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.

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.

An extensive metallurgical investigation was carried out on samples of a failed roller bearing from the support and tilting system of a basic oxygen furnace converter used in the steel melting shop of an integrated steel plant. The converter bearing was fabricated from low-carbon, carburizing grade steel and had failed in service within a year of fitting to a repaired shaft. Microscopic observations of both the broken roller and inner-race samples revealed subsurface cracking and preponderance of brittle oxide and other macroinclusions. Electron probe microanalysis studies confirmed that the brittle oxides that formed stringers were alumina, and the other macroinclusions were complex silicates. Both the alumina and silicate inclusions were deleterious to contact-fatigue properties. Microstructurally, the carburized regions of the broken roller and of inner-race samples contained high-carbon tempered martensite. Microhardness measurements revealed that. Although the core hardness of the roller and the inner-race samples were similar, the surface hardness of the roller was approximately 8.5 HRC units harder than that of the inner-race. SEM observations of the roller fracture surface revealed striations indicative of fatigue, and EDS analyses corroborated a high incidence of silicate inclusions at crack sites. The study suggests that the failure of the bearing occurred because the hardness difference between the roller bearing and the inner-race surfaces resulted in wear of the inner-race. The wear led to shaft misalignment and play during service. The misalignment, coupled with the presence of inclusions, caused fatigue failure of the roller bearing.

The intermediate pressure (IP) turbine of a thermal generating station is driven by steam from the boiler's reheater. On one particular IP turbine, a thick deposit was found on the insides of the rotor blade shrouds in two instances two years apart. The source of the deposits was not known; bulk chemical analysis had simply shown that iron was a major component. Optical microscopy and electron microprobe analysis were used to identify the deposits. In the first instance, the deposit was found to be debris that was left in the reheater tubes during boiler modification and swept to the turbine by the steam. There were still some of these debris particles present when the incident two years later was investigated but generally the second deposit was found to be of two layer oxide particles which were shown to have spalled from 2-14% chromium reheater tube surfaces.

A 150 mm (6 in.) diam, 1.6 mm (0.065 in.) thick alloy 800 1iner from an internal bypass line in a hydrogen reformer was removed from a waste heat boiler because of severe metal loss. Visual and metallographic examinations of the liner indicated severe metal wastage on the inner surface, along with sooty residue. Patterns similar to those associated with erosion/corrosion damage were observed. Microstructural examination of wasted areas revealed a bulk matrix composed of massive carbides, indicating that gross carburization and metal dusting had occurred. X-ray diffraction analysis showed that the carbides were primarily chromium based (Cr 23 C 7 and Cr 7 C 3 ). The sooty substance was identified as graphite. Wasted areas were ferromagnetic and the degree of ferromagnetism was directly related to the degree of wastage. Three actions were recommended: (1) inspection of the waste heat boiler to determine the extent of metal damage in other areas by measuring the degree of ferromagnetism, (2) replacement of metal determined to be magnetic, and (3) closer monitoring of temperatures in the region of the reformer furnace outlet.

Failure analysis of a fishhook that broke during retrieval is described. Although the broken hook was discarded, several companion hooks were analyzed (chemistry, microhardness, metallographic cross section, and tensile properties) as were comparable products made by other hook manufacturers. Tensile test data indicated that the companion hooks were significantly different from hooks made by other manufacturers. The hooks broke into several pieces and failed with little or no plastic deformation, while hooks made by other manufacturers plastically deformed and did not break during testing.

Waterwall tube failure samples removed from a coal- and oil-fired boiler in service for 12 years exhibited localized underdeposit corrosion and hydrogen damage. EDS and XRD revealed that bulk internal deposits collected from the tubes contained metallic copper which can accelerate corrosion through galvanic effects and can promote hydrogen damage. Ultrasonic testing was recommended to locate tubes with severe gouging and corrosion, which are suspect locations for hydrogen damage. The source of the copper should be identified and future chemical cleaning of the boiler should address its presence in the waterwall tubes.

This article describes some of the common elemental composition analysis methods and explains the concept of referee and economy test methods in failure analysis. It discusses different types of microchemical analyses, including backscattered electron imaging, energy-dispersive spectrometry, and wavelength-dispersive spectrometry. The article concludes with information on specimen handling.

Numerous cracks observed on the surface of a forged A470 Class 4 alloy steel steam turbine rotor disc from an air compressor in a nitric acid plant were found to be the result of caustic induced stress-corrosion cracking (SCC). No material defects or anomalies were observed in the disc sample that could have contributed to crack initiation or propagation or secondary crack propagation. Chlorides detected in the fracture surface deposits were likely the primary cause for the pitting observed on the disc surfaces and within the turbine blade attachment area. It was recommended that the potential for water carryover or feedwater induction into the turbine be addressed via an engineering evaluation of the plant's water treatment procedures, steam separation equipment, and start-up procedures.

Corrosion in a closed-loop cooling water system constructed of austenitic stainless steel occurred during an extended lay up of the system with biologically contaminated water. The characteristics of the failure were those of microbiologically influenced corrosion (MIC). The corrosion occurred at welds and consisted of large subsurface void formations with pinhole penetrations of the surfaces. Corrosive attack initiated in the heat affected zones of the welds, usually immediately adjacent to fusion lines. Stepwise grinding, polishing, and etching through the affected areas revealed that voids generally grew in the wrought material by uniform general corrosion. Tunneling or worm-holing was also observed, whereby void extension occurred by initiating daughter voids probably at flaws or other inhomogeneities. Selective attack occurred within the fusion zone, i.e., within the cast two-phase structure of the weld filler itself. The result was a void wall which consisted of a rough and porous ferritic material, a consequence of preferential attack of the austenitic phase and slightly lower rate of corrosive attack of the ferrite phase. The three-dimensional spongy surface was studied optically and with the scanning electron microscope.

A 230 mm (9 in.) thick casing, fabricated from ASTM 235-55 low-carbon steel, of a 450 Mg (500 ton) extrusion press failed after 27 years of service. Initial visual examination revealed an area that exhibited multiple origins and classic beach marks radiating out approximately 75 mm (3 in.) from the origin along the wall of a hydraulic-oil bleed hole. Investigation with a SEM showed corrosion pits along the bleed hole wall, but oxidation and corrosion prevented review of microfractographic details. Vacuum epoxy encapsulation, sectioning of the bleed hole, and metallographic examination revealed a basic microstructure of pearlite and ferrite with bands of slightly finer pearlite, with a large concentration of inclusion stringers in the area of the fracture origin. Further investigation using an energy-dispersive x-ray analyzer showed high concentrations of sulfur and manganese. Thus, the failure appeared to have resulted from corrosion-assisted fatigue, and the inclusion concentration in the fracture-initiated area indicated that the chemical-composition limits for sulfur and manganese would have greatly exceeded material specifications. A higher quality steel was recommended for the replacement unit to lessen the possibility of such gross inclusion segregation and to improve the fracture toughness of the cylinder.

An investigation was conducted to determine the cause of numerous cracks and other defects on the surface of a cast ASTM A743 grade CA-15 stainless steel main boiler feed pump impeller. The surface was examined using a stereomicroscope, and macrofractography was conducted on several cross sections removed from the impeller body. Areas that appeared to have the most severe surface damage were sectioned, fractured open, and examined using SEM. The chemistry of the impeller and an apparent repair weld were also analyzed. The examination indicated that the cracks were shrinkage voids from the original casting process. Surface repair welds had been used to fill in or cover over larger shrinkage cavities. It was recommended that more stringent visual and nondestructive examination criteria be established for the castings.

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.

An E-Brite /Ferralium explosively bonded tube sheet in a nitric acid condenser was removed from service because of corrosion. Visual and metallographic examination of tube sheet samples revealed severe cracking in the heat-affected zone between the outer tubes and the weld joining the tube sheet to the floating skirt. Cracks penetrated deep into the tube sheet, and occasionally into the tube walls. The microstructures of both alloys and of the weld appeared normal. Intergranular corrosion characteristic of end-grain attack was apparent. A low dead spot at the skirt / tube sheet joint allowed the Nox to condense and subsequently reboil. This, coupled with repeated repair welding in the area, reduced resistance to acid attack. Intergranular corrosion continued until failure. Recommendations included changing operating parameter inlet to prevent HNO3 condensation outside the inlet and replacement of the floating skirt with virgin material (i.e., material unaffected by weld repairs).

A CrN coated restrike punch was made of WR-95 (similar to H-11), which was fluidized bed nitrided. The coated punch was used on hot Inconel at about 1040 deg C (1900 deg F). However, a water-soluble graphite coolant was used to maintain the punch temperature at 230 deg C (450 deg F). Visual and binocular inspection at 64+ revealed presence of cracks and complete washout of coating in the working area of the failed punch. Comparison of metallographic cross sections of used and unused punches revealed a significant microstructural transformation in case of the used punch. Presence of a yellow porous layer was clearly evident between the nitrided layer and the coating, in case of the used punch. Cracks were observed to propagate from the outer surface into the bulk. Oxidation was evident along the cracks. The microstructural transformation observed in the case of the used punch was a clear indication of high temperature exposure (due to insufficient cooling) during application. The most probable cause of failure was thermal fatigue.

Mechanical testing is an evaluative tool used by the failure analyst to collect data regarding the macro- and micromechanical properties of the materials being examined. This article provides information on a few important considerations regarding mechanical testing that the failure analyst must keep in mind. These considerations include the test location and orientation, the use of raw material certifications, the certifications potentially not representing the hardware, and the determination of valid test results. The article introduces the concepts of various mechanical testing techniques and discusses the advantages and limitations of each technique when used in failure analysis. The focus is on various types of static load testing, hardness testing, and impact testing. The testing types covered include uniaxial tension testing, uniaxial compression testing, bend testing, hardness testing, macroindentation hardness, microindentation hardness, and the impact toughness test.

A brackish water pump impeller was replaced after four years of service, while its predecessor lasted over 40 years. The subsequent failure investigation determined that the nickel-aluminum bronze impeller was not properly heat treated, which made the impeller susceptible to aluminum dealloying. The dealloying corrosion was exacerbated by erosion because the pump was slightly oversized. The investigation recommended better heat treating procedures and closer evaluation to ensure that new pumps are properly sized.

An aluminum brass seawater surface condenser failed due to pitting after less than one year of service. Large pits filled with a green deposit were evidenced under the nonuniform black scale present over the entire inside surface of the tube. The black deposit was identified as primarily copper sulfide, with zinc and aluminum sulfides while the green deposit was revealed to be copper chloride. The combination of sulfide and chloride attack on the tubes was concluded to have resulted in the failure. Injection of ferrous sulfate upstream of the condenser which could aid the formation of protective oxide films was recommended.

The failure of a boiler operating at 540 °C and 9.4 MPa was investigated by examining material samples from the near-failure region and by thermodynamic analysis. A scanning Auger microprobe, SEM, and commercial thermodynamic software codes were used in the investigation. Results indicated that the boiler failure was caused by grain-boundary segregation of phosphorous, tin, and nitrogen and the in-service formation of carbide films and granules on the grain boundaries.