N. Wanderka

Phase separation in equiatomic AlCoCrFeNi high-entropy alloy

The microstructure of the as-cast AlCoCrFeNi high entropy alloy has been investigated by transmission electron microscopy and atom probe tomography. The alloy shows a very pronounced microstructure with clearly distinguishable dendrites and interdendrites. In both regions a separation into an Al-Ni rich matrix and Cr-Fe-rich precipitates can be observed. Moreover, fluctuations of single elements within the Cr-Fe rich phase have been singled out by three dimensional atom probe measurements. The results of investigations are discussed in terms of spinodal decomposition of the alloying elements inside the Cr-Fe-rich precipitates.

Chemical composition measurements of a nickel-base superalloy by atom probe field ion microscopy

Abstract Single crystals of the rhenium-containing nickel-base superalloy CMSX-4 were investigated using a time of flight atom probe. The distribution of the alloying elements in the two phases, matrix (γ phase) and precipitate (γ′ phase), was studied. The high spatial resolution of the atom probe allows to analyse the γ−γ′ interface. The transition from matrix to γ′ phase takes place within one atomic layer. The boundary is enriched with titanium. Layer-by-layer analysis of (001) planes of the L 1 2 ordered γ′ phase reveals alternating Ni- and Al-rich planes. The probability of site occupation by different elements could be evaluated. An approximate formula of the γ′ phase is given by (Ni 81 Ti 3 Ta 2 Cr 5 Co 7 W 2 ) 3 (Ni 20 Al 70 Ta 6 Co 2 W 2 ). Rhenium is found mainly in the matrix and has a tendency to build clusters.

Positive effect of natural pre-ageing on precipitation hardening in Al–0.44 at% Mg–0.38 at% Si alloy

Age hardening in a purely ternary Al-Mg0.4-Si0.4 (0.44 at% Mg, 0.38at%Si) alloy that is similar to AA6060 was investigated by hardness measurement, TEM and three-dimensional atom probe (3D-AP). In particular, the effect of natural pre-ageing before artificial ageing, which is known to have a positive effect in this alloy, was studied by comparing three different conditions: natural ageing only, artificial ageing for 1.5h at 180 degrees C only and combined natural pre-ageing and subsequent artificial ageing for 1.5h at 180 degrees C. Natural ageing influences the mechanical properties significantly. Naturally aged alloys exhibit a hardening response that is governed by the presence of small clusters. Subsequent artificial ageing of naturally aged specimens increases the value of peak hardness, which is attributed to the increase of the number density of needle-shaped precipitates as compared to the samples without natural ageing. It is assumed that besides these precipitates, the small Si clusters formed at room-temperature storage remain stable during artificial ageing.

Effect of decomposition of the Cr–Fe–Co rich phase of AlCoCrCuFeNi high entropy alloy on magnetic properties

Splat-quenched, as-cast and aged (2h at 600 °C after casting) AlCoCrCuFeNi high entropy alloys were investigated by means of transmission electron microscopy and three-dimensional atom probe (3D-AP). 3D-AP revealed anti-correlated fluctuations of the Cr and Fe-Co compositions in Cr-Fe-Co-rich regions of the as-cast alloy. The ferromagnetic behavior of AlCoCrCuFeNi high entropy alloy was correlated with the decomposition of the Cr-Fe-Co-rich regions into ferromagnetic Fe-Co-rich and antiferromagnetic Cr-rich domains, the size of which was determined by statistical analysis of 3D-AP data. The splat-quenched alloy showed a softer magnetic behavior as compared to the as-cast and aged alloys. The aged alloy possessed a higher saturation magnetization and coercivity as compared to the as-cast alloy.

Microstructural investigation of Sr-modified Al–15 wt%Si alloys in the range from micrometer to atomic scale

Strontium-modified Al-15 wt%Si casting alloys were investigated after 5 and 60 min of melt holding. The eutectic microstructures were studied using complementary methods at different length scales: focused ion beam-energy selective backscattered tomography, transmission electron microscopy and 3D atom probe. Whereas the samples after 5 min of melt holding show that the structure of eutectic Si changes into a fine fibrous morphology, the increase of prolonged melt holding (60 min) leads to the loss of Sr within the alloy with an evolution of an unmodified eutectic microstructure displaying coarse interconnected Si plates. Strontium was found at the Al/Si eutectic interfaces on the side of the eutectic Al region, measured by 3D atom probe. The new results obtained using 3D atom probe shed light on the location of Sr within the Al-Si eutectic microstructure.

On the Path to Optimizing the Al-Co-Cr-Cu-Fe-Ni-Ti High Entropy Alloy Family for High Temperature Applications

The most commonly investigated high entropy alloy, AlCoCrCuFeNi, has been chosen for optimization of its microstructural and mechanical properties by means of compositional changes and heat treatments. Among the different available optimization paths, the decrease of segregating element Cu, the increase of oxidation protective elements Al and Cr and the approach towards a γ-γ′ microstructure like in Ni-based superalloys have been probed and compared. Microscopical observations have been made for every optimization step. Vickers microhardness measurements and/or tensile/compression test have been carried out when the alloy was appropriate. Five derived alloys AlCoCrFeNi, Al23Co15Cr23Cu8Fe15Ni16, Al8Co17Cr17Cu8Fe17Ni33, Al8Co17Cr14Cu8Fe17Ni34.8Mo0.1Ti1W0.1 and Al10Co25Cr8Fe15Ni36Ti6 (all at.%) have been compared to the original AlCoCrCuFeNi and the most promising one has been selected for further investigation.

Modification of Mo-Si alloy microstructure by small additions of Zr

Molybdenum and its alloys are potential materials for high-temperature applications. However, molybdenum is susceptible to embrittlement because of oxygen segregation at the grain boundaries. In order to alleviate the embrittlement small amounts of zirconium were alloyed to a solid solution of Mo-1.5Si alloy. Two Mo-based alloys, namely Mo-1.5Si and Mo-1.5Si-1Zr, were investigated by the complementary high-resolution methods transmission electron microscopy and atom probe tomography. The Mo-1.5Si alloy shows a polycrystalline structure with two silicon-rich intermetallic phases Mo(5)Si(3) and Mo(3)Si located at the grain boundaries and within the grains. In addition, small clusters with up to 10 at% Si were found within the molybdenum solid solution. Addition of a small amount of zirconium to Mo-1.5Si leads to the formation of two intermetallic phases Mo(2)Zr and MoZr(2), which are located at the grain boundaries as well as within the interior of the grain. Transmission electron microscopy shows that small spherical Mo-Zr-rich precipitates (<10nm) decorate the grain boundaries. The stoichiometry of the small precipitates was identified as Mo(2)Zr by atom probe tomography. No Si-enriched small precipitates were detected in the Mo-1.5Si-1Zr alloy. It is concluded that the presence of zirconium hinders their formation.

Analysis of clustering in Al–Mg–Si alloy by density spectrum analysis of atom probe data

Early stages of cluster formation in an Al-Si-Mg alloy were investigated by atom probe tomography and evaluated by a newly developed statistical method based on the nearest neighbour distributions. After solutionising and quenching, an alloy sample was naturally aged for one week. The atom probe data then measured was analysed for Mg, Si or Mg-Si clusters. For comparison specimen artificial aged with well developed precipitates was also investigated. A general approach for the analysis of density spectra was set up, which reduced the problem to the solution of an integral equation. Application of the method to the atom probe data set allowed us to detect clusters and to evaluate the atomic fractions within these clusters. This is also possible for an arbitrary number of nucleated phases. The higher-order next nearest neighbour distributions were used for the estimation of cluster sizes. Combining the density distribution method with a Monte Carlo simulation we found very small Si-Si and Mg-Mg clusters consisting of only a few atoms in the naturally aged state.

Influence of W, Mo and Ti Trace Elements on the Phase Separation in Al8Co17Cr17Cu8Fe17Ni33 based High Entropy Alloy

Compositionally complex alloys, also called high entropy alloys, have been investigated for over a decade in view of different applications, but so far only a small number of alloys can be considered as presenting good enough properties for industrial application. The most common family of elements is Al-Co-Cr-Cu-Fe-Ni. The equiatomic alloy having 5 phases and being too brittle, the composition has been modified in order to improve the mechanical properties. Different compositions have been tested and as a first result ductile Al8Co17Cr17Cu8Fe17Ni33 has been chosen for deeper investigation. It shows a dendritic segregation into Co-Cr-Fe rich cores and Al-Cu-Ni rich interdendritic sites. The as-cast state is characterized mainly by two phases, namely Al-Cu-Ni rich precipitates of L12 structure inside a solid solution matrix. After homogenization both alloys consists of a single solid solution phase. Results are compared to calculations by ThermoCalc. In order to further improve the properties of the alloy the Cr content has been decreased and replaced by trace elements W, Mo and Ti, which, according to ThermoCalc, increase the melting point and the phase transition temperature which leads to the formation of the L12 phase. As-cast and heat treated samples of the base and the modified alloy have been investigated by transmission electron microscopy and three dimensional atom probe. Results of the investigations will be discussed in terms of microstructure, hardness and coherence with Thermo Calc predictions.

The influence of Cu addition on precipitation in Fe–Cr–Ni–Al–(Cu) model alloys

Precipitation in Fe-Cr-Ni-Al-(Cu) model alloys was investigated after ageing for 0.25, 3, 10 and 100h at 798K. Characterization of nanoscale precipitates was performed using three-dimensional atom probe microscopy and transmission electron microscopy. The precipitates are found to be enriched in Ni and Al (Cu) and depleted in Fe and Cr. After 0.25h of ageing the number density of precipitates is approximately 8x10(24)m((-3)), their volume fraction is about 15.5% and they are near-spherical with an average diameter of about 2-3nm. During further ageing the precipitates in the both alloys grow, but the coarsening behaviour is different for both alloys. The precipitates of the Cu-free alloy grow much faster compared with the Cu-containing alloy and their density decreases. Precipitates in Cu-free alloy change to plate shaped even after 10h of ageing, whereas those of Cu-containing alloy remain spherical up to 10h of ageing. The influence of Cu addition on precipitation in these model alloys is discussed with respect to the different coarsening mechanisms.