A heat exchanger failed five years after going into service in an ammonia synthesis plant. Its container, made of Cr-Mo alloy steel (Material No. 1.7362), operated in an environment that did not exceed 400 deg C or 600 atm of hydrogen partial pressure. X-ray examination revealed a fissure in one of the welded seams, which according to microscopic examination, originated in the base material of the container. Higher magnification revealed a narrow zone adjacent to the weld seam permeated with intergranular cracks, the result of hydrogen attack. It also showed the structure to be completely martensitic. Thus, the failure was due to hardening of the base material during welding, and recommendation was made to temper or anneal the welded regions to reduce the effects of hydrogen under pressure.

A detailed failure analysis was conducted on an ammonia refrigerant condenser tube component that failed catastrophically during its initial hours of operation. Evidence collected clearly demonstrated that the weld between a pipe and a dished end contained a sharp unfused region at its root (lack of penetration). Component failure had started from this weld defect. The hydrogen absorbed during welding facilitated crack initiation from this weld defect during storage of the component after welding. Poor weld toughness at the low operating temperature facilitated crack growth during startup, culminating in catastrophic failure as soon as the crack exceeded critical length.

Unalloyed steels and the pure nickel steels frequently used in the past can sustain significant damage from hydrogen attack in ammoniacal environments. The attack causes decarburization that leads to a loosening of the structure due to the precipitation of methane along grain boundaries. It occurs between 200 and 300 deg C, depending on hydrogen pressure. Parts of an apparatus that operate in these types of environments must be checked constantly if they are not made from hydrogen-resistant steel. The results of two such examinations serve to illustrate the challenges.

A cooler of an ammonia synthesis plant was destroyed after three years of service due to the rupture of a distribution manifold. Synthesis gas under high pressure and at about 300 deg C, consisting of 10% NH3 and unconverted gas of 25% N2 and 75% H2 content, was water-cooled externally to room temperature in this unit. The fracture had the typical flat-gray fibrous structure of a material destroyed by hydrogen. Specimens for the metallographic investigation showed that the structure appeared to have been loosened by intergranular separations. DVM notched impact specimens from the affected area yielded low specific impact energy values. These are the significant characteristics of hydrogen attack. The attack penetrated to a depth of 13 to 16 mm. It was recommended that the manifolds be made of hydrogen-resistant steel instead of the unalloyed steel used.

One of the coils in the radiant section of a primary reformer furnace used in an ammonia plant was found leaking. The bottom of one of seven outlet headers (made of ASME SA-452, grade TP316H, stainless steel) was revealed during examination to be ruptured. It was revealed by metallurgical examination that it had failed as a result of intergranular fissuring and oxidation (creep rupture). The ruptured area revealed that the header had failed by conventional long-time creep rupture as a result of exposure to operating temperatures probably between 900 and 955 deg C. Three samples from different sections (ruptured area, slightly bulged but nonruptured area and visually sound metal) were inspected. The presence of pinhead-size intergranular fissures throughout the cross sections of the latter two samples was observed. An ultrasonic attenuation method was employed to investigate the remaining headers. All headers were revealed by ultrasonic readings to be in an advanced stage of creep rupture and no areas were found to be fissured to a degree that they needed immediate replacement. As a conclusion, the furnace was deemed serviceable and it was established that in the absence of local hot spots, the headers would survive for a reasonable period of time.

An arsenical admiralty brass (UNS C44300) finned tube in a generator air cooler unit at a hydroelectric power station failed. The unit had been in operation for approximately 49,000 h. The cooling medium for the tubes was water from a river. Air flowed over the finned exterior of the tubes, while water circulated through the tubes. Investigation (visual inspection, leak testing, history review, 100X micrographs etched in potassium dichromate, chemical analysis, and EDS and XRD analysis of internal tube deposits) supported the conclusion that the cause of the tube leaks was ammonia-induced SCC. Because the cracks initiated on the inside surfaces of the tubes and because the river water was not treated before it entered the coolers, the ammonia was likely present in the river water and probably concentrated under the internal deposits. Recommendations included either eliminating the ammonia (prohibitively expensive in cost and time) or using an alternate material (such as a 70Cu-30Ni alloy or a more expensive titanium alloy) that is resistant to ammonia corrosion as well as to chlorides and sulfur species.

During routine quality control testing, small circuit breakers exhibited high contact resistance and, in some cases, insulation of the contacts by a surface film. The contacts were made of silver-refractory (tungsten or molybdenum) alloys. Infrared analysis revealed the film to be a corrosion layer that resulted from exposure to ammonia in a humid atmosphere. Simulation tests confirmed that ammonia was the corrodent. The ammonia originated from the phenolic molding area of the plant. It was recommended that fumes from molding areas be vented outside the plant and that assembly, storage, and calibration areas be isolated from molding areas.

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.

Tube sheets (found to be copper alloy C46400, or naval brass, and 5 cm (2 in.) thick) of an air compressor aftercooler were found to be cracked and leaking approximately 12 to 14 months after they had been retubed. Most of the tube sheets had been retubed several times previously because of unrelated tube failures. Sanitary (chlorinated) well water was generally used in the system, although filtered process make-up water (river water) containing ammonia was occasionally used. Investigation (visual inspection, chemical analysis, mercurous nitrate testing, unetched 5X micrographs, and 250X micrographs etched in 10% ammonium persulfate solution) supported the conclusion that the tube sheets failed by SCC as a result of the combined action of internal stresses and a corrosive environment. The internal stresses had been induced by retubing operations, and the environment had become corrosive when ammonia was introduced into the system by the occasional use of process make-up water. Recommendations included making a standard procedure to stress relieve tube sheets before each retubing operation. The stress relieving should be done by heating at 275 deg C (525 deg F) for 30 min and slowly cooling for 3 h to room temperature.

A nickel alloy cylinder plated with chromium along its inner liner, installed in a commercial ice cream freezer, showed gray discoloration along its OD surface. The discolored parts exhibited significantly reduced cooling efficiency as compared with new cylinders. During operation, the OD of the cylinder was exposed to liquid ammonia refrigerant containing lubricant from the compressor. The lubricant (mineral oil) was intended to separate from the ammonia and be recirculated through the compressor. Nondestructive portable optical microscopy, XRF, EDS, and XPS analyses showed that the discoloration on the cylinder was associated with metal oxidation products coated with a thin oil film. One of the recommendations was to plate the OD of the cylinder with hard chromium to increase its resistance to erosion. Another recommendation was to reduce the amounts of water contamination in the refrigerant.

An arsenical admiralty brass (UNS C44300) finned tube in a generator air cooler unit at a hydroelectric power station failed. The unit had been in operation for approximately 49,000 h. Stereomicroscopic examination revealed two small transverse cracks that were within a few millimeters of the tube end, with one being a through-wall crack. Metallographic examination of sections containing the cracks showed branching secondary cracks and a transgranular cracking mode. The cracks appeared to initiate in pits. EDS analysis of a friable deposit found on the inside diameter of the tube and XRD analysis of crystalline compounds in the deposit indicated the possible presence of ammonia. Failure was attributed to stress-corrosion cracking resulting from ammonia in the cooling water. It was recommended that an alternate tube material, such as a 70Cu-30Ni alloy or a titanium alloy, be used.

A large pressure vessel designed for use in an ammonia plant failed during hydrostatic testing. It was fabricated from ten Mn-Cr-Ni-Mo-V steel plates which were rolled and welded to form ten cylindrical shell sections and three forgings of similar composition. The fracture surfaces were metallographically examined to be typical for brittle steel fracture and associated with the circumferential weld that joined the flange forging to the first shell section. Featureless facets in the HAZ were observed and were revealed to be the fracture-initiation sites. Pronounced banding in the structure of the flange forging was revealed by examination. A greater susceptibility to cracking was interpreted from the higher hardenability found within the bands. Stress relief was concluded to have not been performed at the specified temperature level (by hardness and impact tests) which caused the formation of hard spots. The mode of crack propagation was established by microstructural examination to be transgranular cleavage. It was concluded that failure of the pressure vessel stemmed from the formation of transverse fabrication cracks in the HAZ fostered by the presence of hard spots. It was recommended that normalizing and tempering temperatures be modified and a revised forging practice explored.

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.

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.