Graphitization, the formation of graphite nodules in carbon and low alloy steels, contributes to many failures in high-temperature environments. Three such failures in power-generating systems were analyzed to demonstrate the unpredictable nature of this failure mechanism and its effect on material properties and structures. In general, the more randomly distributed the nodules, the less effect they have on structural integrity. In the cases examined, the nodules were found to be organized in planar arrays, indicating they might have an effect on material properties. Closer inspection, however, revealed that the magnitude of the effect depends on the relative orientation of the planar arrangement and principle tensile stress. For normal orientation, the effect of embrittlement tends to be most severe. Conversely, when the orientation is parallel, the nodules have little or no effect. The cases examined show that knowledge is incomplete in regard to graphitization, and the prediction of its occurrence is not yet possible.

A carbon-molybdenum (ASTM A209 Grade T1) steel superheater tube section in an 8.6 MPa (1250 psig) boiler cracked because of long-term overheating damage that resulted from prolonged exposure to metal temperatures between 482 deg C (900 deg F) and 551 deg C (1025 deg F). The outer diameter of the tube exhibited a crack (fissure) oriented approximately 45 deg to the longitudinal axis and 3.8 cm (1.5 in.) long. The inner diameter surface showed a fissure in the same location and orientation. Microstructure at the failure near the outer diameter surface exhibited evidence of creep cracking and creep void formation at the fissure. A nearly continuous band of graphite nodules was observed on the surface of the fissure. In addition to the graphite band formation, the microstructure near the failure exhibited carbide spheroidization from long-term overheating in all the tube regions examined. It was concluded that preferential nucleations of graphite nodules in a series of bands weakened the steel locally, producing preferred fracture paths. Formation of these graphite bands probably expedited the creep failure of the tube. Future failures may be avoided by using low-alloy steels with chromium additions such as ASTM A213 Grade T11 or T22, which are resistant to graphitization damage.

Tube 3 from a utility boiler in service for 13 years under operating conditions of 540 deg C (1005 deg F), 13.7 MPa (1990 psi) and 1,189,320 kg/h (2,662,000 lb/h) incurred a longitudinal rupture near its 90 deg bend while Tube 4 from the same boiler exhibited deformation near its bend. Metallographic examination revealed creep voids near the rupture in addition to graphite nodules. Exposure of the SA209 Grade T1A steel tubing to a calculated mean operating temperature of 530 deg C (983 deg F) for the 13 years resulted in graphitization and subsequent creep failure in Tube 3. The deformation in Tube 4 was likely the result of steam washing from the Tube 3 failure. Graphitization observed remote from the rupture in Tube 3 and in Tube 4 indicated that adjacent tubing also was susceptible to creep failure. In-situ metallography identified other graphitized tubes to be replaced during a scheduled outage.

A 25.4 cm (10 in.) diam gray cast iron water main pipe was buried in the soil beneath a concrete slab. The installation was believed to have been completed in the early 20th century. A leak from the pipe resulted in flooding of a warehouse. Once removed, the pipe revealed through-wall perforations and cracking along its axis. The perforations and the crack were at the 6 o'clock position. Investigation (visual inspection, radiography, unetched macrographs, and tensile testing) supported the conclusion that the failure occurred as result of years of exposure to ground water in the soil resulting in graphitic corrosion. Soils containing sulfates are particularly aggressive. Recommendations included pipe replacement. The wall thickness had been sufficiently reduced that the pipe could no longer support the required load. Water mains are designed for more than 100 years life. Ductile iron or coated and lined steel pipe, generally not susceptible to graphitic corrosion, were suggested as suitable replacement materials, and cathodic protection was also considered as a possibility.

A graphite-epoxy tapered-box structure, which consisted of two honeycomb skin panels fastened to a spanwise spar with intermediate chordwise ribs, fractured during testing. Hinge-line deflection of the front spar was revealed. Through-thickness cracks in the forward and trailing edges of the compression-loading skin panel were revealed by nondestructive visual examination. A band of de-lamination between the areas of through-thickness skin fracture at the front and rear spar was revealed. A map of the local directions of crack propagation over the fracture surface was generated by the orientation of river patterns and resin microflow during microscopic examination of sectioned samples of the panel. It was discovered that crack initiation occurred at the periphery of a fastener hole located at the front spar. Propagation occurred chordwise across the compression-loaded skin panel. As a corrective measure, the fastener spacing was reduced to prevent the buckling mode that precipitated fracture.

The gun mount used in two types of self-propelled artillery consists of an oil-filled recoil cylinder and a sand-cast (MIL-I-11466, grade D7003) ductile-iron piston that connects to the gun tube through a threaded rod. The piston contains several orifices through which oil is forced as a means of absorbing recoil energy. During operation, the piston is stressed in tension, pulled by oil pressure on one end and the opposing force of the gun tube on the other. The casting specification stipulated that the graphite be substantially nodular and that metallographic test results be provided for each lot. Investigation (visual inspection, fatigue testing, 0.25x/0.35x/50x magnifications, 2% nital etched 60x/65x magnifications, and SEM views) showed that most of the service fractures occurred in pistons containing vermicular graphite. Recommendations included ultrasonic testing of pistons already in the field to identify and reject those containing vermicular graphite. In addition, metallographic control standards were suggested for future production lots.

A section of cast iron water main pipe contained a hole approximately 6.4 x 3.8 cm (2.5 x 1.5 in.). The pipe was laid in clay type soil. Examination revealed severe pitting around the hole and at the opposite side of the outside diam. A macroscopic examination of a pipe section at the hole area showed that the porosity extended a considerable distance into the pipe wall. Metallographic examination revealed a graphite structure distribution expected in centrifugally cast iron with a hypoeutectic carbon equivalent. Chemical analyses of a nonporous sample had a composition typical of cast iron pipe. Chemical analyses of the porous region had a substantial increase in carbon, silicon, phosphorus, and sulfur. The porous appearance and the composition of the soft porous residue confirmed graphitic corrosion. The selective leaching of iron leaves a residue rich in carbon, silicon, and phosphorus. The high sulfur content is attributed to ferrous sulfide from a sulfate reducing bacteria frequently associated with clay soils. Reinforced coal tar protective coating was recommended.

Deterioration of the vanes and a wearing away of the area surrounding the mainshaft-bearing housing of the pump bowl for a submersible water pump used in a well field were noticed during a maintenance inspection. The bowl was sand cast from gray iron and had been in service approximately 45 months. Visual examination of the vanes and the area surrounding the mainshaft-bearing housing revealed a dark corrosion product that was soft, porous, and of low mechanical strength. There were areas with severe erosion. Macrographs of sections through the pump shell and a vane showed darker areas representing graphitic residue and corrosion products that were not removed by erosion. Exposure of the pump bowl to the well water resulted in graphitic corrosion, which generated a soft, porous graphitic residue impregnated with insoluble corrosion products. Failure of the pump bowl resulted from the continuous erosion of the residue by action of the water within the pump.