchgear aboard seagoing vessels. In this service they were sheltered from the weather but subject to indirect exposure to the sea air. About 50% of the contact-finger retainers failed after five to eight months of service aboard ship. Investigation (visual inspection, 250x images etched with equal parts NH4OH and H2O2, emission spectrographic analysis, and stereoscopic views) supported the conclusion that the cracking was produced by stress corrosion as the combined result of: residual forming and service stresses; the concentration of tensile stress at outer square corners of the pierced slots; and preferential corrosive attack along the grain boundaries as a result of high humidity and occasional condensation of moisture containing a fairly high concentration of chlorides (seawater typically contains about 19,000 ppm of dissolved chlorides) and traces of ammonia. Recommendations included redesign of the slots, shot-blasting the formed retainers, and changing the material to a different type of silicon bronze-copper alloy C64700.

Five cylinders out of a group of nine in a drying machine developed leaks after a few months service in a textile mill. Leakage was reported from locations between the hoop and body and from the circumferential welds. The materials in the affected area were 18/8 Ti and 18/10/3/Mo austenitic stainless steels. Examination of the cracks at high magnification revealed them to be of the stress-corrosion type. The welds were of satisfactory quality. Cracking was also visible at these locations, this again being of the stress corrosion type. The method of cylinder construction introduced a crevice between the outer hoop and the cylinder at the inboard edge so that during washing of the rolls, water could penetrate the crevice and subsequent heating would lead to the concentration of chlorides within the crevice. Redesign of the cylinder to eliminate the crevice was recommended.

A substantial number of copper alloy C27000 (yellow brass, 65Cu-35Zn) ferrules for electrical fuses cracked while in storage and while in service in paper mills and other chemical processing plants. The ferrules, made by three different manufacturers, were of several sizes. One commonly used ferrule was 3.5 cm long by 7.5 cm in diam and was drawn from 0.5 mm (0.020 in.) thick strip. Investigation (visual inspection, metallographic examination, and a mercurous nitrate test, which is an accelerated test used to detect residual stress in copper and copper alloys) of both ferrules from fuses in service and storage in different types of plants, and ferrules from newly manufactured fuses, supported the conclusion that the ferrules failed by SCC resulting from residual stresses induced during forming and the ambient atmospheres in the chemical plants. The atmosphere in the paper mills was the most detrimental, and the higher incidence of cracking of ferrules there was apparently related to a higher concentration of ammonia in conjunction with high humidity. Recommendations included specifying that the fuses meet the requirements of ASTM B 154.

Practical examples of stress-corrosion cracking (SCC) and methods for its prevention were presented. Cracks in chloride-sensitive austenitic steels were very branched and transcrystalline. Etched cross sections of molybdenum-free samples showed chloride-induced cracks running out of the pitted areas. Alternatively polishing and etching micro-sections for viewing at high magnification made crack detail more visible. Optical and scanning electron micrographs showed cracking in austenitic cast steel and cast iron due to both internal tensile and critical residual stresses; the latter causes flake-like spalling. Measures to prevent SCC include stress reduction, use of austenitic steels or nickel alloys not susceptible to grain boundary attack, use of ferritic chromium steels, surface slag removal, control of temperature and chloride concentration, and cathodic protection.