Review of

The Effects of Hydrogen in Steel

by E. R. Slaughter

Hydrogen retained in steel may result in important defects, particularly in heavy sections o f killed carbon steels and alloyed steels.

adsorbs hydrogen processing, principally S TEEL the reaction theironinand water vapor. Inacid from of the finishing operations, reaction of steel with and the cathodic deposition of hydrogen during plating may introduce high concentrations of hydrogen into steel. The sources of hydrogen in steel are important in the study of hydrogen-induced defects, since certain of these defects are caused by hydrogen from steelmaking operations, while other defects are usually caused by hydrogen from other sources. Hydrogen is responsible for four principal types of defects in steel. These defects are porosity, flaking, hydrogen embrittlement, and delayed brittle fracture, or static fatigue. However, each of these defects is not a problem in every grade of steel. This discussion will attempt to describe these four principal defects in steel, and to identify the sources of hydrogen which are most likely responsible for them.
Porosity Hydrogen is more soluble in liquid steel than in solid steel, and it segregates by rejection from the solidified steel to the remaining liquid during solidi-

E. R. SLAUGHTER is-with the Battelle Memorial Institute, Columbus, Ohio.

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Hydrogen-Relolive Volumes

Fig.1-Ductility, shown by pct area reduction in tensile test bars, decreases with increased hydrogen content until a minimum point is reached. The figure shows the range of values for normalized cast carbon steel. 430-JOURNAL OF METALS, APRIL 1956

fication. In fact, hydrogen segregates in steel to a greater extent than does any other element. Therefore, the last liquid to solidify has the highest hydrogen content. Also, because the solubility of hydrogen in steel decreases upon solidification, a portion of the hydrogen may be liberated as gaseous hydrogen to produce blow-hole type porosity or aggravate center-line shrinkage. In steel ingots, porosity due to hydrogen is particularly troublesome in the high-chromium grades. In steel castings, hydrogen can cause porosity regardless of composition. Flaking A very important type of defect caused by hydrogen is known variously as flaking, shatter cracks, or hairline cracks. Flakes are ruptures in massive steel billets, forgings, or rolled products. Sometimesthe orientation of the flakes is random, but occasionally, the flakes are oriented with respect to the surface of the steel. Flakes are often restricted to certain regions of the steel. It has been shown that the presence of hydrogen is a necessary condition for flaking. This hydrogen is ordinarily introduced during the steelmaking operations. In addition to the presence of hydrogen, thermal or transformation stresses are necessary conditions for flakes. For flaking to occur, some stress must exist in the steel for a period of time ranging from several hours to a day or so, while the steel is below 400 F. Hardenability has a large effect on the susceptibility of a steel to flaking, and steels with the greatest hardenability are the most susceptible. The most obvious method for the prevention of flakes is the elimination or reduction of the hydrogen content of the steel. However, the common commercial practice for the prevention of flakes is a slowcooling cycle. The principal beneficial effect of a slow-cooling cycle in preventing flakes is due to the increase in the temperature of transformation. Complete transformation of steel a t high temperatures prevents (flakes by forming a structure which is not susceptible to flaking. A slow-cooling cycle may also eliminate a significant amount of hydrogen by diffusion from a light section, but a slow-cooling cycle does not eliminate a significant amount of hydrogen from the interior of heavy sections. Slow cooling in some cases may be only a tempo. rary expedTent for preventing flakes. The billet which is flake-free due to slow cooling may still con. ..

tain enough hydrogen to cause flakes after a forging operation, if the forging is not cooled slowly.
Hydrogen Embrittlement

Perhaps the most prevalent defect caused by the hydrogen in steel is the loss of ductility at low strain rates, which is called hydrogen embrittlement. While flaking and delayed brittle failure are limited to steels having considerable hardenability, hydrogen embrittlement may affect all ferritic steels and, to a lesser extent, austenitic steels. Hydrogen is unique among alloying elements, in that it causes a loss of. ductility without, a corresponding increase in hardness or strength.' The ductility, as indicated by the reduction in area or the elongation of the tensile specimen, decreases as the hydrogen content increases until the minimum value of ,ductility is reached, Fig. 1.I This loss of ductility occurs only at moderate strain rates; usually the impact resistance of steel is not affected by the presence of hydrogen. Any damage that occurs due to flaking is considered to be permanent. In contrast to this, hydrogen embrittlement is a temporary defect. Steel which has been embrittled by hydrogen can be restored to normal ductility by aging a t low temperatures to eliminate the hydrogen. Hydrogen is lost so rapidly from light sections by room-temperature aging, that hydrogen introduced during steel making may be largely removed before the steel is fabricated or placed in service. Even at room temperature, hydrogen diffuses in steel more rapidly than does carbon at heat-treating temperatures. Therefore, because of this high diffusion rate, hydrogen embrittlement depends, not only on the hydrogen content at the time of solidification, but also on the opportunity for hydrogen removal provided by the aging time prior to fabrication or service. Thickness and temperature have very important effects upon the rate at which hydrogen is lost during aging. Sims, Moore, and Williams' found that aging a l-in.-square cast steel bar for 6 hr a t 400F restored normal ductility, while a 4-in.-square required more than 100 hr at 400F to restore normal ductility at the center of the section, Fig. 2. At room temperature, 60 days of aging was required to restore full ductility to the 1-in.-square bar, while normal ductility was not restored to the 4-in.-section by room-temperature aging for more than 3% years,' Fig. 3. Because of the very important influence of section size, it is not likely that hydrogen from steelmaking operations would be retained in light sections long

enough to give difficulties during service or fabrication. Only in massive wrought sections or castings, is it likely that hydrogen retained from the steelmaking operations would cause difficulty with hydrogen embrittlement. In light sections, hydrogen embrittlement is more apt to be a temporary condition following pickling or electroplating operations.
Delayed Brittle Fracture

For the past several years, the aircraft industry has been greatly concerned over delayed brittle fracture or static fatigue. With the use of steel parts, heat treated to more than 180,000 psi ultimate tensile strength, brittle failures of these parts were encountered. These brittle fractures may occur when the parts are subjected to static loads far below the yield point for considerable periods of time. Service failures have been reported after delay periods of several months. In many instances, test specimens machined from the region of these failures have shown normal properties when tested in the conventional tensile test. There is general agreement that hydrogen is necessary for these failures to occur, and it is also generally agreed that hydrogen from plating or pickling operations is the most likely cause for these delayed brittle failures. The author3 has obtained typical delayed brittle fractures of unnotched, high-strength steel specimens a t stresses which were less than 10 pct of the ultimate tensile strength when the specimens were cathodically charged with hydrogen while under load. In other experiments, specimens charged with hydrogen sustained static loads for 15 days before failure. Hydrogen may cause several types of defects in steel, and it is never beneficial. It is unique among alloying elements in that it reduces ductility without any increase in strength. However, in many grades of steel, the usual amounts of hydrogen retained from steelmaking operations do not cause any commercially important defects. Hydrogen retained in steel from steelmaking operations may cause commercially important defects mainly in killed steels which are to be fabricated in heavy sections. The tendency for the formation of hydrogen-caused defects has proven to be greater with alloy steels than with carbon steels.
References
1C. E. Sims, C. A. Moore, and D. W. Williams: "The Effect of Hydrogen on the Ductility of Cast Steels." Trans. AIME, vol. 176, 1948. p. 283. 2C. E. Sims: "Hydrogen Elimination by Aging." Trans. AIME, ~01. 188, 1950, p. 1321. SE. R. Slaughter, A. R. Elsea, and G. K. Manning: Unpublished work at Battelle Memorial Institute.

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Temperature affects the rate of hydrogen diffusion and hence the time required to restore ductility of steel embrittled by requires 100 hr on 4-in. bars a t 400F. Fig. 3 (above)-Aging requires some 3% years on hydrogen. Fig. 2 (left)-Aging 4-in. bars a t room temperature. APRIL 1956, JOURNAL O F M E T A L S - 4 3 1