Identification of alloys using quantitative chemical analysis is an essential step during a metallurgical failure analysis process. There are several methods available for quantitative analysis of metal alloys, and the analyst should carefully approach selection of the method used. The choice of appropriate analytical techniques is determined by the specific chemical information required, the condition of the sample, and any limitations imposed by interested parties. This article discusses some of the commonly used quantitative chemical analysis techniques for metals. The discussion covers the operating principles, applications, advantages, and disadvantages of optical emission spectroscopy (OES), inductively coupled plasma optical emission spectroscopy (ICP-OES), X-ray spectroscopy, and ion chromatography (IC). In addition, information on combustion analysis and inert gas fusion analysis is provided.

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.

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.

A failure analysis investigation was conducted on a fractured aluminum tailwheel fork which failed moments after the landing of a privately owned, 1955 twin-engine airplane. Nondestructive evaluation via dye-penetrant inspection revealed no discernible surface cracks. The chemical composition of the sand-cast component was identified via optical emission spectroscopy and is comparable to an aluminum sand-cast alloy, AA 712.0. Metallographic evaluation via optical microscopy and scanning electron microscopy revealed a high degree of porosity in the microstructure as well as the presence of deleterious intermetallic compounds within interdendritic regions. Macrohardness testing produced hardness values which are noticeably higher than standard hardness values for 712.0. The primary fracture surfaces indicate evidence of mixed-mode fracture, via intergranular cracking, cleaved intermetallic particles, and dimpled cellular regions in the matrix. The secondary fracture surface demonstrates similar features of intergranular fracture.

Catastrophic pitting corrosion occurred in type 304L stainless steel pipe flange assemblies in an industrial food processor. During regular service the pumped medium was pureed vegetables. In situ maintenance procedures included cleaning of the assemblies with a sodium hypochlorite solution. It was determined that the assemblies failed due to an austenite-martensite galvanic couple activated by a chlorine bearing electrolyte. The martensitic areas resulted from a transformation during cold-forming operations. Solution annealing after forming, revision of the design of the pipe flange assemblies to eliminate the forming operation, and removal of the source of chlorine were recommended.

High-level radioactive wastes generated during the processing of nuclear materials are kept in large underground storage tanks made of low-carbon steel. The wastes consist primarily of concentrated solutions of sodium nitrate and sodium hydroxide. Each of the tanks is equipped with a purge ventilation system designed to continuously remove hydrogen gas and vapors without letting radionuclides escape. Several intergranular cracks were discovered in the vent pipe of one such system. The pipe, made of galvanized steel sheet, connects to an exhaust fan downstream of high-efficiency particulate air filters. The failure analysis investigation concluded that nitrate-induced stress-corrosion cracking was the cause of the failure.

Inspections and microstructural analysis revealed intergranular corrosion of 6061-T6 aluminum alloy aircraft fuel line beneath ferrules. The cause of the corrosion was traced to the fuel line marking process, which involved electrolytic labeling. Although subsequent rinsing of the fuel lines washed off most of the electrolyte, some was trapped between the 6061-T6 tubing and the ferrule. This condition made intergranular corrosion of the fuel lines inevitable. The attack caused grains to become dislodged, giving the appearance of pitting. Corrosion penetrated approximately 0.13 mm (0.005 in.) into the tubing. Experiments indicated that the corrosion products were inactive. It was recommended that another marking process be used that does not involve corrosive materials. The prevention of electrolyte from being trapped between the tubing and ferrules by using a MIL-S-8802 sealant was recommended.

High failure rates in the drive shafts of 40 newly acquired articulated buses was investigated. The drive shafts were fabricated from a low-carbon (0.45%) steel similar to AISI 5046. Investigators examined all 40 buses, discovering six different drive shaft designs across the fleet. All of the failures, a total of 14, were of the same type of design, which according to finite-element analysis, produces a significantly higher level of stress. SEM examination of the fracture surface of one of the failed drive shafts revealed fatigue striations near the OD and ductile dimpling near the ID, evidence of high-cycle fatigue. Based on the failure rate and fatigue life predictions, it was recommended to discontinue the use of drive shafts with the inferior design.

An A-470 steel rotor disk was removed from the high-pressure portion of a steam turbine-powered compressor after nondestructive testing revealed cracks in the shoulder of the disk during a scheduled outage. Samples containing cracks were examined using various methods. Multiple cracks, primarily intergranular were found on the inlet and outlet faces along prior-austenite grain boundaries. The cracks initiated at the surface and propagated inward. Multiple crack branching was observed. Many of the cracks were filled with iron oxide. X-ray photoelectron spectroscopy indicated the presence of sodium on crack surfaces, which is indicative of NaOH-induced stress-corrosion cracking. Failure was attributed to superheater problems that resulted in caustic carryover from the boiler. Two options for disk repair, installing a shrink-fit disk or applying weld buildup, were recommended. Weld repair was chosen, and the rotor was returned to service; it has performed for more than 1 year without further incident.

Chemical analysis is a critical part of any failure investigation. With the right planning and proper analytical equipment, a myriad of information can be obtained from a sample. This article presents a high-level introduction to techniques often used for chemical analysis during failure analysis. It describes the general considerations for bulk and microscale chemical analysis in failure analysis, the most effective techniques to use for organic or inorganic materials, and examples of using these techniques. The article discusses the processes involved in the chemical analysis of nonmetallics. Advances in chemical analysis methods for failure analysis are also covered.

New type 321 corrosion-resistant steel heat shields were cracking during welding operations. A failure analysis was performed. The cause was found to be chloride induced stress-corrosion cracking. Packaging was suspected and confirmed to be the cause of the chloride contamination. A contributing factor was the length of time spent in the packaging, 21 years.

A cast silicon bronze (UNS C86700) impeller that had been severely corroded was submitted for failure analysis. The failed part was used to pump potable water, but service life and chlorine content of the water were unknown. The impeller displayed a Cu-rich red phase on its surfaces and showed a pattern very similar to dezincification. Further investigation to determine the cause of damage using light microscopy and SEM-EDS techniques revealed that the microstructure consisted of multiple phases and that a Si-rich phase was being preferentially attacked, leading to increased porosity. After a thorough examination, it was concluded that the part had failed due to dealloying via desiliconification.

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 controllable pitch propeller (CPP) on a dynamic positioning ship failed after eight months of operation. The CPP design consists of a hollow propeller shaft and a concentrically located pipe that operates inside. The pitch of the propeller blades is controlled hydraulically through the longitudinal displacement of the inner (concentric) pipe. Fractography, microstructural, microhardness, and chemical analyses revealed that the concentric pipe failed due to fatigue. Fatigue cracks initiated along longitudinal welds where wire spacers attach to the external surface of the pipe. The effect of crack-like defects, stress concentration at the weld toe, residual tensile stress, and lack of penetration contributed to a shorter fatigue crack initiation phase and premature failure.

Several 304H stainless steel superheater tubes fractured in stressed areas within hours of a severe caustic upset in the boiler feedwater system. Tests performed on a longitudinal weld joint, which connected two adjacent tubes in the tertiary superheater bank, confirmed caustic-induced stress-corrosion cracking, promoted by the presence of residual welding stresses. Improved maintenance of check valves and routine inspection of critical monitoring systems (conductivity alarms, sodium analyzers, etc.) were recommended to help avoid future occurrences of severe boiler feedwater contamination. Additional recommendations were to eliminate these short longitudinal weld joints by using a bracket assembly joint between the tubes, use a post-weld heat treatment to relieve residual welding stress or select a more stress-corrosion cracking resistant alloy for this particular application.

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.

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.

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.

A steam-pressurized Yankee dryer shell ruptured during normal operation. Cracking had occurred around much of the circumference at the drive end of the shell, which measured 3.7 m (12 ft) in diameter by 3.4 m (11 ft) long with a head bolted to each end. The crack initiated at a 90 deg corner in contact with the edge of the head. The material was a hardened gray cast iron containing 2.8% Ni and 1.2% Mo. Based on the results of visual, nondestructive, metallographic, and chemical analyses, it was concluded that failure occurred after corrosion fatigue cracking had weakened the shell. An ultrasonic examination of all Yankee dryers of the same type was recommended to look for cracking at the edge of the shell. Modification of the head-to-shell joint was recommended as well.

This article covers the three most popular techniques used to characterize the very outermost layers of solid surfaces: Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), and time-of-flight secondary ion mass spectrometry (TOF-SIMS). Some of the more important attributes are listed for preliminary insight into the strengths and limitations of these techniques for chemical characterization of surfaces. The article describes the basic theory behind each of the different techniques, the types of data produced from each, and some typical applications. Also discussed are the different types of samples that can be analyzed and the special sample-handling procedures that must be implemented when preparing to do failure analysis using these surface-sensitive techniques. Data obtained from different material defects are presented for each of the techniques. The examples presented highlight the typical data sets and strengths of each technique.