Thermal Stability of Nanocrystalline Alloys by Solute Additions and A Thermodynamic Modeling

Nanocrystalline alloys show superior properties due to their exceptional microstructure. Thermal stability of these materials is a critical aspect. It is well known that grain boundaries in nanocrystalline microstructures cause a significant increase in the total free energy of the system. A driving force provided to reduce this excess free energy can cause grain growth. The presence of a solute addition within a nanocrystalline alloy can lead to the thermal stability. Kinetic and thermodynamic stabilization are the two basic mechanisms with which stability of a nanoscale grain size can be achieved at high temperatures. The basis of this thesis is to study the effect of solute addition on thermal stability of nanocrystalline alloys.;The objective is to determine the effect of Zr addition on the thermal stability of mechanically alloyed nanocrysatillne Fe-Cr and Fe-Ni alloys. In Fe-Cr-Zr alloy system, nanoscale grain size stabilization was maintained up to 900 °C by adding 2 at% Zr. Kinetic pinning by intermetallic particles in the nanoscale range was identified as a primary mechanism of thermal stabilization. In addition to the grain size strengthening, intermetallic particles also contribute to strengthening mechanisms. The analysis of microhardness, XRD data, and measured grain sizes from TEM micrographs suggested that both thermodynamic and kinetic mechanisms are possible mechanisms. It was found that alpha → gamma phase transformation in Fe-Cr-Zr system does not influence the grain size stabilization.;In the Fe-Ni-Zr alloy system, it was shown that the grain growth in Fe-8Ni-1Zr alloy is much less than that of pure Fe and Fe-8Ni alloy at elevated temperatures. The microstructure of the ternary Fe-8Ni-1Zr alloy remains in the nanoscale range up to 700 °C. Using an in-situ TEM study, it was determined that drastic grain growth occurs when the alpha → gamma phase transformation occurs. Accordingly, there can be a synergistic relationship between grain growth and alpha → gamma phase transformation in Fe-Ni-Zr alloys.;In addition to the experimental study of thermal stabilization of nanocrystalline Fe-Cr-Zr or Fe-Ni-Zr alloys, the thesis presented here developed a new predictive model, applicable to strongly segregating solutes, for thermodynamic stabilization of binary alloys. This model can serve as a benchmark for selecting solute and evaluating the possible contribution of stabilization. Following a regular solution model, both the chemical and elastic strain energy contributions are combined to obtain the mixing enthalpy. The total Gibbs free energy of mixing is then minimized with respect to simultaneous variations in the grain boundary volume fraction and the solute concentration in the grain boundary and the grain interior. The Lagrange multiplier method was used to obtained numerical solutions. Application are given for the temperature dependence of the grain size and the grain boundary solute excess for selected binary system where experimental results imply that thermodynamic stabilization could be operative.;This thesis also extends the binary model to a new model for thermodynamic stabilization of ternary nanocrystalline alloys. It is applicable to strongly segregating size-misfit solutes and uses input data available in the literature. In a same manner as the binary model, this model is based on a regular solution approach such that the chemical and elastic strain energy contributions are incorporated into the mixing enthalpy DeltaHmix, and the mixing entropy DeltaSmix is obtained using the ideal solution approximation. The Gibbs mixing free energy Delta Gmix is then minimized with respect to simultaneous variations in grain growth and solute segregation parameters. The Lagrange multiplier method is similarly used to obtain numerical solutions for the minimum Delta Gmix. The temperature dependence of the nanocrystalline grain size and interfacial solute excess can be obtained for selected ternary systems. As an example, model predictions are compared to experimental results for Fe-Cr-Zr and Fe-Ni-Zr alloy systems.;Consistency between the experimental results and the present model predictions provide a more rigorous criterion for investigating thermal stabilization. However, other possible contributions for grain growth stabilization should still be considered.