Role of Mo and W during Sensitization of Superaustenitic Stainless SteelCrystallography and Composition of Precipitates

STEFAN HEINO This study concerns the crystallographic identification and compositions of precipitates formed in superaustenitic stainless steel. Three experimental alloys, all containing 24 wt pct Cr, 22 wt pct Ni, and 0.5 wt pct N but with varying amounts of Mo and W, were investigated after sensitization heat treatment (aging) at 900 C. The contents of Mo and W in the three alloys were 7 wt pct Mo, (6 wt pct Mo 2 wt pct W) and (5 wt pct Mo 5 wt pct W), respectively. While and were the main secondary phases found in the W-free alloy, replacement of Mo by W was found to promote the formation of Laves-related phases with high Mo W content. The complex crystallographic nature of Laves-related precipitates was exemplified through the formation of intergrowing C14 Laves, , and C phases, all with closely related crystal structures. There was no difference in chemical composition between the three phases. Prolonged aging resulted in intragranular precipitation of different intermetallic phases, as well as formation of nitrogen bearing phases, and Cr2N, adjacent to previously formed intermetallic precipitates. The content of Mo W was found to decrease with increasing aging time for all secondary phases.

I. INTRODUCTION

THE increased demands to improve the pitting and crevice corrosion properties of materials used in seawater handling or chemical industry have resulted in the development of superaustenitic stainless steels. Characteristic of this group of iron-based materials is high critical temperatures for pitting (CPT) and crevice corrosion (CCT) in chloride containing environments. Typically, the CPT values in 1 M NaCl can be raised from around 20 C in standard AISI 304 grades to around 100 C in the most highly alloyed superaustenitic stainless steel grades.[1] A rough classification of austenitic stainless steels with respect to the resistance to pitting corrosion is the pitting resistance equivalent (PRE), which is based on the chemical composition. Main alloying elements in superaustenitic alloys are Fe, Cr, Ni, Mo, Mn, and N, all kept in solid solution in the austenite. In some alloys, an alternative alloying strategy has been to partially replace Mo by W and still keeping a high N level.[2] In addition to the improved corrosion properties, improved mechanical properties are also achieved, mainly as a result of the high amount of interstitial N dissolved in the austenite. Two of the most corrosion-resistant superaustenitic alloys available today are Avesta Sheffield 654 SMO* (7.3 wt pct
*654 SMO is a registered trademark of Avesta Sheffield AB.

steels are shown in Table I. In a recent study,[5] 654 SMO was found to have a slightly lower structural stability but, nevertheless, showed similar or slightly higher CCT both in solution treated and sensitized condition. After aging at 700 C, the same CCT was obtained, while other aging temperatures resulted in slightly higher CCT values for 654 SMO. Both the slightly lower structural stability and deviations in CCT for Avesta Sheffield 654 SMO compared to Uranus B66 were thought to have their origins in a somewhat higher as-received alloying level for the former alloy. It should be noted that the difference in corrosion properties between these two alloys still is very small.

The Influence of Cr, Mo, and N on Precipitation In order to improve the corrosion properties, Mo is added to austenitic stainless steels. One of the most common types of Mo containing austenitic alloys is AISI 316. Alloys of this type are available with different C content depending on the application and may be alloyed with nitrogen to various extents, normally below 0.3 wt pct. At high-temperature exposure in the range of 700 C to 1100 C, the AISI 316-type alloys may be prone to secondary phase formation. Typical secondary phases that form in these alloys are , , and Laves and different types of carbides, e.g., Cr23C6 and M6C. The carbides are usually the first phases to form, but they are gradually replaced by intermetallic phases after longer aging time.[6] For alloys similar to AISI 316, Wiegand and Doruk[7] found the precipitation of phase to be favored by low carbon content, reflecting low carbon solubility in the phase. Indications of a higher solubility of interstitial elements were found for and Laves phases, which could explain the minor effect of C on the precipitated amounts of these two phases. Further addition of Mo, above the levels for the AISI 316 alloys, increases the sensitivity to precipitation of secondary
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Mo, 0.5 wt pct N) and Creusot-Loire Industries Uranus**

**Uranus is a trademark of Creusot-Loire Industrie.

B66 (6 wt pct Mo 2 wt pct W, 0.4 wt pct N), where the latter has Mo partially replaced by W. The chemical compositions and the corresponding PRE numbers of these

Dr. STEFAN HEINO is with the Department of Engineering Metals, Chalmers University of Technology, Chalmers University of Technology, SE-412 96 Goteborg, Sweden. Manuscript submitted February 14, 2000.
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