Mechanisms of Sensitization and Stablization of Incoloy Nickel-lron-Chromium Alloy 825* E. L. RAYMOND* Abstract {) ickeliron-chromium Alloy 825 can become sensitive to intergranular attack by to temperatures in the 1200-1400 F (649-760 C) range. Sensitivity to intergranular attack (as measured by the Huey test) can be correlated to the presence of = chromium-depleted area adjacent to the grain boundary. This area is caused by the cellular precipitation of chromium-rich Mz sCg during sensitizing treatments. The chromium-depleted ‘but because the carbides grow by boundary migration the in boundary. Incoloy Alloy 825 can be stablized ageinet intergranular attack by eliminating the chromium-deploted area. The degree of stablization is related to the amount of car solution after the stablizing treatment. The titanium content of the alloy helps to effect stablization, Because it has a greater affinity for ‘carbon than does chromium, the titanium reacts to form stable carbides and thus reduces ‘chromium depletion, Maximum stablization of Incoloy Alloy 825 cannot be obtained if titanium carbide is used as the sole stablizing mechanism. The principal mechanism of stablization for this alloy is that of precipitating the M23C, at a temperature where the diffusion of chromium is sufficiently rapid to prevent chromium depletion, This occurs at ‘temperatures in the 1700-1800 F (927-982 C) range. AnrercraxuLar corrosion Cocalized attack along grain boundaries) in certain media commonly occurs in nickeliron-chromium alloys when they are improperly heat-treated to produce sensitization. When such an alloy is exposed to sensitizing temperatures, in the range of 800-1500 F (427-816 C), chromium-rich carbides precipitate at the grain boundaries. This precipitation depletes the area adjacent to the grain boundaries of chromium and attack will occur in these areas. ‘There are three methods of combating intergranular corrosion when susceptible materials must be heated in the sensitizing range. One is to maintain the carbon level as low as possible to restrict the amount of precipitation that can occur. The second is to add some element such as titanium that will combine with carbon more readily than will chromium, The third is to allow chromium carbides to form, but control their mode of precipitation in such a way that chromium depletion is eliminated, In the 42 nickel, 30 iron, 21.5 chromium alloy (incoloy) alloy 825), all three methods are used together to result in an alloy that is used to handle a wide variety of corrosives, some of unusual severity. Recent studies in the Huntington Alloy Products Division laboratories on Alloy 825 have added significantly to knowledge of the mechanism causing sensitization and the corresponding mechanism by which the alloy is stabilized *A paper presented at a meeting of the South Central Region, [ational Association of Corrosion Engineers, Denver, Colo., October 16-19, 1967. ‘Huntington Alloy Products Division, The International Nickel Co., Ine., Huntington, W. Va 180 against attack. The results of these studies indicate that the mode of precipitation of the chromium carbide has a greater effect on stabilization and sensitization than previously realized Materials and Methods The chemical compositions of the Incoloy Alloy 825 and Inconel) Alloy X-750 cold-rolled sheet used in the study are shown in Table 1 ‘The mechanisms of sensitization and stabilization of the alloys were studied by transmission electron microscopy and analysis of extracted carbide residues. Samples for the electron-microscopy portion of the study were divided into two groups. Those for the extraction-replica portion of the study were heat-treated, mounted, mechanically polished, etched in a solution of 5 percent HCI in methanol and replicated by a standard two-stage, plastic-carbon technique. ‘The other group, for thin-foil study, was heat-treated, jet-machined to 0.020-in thick, 1/8:in-diameter discs were cut and foils were prepared by a standard two-stage technique. The samples for the X-ray portion of the study were first heat-treated. The sample surface was cleaned by sanding and electrolytically dissolving the sample for 4 hours in a solution of 10 percent HCl in methanol. The specimens were removed and weighed, then reimmersed in fresh electrolyte, extracted after 24 hours, removed and weighed again. The residue in the electrolyte and at the bottom of the cell was concentrated by centrifuging, dried, and weighed. From these results, the percent sample in the carbide residue was tradenames of International Nickel Co., Ine. CORROSION-NACETABLE 1 — Chemical Composition of Specimens Studied (Percent) Alloy c Ma Fe si cu Ni cr Al Ti Mob Incoloy alloy 825 003065 2989 0.27 142.812.8099 2.61 = Inconel alloy 7500.05 0576.56 0.25005 72.86 18.66 0.70 2.35 - 092 calculated, The carbide residues were then analyzed by X-ray diffraction, X-ray emission spectrography and wet chemical analysis to determine the amount and form of carbides present. Because all of the chromium carbides were present as Mz3Cs, the chromium, titanium and columbium abundances in the residues were used to establish the TTT (time-temperature-transformation) diagrams shown in Figures 2, 15 and 24, the carbon-solubility curve of Figure 18, and the partial Ti-C-matrix ternary shown in Figure 19. ‘The samples for the Huey test portion of the study were prepared according to the ASTM Recommended Practice A 262. These results enabled the TTS (time-temperature sensitization) diagrams of Figures 1, 22 and 23 to be established. Discussion ‘The Huey test measures the sensitivity of a material to intergranular attack through its resistance to the attack of @ 65 percent solution of boiling nitric acid. Because various materials sensitize at different temperatures and times of exposure in the 800-1500 F (427-816 C) range, the results of, a Huey testing program are usually plotted on a TTS diagram. A TTS diagram for Incoloy Alloy 825 is shown in Figure 1. This TTS diagram has iso-sensitization contours similar in shape to iso-transformation contours seen in TTT diagrams. The corresponding TIT diagram for Mz3Cg precipitation in Incoloy Alloy 825 is shown in Figure 2. The contours present in this diagram show the similarity to the TTS contours mentioned above. ‘Mechanisms of Sensitization Most investigators that have studied the 18-8 stainless steels have concluded that grain-boundary precipitation of chromium-tich Mz 3Cg in the 800-1500 F range is responsible for sensitization. Some investigators have concluded that the precipitation ‘of Mz3Ce in the grain boundaries causes that area immediately adjacent to the carbide to be depleted in chromium, Preferential attack occurs in the chromium-depleted zone and the material is said to be sensitive to intergranular attack. Hatwell! concluded that the Ma aCg precipitated in a dendritic form in the plane of the grain boundary as shown in Figure 3, and the area in the grain boundary between the Mz Cg dendrites was depleted in chromium. Bain? postulated that the Mz3Cg grew in the plane of the grain boundary by drawing chromium and carbon from the grain interior by volume diffusion, He assumed that the chromium-concentration gradient was perpendicular to the boundary as shown in Figure 4 and that it was due to the large difference in the volume-diffusion rate of chromium and carbon, Stickler and Vinckier? believe that the corrosion is of an electrochemical nature caused by the carbide being very noble relative to the matrix. They believe that the carbide morphology is the most important variable. The formation of thin continuous sheets of carbide in the grain boundary as shown in Figure 5 causes maximum sensitization since this ott czmpy ¥ vo i i i = 1200] seo or ast ts sity Time, br Figure 1 ~ Time-temperature-sensitization diagram for Alloy 825 annealed at 2200 F/1 hr prior to sensitizing ‘oatment. Vol. 24, No. 6, June, 1968 Figure 2 — Time-temperature-transtormation diagram for Mz3Cg in Alloy 825 with amount of Mz3Ce indicated by chromium content of residue, ‘Carbon residue analysis for as-anneated (2200 F/1 he) material: 3 Cr, 87 Ti. 181morphology would provide the most continuous path for corrosion to follow. The formation of more widely separated geometrical particles in the grain boundaries as shown in Figure 6 renders the alloy less sensitive because it breaks the continuity of the corrosion path. The carbide morphology in the above studies, and most others on 18-8 stainless steels, was established by electron- Chromium: Depleted Zones hd Ure Figure 3 — Schematic of Mz5C precipitated in a dendritic form. Grain boundary is in plane of page. ze % Chromium —> 0 Distance From Grain Boundary Figure 4 — Diagram of Chromium-concentration gradient perpendicular to the grain boundary. BB as Bea Mas Figure 5 — Schematic of thin, continuous sheets of pre- cipitated carbide in grain boundary. 182 microscope examination of extraction replicas. Although this type of examination accurately determines the morphology of carbide particle, rearrangement during etching and replica- tion makes it almost impossible to determine if the carbide precipitated by growth in the plane of the boundary or perpendicular to the plane of the boundary. The carbide morphology in the above studies and most others on 18-8 stainless steels, was established by electron-microscope examination of extraction replicas. Although this type of examination accurately determines the morphology of the carbide particle, rearrangement during etching and replication make it almost impossible to determine if the carbide precipitated by growth in the plane of the boundary or perpendicular to the plane of the boundary. Recent examination by Lewis and Hattersley* of a nickeliron-chromium-base alloy by thin-foil_ techniques revealed that the Mz3Cg did not grow in the plane of the boundary, but perpendicular to it by a discontinuous mode of precipitation as shown in Figure 7. It was felt that if this is Figure 6 — Schematic of widely separated carbide particles itated in grain boundary. Figure 7 — Specimen showing Mag formed perpendicular to plane of grain boundary, Thin fol CORROSION-NACE