In-situ time-resolved small-angle neutron scattering (SANS) experiments were conducted on homogenised cold-rolled ternary Fe-Au-W alloys during aging for 12 h at temperatures of 650 to 700 °C in order to study the kinetics of the nanoscale precipitation. For comparison the precipitation kinetics in the binary counterparts Fe-Au and Fe-W alloys were also studied. In the ternary Fe-Au-W alloy nanoscale Au-rich precipitates were observed by both transmission electron microscopy (TEM) and SANS, while no significant W-rich precipitation was observed. The SANS pattern of the cold-rolled Fe-Au-W alloy clearly reveals a preferred orientation for the plate-shaped nanoscale Au-rich precipitates. As these Au-rich precipitates have a fixed orientation relation with the matrix lattice this preferred orientation originates from the texture of the bcc matrix grains, as confirmed by X-ray diffraction (XRD) pole figure measurements. The effect of texture on the nuclear and the magnetic SANS signal during the precipitation kinetics was included in the data analysis. This enables us to monitor the temperature dependence of the precipitation kinetics for the Au-rich precipitates in the Fe-Au-W alloy during aging at temperatures of 650, 675 and 700 °C. It is found that an increase in aging temperature results in a faster kinetics and a lower final precipitate fraction.

A set of numerical and analytical models is presented to predict the growth and contraction of grain-boundary creep cavities in binary self-healing alloys. In such alloys, the healing is realised by preferential precipitation of supersaturated solutes at the free surface of the cavity. The cavity grows due to the diffusional flux of vacancies towards the cavity, which is driven by the stress gradient along the grain boundary. Upon deposition of healing solute atoms on the cavity wall, effectively vacancies are removed from the cavity due to the inverse Kirkendall effect. The competition between the inward and outward vacancy fluxes results in a time-dependent filling ratio (i.e. the fraction of the vacancies removed from the original cavity) of the creep cavity. It is found that for stress levels lower than a critical stress σ_cr, the filling ratio can proceed to unity, i.e. to complete filling and annihilation of the pore. For applied stresses higher than σ_cr, complete filling is not achieved and the open volume of the creep cavity will continue to grow once a maximum filling ratio is reached at the critical time t_cr. The critical stress σ_cr, critical time t_cr, and time for complete filling t_h (if fully filling is achievable) are derived from the models for different combinations of parameters. The results from the analytical model and from previous nanotomography experiments are compared and are found to be in good agreement. Graphical abstract: [Figure not available: see fulltext.]

Constant stress creep experiments at 550 °C were performed on a high-purity Fe-3Au-4W (wt.%) ternary alloy with about 1 at.% supersaturation for Au and W in order to study self healing of grain-boundary cavities by both Au-rich and W-rich precipitates. Using synchrotron X-ray nano-tomography, the development of the creep cavities and the healing precipitates at different stages of creep was visualised using two spatial resolutions (30 and 100 nm voxel size) for separate samples taken after different loading times. The healing kinetics was found to strongly depend on the nucleation time of the cavities. Cavities nucleated at an early stage of creep could be fully healed, while the healing of the late-nucleated cavities is much slower due to a decrease in the diffusional flux of the healing supersaturated solutes over time, as a result of (i) a decrease in inter-cavity spacing caused by cavity nucleation and (ii) a gradual depletion of the supersaturated solutes near the grain boundaries. The interaction between the competing healing mechanisms for creep cavities by Au-rich and W-rich precipitates is discussed. It was found that Au-rich precipitates are formed much faster than the W-rich precipitates, and thereby effectively provide creep damage healing on different time scales.

The effect of thermal aging of homogenized Fe-Au and Fe-Au-W alloys, irradiated at room temperature with hydrogen ions, was studied for an aging treatment at 300 °C for aging times up to 100 h. The aging behavior of the Fe-based alloys is compared to the results for pure Fe. The precipitation behavior of Au-rich and W-rich precipitates and its correlation to the H⁺ irradiation-induced defects is investigated by variable energy positron annihilation spectroscopy (VEPAS). The formation of open-volume defects after irradiation is monitored by an increase in the S parameter, while the recovery of the vacancy-like defects and the formation of precipitates are signalled by an increase in the W parameter. Au-rich precipitation continuously develops during long-term aging, as indicated by the increase in the W parameter. The change of the W parameter in the Fe-Au-W alloy is not only due to the effect of solute W on the Au precipitates, but also because of the interface of W-rich Laves phase with matrix.

Autonomous healing of creep-induced grain boundary cavities by Au-rich and W-rich precipitates was studied in a Fe-3Au-4W (wt pct) alloy at a fixed temperature of 823 K (550 °C) with different applied stresses. The ternary alloy, with two supersaturated healing solutes, serves as a model system to study the interplay between two separate healing agents. The creep properties are evaluated and compared with those of the previously studied Fe-Au and Fe-W binary systems. The microstructures of the creep-failed samples are studied by electron microscopy to investigate the cavity filling behavior and the mass transfer of supersaturated solute to the defect sites. Compared to the Fe-Au and Fe-W alloys, the new Fe-Au-W alloy has the lowest steady-state strain rate and the longest lifetime. The site-selective filling of the creep-induced cavities is attributed to two different categories of precipitates: micron-sized Au-rich precipitates and nano-sized W-rich precipitates. The Au-rich precipitates are found capable to fully heal the cavities, while the W-rich precipitates show only a limited degree of healing. The two types of precipitates show a reluctance to coexistence, and the formation of W-rich precipitates is suppressed strongly. A model is proposed to describe the competitive healing behavior of the Au-rich and W-rich precipitates.

Abstract: The precipitation of supersaturated solutes at free surfaces in ternary Fe–3Au–4W and binary Fe–3Au and Fe–4W alloys (composition in weight percentage) for different ageing times was investigated at a temperature of 700 °C. The time evolution of the surface precipitation is compared among the three alloys to investigate the interplay between the Au and W solutes in the ternary system. The Au-rich grain-interior surface precipitates show a similar size and kinetics in the Fe–Au–W and Fe–Au alloys, while the W-rich grain-interior surface precipitates show a smaller size and a higher number density in the Fe–Au–W alloy compared to the Fe–W alloy. The kinetics of the precipitation on the external free surface for the ternary Fe–Au–W alloy is compared to the previously studied precipitation on the internal surfaces of the grain-boundary cavities during creep loading of the same alloy. Graphical abstract: [Figure not available: see fulltext.]