HYDROGEN EFFECTS IN REFRACTORY METALS W. T. Chandler and R. J. Walter Abstract, The effects of hydrogen on the refractory metals molybdenum, tungsten, columbium, and tantalum are reviewed. Solubility, permeability, and dif~ fusion of hydrogen in the refractory metals, refractory metal-hydrogen phase diagrams, snd the effects of absorbed hydrogen and hydrogen environ ments on mechanical properties are covered. Molybdenum and tungsten have very low solubilities for hydrogen and are essentially unaffected by hy- drogen. Columbium and tantalua can absorb large quantities of hydrogen ‘and form hydrides, and are greatly eubrittled by relatively small amounts of hydrogen at low teaperatures. Hovever, the solubility of hydrogen in columbius and tantalum decreases to low values above approximately 1600 F (8700), the hydrides are stable only at relatively lov temperatures, and relatively large quantities of hydrogen are required to cause embrittlement at elevated temperatures. Eabrittlenent of columbium and tantalum by by- drogen at room teaperature and below is usually associated with hydride formation. No investigations have been made of the mechanism of eabrit~ tlenent by hydrogen at higher temperatures, Columbium and tantalum specimens vill fragment vhen cooled from elevated temperatures in hydrogen or, under certain conditions, when exposed to hydrogen at room temperature, W. T, Chandler is a Principal Scientist and R. J. Walter is a Member of the Technical Staff at Rocketdyne, a Division of North American Rockwell Corporation, Canoga Park, California. This paper vas presented at the Symposium on Metallurgy and Technology of Refractory Metal Alloys, Washington, D.C,, 25-26 April 1968, Sponsored by the Metallurgical Society of AIME and the National Aeronautics and Space Administration, 197198 W. T. CHANDLER AND R. J. WALTER INTRODUCTION The group of elements called refractory metals, here defined as metals having a melting point above 3500 F (1927 C), include metals which can ab- sorb large quantities of hydrogen and vhose properties are greatly affected by hydrogen and other metale vhich can absorb only very little hydrogen and whose properties are, under most circumstances, not significantly affected by hydrogen. Metals in general have often been classified into endothermic and exothermic occluders of hydrogen (1, 2) according to whether the heat of absorption is negative or positive. Although this classification has no particular fundamental significance, it serves to classify metals into two groups having different general characteristics with regard to hydrogen absorption. With endothermic occluders, the amount of hydrogen which can be absorbed is small and increases with increasing temperature, and hydrides or other second phases are not formed. Molybdenum and tungsten are refrac- tory metals vhich have low solubilities for hydrogen and are probably endo- thermic occluders. Nonrefractory metals which have lov solubilities for hydrogen are: iron, nickel, chromium, copper, platinum, and gold, Even ‘though the amount of bydrogen which can be absorbed by endothermic occluders is small, some are susceptible to hydrogen eubrittlement; a prime example is iron, In contrast, the exothermic occluding metals can absorb large quantities of hydrogen, the amount of hydrogen which can be absorbed increases vith decreasing temperature, and hydrides are formed. Columbium, hafnium, and tantalum are refractory metal exothermic occluders. Other examples of exothermic occluders are: palladium, thorium, titanium, uranium, vanadium, and zirconium, It is evident that the exothermic occluders include the metals whose properties are the most seriously affected by hydrogen. Un- doubtly because of this, hydrogen effects have been investigated to a much greater extent for exothermic occluders, with the important exception of For the refractory metals not listed above, i.e., iridium, osmium, rhenium, rhodium, ruthenium, and technetium, there is very little inform— tion on'the absorption of hydrogen or its effects on properties, and data from different investigators are conflicting. Hydrogen which is absorbed into a metal may affect the mechanical properties as a result of: (1) the presence of the hydrogen in solid solu- tion, (2) the formation of a hydride (or other second phase), and (3) 0 chemical reaction with alloying elements in the metal.” The last of these is, ina sense, a secondary effect of hydrogen but can be serious, An exemple is the decarburization of steels vith the formation of mevhone which collects in voide at high pressure ond can result in cracking. Also, the renoval of carbon will, in itaelf, affect properties, possibly seriously. Such chemical reactions will occur most readily at elevated tenperatures and high hydrogen pressures, but the resultant renoval of alloying elenents (including other interstitials) or the formtion of hydrides with then could then affect properties at any tenperature.