Ernst Kozeschnik

Influence of silicon on cementite precipitation in steels

Abstract The mechanism by which relatively small concentrations of silicon influence the precipitation of cementite from carbon supersaturated austenite and ferrite are investigated. It is found that one condition for the retardation of cementite is that the latter must grow under para-equilibrium conditions, i.e. the silicon must be trapped in the cementite. However, this is not a sufficient condition in that it can only be effective in retarding the transformation rate if the overall driving force for the reaction is not large. It is demonstrated that the experience that silicon retards the tempering of martensite requires the presence of lattice defects which can reduce the amount of carbon available for precipitation and the associated driving force.

Experimental studies and thermodynamic simulation of phase transformations in high Nb containing γ-TiAl based alloys

Abstract Solid-state phase transformations and phase transition temperatures in Ti-45 at.% Al and Ti-45 at.% Al-(5, 7.5, 10) at.% Nb alloys were analyzed experimentally and compared to thermodynamic calculations. Results from scanning electron microscopy, high-energy and conventional X-ray diffraction as well as differential scanning calorimetry were used for the characterization of the prevailing phases and phase transformations. For the prediction of phase stabilities and phase transition temperatures, thermodynamic calculations using the CALPHAD method were conducted. In order to achieve better agreement between calculated and experimental results, a commercially available database was modified using our own results from thermo-physical measurements and annealing treatments.

Mechanical stabilisation of eutectoid steel

Abstract Martensitic transformation involves the translation of a glissile interface, whose motion can be retarded by defects introduced into the parent austenite. Quantitative measurements of this process of mechanical stabilisation in a eutectoid steel have been compared successfully against a recent theory for the phenomenon.

Kinetics of AlN precipitation in microalloyed steel

In this work, the thermodynamic information on AlN formation in steel and experimental data on AlN precipitation kinetics are reviewed. A revised expression for the Gibbs energy of AlN is presented with special emphasis on microalloyed steel. Using the software package MatCalc, computer simulations of AlN precipitation are performed and compared with independent experimental results from the literature. A new model for grain boundary precipitation is employed, which takes into account fast short-circuit diffusion along grain boundaries as well as slower bulk diffusion inside the grain, together with the classical treatment for randomly distributed precipitates with spherical diffusion fields. It is demonstrated that the precipitation of AlN can be modelled in a consistent way if precipitation at grain boundaries and dislocations is taken into account, dependent on chemical composition, grain size and annealing temperature. It is also demonstrated that, for consistent simulations, the influence of volumetric misfit stress must be taken into account for homogeneous precipitation of AlN in the bulk and heterogeneous precipitation at dislocations.

Mean-field model for the growth and coarsening of stoichiometric precipitates at grain boundaries

In this paper, a model for growth and coarsening of precipitates at grain boundaries is developed. The concept takes into account that the evolution of grain boundary precipitates involves fast short-circuit diffusion along grain boundaries as well as slow bulk diffusion of atoms from the grain interior to the grain boundaries. The mathematical formalism is based on a meanfield approximation, utilizing the thermodynamic extremal principle. The model is applied to the precipitation of aluminum nitrides in microalloyed steel in austenite, where precipitation occurs predominately at the austenite grain boundaries. It is shown that the kinetics of precipitation predicted by the proposed model differs significantly from that calculated for randomly distributed precipitates with spherical diffusion fields. Good agreement of the numerical solution is found with experimental observations as well as theoretical treatment of precipitate coarsening.

Interstitial diffusion in systems with multiple sorts of traps

The role of several sorts of traps for one diffusing interstitial component is investigated. The site fraction of this component in each trap is calculated due to the local thermodynamic equilibrium condition with its site fraction in the lattice. Combining Ficks first law for diffusive fluxes of individual site fractions with the equilibrium condition and the mass balance allows deriving an extended nonlinear diffusion equation. If the molar volumes of the trap positions are constant with respect to time, then a generalized chemical diffusion coefficient can be derived, which allows performing the diffusion study in terms of the total concentration of the interstitial component. As an alternative way, the total diffusion flux can also be treated as the sum of diffusion fluxes of individual fractions combined with local redistribution of individual fractions based on the thermodynamic local equilibrium condition. Both concepts are presented in simulations for the diffusion of hydrogen in the system with traps as immobile dislocations, substitutional impurities and interfaces of incoherent carbide nanoprecipitates. Both concepts provide equivalent results and exhibit an asymmetric behaviour with respect to a charging/discharging process.

Precipitation in Al-Alloy 6016 – The Role of Excess Vacancies

6xxx Al alloys owe their superior mechanical properties to the precipitation of finely dispersed metastable β´´ precipitates. These particles are formed in the course of optimized heat treatments, where the desired microstructure is generated in a sequence of precipitation processes going from MgSi co-clusters and GP zones to β´´ and β´ precipitates and finally to the stable β and Si diamond phases. The entire precipitation sequence occurs at relatively low temperatures (RT to approx. 200 °C) and is mainly controlled by the excess amount of quenched-in vacancies, which drive the diffusional processes at these low temperatures. Very recently a novel model for the prediction of the excess vacancy evolution controlled by the annihilation and generation of vacancies at dislocation jogs, grain boundaries and Frank loops was developed and implemented in the thermo-kinetic software MatCalc. In the present work, we explore the basic features of this model in the simulation of the excess vacancy evolution during technological heat treatments. The focus of this article lies on the effect of vacancy supersaturation during different heat treatment steps, such as quenching, heating, natural and artificial aging.

Thermo-kinetic computer simulation of differential scanning calorimetry curves of AlMgSi alloys

Abstract The microstructure evolution in heat-treatable Al-alloys is characterized by a complex sequence of precipitation processes. These can be either endothermic or exothermic in nature and they can be investigated by thermal analysis. The individual peaks identified in a differential scanning calorimetry (DSC) analysis can be correlated to the nucleation, growth and dissolution of certain types of precipitates. Simultaneously, these data can also be obtained by thermo-kinetic simulation based on models implemented, for instance, in the software MatCalc. The simulations make use of information stored in thermodynamic databases, including stable and metastable phases. In the present work, a thermo-kinetic computational analysis of Al–Mg–Si DSC curves is carried out. The comparison with experimentally observed DSC signals for precipitation and dissolution of metastable GP-zones, β″, β′, as well as stable β-Mg2Si and Si precipitates provides a quantitative insight into the kinetics and sequence of precipitation during DSC probing. The combination of thermo-kinetic and experimental DSC analysis offers new possibilities in interpretation of DSC peaks with multiple metastable phases. In the present paper, we discuss the linking of the simulated precipitation sequence with the measured DSC signal. In addition, with the proposed methodology, a consistent set of parameters to describe the non-equilibrium kinetic parameters of a specific alloy system can be obtained, which can substantially aid in alloy and process development.

Numerical simulation of NbC precipitation in microalloyed steel

This work describes with the investigation of the precipitation kinetics of NbC in microalloyed steel. Using the thermo-kinetic software MatCalc, computer simulations of NbC precipitation are carried out and compared with several independent experimental results, measured in austenite and ferrite. The selected experiments involve a variety of different dislocation densities originating from distinct thermo-mechanical treatments. Two separate populations of NbC precipitates are accounted for in the simulations, representing precipitates on grain boundaries as well as dislocations. Furthermore, three different diffusion mechanisms are taken into account, which are bulk diffusion in the undisturbed crystal, accelerated diffusion along the dislocation core and fast diffusion along grain boundaries. It is demonstrated that deformation-induced dislocation densities higher than 1013 m−2 lead to prominent diffusion along dislocation networks. Therefore, in such cases, the precipitation kinetics of NbC is dominated by the pipe diffusion mechanism, and the precipitation process is several orders of magnitude faster compared with NbC precipitation in unstrained, well-annealed microstructures.

Ortho-equilibrium and para-equilibrium phase diagrams for interstitial / substitutional iron alloys

Abstract A mathematical model for the evaluation of compositionally constrained thermodynamic equilibrium has recently been implemented into the computer program MatCalc. This model is applied to the calculation of para-equilibrium phase diagrams for some ternary model iron alloy systems FeXC, with X = Mn, Ni, Cr and Mo. The results are compared to the corresponding full equilibrium (ortho-equilibrium) phase diagrams and the impact of each element on the austenite / ferrite / carbide transformation in steels is analyzed. The para-equilibrium phase diagrams are considerably more simple than the potentially complex ortho-equilibrium phase diagrams, showing cementite formation as the only stable carbide under para-equilibrium conditions. The driving forces for precipitation of cementite and the complex chromium carbides in the FeCrC system are evaluated as a function of the precipitate composition. The evaluation of the driving forces under para-equilibrium conditions predicts carbide precipitation behavior that agrees with experimental findings.