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.

During a routine inspection on an aircraft assembly line, an airframe attachment bolt was found to be broken. The bolt was one of 12 that attach the lower outboard longeron to the wing carry-through structure. Failure occurred on the right-hand forward bolt in this longeron splice attachment. The bolt was fabricated from PH13-8Mo stainless steel heat treated to have an ultimate tensile strength of 1517 to 1655 MPa (220 to 240 ksi). A water-soluble coolant was used in drilling the bolt hole where this fastener was inserted. Investigation (visual inspection, 265 SEM images, hardness testing, auger emission spectroscopy and secondary imaging spectroscopy, tensile testing, and chemical analysis) supported the conclusion that failure of the attachment bolt was caused by stress corrosion. The source of the corrosive media was the water-soluble coolant used in boring the bolt holes. Recommendations included inspecting for corrosion all the bolts that were installed using the water-soluble coolant at the spliced joint areas, rinsing all machined bolt holes with a noncorrosive agent, and installing new PH13-8Mo stainless steel bolts with a polysulfide wet sealant.

New aircraft wing panels extruded from 7075-T6 aluminum exhibited an unusual pattern of circular black interrupted lines, which could not be removed by scouring or light sanding. The panels, subsequent to profiling and machining, were required to be penetrated inspected, shot peened, H2SO4 anodized, and coated with MIL-C-27725 integral fuel tank coating on the rib side. Scanning electron microscopy and microprobe analysis (both conventional energy-dispersive and Auger analyzers) showed that the anodic coating was applied over an improperly cleaned and contaminated surface. The expanding corrosion product had cracked and, in some places, had flaked away the anodized coating. The corrodent had penetrated the base aluminum in the form of subsurface intergranular attack to a depth of 0.035 mm (0.0014 in.). It was recommended that a vapor degreaser be used during cleaning prior to anodizing. A hot inhibited alkaline cleaner was also recommended during cleaning prior to anodizing. The panels should be dichromate sealed after anodizing. The use of deionized water was also recommended during the dichromate sealing operation. In addition, the use of an epoxy primer prior to shipment of the panels was endorsed. Most importantly, surveillance of the anodizing process itself was emphasized.

During a routine inspection on an aircraft assembly line, an airframe attachment bolt was found to be broken. The bolt was one of 12 that attach the lower outboard longeron to the wing carry-through structure. Failure occurred on the right-hand forward bolt in this longeron splice attachment. The bolt was fabricated from PH13-8Mo stainless steel heat treated to have an ultimate tensile strength of 1517 to 1655 MPa (220 to 240 ksi). A water-soluble coolant was used in drilling the bolt hole where this fastener was inserted. Investigation (visual inspection, 265 SEM images, hardness testing, auger emission spectroscopy and secondary imaging spectroscopy, tensile testing, and chemical analysis) supported the conclusion that failure of the attachment bolt was caused by stress corrosion. The source of the corrosive media was the water-soluble coolant used in boring the bolt holes. Recommendations included inspecting for corrosion all the bolts that were installed using the water-soluble coolant at the spliced joint areas, rinsing all machined bolt holes with a noncorrosive agent, and installing new PH13-8Mo stainless steel bolts with a polysulfide wet sealant.

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 stamped coin exhibited visible discolored areas, seen as a tan haze on the surface. The discoloration was considered merely cosmetic. The nonstained and stained regions were studied using SEM/EDS. Greater amounts of aluminum and magnesium were found in the stained area as compared with the nonstained region. Some carbon and oxygen were detected in both areas, which may be suggestive of organic substances. Fourier transform infrared spectroscopy (FTIR) revealed traces of hydrocarbons and ether/alcohol materials in the stained area, suggesting that the stain was associated with a cellulose or carbohydrates (sugars). These findings, along with the appearance, suggest that a sugar-containing substance, such as coffee or a soft drink, dried onto the surface of this coin and caused the observed discoloration.

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.

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.

The paper discusses the analysis of a coating defect on a high phosphorus electroless nickel (Ni-11 wt. % P) deposit plated on an aluminum alloy substrate. Preliminary investigations had indicated that the elongated defects were possibly caused by the entrapment of long fibers or particles during the plating. The possible sources of fibers were identified. The SEM/EDS analysis of fibers collected from the air duct filters correlated very well with the defect shape and the EDS profile collected from under the defect site. It appears that the fibers from air duct filters directly above the plating line were blown into the plating tank and getting co-deposited. The paper describes the step-by-step analysis of the defect that led to successful identification of the root cause of the defect.

This article focuses on the visual or macroscopic examination of damaged materials and interpretation of damage and fracture features. Analytical tools available for evaluations of corrosion and wear damage features include energy dispersive spectroscopy, electron probe microanalysis, Auger electron spectroscopy, secondary ion mass spectroscopy, and X-ray powder diffraction. The article discusses the analysis and interpretation of base material composition and microstructures. Preparation and examination of metallographic specimens in failure analysis are also discussed. The article concludes with a review of the evaluation of polymers and ceramic materials in failure analysis.

This article provides information on the chemical characterization of surfaces by Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), and time-of-flight secondary ion mass spectrometry (TOF-SIMS). It describes the basic theory behind each of these techniques, the types of data produced from each, and some typical applications. The article explains the strengths of AES, XPS, and TOF-SIMS based on data obtained from the surface of a slightly corroded stainless steel sheet.