The Development of High Strength Corrosion Resistant Precipitation Hardening Cast Steels

Open Access
Abrahams, Rachel Ann
Graduate Program:
Industrial Engineering
Doctor of Philosophy
Document Type:
Date of Defense:
October 06, 2010
Committee Members:
  • Robert Carl Voigt, Dissertation Advisor
  • Robert Carl Voigt, Committee Chair
  • Richard Allen Wysk, Committee Member
  • Edward Demeter, Committee Member
  • Dr Chantal Binet, Committee Member
  • Martensitic Cast Steels
  • Precipitaion Hardening Cast Steels
  • CB7Cu-1
  • Stainless Maraging Steels
Precipitation Hardened Cast Stainless Steels (PHCSS) are a corrosion resistant class of materials which derive their properties from secondary aging after a normalizing heat treatment step. While PHCSS materials are available in austenitic and semi-austenitic forms, the martensitic PHCSS are most widely used due to a combination of high strength, good toughness, and corrosion resistance. If higher strength levels can be achieved in these alloys, these materials can be used as a lower-cost alternative to titanium for high specific strength applications where corrosion resistance is a factor. Although wrought precipitation hardened materials have been in use and specified for more than half a century, the specification and use of PHCSS has only been recent. The effects of composition and processing on performance have received little attention in the cast steel literature. The work presented in these investigations is concerned with the experimental study and modeling of microstructural development in cast martensitic precipitation hardened steels at high strength levels. Particular attention is focused on improving the performance of the high strength CB7Cu alloy by control of detrimental secondary phases, notably delta ferrite and retained austenite, which is detrimental to strength, but potentially beneficial in terms of fracture and impact toughness. The relationship between age processing and mechanical properties is also investigated, and a new age hardening model based on simultaneous precipitation hardening and tempering has been modified for use with these steels. Because the CB7Cu system has limited strength even with improved processing, a higher strength prototype Fe-Ni-Cr-Mo-Ti system has been designed and adapted for use in casting. This prototype is expected to develop high strengths matching or exceed that of cast Ti-6Al-4V alloys. Traditional multicomponent constitution phase diagrams widely used for phase estimation in conventional stainless steels, give poor estimates of secondary phases in PHCSS. No measureable retained austenite was observed in any of the CB7Cu-1 steels studied, in spite of the fact that austenite is predicted by the constitution diagrams. A designed experiment using computationally derived phase equilibrium diagrams and actual experimental tests on CB7Cu of different compositions suggests that the ferrite phase is less stable than the constitution diagrams for austenitic stainless steels suggest. Delta ferrite was also more stable in slower-cooled sand cast material as compared to thin, fast-cooled investment cast material. High temperature solutionizing treatments were effective in dissolving delta ferrite at temperatures above 1900°F (~1040°C). Delta ferrite dissolution was found to proceed at high rates during initial dissolution, and then was found to slow after 1 hour. Diffusion during the later stages is well-predicted by classical diffusion models. Repeated solution treatments were found to modestly increase both ductility and strength, likely due to subgrain refinement through austenite regrowth. Multistaged aging provided superior strength and toughness increases over similarly peak-aged and near peak-aged material aged at a single temperature. Peak-aged material fractography suggested that low energy quasi-cleavage fracture was likely due to age precipitate embrittlement along with some nucleation of MnS particulates at prior austenite grain boundaries. Yield strengths approaching 190 ksi (1310MPa) can be achieved in CB7Cu-1 if appropriate best-practices "+" processing techniques are used. This includes hot isostatic processing to reduce solidification segregation and heal microporosity, high temperature homogenization for effective age hardening and ferrite reduction, double-cycle solutionizing for structure refinement, and multistaged age strengthening for finer precipitate control. The experimental prototype 11-11PH (Fe-Ni-Cr-Ti-Mo) casting alloys was cast and was found to be delta-ferrite free in the as-cast condition. In this material, proper quench processing to eliminate excessive retained austenite was found to be most influential in terms of high strengths. It was also found that cooling below 0°C provided the best combination of strength and toughness, with the specific strength of the material exceeding that of cast Ti-6Al-4V material. Fractography studies suggest that titanium carbonitride and titanium carbon-nitride-sulfide inclusions limit the toughness of cast materials due to long exposures to ideal growth conditions during initial cooling. OIM studies also suggest that the retained austenite in properly processed 11-11PH alloy takes on an interlath structure, which likely contributes to toughness of the alloy, even at high-strength, peak aged conditions. Yield strengths approaching 235 ksi (1620 MPa) were achieved during initial heat treatment trials. It is expected that further improvements in properties can be achieved with continued improvement of processing for this new cast alloy system.