Housings (being tested as part of a material conversion) from an electrical appliance failed during an engineering evaluation. They had been injection molded from a commercial polycarbonate/PET blend. Parts produced from the previous material, a nylon 6/6 resin, had consistently passed the testing regimen. Grease was applied liberally within the housing assembly during production. Investigation included visual inspection, 24x SEM images, micro-FTIR in the ATR mode, and analysis using DSC. No signs of material contamination were found, but the thermograms showed a crystallization of the PET resin. The grease present within the housing assembly, analyzed using micro-FTIR, was composed of a hydrocarbon-based oil, a phthalate-based oil, lithium stearate, and an amide-based additive. The conclusion was that the appliance housings failed through environmental stress cracking caused by a phthalate-based oil that was not compatible with the PC portion of the resin blend. Thus, the resin conversion was the root cause of the failures. Additionally, during the injection molding process the molded parts had been undercrystallized, reducing their mechanical strength. More importantly, the resin had been degraded, producing a reduction in the molecular weight and reducing both the mechanical integrity and chemical-resistance properties of the parts.

This article provides a discussion on the structural ceramics used in gas turbine components, the automotive and aerospace industries, or as heat exchangers in various segments of the chemical and power generation industries. It covers the fundamental aspects of chemical corrosion and describes the corrosion resistance characteristics of specific classes of refractories and structural ceramics. The article also examines the prevention strategies that minimize corrosion failures of both classes of materials.

A chemical storage vessel failed while in service. The failure occurred as cracking through the vessel wall, resulting in leakage of the fluid. The tank had been molded from a high-density polyethylene (HDPE) resin. The material held within the vessel was an aromatic hydrocarbon-based solvent. Investigation (visual inspection, stereomicroscopic examination, 20x/100x SEM images, micro-FTIR in the ATR mode, and analysis using DSC and TGA) supported the conclusion that the chemical storage vessel failed via a creep mechanism associated with the exertion of relatively low stresses. The source of the stress was thought to be molded-in residual stresses associated with uneven shrinkage. This was suggested by obvious distortion evident on cutting the vessel. Relatively high specific gravity and the elevated heat of fusion indicated that the material had a high level of crystallinity. In general, increased levels of crystallinity result in higher levels of molded-in stress and the corresponding warpage. The significant reduction in the modulus of the HDPE material, which accompanied the saturation of the resin with the aromatic hydrocarbon-based solvent, substantially decreased the creep resistance of the material and accelerated the failure.

Corrosion is the deterioration of a material by a reaction of that material with its environment. The realization that corrosion control can be profitable has been acknowledged repeatedly by industry, typically following costly business interruptions. This article describes the electrochemical nature of corrosion and provides the typical analysis of environmental- and corrosion-related failures. It presents common methods of testing of laboratory corrosion and discusses the processes involved in the prevention of environmental- and corrosion-related failures of metals and nonmetals.

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.

This investigation characterizes five surgical stainless steel piercings and one niobium piercing that caused adverse reactions during use, culminating with the removal of the jewelry. Chemical composition shows that none of the materials are in accordance with ISO standards for surgical implant materials. Additionally, none of the stainless steel piercings passed the pitting-resistance criterion of ISO 5832-1, which implies that [%Cr + 3.3(%Mo)] > 26. Under microscopic examination, most of the jewelry revealed the intense presence of linear irregularities on the surface. The lack of resistance to pitting corrosion associated with the poor surface finishing of the stainless steel jewelry may induce localized corrosion, promoting the release of cytotoxic metallic ions (such as Cr, Ni, and Mo) in the local tissue, which can promote several types of adverse effects in the human body, including allergic reactions. The adverse reaction to the niobium jewelry could not be directly associated with the liberation of niobium ions or the residual presence of cytotoxic elements such as Co, Ni, Mo, and Cr. The poor surface finish of the niobium jewelry seems to be the only variable of the material that may promote adverse reactions.

A high-chromium white cast iron shell liner installed in an ore crusher sustained impact damage in the course of operation. Visual-optical examination revealed horizontal cracks on the surface of the liner along with particles that had fractured off. Metallographic examination indicated a heavily deformed surface layer with chip formation at the wear surface. The chemical composition of the liner was found to be Fe-2.74C-0.75Mn-0.55Si-0.51Ni-19.4Cr-1.15M. This alloy is highly resistant to abrasive wear, yet at the same time, prone to chipping because little plastic displacement will occur at the surface. The liner failed as a result of severe abrasion caused by the impact of taconite rock. This was a material-selection problem in that the wrong alloy was used for a condition not anticipated in the original choice.

Two large tension springs fractured during installation. The springs were manufactured from a grade 9254 chromium-silicon steel spring wire. The associated material specification allows wire in the cold-drawn or oil-tempered (quenched-and-tempered) condition. The specified wire tensile strength range was 1689 to 1793 MPa (245 to 260 ksi). The finished springs were to be shot peened for greater fatigue resistance. Investigation (visual inspection, 3x images, 2% nital etched 148x SEM images, chemical analysis, hardness testing, and EDS analysis) supported the conclusion that the springs failed during installation due to the presence of preexisting defects. Crack surfaces were found to be corroded and phosphate coated, indicating that the cracks occurred during manufacture. Installation, which presumably entailed some axial extension, resulted in ductile overload failure at the crack sites. Recommendations included evaluating the manufacturing steps to identify the process(es) wherein the cracking was likely occurring. It was further recommended that a suitable nondestructive method such as magnetic particle inspection be implemented.

An impact breaker bar showed signs of rapid wear. The nominal composition of this chromium alloy cast iron was Fe-2.75C-0.75Mn-0.5Si-0.5Ni-19.5Cr-1.1Mo. The measured hardness of this bar was 450 to 500 HRB. The desired hardness for this material after air hardening is 600 to 650 HRB. The microstructure consisted of eutectic chromium carbides (Cr7C3) in a matrix of retained austenite and martensite intermingled with secondary carbides. Analysis (visual inspection and 500x view of sections etched with Marble's reagent) supported the conclusion that the low hardness resulted from an excessive amount of retained austenite. This caused reduced wear resistance and thus rapid wear in service. Recommendations included avoiding an excessive austenitizing temperature and excessive cooling rates from the austenitizing temperature and controlling the chemical composition to avoid excessive hardenability for the section size involved.

Wet natural gas was dried by being passed through a carbon steel vessel that contained a molecular-sieve drying agent. The drying agent became saturated after several hours in service and was regenerated by a gas that was heated to 290 to 345 deg C in a salt-bath heat exchanger. The tee joint in the piping between the heat exchanger and the sieve bed failed after 12 months. A hole in the tee fitting and a corrosion product on the inner surface of the pitting was revealed by visual examination. Iron sulfide was revealed by chemical analysis of the scale which indicated hydrogen sulfide attack on the carbon steel. The presence of oxygen was indicated by the carbon and sulfur found in the scale on the piping and in the sieves indicated that oxygen combined with moisture produced conditions for attack of hydrogen sulfide on carbon steel. Turbulence with some effect from the coarse grain size was interpreted to have contributed. The piping material was changed from carbon steel to AISI type 316 stainless steel as it is readily weldable and resistant to corrosion by hydrogen sulfide.

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.

Admiralty brass (Alloy C44300) cooling tubes which were part of a heat exchanger in a turbogenerator that provided electricity to a manufacturing plant failed. A mixture of non-recirculating city and “spring pit” water flowed through bundles of tubes to cool the oil in which they are immersed. However, a problem developed when several of the brass tubes cracked transversely, allowing cooling water to mix with the oil. The presence of a tensile stress, intergranular cracks, and a corrosion product suggested the tube failures resulted from stress-corrosion cracking. The main corrosion product was cupric hydroxychloride. In addition to switching to a more corrosion-resistant alloy, extreme care should be taken in the manufacturing of the replacement tube bundles to avoid imparting any residual tensile stresses in the tubing. Analyses of city and spring-pit water were recommended also, to determine which contained the least-harmful corrosive chemicals.

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.

Leakage was detected in a malleable iron elbow (ASTM A 47, grade 35018) after only three months in service. Life expectancy for the elbow was 12 to 24 months. The piping alternately supplied steam and cooling water to a tire-curing press. The supply line and elbow were subjected to 14 heating and cooling cycles per hour for at least 16 h/day, or a minimum of 224 cycles/day. Steam and water pressure were 1035 kPa (150 psi) and 895 kPa (130 psi) respectively, and water-flow rate was estimated to be 1325 L/min (350 gal/min) based on pump capacity. Water-inlet temperature was 10 to 15 deg C (50 to 60 deg F) and outlet temperature was 50 to 60 deg C (120 to 140 deg F). The pH of the water was 6.9. Investigation (visual inspection, chemical analysis, and 67x nital etched micrographs) supported the conclusion that the elbows had been given the usual annealing and normalizing treatment for ferritizing malleable iron. This resulted in lower resistance to erosion and corrosion than pearlitic malleable iron. Recommendations included replacing the elbows with heat-treated fittings with a pearlitic malleable microstructure.

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.

Failure of a case hardened steel shaft incorporated fuel pump in a turbine-powered aircraft resulted in damage to the aircraft. The disassembled pump was found to be dry and free of any contamination. Damage was exhibited on the pressure side of each spline tooth in the impeller and the relatively smooth cavities and undercutting of the flank on this side indicated that the damage was caused by an erosion or abrasion mechanism. A relatively smooth worn area was formed at the center of each tooth due to an abrasive action and an undulating outline with undercutting was observed on the damaged side. Particles of sand, paint, or plastic, fibers from the cartridge, brass, and steel were viewed in the brown residue on the filter cartridge under a low power microscope and later confirmed by chemical analysis. Large amount of iron was identified by application of a magnet. It was concluded that the combined effect of vibration and abrasive wear by sand and metal particles removed from the splines damaged the shaft. Case hardened spline teeth surface was recommended to increase resistance to wear and abrasion.

The US Army Research Laboratory performed a failure investigation on a broken main landing gear mount from an AH-64 Apache attack helicopter. A component had failed in flight, and initially prevented the helicopter from safely landing. In order to avoid a catastrophe, the pilot had to perform a low hover maneuver to the maintenance facility, where ground crews assembled concrete blocks at the appropriate height to allow the aircraft to safely touch down. The failed part was fabricated from maraging 300 grade steel (2,068 MPa [300 ksi] ultimate tensile strength), and was subjected to visual inspection/light optical microscopy, metallography, electron microscopy, energy dispersive spectroscopy, chemical analysis, and mechanical testing. It was observed that the vacuum cadmium coating adjacent to the fracture plane had worn off and corroded in service, thus allowing pitting corrosion to occur. The failure was hydrogen-assisted and was attributed to stress corrosion cracking (SCC) and/or corrosion fatigue (CF). Contributing to the failure was the fact that the material grain size was approximately double the required size, most likely caused from higher than nominal temperatures during thermal treatment. These large grains offered less resistance to fatigue and SCC. In addition, evidence of titanium-carbo-nitrides was detected at the grain boundaries of this material that was prohibited according to the governing specification. This phase is formed at higher thermal treatment temperatures (consistent with the large grains) and tends to embrittle the alloy. It is possible that this phase may have contributed to the intergranular attack. Recommendations were offered with respect to the use of a dry film lubricant over the cadmium coated region, and the possibility of choosing an alternative material with a lower notch sensitivity. In addition, the temperature at which this alloy is treated must be monitored to prevent coarse grain growth. As a result of this investigation and in an effort to eliminate future failures, ARL assisted in developing a cadmium brush plating procedure, and qualified two Army maintenance facilities for field repair of these components.

A clamp used for securing the hot-air ducting system on fighter aircraft fractured in an area adjacent to a slot near the end of the strap after two or three years of service. The strap was 0.8 mm (0.032 in.) thick, and the V-section was 1.3 mm (0.050 in.) thick; both were made of 19-9 DL heat-resisting alloy. The operating temperature of the duct surrounded by the clamp was 425 to 540 deg C (800 to 1000 deg F). The life of the clamp was expected to equal that of the aircraft. Investigation (visual inspection, chemical analysis, hardness testing, and 540x/2700x images etched with oxalic acid) supported the conclusion that the clamp fractured by SCC because the work metal was sensitized. Sensitization occurred during long-term exposure to the service temperature; the effects of sensitization were intensified as a result of cold forming. Recommendations included using a work metal that is less susceptible to intergranular carbide precipitation.

Nickel anodes failed in several electrolysis cells in a heavy-water upgrading plant. Dismantling of a cell revealed gouging and the presence of loosely attached black porous masses on the anode. The carbon steel top, plate was severely corroded. An appreciable quantity of black powder was also present on the bottom or the cell. SEM/EDX studies of the outer and inner surfaces of the gouged anode showed the presence of iron globules at the interface between the gouged and the unattacked anode. The chemical composition of the black powder was determined to be primarily iron. Cell malfunction was attributed to the accelerated dissolution of the carbon steel anode top, dislodgment of grains from the material, and subsequent closing of the small annular space between the anode and the cathode by debris from the anode top. Cladding of the carbon steel top with a corrosion-resistant material, such as nickel, nickel-base alloy, or stainless steel, was recommended.

Replacement sprockets installed on chain drive shafts for winding fibers exhibited excessive wear. Metallographic and chemical analyses conducted on the original and replacement sprockets showed that the material of the replacement sprocket was 1020 low-carbon steel, whereas the original (and specified) material was medium-carbon 1045 steel. The low-carbon steel also had lower hardness because of a lower pearlite fraction in the microstructure. It was recommended that replacement sprockets be made of normalized 1045 steel. It was further suggested that wear resistance could be improved by through hardening or induction surface hardening of the teeth.