One inch diam Type 304 stainless steel piping was designed to carry containment atmosphere samples to an analyzer to monitor hydrogen and oxygen levels during operational and the design basis accident conditions that are postulated to occur in a boiling water reactor. Only one of six lines in the system had thru-wall cracks. Shallow incipient cracks were detected at the lowest elevations of one other line. The balance of the system had no signs of SCC attack. Chlorides and corrosion deposits in varying amounts were found throughout the system. The failure mechanism was transgranular, chloride, stress-corrosion cracking. Replacement decisions were based on the presence of SCC attack or heavy corrosion deposits indicative of extended exposure time to chloride-contaminated water. The existing uncracked pipe, about 75 percent of the piping in the system, was retained despite the presence of low level surface chlorides. Controls were implemented to insure that temperatures are kept below 150 deg F, or, walls of the pipe are moisture-free or the cumulative wetted period will never exceed 30 h.

A steam-condensate line (type 316 stainless steel tubing) began leaking after five to six years in service. The line carried steam condensate at 120 deg C (250 deg F) with a two hour heat-up/cool-down cycle. No chemical treatment had been given to either the condensate or the boiler water. To check for chlorides, the inside of the tubing was rinsed with distilled water, and the rinse water was collected in a clean beaker. A few drops of silver nitrate solution were added to the rinse water, which clouded slightly because of the formation of insoluble silver chloride. This and additional investigation (visual inspection, and 250x micrograph etched with aqua regia) supported the conclusion that the tubing failed by chloride SCC. Chlorides in the steam condensate also caused corrosion of the inner surface of the tubing. Stress was produced when the tubing was bent during installation. Recommendations included providing water treatment to remove chlorides from the system. Continuous flow should be maintained throughout the entire tubing system to prevent concentration of chlorides. No chloride-containing water should be permitted to remain in the system during shutdown periods, and bending of tubing during installation should be avoided to reduce residual stress.

A section of clear polymeric tubing failed while in service. The failed sample had been used in a chemical transport application. The tubing had also been exposed to periods of elevated temperature as part of the operation. The tubing was specified to be a polyvinyl chloride (PVC) resin plasticized with trioctyl trimellitate. Investigation included visual inspection, micro-FTIR in the ATR mode, and thermogravimetric analysis. The spectrum on the failed tubing exhibited absorption bands indicative of a PVC resin containing an adipate-based plasticizer. Thermograms of the failed pieces and a reference sample of tubing that performed well showed that the reference material contained a trimellitate-based plasticizer and that the failed material contained an adipate-based material. The conclusion was that the failed tubing had been produced from a formulation that did not comply with the specified material and, as a result, was not as thermally stable as the reference material.

A 680,000 kg (750 ton) per day ammonia unit was shut down following a fire near the outlet of the waste heat exchanger. The fire had resulted from leakage of ammonia from the type 316 stainless steel outlet piping. The outlet piping immediately downstream from the waste heat exchanger consisted of a flange made from a casting, and a reducing cone, a short length of pipe, and a 90 deg elbow, all made of 13 mm thick plate. A liner wrapped with insulation was welded to the smaller end of the reducing cone. All of the piping up to the flange was wrapped with insulation. Investigation (visual inspection, 10x unetched images, liquid-penetrant inspection, and chemical analysis of the insulation) supported the conclusion that the failure occurred in the area of the flange-to-cone weld by SCC as the result of aqueous chlorides leached from the insulation around the liner by condensate. Recommendations included eliminating the chlorides from the system, maintaining the temperature of the outlet stream above the dewpoint at all times, or that replacing the type 316 stainless steel with an alloy such as Incoloy 800 that is more resistant to chloride attack.

Eddy current inspection was performed on a vertical evaporator unit (that contained 180 tubes) used in a chemical processing plant. It was advised that the tube material was type 316 stainless steel. The shell-side fluid was condensate and gaseous methylene chloride, while the tube-side fluid was contaminated liquid methylene chloride. More than 100 tubes exhibiting severe outer surface pitting and cracklike indications near each tube sheet were revealed during eddy current inspection. It was observed that the indications correlated with rust-stained, pitted, and cracked areas on the outer surfaces. The cracking was revealed by metallographic examination to have initiated from the outer surface, frequently at pits, and penetrated the tube wall in a transgranular, branching fashion. The crack features were characteristic of chloride stress-corrosion cracking. A change in tube material was recommended to avoid future failures and loss of service.

Hydrogen-assisted stress-corrosion cracking failure occurred in four AISI 4137 chromium molybdenum steel bolts having a hardness of 42 HRC. The normal service temperature (400 deg C, or 750 deg F) was too high for hydrogen embrittlement but, the bolts were subjected also to extended shutdown periods at ambient temperatures. The corrosive environment contained trace hydrogen chloride and acetic acid vapors as well as calcium chloride if leaks occurred. The exact service life was unknown. The bolt surfaces showed extensive corrosion deposits. Cracks had initiated at both the thread roots and the fillet under the bolt head. Multiple, branched cracking was present in a longitudinal section through the failed end of one bolt, typical of hydrogen-assisted SCC in hardened steels. Chlorides were detected within the cracks and on the fracture surface. The failed bolts were replaced with 17-4 PH stainless steel bolts (Condition H 1150M) having a hardness of 22 HRC.

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.

Field metallography and replication were performed on a type 316 stainless steel column in diglycol amine vacuum service to determine the cause of visible OD pitting on the column in several areas above the insulation support rings. The examination revealed transgranular stress-corrosion cracking beneath the pitted areas on the OD. The likely cause of the cracking was chloride stress corrosion, with chlorides deriving from the marine atmosphere and concentrating under the insulation around the support rings. A complete insulation evaluation, including repair or replacement, was recommended to prevent chloride buildup. Painting of the steel surface with an epoxy-phenolic or epoxy-coal tar was also suggested.

A nuclear steam-generator vessel constructed of 100-mm thick SA302, grade B, steel was found to have a small leak. The leak originated in the circumferential closure weld joining the transition cone to the upper shell. The welds had been fabricated from the outside by the submerged arc process with a backing strip. The backing was back gouged off, and the weld was completed from the inside with E8018-C3 electrodes by the shielded metal arc process. Striations of the type normally associated with progressive or fatigue-type failures including beach marks that allowed tracing the origin of the fracture to the pits on the inner surface of the vessel were revealed. Copper deposits with zinc were revealed by EDS examination of discolorations. Pitting was revealed to have been caused by poor oxygen control in the steam generators and release of chloride into the steam generators. It was concluded by series of controlled crack-propagation-rate stress-corrosion tests that A302, grade B, steel was susceptible to transgranular stress-corrosion attack in constant extension rate testing with as low as 1 ppm chloride present. It was recommended to maintain the coolant environment low in oxygen and chloride. Copper ions in solution should be eliminated or minimized.

A type 321 stainless steel downcomer expansion joint that handled process gases was found to be leaking approximately 2 to 3 weeks after installation. The expansion joint was the second such coupling placed in the plant after failure of the original bellows. The failed joint was disassembled and examined to determine the cause of failure. Energy-dispersive x-ray analysis revealed significant peaks for chlorine and phosphorus, indicating failure by chloride stress-corrosion cracking (SCC). Cracks in the liner and bellows exhibited a branched pattern also typical of SCC. Cracks through the inner liner initiated on the outer surface of the liner and propagated inward, whereas cracks in the bellows originated on the inner surface and propagated outward. Stress-corrosion cracking of the assembly was caused by chloride contaminants trapped inside the bellows following hydrostatic testing. Checking the test fluid for chloride and removing all fluids after hydrostatic testing were recommended to prevent further failure.

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.

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.

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.

AISI type 321 stainless steel heat exchanger tubes failed after only three months of service. Macroscopic examination revealed that the leaks were the result of localized pitting attack originating at the water side surfaces of the tubes. Metallographic sections were prepared from both sets of tubes. Microscopic examination revealed that the pits had a small mouth with a large subsurface cavity which is typical of chloride pitting of austenitic stainless steel. However, no pitting was found in other areas of the system, where the chloride content of the process water was higher. This was attributed to the fact that they were downstream from a deaeration unit. It was concluded that the pitting was caused by a synergistic effect of chlorine and oxygen in the make-up water. Because it was not possible to install a deaeration unit upstream of the heat exchangers, it was recommended that a molybdenum-bearing stainless steel such as 316L or 317L be used instead of 321.

One-quarter inch diameter 304 stainless steel cooling tower hanger rods failed by chloride-induced stress-corrosion cracking (SCC). The rods were located in an area of the cooling tower where the air contains drop lets of water below the mist eliminators and above the flow of water The most extensive cracking was observed in the rod nuts and in the portions of the rod which were covered by the nuts. Cracking was transgranular with extensive branching, and some corrosion occurred along the crack paths. The clamping force from the nuts used on both sides of the supported member and residual stresses from thread rolling likely contributed to the stresses for the cracking mechanism, along with the stresses induced by the supported load. The external surfaces of the hanger rods were reportedly exposed to a chloride-containing atmosphere, likely due to the biocide. Type 304 stainless steel is not a suitable material for this application, and materials that resist SCC, such as Inconel, should be considered.

A process vessel heating coil, consisting of several 3 ft diam turns, was supplied with steam at 400 psi and a temperature of 343 deg C (650 deg F). At bi-weekly intervals well water was introduced to effect rapid cooling of the contents. After about eight months, leakage developed from a circumferential crack on the underside of the uppermost turn. Shorter cracks were found at a similar location on the bottom turn, and further leakage occurred at pinhole perforations adjacent to the crack in the top turn and near to a butt-weld in the coil. Microscopic examination revealed that the cracks were predominantly of the intergranular variety. In addition, transgranular cracks were present. Material was an austenitic stainless steel of the type specified but the absence of columbium and titanium in significant amounts showed that it was not stabilized against intergranular carbide precipitation. The transgranular cracks indicated that failure was due partly to stress-corrosion. It was concluded that the chlorides provided the main corrodent for both the stress and intercrystalline-corrosion cracking.

After about four years of service, cracks appeared on the internal or process-side surfaces of four evaporator pans in a sugar concentrator. The pans consisted of a Mo stabilized austenitic stainless steel inner vessel surrounded by a mild steel steam jacket. Corrosion of the external surface had taken place in the form of confluent pitting over a band adjacent to the fillet weld which attached the pan to the blocking ring. Numerous cracks were present in this corroded zone. Microscopical examination of several specimens cut from the sample revealed that the internal cracks in the pan itself originated from the external side of the plate, i.e. from the region covered by the shrouding ring. They were predominantly of the transgranular type. Because the cracks were not of the intergranular type as usually found with weld decay, they were considered to be indicative of stress-corrosion cracking. Stresses responsible for the cracking resulted from weld contraction. The pans had been hosed down periodically with water from local boreholes to remove sugar from the external surfaces, which introduced the corrosive medium.

A corrosion resistant chromium nickel steel (X 2 Cr-Ni-Mo 18 10) worm drive used in a chemical plant at 80 deg C and 100 to 200 atm pressure to transport media containing chloride failed during normal operation. Visual inspections showed that the entire surface of the gear was covered with fine branching cracks and was flaking off. Microscopic examination showed that the unetched polished material had disintegrated to an average depth of 1 mm below the surface. A micrograph of the etched surface revealed numerous deformation lines and transgranular cracking. The failure was thus due to stress-corrosion cracking and additional corrosion due to ventilation elements. Because austenitic chromium nickel steels are prone to stress-corrosion cracking, particularly in the presence of chlorine compounds at high temperatures, and because austenitic rust- and acid-resistant steels are prone to smearing and work hardening during machining, it was recommended that these types of steels be machined only with sharp, short tools mounted in rigid structures. In addition, residual stresses should be eliminated by post-process annealing in a protective atmosphere.

An air compressor was installed at a chemical plant in which nitric acid was produced by burning ammonia with air. It was a 5000 hp, 5-stage centrifugal machine running at 6000 rpm, compressing air to 5 atm. Failure of the first stage impeller occurred due to a segment from the back plate becoming detached. On the remaining portion, cracks were visible running between the holes for rivets by which the vanes were attached. Metallographic examination of selected sections from the backplate revealed the material to be in the hardened and tempered condition, and the cracking to have initiated on the internal surface of the plate at the crevice between the plate and the vane. It was evident that the impeller failed by stress-corrosion cracking, which initiated in the crevice between the vanes and back plate and propagated through the plate along the line of the rivets where working stresses would be greatest. The compressor intake was situated in the vicinity of nitric acid pumps which had a history of leakage troubles, and which had evidently given rise to the nitrates found on the impeller.

Type 302 stainless steel springs used in a printing operation failed by breaking into several pieces after two months in service. The springs were operating over a very small deflection and were regulating the flow of ink, in which they were constantly immersed. Fatigue fractures on every piece of the spring were revealed by visual examination. Each of the fractures was found to be oriented at 45 deg to the wire axis. Clear evidence of pitting corrosion at the fatigue fracture origin was also observed. Free chloride ions were revealed to be present in the ink in which the spring was operating. An alternative ink that contained no free chloride ions was recommended.