Metal-induced embrittlement is a phenomenon in which the ductility or fracture stress of a solid metal is reduced by surface contact with another metal in either liquid or solid form. This article summarizes the characteristics of solid metal induced embrittlement (SMIE) and liquid metal induced embrittlement (LMIE). It describes the unique features that assist in arriving at a clear conclusion whether SMIE or LMIE is the most probable cause of the problem. The article briefly reviews some commercial alloy systems where LMIE or SMIE has been documented. It also provides some examples of cracking due to these phenomena, either in manufacturing or in service.

Two clevis-head self-retaining bolts used in the throttle-control linkage of a naval aircraft failed on the aircraft assembly line. Specifications required the bolts to be heat treated to a hardness of 39 to 45 HRC, followed by cleaning, cadmium electroplating, and baking to minimize hydrogen embrittlement. The bolts broke at the junction of the head and shank. The nuts were, theoretically, installed fingertight. The failure was attributed to hydrogen embrittlement that had not been satisfactorily alleviated by subsequent baking. The presence of burrs on the threads prevented assembly to finger-tightness, and the consequent wrench torquing caused the actual fractures. The very small radius of the fillet between the bolt head and the shank undoubtedly accentuated the embrittling effect of the hydrogen. To prevent reoccurrence, the cleaning and cadmium-plating procedures were stipulated to be low-hydrogen in nature, and an adequate post plating baking treatment at 205 deg C (400 deg F), in conformity with ASTM B 242, was specified. A minimum radius for the head-to-shank fillet was specified at 0.25 mm (0.010 in.). All threads were required to be free of burrs. A 10-day sustained-load test was specified for a sample quantity of bolts from each lot.

Brittle intergranular fracture, typical of a hydrogen-induced delayed failure, caused the failure of an AISI 4340 Cr-Mo-Ni landing gear beam. Corrosion resulting from protective coating damage released nascent hydrogen, which diffused into the steel under the influence of sustained tensile stresses. A second factor was a cluster of non-metallic inclusions which had ‘tributary’ cracks starting from them. Also, eyebolts broke when used to lift a light aircraft (about 7000 lb.). The bolt failure was a brittle intergranular fracture, very likely due to a hydrogen-induced delayed failure mechanism. As for the factors involved, cadmium plating, acid pickling, and steelmaking processes introduce hydrogen on part surfaces. As a second contributing factor, both bolts were 10 Rc points higher in hardness than specified (25 Rc), lessening ductility and notch toughness. A third factor was inadequate procedure, which resulted in bending moments being applied to the bolt threads.

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.

A bracket which formed part of the carrier of a chain conveyor system used to transport components through a continuous oven fractured. A brittle crack originated on the inside of the right-angled bend, the surface having oxidized subsequently. The remaining portion of the fracture resulted from fatigue. Shallow oxidized regions adjacent to the inside surface of the bend indicated pre-existing cracks. A sulphur print on the edge of the bracket showed the material was rolled from a rimming steel ingot. The general appearance of the fracture, and the fact failure took place where embrittlement had developed following plastic straining and service at a temperature of 260 deg C (500 deg F) suggested that failure resulted from strain-age embrittlement.

Brief overheating of the 89 mm OD 6.4 mm wall thickness titanium heater tubes (ASTM B337, grade 2) was caused by a flow stoppage in a leach heater. Blue-tinted areas and patches of flaky white, yellow, and brown oxide scale was revealed on visual examination. It was disclosed by subjecting the overheated tube to a flattening test that the tube no longer met ASTM B 337 specifications. Large grain size and numerous needlelike hydride particles were disclosed in the microstructure of the overheated tube. Heating to approximately 815 deg C was revealed by the presence of the flaky oxide and increased grain size. Hydrogen and oxygen absorption was revealed by the presence of hydrides and the shallow surface embrittlement and thus susceptibility to cracking at ambient temperatures was observed. It was concluded that the titanium tubes were embrittled due to overheating the tubes and the severe surface embrittlement resulted from oxygen absorption which made the surface layers susceptible to cracking under start up and shutdown. Replacement tubes made of a heat-resistant alloy (e.g., Hastelloy C-276) were recommended.

Waspaloy (AMS 5586) fabricated inner ring of a spray-manifold assembly failed transversely through the manifold tubing at the edge of the tube and support sleeve brazed joint. The assembly was brazed with AWS BAu-4 filler metal (AMS 4787). Fatigue beach marks propagating from extremities of a granular gold-tinted surface region adjacent to the tube-to-sleeve brazed joint and extending circumferentially were revealed by microscopic examination. Embrittlement of the tube caused by molten braze metal penetration along grain boundaries was evidenced by micrographs of a granular portion of the fracture. It was revealed by the initial fracture profile that fatigue cracks begun as an intergranular separation and subsequently became transgranular. It was concluded that failure of the tube was caused by excessive alloying between the braze metal and the Waspaloy. Reduced temperatures during torch debrazing or rebrazing were recommended to minimize molten braze metal penetration.

Fracture of a cadmium-plated accumulator ring forged from 4140 steel was discovered during inspection and disassembly of a hydraulic-accumulator system stored at a depot. The ring had broken into five small and two large segments. The small segments of the broken ring displayed very flat fracture surfaces with no apparent yielding, but the two large segments did show evidence of bending (yielding) near the fractures. In addition, some segments contained fine radial cracks. Analysis (visual inspection, optical microscopy on polished-and-etched specimens, hardness testing, and chemical analysis) supported the conclusion that the failure was caused due to brittle fatigue, as evidenced by the intergranular nature of the fracture path. Also, hydrogen penetration occurred during the plating operation and was not relieved subsequently as required.

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.

Hydrogen embrittlement is the brittleness affecting copper and copper alloys containing oxygen which develops during heat treatment at temperatures of about 400 deg C (752 deg F) and above in an atmosphere containing hydrogen. The phenomenon of hydrogen embrittlement of copper and its alloys is illustrated by examples from practice and reference is made to data from recent publications on the subject. Embrittlement due to this cause can only be identified by microscopic examination because other modes of failure in copper; e.g., from heat cracking, mechanical overload, the formation of low melting point eutectics or corrosion; show a similar appearance when investigated on a macroscopic scale.

Cadmium-plated high-strength steel bolts were used to facilitate quick disassembly of a vehicle. One bolt was found fractured across the root of a thread after being torqued in place for one week. The bolts were made of 8735 steel heat treated to a tensile strength of 1241 to 1379 MPa (180 to 200 ksi) with a hardness of 39 to 43 HRC, followed by cadmium plating. The bolt that failed and several that did not were examined. It was found that failure of the bolts was the result of time-dependent hydrogen embrittlement. Had the remaining bolts been torqued to the normal stress levels, all would have failed within two weeks. The bolts were baked, as specified by ASTM B 242, at 205 deg C (400 deg F) for 30 min. No further failures occurred. Baking for 30 min is the minimum baking time; however, baking times up to 24 h are recommended for greater safety.

During an inspection of a structure two weeks after assembly, the heads of several cadmium-plated AISI 8740 steel fasteners were found to be completely separated from their respective shanks. SEM examination of the fracture surfaces revealed a brittle, intergranular fracture mode, indicating hydrogen embrittlement. An investigation was conducted to determine the extent of hydrogen embrittlement in the various lots of cadmium-plated 8740 steel fasteners. It was found that hydrogen embrittlement was caused by the use of a bright, impervious cadmium electroplate that hindered diffusion of mobile hydrogen outward from the surface of the pin. After the cadmium layer was removed, the mobile hydrogen contained on the surface of the steel and in the electroplated deposit was released, and the embrittlement problem was alleviated. To prevent reoccurrence, the bright cadmium layer was stripped from the pins, which were then baked and repeated with a dull, porous cadmium layer that allowed outward diffusion of hydrogen. The pins were baked again after deposition of the porous cadmium layer. This eliminated the problem.

A type 431 stainless steel mushroom-head closure fractured in service at a hydrogen pressure of 3000 atm. Fracture occurred at room temperature after miscellaneous chemical service that included exposures to hydrogen at temperatures from ambient to 350 deg C (662 deg F). Investigation (visual inspection and 2400x/6600x TEM analysis) supported the conclusion that failure was caused by hydrogen embrittlement, not SCC as might have been suspected. No recommendations were made.

A plastic bracket exhibited relatively brittle material properties, which ultimately led to catastrophic failure. The part had been injection molded from a medium-viscosity polycarbonate resin and had been in service for a short duration prior to the failure. Investigation (visual inspection and analysis using micro-FTIR in the ATR mode) revealed the spectrum showed changes in the relative intensities of several bands, as compared to the results representing the base material. A spectral subtraction was performed, and the results produced a good match with diphenyl carbonate, which is a common breakdown product produced during the decomposition of polycarbonate. The conclusion was that the most likely cause of the molecular degradation was improper drying and/or exposure to excessive heat during the injection molding process that in turn caused the material degradation.

A vessel made of ASTM A204, grade C, molybdenum alloy steel and used as a hydrogen reformer was found to have cracked in the weld between the shell and the lower head. Six samples from different sections were investigated. The crack was found to be initiated at the edge of the weld in the coarsegrain portion of the HAZ. The microstructure was found to be severely embrittled and severely gassed in an area around the crack. The microstructure of the metal in the head was revealed to be banded and contained spheroidal carbides. The lower head was established by hardness values and microscopic examination to have been overheated for a sufficiently long time to reduce the tensile strength below the minimum required for the steel. It was interpreted that the wide difference in tensile strength between head and weld metal (including HAZ) formed a metallurgical notch that enhanced the diffusion of hydrogen into the metal in the cracked region. The resultant embrittlement and associated fissuring was established to have caused the failure. The hydrogen was diffused out by wrapping the vessel in asbestos and heating followed by cooling as prescribed by ASME code.

Metallography is an important component of failure analysis. In the case of a liquid metal embrittlement (LME) failure it is usually conclusive if a third phase constituent can be formed inside of the cracks after failure. In the case where it is necessary to characterize the third phase material, one can use various x-ray spectrographic techniques in conjunction with a scanning electron microscope (SEM). This study describes those metallographic and SEM analysis techniques for determining the mode of failure for a locomotive traction motor by LME.

Single 6.4 mm (0.25 in.) post-tensioning wires failed in a parking garage in the southern portion of the United States. Several failed wires were removed and the lengths were examined for signs of corrosion using SEM metallography. The scans showed localized shallow pitting, and chloride was detected in some of the pits. The test also revealed an initial crack that was probably caused by hydrogen embrittlement. Since no chloride was detected on the fracture surface, and none was detected in the overlying concrete, the corrosion appears to have begun prior to the wires' placement in the concrete.

An AISI 4340 Ni-Cr-Mo alloy steel draw-in bolt and the collet from a vertical-spindle milling machine broke during routine cutting of blind recesses after relatively long service life. Based on fracture surface features, it was suspected that the draw-in bolt was the first to fracture, followed by failure of the collet, which shattered one of its arms when it struck the work table. Scanning electron microscopy showed the presence of hairline crack indications along grain facets on the fracture surface of the bolt. This, coupled with stepwise cracking in the material, generally raised suspicion of hydrogen embrittlement. It appeared that fracture in service progressed transgranularly to produce delayed failure under dynamic loading. The pickling process used to remove heat scale was suspected to be the source of hydrogen on the surface of the bolt. The manufacturer was requested to change its cleaning practice from pickling to grit blasting.

A large pressure vessel that had been in service as a hydrogen sulfide (H2S) absorber developed cracks and began leaking at a nozzle. The vessel contained a 20% aqueous solution of potassium hydroxide (KOH), potassium carbonate (K2CO3), and arsenic. The vessel wall was manufactured of ASTM A516, grade 70, low-carbon steel plate. A steel angle had been formed into a ring was continuously welded to the inside wall of the vessel. The groove formed by the junction of the lower tray-support weld and the top part of the weld around the nozzle was found to have a crack. Pits and scale near the crack origin were revealed by microscopic examination and cracking was found to be transgranular. Periods of corrosion alternated with sudden instances of cleavage, under a tensile load, along preferred slip planes were interpreted during examination with a microscope. It was concluded that the combination of the residual plus operating stresses and the amount of KOH present would have caused stress corrosion as a result of caustic embrittlement. It was recommended that the tray support should be installed higher on the vessel wall to prevent coincidence of the lower tray-support weld with the nozzle weld.

Molded plastic couplings used in an industrial application exhibited abnormally brittle properties, as compared to previously produced components. The couplings were specified to be molded from a custom-compounded glass-filled nylon 6/12 resin. An inspection of the molding resin used to produce the discrepant parts revealed that the pellets were of two general types, neither of which matched the pellets from a retained resin lot. Investigation included visual inspection, micro-FTIR in the ATR mode, and analysis using DSC. The thermograms supported the conclusion that the brittle couplings contained a significant level of contamination, polypropylene and nylon 6/6. The source of the polypropylene was likely the purging compound used to clean the compounding extruder. The origin of the nylon 6/6 resin was unknown but may represent a previously compounded resin.