X-ray spectroscopy is generally accepted as the most useful ancillary technique that can be added to any scanning electron microscope (SEM), even to the point of being considered a necessity by most operators. While “stand-alone” x-ray detection systems are used less frequently in failure analysis than the more exact instrumentation employed in SEMs, the technology is advancing and is worthy of note due to its capability for nondestructive analysis and application in the field. This article begins with information on the basis of the x-ray signal. This is followed by information on the operating principles and applications of detectors for x-ray spectroscopy, namely energy-dispersive spectrometers, wavelength-dispersive spectrometers, and handheld x-ray fluorescence systems. The processes involved in x-ray analysis in the SEM and handheld x-ray fluorescence analysis are then covered. The article ends with a discussion on the applications of x-ray spectroscopy in failure analysis.

An Incoloy 800H (UNS N08810) transfer line on the outlet of an ethane-cracking furnace failed during decoking of the furnace tubes after nine years in service. A metallographic examination using optical and scanning electron microscopy as well as energy-dispersive x-ray spectroscopy revealed that the failure was due to sulfidation. The source of the sulfur in the furnace effluent was either dimethyl disulfide, injected into the furnace feed to prevent coke formation and carburization of the furnace tubes, or contamination of the feed with sulfur bearing oil.

Within the first few months of operation of an 8 km (5 mile) long 455 mm (18 in.) diam high-pressure steam line between a coal-fired electricity-generating plant and a paper mill, several of the Inconel 600 bellows failed. The steam line operated at 6030 kPa (875 psi) and 420 deg C (790 deg F). Metallographic sections, energy-dispersive x-ray spectra, chemical analyses, tensile tests, and Auger microscope analyses showed the failed bellows met the specifications for the material. However, investigation also showed entire oxide thickness was contaminated with relatively large amounts of sodium, calcium, potassium, aluminum, and sulfur, alkali, alkali earth, and other contaminants that completely permeated even the thin oxides on the fracture surfaces. Additional investigation of the purity of the steam itself as reported by the power plant showed that corrosion and cracks were ultimately caused by the steam. While under normal operation, the steam's purity posed no problem to the material, during boiler cleaning operations, the generating plant had allowed contamination to get into the steam line.

A failure analysis case study on railroad rails is presented. The work, performed under the sponsorship of the Department of Transportation, addresses the problem of shell and detail fracture formation in standard rails. Fractographic and metallographic results coupled with hardness and residual stress measurements are presented. These results suggest that the shell fractures form on the plane of maximum residual tensile stresses. The formation of the shells is aided by the presence of defects in the material in these planes of maximum residual stress. The detail fracture forms as a perturbation from the shell crack under cyclic loading and is constrained to develop as an embedded flaw in the early stages of growth because the crack is impeded at the gage side and surface of the rail head by compressive longitudinal stresses.

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 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.

Pendant-style reheater, constructed of ASME SA-213, grade T-11, steel ruptured. A set of four tubes, specified to be 64 mm OD x 3.4 mm minimum wall thickness was examined. A small quantity of loose debris was removed from the inside of one of the tubes. The major constituent was revealed by EDS analysis of the debris to be iron with traces of phosphorus, manganese, sodium, calcium, copper, zinc, potassium, silicon, chromium, and molybdenum. Thus the debris was interpreted to be the scale from ID of the tube with boiler feedwater chemicals from the attemperation spray. The likely cause of failure was concluded to be exfoliation of the scale from the ID surface of the tube. Creep failures were interpreted to be caused by localized temperatures higher than the maximum service temperature. Replacement of the affected tubes was recommended. Inspection of the tubes by radiography to find the circuits with the greatest accumulation of debris and replacing them as necessary was recommended on an annual basis.

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.

A brazing-furnace muffle 34 cm (13 in.) wide, 26 cm (10 in.) high, and 198 cm (78 in.) long, was fabricated from nickel-base high-temperature alloy sheet and installed in a gas-fired furnace used for copper brazing of various assemblies. The operating temperature of the muffle was reported to have been closely controlled at the normal temperature of 1175 deg C (2150 deg F); a hydrogen atmosphere was used during brazing. After about five months of continuous operation, four or five holes developed on the floor of the muffle, and the muffle was removed from service. Analysis (visual inspection, x-ray spectrometry, and metallographic examination) supported the conclusion that the muffle failed by localized overheating in some areas to temperatures exceeding 1260 deg C (2300 deg F). The copper found near the holes had dripped to the floor from assemblies during brazing. The copper diffused into the nickel-base alloy and formed a grain-boundary phase that was molten at the operating temperature. The presence of this phase caused localized liquefaction and weakened the alloy sufficiently to allow formation of the holes. No recommendations were made.

A kiln, 7.6 m (25 ft) long with a 1 m (3 ft) internal diameter and a 6.3 mm (0.25 in.) wall thickness, is used to regenerate spent charcoal returned by water utilities. This charcoal contains up to 0.57% S and 2.04% Cl. The kiln is made of Inconel 601 (N06601) welded using Inconel 617 (N06617) as a filler alloy. Wet charcoal is fed in at one end of the kiln and travels while being tumbled within the inclined rotating vessel. Temperatures range from 480 deg C (900 deg F) (Zone 1) to 900 deg C (1650 deg F) (Zones 2 and 3). Steam is introduced at the discharge end at 95 g/s (750 lb/h), 34 to 69 kPa (5 to 10 psi), and 125 deg C (260 deg F). The kiln developed perforations within eight months of operation. Investigation (visual inspection, metallurgical analysis, energy-dispersive spectroscopy, and 44X micrographs) supported the conclusion that the sulfur and chlorine in the charcoal attacked the Inconel 601, forming various sulfides and chlorides. Recommendations included on-site testing, and installation of test coupons of various alloys before fabricating another kiln. The suggested alloys were RA85H, 800HT, HR-120, Haynes 556, and HR-160.

Suspension lugs fabricated from AISI 4340 steel used to facilitate loading of bombs onto the underside of military aircraft could not sustain required loads during routine proof load testing. Three failed lugs underwent visual examination, chemical analysis, metallography, hardness testing, scanning electron microscopy, and energy-dispersive x-ray spectroscopy. It was determined that the failures were due to forging defects. Both forging laps and seams acted as stress concentrators when the lugs were loaded during proof testing.

Cracks, with no other damage, were observed in a niobium alloy (Nb-106) part when it was pulled from several months of protective storage for assembly into a rocket nozzle. SEM views showed the cracks to be intergranular, with contaminant particles on a large number of the grain facets. EDX analysis showed they consisted of niobium and fluorine. Plastic replicas, prepared by standard TEM techniques, were analyzed with selected-area electron diffraction, showing a pattern match for niobium tetrafluoride. Auger analyses showed electron spectra containing peaks representing carbon, oxygen, nitrogen, fluorine, and chlorine. Investigation into the processing history of the part showed the tenacious oxide film formed by the affinity of niobium for oxygen - even when heat treated in a vacuum – was removed with a combination of strong acids: nitric, hydrochloric, hydrofluoric, and lactic, resulting in the contaminants found on the surface. Thus, residues of the cleaning acid on the part had caused SCC during storage, with the tensile stresses necessary to generate SCC assumed to have been residual stresses from the heat treatment. Recommendation was made that more stringent cleaning procedures to remove any trace of the cleaning acids be used.

Alloy steel forgings used as structural members of a ski chair lift grip mechanism were identified to have contained forging laps (i.e., sharp-notched discontinuities) during an annual magnetic particle inspection of all chair lift grip structural members at a mountain resort. The material was confirmed to be 34Cr-Ni-Mo6. A heavy oxide on the dark area of one of the broken-open laps was revealed by scanning electron microscopy in conjunction with EDS. A bright area that contained ductile dimple rupture was observed adjacent to the dark area. The oxidized portion of the fracture was established to be the preexisting forging lap while the bright area was created during the breaking-open process. As a corrective action all forgings showing laps were recommended to be removed from service. Critical review and revision of the forging process and revisions to the nondestructive evaluation procedures at the forging supplier was recommended.

A number of seamless pipe nipples of 70 mm diam and 3.5 mm wall thickness made of steel type 35.8 were oxyacetylene welded to collectors of greater wall thickness with a round bead. X-ray examination showed crack initiation in the interior of the nipples close to the root of the weld seam. The cracks only appeared where the originally deposited bead was remelted in the regions of overlap. Given the construction and welding technique used, it would have been preferable to make the nipples of a steel lower in sulfur content. However, by taking advantage of all the potential in shaping and welding technology, it should be possible to prevent crack formation with steel type 35.8 of normal composition.

The presence of subsurface cracks in a longitudinal weld seam of an AISI type 316 stainless steel heat-exchanger shell was revealed by radiographic testing. Numerous intergranular cracks associated with the root pass of the weld, which had propagated both parallel and normal to the weld seam, were revealed by metallographic examination (hot shortness). It was indicated by energy-dispersive spectroscopy that type 316 electrode was not used for the root pass and instead a nickel-copper alloy electrode was employed. It was thus concluded that cracking was caused due to the use of an incorrect electrode for the root pass as these electrodes are crack sensitive if overheated. The weld seam was completely ground out and replaced with the correct electrode material as a corrective measure.

Problems with materials compatibility were encountered in pyrotechnically driven devices used in a number of ordnance applications requiring rapid mechanical actuation. A fine bridgewire is located in contact with the chemical pyrotechnic, and the charge is ignited by electrical heating of the bridgewire. Evidence of severe corrosion was revealed on examination of the nickel-chromium-iron alloy bridgewire and the nickel-iron alloy pins. Metallic elements in the pin or bridgewire and substantial amounts of chlorine were detected from the x-ray spectra. Morphological changes indicative of decomposition and dissolution were revealed to have occurred in regions of the pyrotechnic that had been in contact with the bridgewire and pin surfaces by examination of the titanium-potassium perchlorate (Ti-K-Cl-O4) pyrotechnic. Substantial amounts of water were revealed to be associated with the surfaces of the titanium particles in the pyrotechnic by nuclear magnetic resonance. It was proposed that the chlorine-containing residue combined with the water from the pyrotechnic to form a thin aqueous film corroding the bridgewire and pins. A new cleaning procedure was implemented for the glass headers to eliminate the chloride contamination and a vacuum drying procedure was instituted for the pyrotechnic.

Failure analysis of a mobile harbor crane wheel hub that included SEM and EDS analyses demonstrated that the mechanism of failure was fatigue. The wheel hub was a ductile cast iron component that had been subjected to cyclic loading during a ten-year service period. The fracture surface of the fatigue failure also contained corrosion deposit, suggesting that cracking occurred over a period of time sufficient to allow corrosion of the cracked surfaces. Replacement and alignment of the failed wheel hub was recommended along with inspection of the nonfailed wheel hubs that remained on the crane.

A large number of electropolished copper parts showed evidence of discoloration (tinting) after electropolishing. Because these parts are used in a high-vacuum application, even trace amounts of organic materials would be problematic. Scanning electron microscopy of nondiscolored and discolored areas both showed trace amounts of residue in the form of adherent deposits. EDS, FTIR spectroscopy, XPS, and secondary ion mass spectroscopy (SIMS) analyses indicated that the discoloration to the copper components was due to the development of CuO at localized regions. It was recommended that process changes be made to completely remove residual processing fluids from the part surfaces before electropolishing. The use of more aggressive detergents was suggested, and it was recommended also that a filtering and recirculating system be considered for use in the cleaning and electropolishing tanks.

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.

AISI type 410 stainless steel tube bundles in a heat exchanger experienced leakage during hydrostatic testing even before being in service. The inside surfaces of the tubes was observed to have been pitted. Chloride-ion pitting was revealed by the undercutting in the cross section of a pit and further confirmed by x-ray spectrometry. It was concluded that the failure was caused by pitting due to chlorides in the water used to flush the tubes before service. The use of brackish water to flush or test stainless steel equipment was recommended to avoid pitting.