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.

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.

A type 17-4PH stainless steel tube exhibited brown discoloration after a pickling operation. EDS analysis of the extracted substance revealed relatively high levels of iron and chromium, along with lower amounts of aluminum, silicon, sulfur, chlorine, calcium, manganese, and nickel. The iron, chromium, and nickel are likely in the form of dissolution products from the pickling solution. FTIR analysis revealed the presence of polypropylene and poly(ethylene:propylene). The EDS results showed that the discoloration of the tube was associated with oxidation products of the tube material, as well as adherent organic residue. Analysis by FTIR of the residue revealed detectable levels of two polymeric substances, which were later determined to be construction materials of the pickling tank. It was recommended that more frequent cleaning and/or replacement of the pickling solution be put into place and another type of tank material be considered.

Several glass wool insulation sections from a heat-treat furnace showed visible, but only cosmetic discoloration. EDS showed the presence of silicon, aluminum, and oxygen in the nondiscolored region, and these elements are consistent with glass wool. Relatively high levels of chromium and nickel were detected in the discolored area, along with lower amounts of iron, manganese, sodium, calcium, cobalt, and sulfur, in addition to the surrounding glass wool elements. Results of this limited evaluation showed the discoloration was caused by the presence of elevated levels of chromium, nickel, and aluminum. The visual appearance, along with the EDS findings, suggested these elements were present in the form of oxides. These oxides were likely deposited from adjacent structural components of the furnace, which had oxidized during operation.

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.

An electronic sensor coil failed continuity testing, indicating that a break was present in the polymer-coated wire. An area of the wire showed a green discoloration and the break in the wire was located in this same region. The discoloration was suspected to be an indicator of what caused the failure. SEM/EDS and FTIR results showed the break in the coil wire was associated with corrosion. The corrosion debris contained relatively high levels of sodium and chlorine, which were likely in the form of salt. Some salt deposits were noted also in other areas along the wire surface. The findings suggested salt or salt water had leaked into the sensor and caused localized corrosion to the wire, possibly at an area where preexisting damage was present in the coating. Separation occurred in the wire when the current density at the reduced cross section caused excessive localized heating, which led to melting of the wire.

A section from a stainless steel kitchen sink showed a round red stain on its surface after a short time in storage. Several of these sinks were stacked together and separated by felt pads while in storage, and the mating sink showed a nearly identical stain in the same area, while no stains were noted on any of the other sinks in the stack. The stain was located near one of the pads; however, no discoloration was noted at the pad location. EDS analysis showed the base metal to be austenitic stainless steel, such as type 304. FTIR analysis of the stain revealed carboxylic salts and salts of organic acids, in addition to hydroxyl functionality. The discoloration was caused by localized rusting of the sink from prolonged exposure to a chloride containing substance. The appearance suggests that the substance may actually have been a drop of perspiration (sweat) from a factory worker. Based on these findings, one of the recommendations was to use thicker pads between the sinks to allow any such liquids to dry before causing corrosion damage.

Two acrylic-coated polymeric motorcycle components exhibited fisheye blemishes after painting. SEM and EDS results showed relatively high levels of sulfur and chlorine associated with the blemishes in both parts. This suggested some adherent residual substances, possibly in the form of processing fluids and/or cleaning agents, were left on the surface just prior to painting and resulted in the observed fisheye blemishes. One of the components also showed evidence of mechanical damage, in addition to detectable iron, which suggests that the part surface may have been damaged from contact with a ferrous material, such as a steel chip.

A batch of bimetal foil/epoxy laminates was rejected because of poor peel strength. The laminates were manufactured by sintering a nickel/phosphorus powder layer to a copper foil, cleaning, then chromate conversion coating the nickel-phosphorus surface, and laminating the nickel-phosphorus side of the clad bimetal onto an epoxy film, so that the end product contained nickel-phosphorus sandwiched between copper and epoxy, with a chromate conversion layer on the epoxy side of the nickel-phosphorus. Peel testing showed abnormally low adhesion strength for the bad batch of peel test samples. Comparison with normal-strength samples using XPS indicated an 8.8% Na concentration on the surface of the bad sample; the good example contained less than 1% Na on the surface. After 15 min of argon ion etching, depth profiling showed high concentrations of sodium were still evident, indicating that the sodium was present before the chromate conversion treatment was performed. A review of the manufacturing procedures showed that sodium hydroxide was used as a cleaning agent before the chromate conversion coating. Failure cause was that apparently the sodium hydroxide had not been properly removed during water rinsing. Thus, recommendation was to modify that stage in the processing.

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.

After a quick-release fitting of an ejection seat broke, an investigation was performed to determine the manner and cause of crack propagation. Most fractography-based investigations aim to characterize only qualitative characteristics, such as the fracture orientation and origin position, topology, and details of interactions with microstructural features. The aim of this investigation was to use quantitative fractography as a tool to extract information, including striation spacing and size of the stretched zone, in order to make a direct correlation with fracture mechanic concepts. As the crack propagated, striations were created on the fracture surface as a result of service-induced load changes. The size of the striations were measured to estimate crack propagation rate. Remaining lifetime estimates were also made. The dimensions of plastically stretched zones found at the tips of the cracks were evaluated using electron micrograph stereo image pairs to characterize local fracture toughness. To complete the failure analysis, nondestructive evaluation, metallographic examination, and chemical investigations were carried out. No secondary cracks could be found. Most of the broken parts showed that the microstructure, the hardness, and the chemical composition of the Al-alloy were within the specification, but some of the cracked parts were manufactured using a different material than that specified.

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.

This investigation characterizes five surgical stainless steel piercings and one niobium piercing that caused adverse reactions during use, culminating with the removal of the jewelry. Chemical composition shows that none of the materials are in accordance with ISO standards for surgical implant materials. Additionally, none of the stainless steel piercings passed the pitting-resistance criterion of ISO 5832-1, which implies that [%Cr + 3.3(%Mo)] > 26. Under microscopic examination, most of the jewelry revealed the intense presence of linear irregularities on the surface. The lack of resistance to pitting corrosion associated with the poor surface finishing of the stainless steel jewelry may induce localized corrosion, promoting the release of cytotoxic metallic ions (such as Cr, Ni, and Mo) in the local tissue, which can promote several types of adverse effects in the human body, including allergic reactions. The adverse reaction to the niobium jewelry could not be directly associated with the liberation of niobium ions or the residual presence of cytotoxic elements such as Co, Ni, Mo, and Cr. The poor surface finish of the niobium jewelry seems to be the only variable of the material that may promote adverse reactions.

A cast steel bracket manufactured in accordance with ASTM A 148 grade 135/125 steel failed in railroad maintenance service. Ancillary property requirements included a 285 to 331 HB hardness range and minimum impact energy of 27 J (20 ft·lbf) at -40 deg C (-40 deg F). The conditions at the time of failure were characterized as relatively cold. Investigation (visual inspection, chemical analysis, and unetched 119x and 2% nital etched 119x SEM images) supported the conclusion that the bracket failed through brittle overload fracture due to a number of synergistic factors. The quenched-and-tempered microstructure contained solidification shrinkage, inherently poor ductility, and type II Mn-S inclusions that are known to reduce ductility. The macro and microscale fracture features confirmed that the casting was likely in low-temperature service at the time of failure. The composition and mechanical properties of the casting did not satisfy the design requirements. Recommendations included exerting better composition control, primarily with regard to melting, deoxidation, and nitrogen control. Better deoxidation practice was recommended to generate the more desirable Mn-S inclusion morphology, and reevaluation of the casting design was suggested to minimize shrinkage.

After about a year of uninterrupted service, one of the blow pipes on a blast furnace developed a bulge measuring 300 x 150 x 12 mm. The conical shaped section was removed from the furnace and examined to determine why it failed. The investigation consisted of visual inspection, chemical analysis, microstructural characterization, and mechanical property testing. The pipe was made from nonresulfurized carbon steel as specified and was lined with an alumina refractory. Visual inspection revealed cracks in the refractory lining, which corresponded with the location of the bulge. Microstructural and EDS analysis yielded evidence of overheating, revealing voids, scale, grain boundary oxidation, decarburization, and grain coarsening on the inner surface of the pipe, which also suggest the initiation of creep. Based on the information gathered during the investigation, the blow pipe was exposed to high temperatures when the liner cracked and subsequently bulged out due to creep.

This article reviews analytical techniques that are most often used in plastic component failure analysis. The description of the techniques is intended to familiarize the reader with the general principles and benefits of the methodologies, namely Fourier transform infrared spectroscopy, energy-dispersive x-ray spectroscopy, differential scanning calorimetry, thermogravimetric analysis, and dynamic mechanical analysis. The article describes the methods for molecular weight assessment and mechanical testing to evaluate plastics and polymers. The descriptions of the analytical techniques are supplemented by a series of case studies to illustrate the significance of each method. The case studies also include pertinent visual examination results and the corresponding images that aided in the characterization of the failures.

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.

This article discusses the operating principles, advantages, and limitations of scanning electron microscopy, atomic force microscopy, x-ray photoelectron spectroscopy, and secondary ion mass spectroscopy that are used to analyze the surface chemistry of plastics.

This article discusses the most common thermal analysis methods for thermosetting resins. These include differential scanning calorimetry, thermomechanical analysis, thermogravimetric analysis, and dynamic mechanical analysis. The article also discusses the characterization of uncured thermosetting resins as well as the curing process. Then, the techniques to characterize the physical properties of cured thermosets and composites are presented. Several examples of stress-strain curves are shown for thermosets and thermoplastic polymers.

An electron probe microanalyzer was applied to the study of service failures (due to severe heating) of aluminum wire connections in residential electrical circuits. Perturbed regions in which the composition underwent a change during the failure were revealed by optical and scanning electron microscopy of the contacts. A sequence of iron-aluminum compositions that shift from the pure aluminum of the wire to the nearly pure iron of the screw was revealed by analyses of two distinct layers formed on the aluminum/iron region. The compositions were found to correspond to specific intermetallic compounds found in the aluminum-iron phase diagram. Similar compositional variations were noted at the aluminum/brass interface. It was concluded that the failure of the electrical junction due to extreme heating was related to the formation of intermetallic compounds at the current carrying interfaces. These intermetallics were established to have a high resistance causing significant resistive heating.