Part IX – September 1968 - Papers - Contribution to the Study of Hot Corrosion

Experiments on both suljidation and hot corrosion have been carried out using ternary Ni-Cr-X alloys and commercial nickel-base superalloys. It has been shown that lhere are certain micro structural similarities between sulfidation using H,S/H2 mixtures and hot corvosion using Na,S04 in "crucible" experiments or hot corrosion tests using a flame tunnel apparatus. It is proposed that two key processes in the hot cowosion process are: 1) formation of chromium sulfides which deplete the alloy matrix, and 2) oxidation which can be accelerated because of chromium depletion. Other processes play an important role in the hot corrosion process, such as accelerated oxidation attack due to the presence of a N& S04 or N&SO,- NaC2 film which inhibits the formation of a protective external oxide scale. However, this latter phenomenon was not studied in this work. THE term hot corrosion has come to mean a combination of sulfur and oxygen attack on nickel-base or cobalt-base superalloys used as gas turbine blades or partitions. This attack can be initiated by any combustion process in air involving fuel containing sulfur if the sulfur level is sufficiently high. Levels of 5 pet SO2l for example, in the combusting gas have been observed to produce hot corrosion attack on nickel-base alloys. The important immediate corroding medium in aircraft gas turbines, however, has been established to be Na2S04, formed from reaction between NaCl from sea air and sulfur in the fuel.' The Na2S04 concentrates the sulfur sufficiently so that superalloy parts heated in the range 1400" to 1900°F can become sulfided by reducing the Na2S04 film which forms on the parts, and this reaction allows sulfur to gain access to the alloy. The sulfur thus released diffuses into the superalloy and forms primarily chromium sulfides of various compositions, but frequently Cr2S, has been identified. Figs. 1 and 2 show the morphology typical of hot corrosion of a cobalt-base superalloy X-45 (25 Cr, 10 Ni, 7.5 W, 0.25 C) and a nickel-base alloy, Udimet 500 (19 Cr, 19 Co, 4 Mo, 3 Ti, 2.9 Al, 0.07 C). Both alloy samples were subjected to the same hot corrosion conditions: 616 hr at 1600°F in a combusted 2.9 pct S distillate oil containing 125 ppm Na as NaC1. It will be noted at once that the nickel-base alloy is much more severely attacked. The depth of corrosion is much greater and the number and size of the sulfides present are much greater. Both alloys show a duplex oxide scale, which is more noticeable in the X-45 alloy. The external scale is probably a spinel in both cases, with CrQ3 lying next to the alloy. Many investigators1 -"ve been concerned with hot corrosion phenomena, but there has been a lack of unanimity of opinion as to the details of the hot corrosion mechanism. More than one definition of hot corrosion is possible. Some investigators con- sider as a measure of hot corrosion only the weight gain due to an accelerated oxidation. However another point of view is that the total depth of affected alloy may be used as a measure. While it is recognized that surface oxidation attack is greatly accelerated by the presence of salts like Na2S04 or Na2S04-NaC1 mixtures, sulfur penetration into the alloy also undoubtedly produces very important effects. The region of sul-fide penetration which is so prominent in Fig. 2 is one of the outstanding characteristics of hot corrosion. For highly stressed parts, such as first-stage buckets, this sulfur-penetrated region can be more significant in mechanical property loss than the reduction of cross section produced by the formation of the massive external scale. In addition, evidence will be presented that this sulfided region can be less resistant to subsequent oxidation attack. Since it appears that the sulfided region below the surface oxide scale plays an important role in the overall corrosion process,