TWELVE STAINLESS STEELS XII-1. INTRODUCTION There is a wide variety of stainless steels, but they ail have a common characteristic— they contain more than 11.5%Cr. Obviously, the existence of this important class of alloys depends upon the availability of Cr at reasonable cost. Stainless steels are used because of their corrosion resistance, oxidation resistance, and pleasing appearance, all of which are derived from their Cr content. They are customarily divided into five types: 1. Ferritic, containing 12-30%Cr and low C 2. Martensitic, with 12-17%Cr and 0.1 to 1.0%C 3. Austenitic, containing 17-25%Cr and 8-20%Ni 4. Duplex alloys, with 23-30%Cr, 2.5-7%Ni, and additions of Ti or Mo 5. Precipitation hardening alloys, which can have an austenitic or martensitic base, with additions of Cu, Ti, Al, Mo, Nb, or N Streicher! has provided a summary of the history of these alloys, their current applica- tions, and future prospects. The physical metallurgy of these commercial steels is best approached through the three binary phase diagrams, Fe-Cr, Fe-Ni, and Ni-Cr, and the ternary diagram Cr~Fe-Ni. ‘M.A. Streicher, Stainless Steel 77, Climax Molybdenum Co., Greenwich, Connecticut, 1977, p.l. 326STAINLESS STEELS 327 We % Cr 0 10 20 30 40 50 60 70 80 90 100 1900 1800 1700 1600 be. 1500 1400 1300 | 1200 L. 1100 TEMPERATURE (°C) 1000 |- Figure XIL1, The iron— chromium system. (N. Yukawa, N. Hida, T, Imuza, M. Kawamura, and Y. Mizuno, 0 10 20 30 40 50 60 70 80 90 100 Mer. Trans., 3:887 (1972), by Fe At % Cr Cr permission.) XII-2. PHASE DIAGRAMS The Fe-Cr system (Fig. XII-1) is the basis for all stainless steels, so we will begin there. Chromium stabilizes ferrite, leading to a closed gamma loop, with a maximum solubility of about 12%Cr in austenite at about 1000°C. Below about 830 and above about 1390°C austenite does not exist. Yukawa et al." report the presence of a Cr-rich, high-temperature phase which they call 6, which should not be confused with “delta ferrite.” This has a bec structure, WO type. Addition of C or N, which are strong austenite stabilizers, expands the y loop, thereby increasing the solubility of Cr in austenite. The « + 7 region is especially expanded, 0.2%(C + N) extending it from 13 to 27%Cr. ''N. Yukawa, N. Hida, T. Imura, M. Kawamura, and Y, Mizuno, Met, Trans, 3:887 (1972).328 THE PHYSICAL METALLURGY OF STEELS The lower portion of the Fe-Cr system is shown in Fig. XII-2. The o phase, FeCr, is tetragonal, with 30 atoms per unit cell. This phase forms very slowly in (he tempera- ture range between 800 and 600°C. Its composition range in the binary ally is small, about 46 to 53 at % Cr. At temperatures below about 520°C it decomposes to a+ a’ by a eutectoidal transformation, but this reaction is also very slow. Sigma phase can be prevented from forming by rapid cooling, and when this is done the «’ phase forms at temperatures below about 520°C by spinodal decomposition. The a’ contains about 90%Cr (Fig. XIL-2). Its precipitation leads to the so-called 475°C embrittlement. The « and a’ phases, Fecich and Cr-rich ferrite, differ in lattice parameter by only about 0.2%. The Fe-Ni system (Fig. X{I-3) at temperatures above about 450°C is now gener- ally accepted. The solubility of Ni in a Fe reaches a maximum between 400 and 500°C (Fig. XII-4). Nickel stabilizes y so that the field extends at 30%Ni from about 500 to about 1450°C. The transformation of y on cooling is very sluggish, so a high degree of undercooling can be obtained, which provides the driving force for the highly useful martensitic transformation in Fe-Ni alloys. The Ms temperature drops very sharply with increasing Ni content, from about 200°C at 20%, to 0°C at 30%, to about —220°C at 34%. 1500 1400 3 1300 x z w a © w 2 1200 © é E © = 1100 a e a Z 1000 0 01 02 03 04 05 06 07 08 09 ATOMIC FRACTION OF Cr Figure XII-2. Lower temperature portion of the iron-chromium system, (R.O. Williams, Trans. AIME, 212:497 (1958), by permission.)