This article provides an overview of the classification of hydrogen damage. Some specific types of the damage are hydrogen embrittlement, hydrogen-induced blistering, cracking from precipitation of internal hydrogen, hydrogen attack, and cracking from hydride formation. The article focuses on the types of hydrogen embrittlement that occur in all the major commercial metal and alloy systems, including stainless steels, nickel-base alloys, aluminum and aluminum alloys, titanium and titanium alloys, copper and copper alloys, and transition and refractory metals. The specific types of hydrogen embrittlement discussed include internal reversible hydrogen embrittlement, hydrogen environment embrittlement, and hydrogen reaction embrittlement. The article describes preservice and early-service fractures of commodity-grade steel components suspected of hydrogen embrittlement. Some prevention strategies for design and manufacturing problem-induced hydrogen embrittlement are also reviewed.

Hydrogen damage is a term used to designate a number of processes in metals by which the load-carrying capacity of the metal is reduced due to the presence of hydrogen. This article introduces the general forms of hydrogen damage and provides an overview of the different types of hydrogen damage in all the major commercial alloy systems. It covers the broader topic of hydrogen damage, which can be quite complex and technical in nature. The article focuses on failure analysis where hydrogen embrittlement of a steel component is suspected. It provides practical advice for the failure analysis practitioner or for someone who is contemplating procurement of a cost-effective failure analysis of commodity-grade components suspected of hydrogen embrittlement. Some prevention strategies for design and manufacturing problem-induced hydrogen embrittlement are also provided.

A 75 mm OD x 7.4 mm wall thickness carbon steel boiler tube ruptured. A substantial degree of corrosion on the water-side surface leaving a rough area in the immediate vicinity of the rupture was revealed by visual examination. Decarburization and extensive discontinuous intergranular cracking was revealed by microscopic examination of a cross section through the tube wall at the fracture. It was concluded that the rupture occurred because of hydrogen damage involving the formation of methane by the reaction of dissolved hydrogen with carbon in the steel. Hydrogen was produced by the chemical reaction that corroded the internal tube surface. Steel embrittled by hydrogen can be restored only if grain boundary cracking or decarburization had not occurred but since the material embrittled in this manner, its replacement was recommended.

Fasteners, made in high-production progressive dies from 0.7 mm thick cold-rolled 1060 steel, were used to secure plastic fabric or webbing to the aluminum framework of outdoor furniture. It was found that approximately 30% of the fasteners cracked and fractured as they were compressed to clamp onto the framework prior to springback. The heat treatment cycle of the fasteners consisted of austenitizing, quenching, tempering to obtain a tempered martensite microstructure, acid cleaning, zinc electroplating, coating with a clear dichromate and thereafter baking to remove the nascent hydrogen. It was revealed that fasteners treated in this manner were brittle due to hydrogen embrittlement as the baking process was found to not be able to remove all the nascent hydrogen which had induced during acid cleaning and electroplating. The heat treatment cycle was modified to produce a bainitic structure and the method of plating the fastener with zinc was changed from electroplating to a mechanical deposition process to thus avoid hydrogen embrittlement.

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.

Diode leads that were to be made from OFHC copper were instead made from copper with high oxygen content. The leads had a nickel underplating, a gold final plating, and were brazed to the diode package in a hydrogen atmosphere. After brazing, the leads became embrittled. SEM examination of the fractured leads revealed voids and some oxidized areas surrounded by ductile fracture areas. High pressure steam pockets observed as voids in the microstructure caused hydrogen embrittlement of the leads. The obvious corrective action was to ensure that the lead material was OFHC copper.

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.

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.

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.

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.

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.

Ground maintenance personnel discovered hydraulic fluid leaking from two small cracks in a main landing gear cylinder made from AISI 4340 Cr-Mo-Ni alloy steel. Failure of the part had initiated on the ID of the cylinder. Numerous cracks were found under the chromium plate. A 6500x electron fractograph showed cracking was predominantly intergranular with hairline indications. Leaking had occurred only 43 h after overhaul of the part. Total service time on the part was 9488 h. It was concluded that cracking on the ID was caused by hydrogen embrittlement which occurred during or after overhaul. The specific source of hydrogen which produced failure was not ascertainable.

A few Cr-Mo steel piston rods from different production batches were found identically cracked in the eye end near the radius after chrome plating and baking treatment. Two of them cracked in the plating stage itself instantly broke on slight tapping. Cracking initiated from the outer base surface of the forked eye end. The 40 mm diam forged piston rods were subjected to plating after heavy machining on the part without any stress-relieving treatment. Also, time lapses between plating and baking were varied from 3 to 11 h. The brittle cracking along forked eye-end radius portion was attributed to hydrogen embrittlement that occurred during chrome plating.

The draw-in bolt and collet from a vertical-spindle milling machine broke during routine cutting of blind recesses after a relatively long service life. The collet ejected at a high rotational speed due to loss of its vertical support and shattered one of its arms upon impact with the work table. SEM fractography and metallographic examinations conducted on the bolt revealed hairline indications along grain facets on the fracture surface and stepwise cracking in the material, both indicating failure by hydrogen embrittlement. Similar draw-in bolts were discarded and replaced with bolts manufactured using controlled processes.

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.

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.

Several stainless steel bolts used on a Titan Space Launch Vehicle broke at the shank and failure was attributed to stress-corrosion cracking. But results could not be duplicated in the laboratory with salt-solution immersion tests until the real culprit was established: the secondary effect of galvanic coupling, hydrogen embrittlement.

The power-type counterbalance spring, formed from hardened-and-tempered carbon steel strip and subsequently subjected to phosphating treatment, fractured at the two locations during fatigue testing. A rust colored dark band at the inside edge of the fracture surface was disclosed during investigation. Etch pits were revealed by the cleaned surface which were never observed on properly phosphated coating. It was interpreted that the spring had been subjected to an abnormal acid attack in pickling or phosphating which had resulted in considerable absorption of hydrogen by the metal and hence embrittlement. The part was concluded to have cracked during phosphating or excessive acid pickling before phosphating.

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.

Several cadmium-plated carbon steel socket head cap screws that were part of a slide valve assembly on a regenerator line in a petrochemical plant failed during initial loading. Metallographic and XDS chemical analysis in conjunction with SEM examination of one failed and one unfailed cap screw indicated that the screws had failed by hydrogen embrittlement. The plating process was the likely source of the hydrogen. It was recommended that the remainder of the cap screws from the same lot as the failed screws be baked at approximately 190 deg C (375 deg F) for 24 h.