Thermodynamic and Kinetic Simulations Used for the Study of the Influence of Precipitates on Thermophysical Properties in NiTiCu Alloys Obtained by Spark Plasma Sintering.

The thermodynamic and kinetic simulations based on the re-assessment of the thermodynamic and kinetic database of the Ni-Ti-Cu system were employed to predict the phenomena of mechanical alloying, spark plasma sintering and thermal properties of the intriguing Ni-Ti-Cu system. Thermodynamic calculations are presented for the stable and unstable phases of NiTiCu materials and support a correlation with the evolving microstructure during the technological process. Also, the thermal conductivity, the thermal diffusivity and the specific heat of spark plasma sintered and aged Cu-alloyed NiTi-based shape memory alloys (NiTiCu) with two compositions, Ni45Ti50Cu5 and Ni40Ti50Cu10, are evaluated and the influence of mechanical alloying and precipitates on thermal properties is discussed. Measurements of these thermal properties were carried out from 25 °C up to 175 °C using the laser flash method, as well as differential scanning calorimetry. The thermal hysteresis of the 20 mm diameter samples was between 8.8 and 24.5 °C. The observed T0 temperatures from DSC experimental transformation features are in reasonable accordance with the thermodynamic predictions. The determined k values are between 20.04 and 26.87 W/m K and in agreement with the literature results. Moreover, this paper can provide some suggestions for the preparation of NiTiCu shape memory alloys and their applications.

Structure and Migration Mechanisms of Small Vacancy Clusters in Cu: A Combined EAM and DFT Study.

Voids in face-centered cubic (fcc) metals are commonly assumed to form via the aggregation of vacancies; however, the mechanisms of vacancy clustering and diffusion are not fully understood. In this study, we use computational modeling to provide a detailed insight into the structures and formation energies of primary vacancy clusters, mechanisms and barriers for their migration in bulk copper, and how these properties are affected at simple grain boundaries. The calculations were carried out using embedded atom method (EAM) potentials and density functional theory (DFT) and employed the site-occupation disorder code (SOD), the activation relaxation technique nouveau (ARTn) and the knowledge led master code (KLMC). We investigate stable structures and migration paths and barriers for clusters of up to six vacancies. The migration of vacancy clusters occurs via hops of individual constituent vacancies with di-vacancies having a significantly smaller migration barrier than mono-vacancies and other clusters. This barrier is further reduced when di-vacancies interact with grain boundaries. This interaction leads to the formation of self-interstitial atoms and introduces significant changes into the boundary structure. Tetra-, penta-, and hexa-vacancy clusters exhibit increasingly complex migration paths and higher barriers than smaller clusters. Finally, a direct comparison with the DFT results shows that EAM can accurately describe the vacancy-induced relaxation effects in the Cu bulk and in grain boundaries. Significant discrepancies between the two methods were found in structures with a higher number of low-coordinated atoms, such as penta-vacancies and di-vacancy absortion by grain boundary. These results will be useful for modeling the mechanisms of diffusion of complex defect structures and provide further insights into the structural evolution of metal films under thermal and mechanical stress.

Thermodynamic Modelling and Microstructural Study of Z-Phase Formation in a Ta-Alloyed Martensitic Steel.

A thermokinetic computational framework for precipitate transformation simulations in Ta-containing martensitic Z-steels was developed, including Calphad thermodynamics, diffusion mobility data from the literature, and a kinetic parameter setup that considered precipitation sites, interfacial energies and dislocation density evolution. The thermodynamics of Ta-containing subsystems were assessed by atomic solubility data and enthalpies from the literature as well as from the experimental dissolution temperature of Ta-based Z-phase CrTaN obtained from differential scanning calorimetry. Accompanied by a comprehensive transmission electron microscopy analysis of the microstructure, thermokinetic precipitation simulations with a wide-ranging and well-documented set of input parameters were carried out in MatCalc for one sample alloy. A special focus was placed on modelling the transformation of MX into the Z-phase, which was driven by Cr diffusion. The simulation results showed excellent agreement with experimental data in regard to size, number density and chemical composition of the precipitates, showing the usability of the developed thermokinetic simulation framework.

Characterisation of a High-Performance Al-Zn-Mg-Cu Alloy Designed for Wire Arc Additive Manufacturing.

Ever-increasing demands of industrial manufacturing regarding mechanical properties require the development of novel alloys designed towards the respective manufacturing process. Here, we consider wire arc additive manufacturing. To this end, Al alloys with additions of Zn, Mg and Cu have been designed considering the requirements of good mechanical properties and limited hot cracking susceptibility. The samples were produced using the cold metal transfer pulse advanced (CMT-PADV) technique, known for its ability to produce lower porosity parts with smaller grain size. After material simulations to determine the optimal heat treatment, the samples were solution heat treated, quenched and aged to enhance their mechanical performance. Chemical analysis, mechanical properties and microstructure evolution were evaluated using optical light microscopy, scanning electron microscopy, energy dispersive X-ray spectroscopy, X-ray fluorescence analysis and X-ray radiography, as well as tensile, fatigue and hardness tests. The objective of this research was to evaluate in detail the mechanical properties and microstructure of the newly designed high-performance Al-Zn-based alloy before and after ageing heat treatment. The only defects found in the parts built under optimised conditions were small dispersed porosities, without any visible cracks or lack of fusion. Furthermore, the mechanical properties are superior to those of commercial 7xxx alloys and remarkably independent of the testing direction (parallel or perpendicular to the deposit beads). The presented analyses are very promising regarding additive manufacturing of high-strength aluminium alloys.

Simulation of Dynamic and Meta-Dynamic Recrystallization Behavior of Forged Alloy 718 Parts Using a Multi-Class Grain Size Model.

Dynamic and meta-dynamic recrystallization occur during forging of alloy 718 aircraft parts and thus change the microstructure during a multistep production route. Since the prediction of the resulting grain structure in a single grain fraction is not able to describe microstructures with bimodal or even multimodal distributions, a multi-class grain size model has been deployed to describe the recrystallization mechanisms during thermomechanical treatments and predict the resulting grain size distributions more accurately. As forging parameters, such as temperature, strain rate and maximum strain influence the flow curve and consequently the recrystallization behavior, a series of double cone compression experiments has been carried out and used to verify and adapt the material parameters for the multi-class grain size model. The recrystallized fractions of the numerical and experimental results are compared and differentiated in view of the recrystallization mechanism, i.e., dynamic and meta-dynamic recrystallization. The strong dependence of the recrystallization kinetics on the initial grain size is highlighted, as well as the influence of different strain rates, which shall represent typical forging equipment.

Analysis of Sn-Bi Solders: X-ray Micro Computed Tomography Imaging and Microstructure Characterization in Relation to Properties and Liquid Phase Healing Potential.

This work provides an analysis of X-ray micro computed tomography data of Sn-xBi solders with x = 20, 30, 35, 47, 58 wt.% Bi. The eutectic thickness, fraction of eutectic and primary phase are analyzed. Furthermore, the 3D data is evaluated by means of morphology parameters, such as, shape complexity, flatness, elongation and mean intercept length tensor. The investigated alloys are categorized in three groups based on their morphology, which are described as "complex dominant", "complex- equiaxed" and "mixed". The mechanical behavior of Sn-Bi alloys in the semi-solid configuration and the correlation with microstructural parameters are discussed. A varying degree of geometric anisotropy of the investigated alloys is found through the mean intercept length tensor. Representative volume element models for finite element simulations (RVE-FEM) are created from tomography data of each alloy to analyze a correlation of geometric and elastic anisotropy. The simulations reveal an elastic isotropic behavior due to the small difference of elastic constants of primary and eutectic phase. A discussion of properties in the semi-solid state and liquid phase healing is provided.

An efficient method to reconstruct free energy profiles for diffusive processes in transition interface sampling and forward flux sampling simulations.

We propose a Reweighted Partial Path (RPP) method to compute free energy profiles for diffusive processes in single Transition Interface Sampling (TIS) or Forward Flux Sampling (FFS) simulations. The method employs a partial path reweighting strategy, based on the memory loss assumption for diffusive systems, to derive the equilibrium distribution of states along a chosen order parameter from TIS or FFS trajectories. No additional calculations such as reverse TIS or umbrella sampling are required. The application of the RPP method is demonstrated by calculating the nucleation free energy of early-stage Cu precipitates in a dilute Fe-Cu alloy.

Atomistic and continuums modeling of cluster migration and coagulation in precipitation reactions.

The influence of vacancy preference towards one of the constituents in a binary system on the formation of precipitates was investigated by atomistic and continuums modeling techniques. In case of vacancy preference towards the solute atoms, we find that the mobility of individual clusters as well as entire atom clusters is significantly altered compared to the case of vacancy preference towards the solvent atoms. The increased cluster mobility leads to pronounced cluster collisions, providing a precipitate growth and coarsening mechanism competitive to that of pure solute evaporation and adsorption considered in conventional diffusional growth and Ostwald ripening. A modification of a numerical Kampmann-Wagner type continuum model for precipitate growth is proposed, which incorporates the influence of both mechanisms. The prognoses of the modified model are validated against the growth laws obtained with lattice Monte Carlo simulations and a growth simulation considering solely the coalescence mechanism.