This article addresses some established protocols for characterizing thermoplastics and whether they are homogeneous resins, alloyed, or blended compositions or highly modified thermoplastic composites. It begins with a discussion on characterizing mechanical, rheological, and thermal properties of polymer. This is followed by a section describing molecular weight determination using viscosity measurements. Next, the article discusses the use of cone and plate and parallel plate geometries in melt rheology. It then reviews the processes involved in the analysis of thermoplastic resins by chromatography. Finally, the article covers three operations of thermoanalysis, namely differential scanning calorimetry, thermogravimetric analysis, and thermomechanical testing.

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.

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.

The stub-shaft assembly which was part of the agitator shaft in a polyvinyl chloride reactor, fractured in service after a nut that retained a loose sleeve around the smaller-diam section of the shaft had been tightened several times to reduce leakage. The shaft was made of ASTM A105, grade 2 steel, and the larger-diam section was covered with a type 316 stainless steel end cap. The cap was welded to each end using type ER316 stainless steel filler metal. The forged steel shaft was revealed to have fractured at approximately 90 deg to the shaft axis in the weld metal and not in the heat-affected zone of the forged steel shaft. Microscopic investigation and chemical analysis of the steel shaft revealed presence of martensite (offered a path of easy crack propagation) around the fusion line and dilution of the weld metal by the carbon steel shaft. The microstructure was found to be martensitic as the fusion line was approached. The forged steel shaft was concluded to have failed by ductile fracture and possible reasons were discussed. Corrective measures adopted in the replacement shaft were specified.

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.

Leakage was detected in a malleable iron elbow (ASTM A 47, grade 35018) after only three months in service. Life expectancy for the elbow was 12 to 24 months. The piping alternately supplied steam and cooling water to a tire-curing press. The supply line and elbow were subjected to 14 heating and cooling cycles per hour for at least 16 h/day, or a minimum of 224 cycles/day. Steam and water pressure were 1035 kPa (150 psi) and 895 kPa (130 psi) respectively, and water-flow rate was estimated to be 1325 L/min (350 gal/min) based on pump capacity. Water-inlet temperature was 10 to 15 deg C (50 to 60 deg F) and outlet temperature was 50 to 60 deg C (120 to 140 deg F). The pH of the water was 6.9. Investigation (visual inspection, chemical analysis, and 67x nital etched micrographs) supported the conclusion that the elbows had been given the usual annealing and normalizing treatment for ferritizing malleable iron. This resulted in lower resistance to erosion and corrosion than pearlitic malleable iron. Recommendations included replacing the elbows with heat-treated fittings with a pearlitic malleable microstructure.

After about two years in service, a 303 stainless steel valve in contact with a carbonated soft drink in a vending machine occasionally dispensed a discolored drink with a sulfide odor. According to the laboratory at the bottling plant, the soft drink in question was strongly acidic, containing citric and phosphoric acids and having a pH of 2.4 to 2.5. Investigation (visual inspection, chemical analysis, immersion testing in the soft drink, and 100x unetched micrographs) supported the conclusion that the failure was caused by the size and distribution of sulfide stringers in the alloy used in the valve. Manganese sulfide stringers in the valve were exposed at end-grain surfaces in contact with the beverage. The stringers, which were anodic to the surrounding metal, were subject to corrosion, producing a hydrogen sulfide concentration in the immediately adjacent liquid. Recommendations included changing the valve material to type 304 stainless steel.

Socket head cap screws used in a naval application were failing in service due to delayed fracture. The standard ASTM A 574 screws were zinc plated and dichromate coated. Investigation (visual inspection, 1187 SEM images, chemical analysis, and tension testing) of both the failed screws and two unused, exemplar fasteners from the same lot supported the conclusion that the cap screws appear to have failed due to hydrogen embrittlement, as revealed by delayed cracking and intergranular fracture morphology. Static brittle overload fracture occurred due to the tension preload, and prior hydrogen charging that occurred during manufacturing. The probable source of charging was the electroplating, although postplating baking was reportedly performed as well. Recommendations included examining the manufacturing process in detail.

During a routine inspection, cracks were discovered in several aluminum alloy (similar to either 2014 or 2017) coupling nuts on the fuel lines of a missile. The fuel lines had been exposed to a marine atmosphere for six months while the missile stood on an outdoor test stand near the seacoast. A complete check was then made, both visually and with the aid of a low-power magnifying glass, of all coupling nuts of this type on the missile. Investigation (visual inspection, spectrographic and chemical analysis, and metallographic examination) supported the conclusion that the cracking of the aluminum alloy coupling nuts was caused by stress corrosion. Contributing factors included use of a material that is susceptible to this type of failure, sustained tensile stressing in the presence of a marine (chloride-bearing) atmosphere, and an elongated grain structure transverse to the direction of stress. The elongated grain structure transverse to the direction of stress was a consequence of following the generally used procedure of machining this type of nut from bar stock. Recommendations included changing the materials specification for new coupling nuts for this application to permit use of only aluminum alloys 6061-T6 and T651 and 2024-T6, T62, and T851.

Plate perforation occurred in the cylindrical section and walls of the inlet foot (2.38 mm thick Incoloy 825 plate welded using INCO welding rod 135) of an inert gas fire prevention system in an oil tanker. Cross-sectional microprobe analysis showed the corrosion product to contain sulfur, mainly from the flue gas, and calcium and chlorine, mainly from the sea water. The gray corrosion product was interspersed with rust and a black carbonaceous deposit. Corrosion pitting and poor weld penetration, with carbide precipitation and heavy etching at grain boundaries, indicated sensitization and susceptibility to aqueous intergranular corrosion. Chemical analysis showed the predominant acid radical to be sulfate (6.20% in the carbonaceous deposit and 0.60% in the corrosion product), suggesting that oxidation of SO2 in the flue gas caused the corrosion. Moisture condensation, the carbon acting as a cathode, and alloy susceptibility to intergranular corrosion contributed to the corrosion.

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.

One of 14 vertical radiant tubes (RA 333 alloy) in a heat-treating furnace failed when a hole about 5 x 12.5 cm (2 x 5 in.) corroded completely through the tube wall. The tube measured 183 cm (72 in.) in length and 8.9 cm (3 in.) in OD and had a wall thickness of about 3 mm (0.120 in.). Failure occurred where the tube passed through the refractory hearth (floor) of the furnace. Although the furnace atmosphere was neutral with respect to the work, it had a carburizing potential relative to the radiant tubes. Analysis (visual inspection, 250x spectroscopic examination of specimens etched with mixed acids, metallographic examination, and chemical analysis) supported the conclusions that the premature failure of the tube by perforation at the hearth level resulted from (1) corrosion caused by sulfur contamination from the refractory cement in contact with the tube and (2) severe local overheating at the same location. Recommendations included replacing all tubes using a low sulfur refractory cement in installation and controlling burner positioning and regulation more closely to avoid excessive heat input at the hearth level.

Over a period of about one year, three RA 330 alloy salt pots from a single heat-treating plant were submitted to failure analysis. All of the pots, which had 9.5 mm thick walls, were used primarily to contain neutral salts at temperatures from about 815 to 900 deg C (1500 to 1650 deg F). However, some cyaniding was also performed in these pots, which, when not in use, were idled at 760 deg C (1400 deg F). It was reported that sludge was removed from the bottom of the pots once a day. Normal pot life varied from about 6 to 20 months. The pots were removed from the furnace, visually inspected, and rotated 120 deg every three weeks to ensure that no single location was overheated for a prolonged period of time. Analysis (visual inspection, chemical analysis, metallographic examination, and x-ray analysis, 60x micrograph etched with 10% oxalic acid) supported the conclusion that the cause of failure of each of the three salt pots was severe intergranular corrosion accompanied by substantial chromium depletion. No recommendations were made.

Two large tension springs fractured during installation. The springs were manufactured from a grade 9254 chromium-silicon steel spring wire. The associated material specification allows wire in the cold-drawn or oil-tempered (quenched-and-tempered) condition. The specified wire tensile strength range was 1689 to 1793 MPa (245 to 260 ksi). The finished springs were to be shot peened for greater fatigue resistance. Investigation (visual inspection, 3x images, 2% nital etched 148x SEM images, chemical analysis, hardness testing, and EDS analysis) supported the conclusion that the springs failed during installation due to the presence of preexisting defects. Crack surfaces were found to be corroded and phosphate coated, indicating that the cracks occurred during manufacture. Installation, which presumably entailed some axial extension, resulted in ductile overload failure at the crack sites. Recommendations included evaluating the manufacturing steps to identify the process(es) wherein the cracking was likely occurring. It was further recommended that a suitable nondestructive method such as magnetic particle inspection be implemented.

After two weeks of operation, a poppet used in a check valve to control fluid flow and with a maximum operating pressure of 24 MPa (3.5 ksi) failed during operation. Specifications required that the part be made of 1213 or 1215 rephosphorized and resulfurized steel. The poppet was specified to be case hardened to 55 to 60 HRC, with a case depth of 0.6 to 0.9 mm (0.025 to 0.035 in.); the hardness of the mating valve seat was 40 HRC. Analysis showed that the fracture occurred through two 8 mm (0.313 in.) diam holes at the narrowest section of the poppet. The valve continued to operate after it broke, which resulted in extensive loss of metal between the holes. 80x micrograph and 4x macrograph of a 5% nital etched longitudinal section, and chemical analyses showed the poppet did fit 1213 or 1215 specs. However, hardness measurements showed surface hardness was excessive-61 to 65 HRC instead of the specified 55 to 60 HRC. Thus, the poppet failed by brittle fracture, and cracking occurred across nonmetallic inclusions. Recommendation was to redesign the valve with the poppet material changed to 4140 steel, hardened, and tempered to 50 to 55 HRC.

A failed tapered-ring sprocket locking device consisted of an assembly of four tapered rings that are retained by a series of cap screws. The middle wedge-shaped rings were pulled closer as the screws were tightened forcing the split inner ring to clamp tightly onto the shaft. One of the wedge-shaped middle rings fractured prior to having been fully torqued, preventing the sprocket from being locked to the shaft. “Woody” fracture features, as a result of decohesion between a high volume fractions of manganese sulfide stringers and the matrix, was revealed during examination. The material was revealed by chemical analysis to be resulfurized grade of carbon steel (SAE type 1144, UNS G11440) which has enhanced longitudinal tensile properties but low transverse properties. It was observed that when the fastening screws were torqued, a significant hoop stress was placed on the middle rings and it caused the failure at the large inclusion present at the minimum section thickness zone of the middle ring. It was concluded that since the material contained a high volume fraction of these inclusions, the material choice was not appropriate for this application. A nonresulfurized grade of low-alloy steel was suggested as recommendation.

A nozzle in a wastewater vaporizer began leaking after approximately three years of service with acetic and formic acid wastewaters at 105 deg C (225 deg F) and 414 kPa (60 psig). The shell of the vessel was weld fabricated from 6.4 mm (0.25 in.) E-Brite stainless steel plate and measured 1.5 m (58 in.) in diameter and 8.5 m (28 ft) in length. Investigation (visual inspection, chemical analysis, radiography, dye-penetrant inspection, and hydrostatic testing of all E-Brite welds, 4x images, 100x/200x images electrolytically etched with 10% oxalic acid, and V-notch Charpy testing) supported the conclusion that failure of the nozzle weld was the result of intergranular corrosion caused by the pickup of interstitial elements and subsequent precipitation of chromium carbides and nitrides. Carbon pickup was believed to have been caused by inadequate joint cleaning prior to welding. The increase in the weld nitrogen level was a direct result of inadequate argon gas shielding of the molten weld puddle. Two areas of inadequate shielding were identified: improper gas flow rate for a 19 mm (0.75 in.) diam gas lens nozzle, and contamination of the manifold gas system. Recommendations included changes in the cleaning and welding process.

Some 99.90 pure tin tubes (0.15 mm thick) used for packaging a chemical compound cracked on bending and underwent brittle fracture prior to filling, while others remained ductile and showed no sign of failure. Examination showed that specimens prepared by mechanical methods such as electrolytic and hand polishing and the vibration method resulted in poor edge and crack edge definition due to material thickness. Etching experiments involved a grain surface attack and hence produced a rather strong surface relief from which the grain boundary cracks could again not clearly be differentiated. The sections were therefore examined unetched in polarized light. The microstructure of the cracked tubes was shown to have much smaller grains than the ductile and showed cracks from the surface down along the grain boundaries. Material hardness also differed between the unusable tubes and the ductile, and chemical analysis showed a higher level of aluminum in the brittle specimens. Failure obviously occurred due to the high material aluminum content that increased hardness which then caused embrittlement at the surface which led to cracks or fracture on bending. Since no explanation of how the aluminum entered the tin was available, no recommendations could be made.