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.

The scanning electron microscope (SEM) is one of the most versatile instruments for investigating the microscopic features of most solid materials. The SEM provides the user with an unparalleled ability to observe and quantify the surface of a sample. This article discusses the development of SEM technology and operating principles of basic systems of SEM. The basic systems covered include the electron optical column, signal detection and display equipment, and the vacuum system. The processes involved in the preparation of samples for observation using an SEM are described, and the application of SEM in fractography is discussed. The article covers the failure mechanisms of ductile failure, brittle failure, mixed-mode failure, and fatigue failure. Lastly, image dependence on microscope type and operating parameters is also discussed.

A steam heated exchanger was designed for concentrating sulfuric acid. Tantalum was selected for the tubing and the tube sheet liner because of its outstanding corrosion resistance. However, although the exchanger passed a searching shop inspection, it leaked during site testing. Considerable argument ensued about whether the cracking observed was due to poor welding during fabrication, or through abuse during handling on site. An SEM examination of the fractures revealed high cycle, low amplitude fatigue, and the problem was traced to vibration during road transport. Further failures were avoided by improved design and packing. This paper illustrated the value of SEM fractography when a rapid investigation is needed under the pressures of a fast moving project.

Failure analysis was performed on threaded Ti-6Al-4V fasteners that had fractured in the threads during installation. Scanning electron microscopy (SEM) and optical metallography revealed that the fractures initiated in circumferential shear bands present at the thread roots. The fractures propagated by microvoid coalescence typical of that observed in notched tensile specimen fractures of the same material. For comparison, Ti-6Al-4V fasteners from various commercial sources were tested to failure in uniaxial tension and examined in the SEM. In all cases, the fracture appearances were similar to that exhibited by the fasteners that failed during installation. In addition, results of optical microscopy indicated that the geometry and extent of the shear bands appeared to depend on the fabrication process employed by the individual manufacturers. Causes of shear band formation are discussed along with potential methods to eliminate these microstructural in homogeneities.

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.

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.

Grease-wiper springs for cams formed from stampings of 0.25-mm thick carbon spring steel (0.65 to 0.80% C) fractured at the 0.025 mm radius on the stamped 135 deg corner at a 90 deg bend after 5,000,000 cycles. Tool marks 2 to 2.3 mm from the center of the stamped bend were disclosed by visual examination. Fatigue striations originating from cracks at the 0.025 mm radius inside corner at the bend were revealed by SEM of the fractured surface. The maximum stress at the bend, in stock of maximum thickness and as a function of the radius of the 135 deg corner, was indicated by stress calculations to be very close to the maximum allowable fluctuating stress for the material. The wiper springs were concluded to be fractured in fatigue and the cyclic loading resulted from cam rotation. The maximum applied stress approached the allowable limit due to high stress-concentration factor in the spring (caused by the very small inside radius). The corner radius was increased to 0.76 mm and the tools were re-polished to avoid tool marks.

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 welded ferritic stainless steel heat exchanger cracked prior to service. The welding filler metal was identified as an austenitic stainless steel and the joining method as gas tungsten arc welding. Investigation (visual inspection, SEM images, 5.9x images, and 8.9x/119x images etched with Vilella's reagent followed by electrolytic etching in 10% oxalic acid) supported the conclusion that the heat exchanger cracked due to weld cold cracking or postwelding brittle overload that occurred via flexure during fabrication. The brittle nature of the weld was likely due to a combination of high residual stresses, a mixed microstructure, inclusions, and gross grain coarsening. These synergistic factors resulted from extreme heat input during fillet welding. Recommendations included altering the welding variables such as current, voltage, and travel speed to substantially reduce the heat input.

Parts of 21Cr-6Ni-9Mn stainless steel that had been forged at about 815 deg C (1500 deg F) were gas tungsten arc welded. During postweld inspection, cracks were found in the HAZs of the welds. Welding had been done using a copper fixture that contacted the steel in the area of the HAZ on each side of the weld but did not extend under the tungsten arc. In SEM examination, the cracks appeared to be intergranular and extended to a depth of approximately 1.3 mm (0.05 in.). The crack appearance suggested that the surface temperature of the HAZ could have melted a film of copper on the fixture surface and that this could have penetrated the stainless steel in the presence of tensile thermal-contraction stresses. The cracks in the weldments were a form of liquid-metal embrittlement caused by contact with superficially melted copper from the fixture and subsequent grain-boundary attack of the stainless steel in an area under residual tensile stress. The copper for the fixtures was replaced by aluminum. No further cracking was encountered.

An AISI 4340 threaded steel connecting rod that was part of a connecting linkage used between a parachute and an instrumented drop test assembly fractured under high dynamic loading when the assembly was dropped from an airplane. A large flaw that originated from the root of a machined thread groove was visible on the fracture surface. Heavy oxidation at elevated temperatures was indicated as most of the surface of the flaw was black. Fine secondary cracks aligned transverse to the growth direction was revealed by scanning electron microscopy. It was established that intergranular cracking observed in this alloy was caused during heat treating as the thread root served as an effective stress concentration and induced quench cracking. It was found that fracture in the overload region occurred by a ductile void growth and coalescence process. Premature failure of the threaded rod was thus attributed to the presence of the quench crack flaw caused by an improper machining sequence and heat treatment practice.

Visual examination, optical and scanning electron microscopy were used to determine the cause of failure in the connector groove of a marine riser coupling. The specified steel was AISI 4142 (0.40 to 0.45% C; 0.75 to 1.00% Mn; 0.20 to 0.35% Si; 0.80 to 1.10% Cr; 0.15 to 0.25% Mo) normalized from 9000C. Microscopic examination revealed the crack's initiation point and subsequent propagation. SEM examination of chemically stripped corrosion showed that corrosion fatigue and stress corrosion might have contributed to the initial slow crack growth. Impact tests revealed a fracture transition temperature in excess of 1000C. The sequence of events leading to failure was detailed. The main recommendation was to quench and temper existing couplings and to use a lower carbon quenched and tempered steel for new couplings.

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.

A cadmium-plated 4340 Ni-Cr-Mo steel ballast elbow assembly was submitted for failure analysis to determine the element or radical present in an oxidation product found inside the elbow assembly. Energy-dispersive x-ray analysis in the SEM showed that iron was the predominant species, presumably in an oxide form. The inside surface had the appearance of typical corrosion products. Hardness measurements indicated that the 4340 steel was heat treated to a strength of approximately 862 MPa (125 ksi). It was concluded that the oxide detected on the ballast elbow was iron oxide. The possibility that the corrosion products would eventually create a blockage of the affected hole was great considering the small hole diameter (4.2 mm, or 0.165 in.). It was recommended that a quick fix to stop the corrosion would be to apply a corrosion inhibitor inside the hole. This, however, would cause the possibility of inhibitor buildup and the eventual clogging of the hole. A change in the manufacturing process to include a cadmium plating on the hole inside surface was recommended. This was to be accomplished in accordance with MIL specification QQ-P-416, Type II, Class 1. A material change to 300-series stainless steel was also recommended.

A failed laser mirror and another complete mirror of the same construction were analyzed. The laser mirror consisted of three layers of material brazed together to form channels through which the cooling water flows. Samples were analyzed with light optical and scanning electron microscopy. The corrosion product contained molybdenum and copper with a trace of gold. The base material was analyzed as molybdenum with negligible alloying additions. The primary mode of corrosion attack on the base material appeared to be intergranular, although uniform corrosion was evident also. It was concluded that corrosion attack sufficiently weakened the base material and the brazed joints, allowing catastrophic failure of the mirror due to the pressure of the cooling water. It was recommended that the mirrors be cleaned of all corrosion products present as a result of past service conditions and proof tested. It was recommended that the water system consisting of deionized water and formaldehyde be replaced with water having a low oxygen content and a cathodic inhibitor (oxygen scavenger).

A component of a water filtration unit failed while being used in service for approximately eight months. The filter system had been installed in a commercial laboratory, where it was stated to have been used exclusively in conjunction with deionized water. The failed part had been injection molded from a 30% glass-fiber and mineral-reinforced nylon 12 resin. Investigation, including visual inspection, 118x SEM images, 9x micrographs, energy-dispersive x-ray spectroscopy, micro-FTIR in the ATR mode, and TGA, supported the conclusion that the filter component failed as a result of molecular degradation caused by the service conditions. Specifically, the part material had undergone severe chemical attack, including oxidation and hydrolysis, through contact with silver chloride. The source of the silver chloride was not established, but one potential source was photographic silver recovery.

Piping and structural components used in space launch facilities such as NASA's Kennedy Space Center and the Air Force's Cape Canaveral Air Station face extreme operating conditions. Launch effluent and residue from solid rocket boosters react with moisture to form hydrochloric acid that settles on exposed surfaces as they are being subjected to severe mechanical loads imparted during lift-off. Failure analyses were performed on 304 stainless steel tubing that ruptured under such conditions, while carrying various gases, including nitrogen, oxygen, and breathing air. Hydrostatic testing indicated a burst strength of 13,500 psi for the intact sections of tubing. Scanning electron microscopy and metallographic examination revealed that the tubing failed due to corrosion pitting exacerbated by stress-corrosion cracking (SCC). The pitting originated on the outer surface of the tube and ranged from superficial to severe, with some pits extending through 75% of the tube's wall thickness. The SCC emanated from the pits and further reduced the service strength of the component until it could no longer sustain the operating pressure and final catastrophic fracture occurred. Corrosion-resistant coatings added after the investigation have proven effective in preventing subsequent such failures.

A failure analysis was conducted on a flow-sensing device that had cracked while in service. The polysulfone sensor body cracked radially, adjacent to a molded-in steel insert. This article describes the investigative methods used to conduct the failure analysis. The techniques utilized included scanning electron microscopy, Fourier transform infrared spectroscopy, differential scanning calorimetry, thermomechanical analysis, and melt flow rate determination. It was the conclusion of the investigation that the part failed via brittle fracture, with evidence also indicating low cycle fatigue associated with cyclic temperature changes from normal service. The design of the part and the material selection were significant contributing factors because of stresses induced during molding, physical aging of the amorphous polysulfone resin, and the substantial differential in coefficients of thermal expansion between the polysulfone and the mating steel insert.

A number of machined end frame steel forgings made of Cr-Si-Mn alloy showed tiny cracks during magnetic particle inspection after heat treatment. The cracks were mostly confined to base edges and fillet radius. No significant abnormality was observed in chemical composition and microstructure. SEM, optical microscopy, and gas analysis revealed that the subsurface discontinuous cracks at the bore edges and in the fillet radius of the heat-treated end frame component had occurred due to hydrogen embrittlement, and not because of faulty heat treatment. This conclusion was supported by the presence of cracklike indications in machined bore surface of the annealed part.

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.