Tuning phase-stability and short-range order through Al-doping in (CoCrFeMn)100-xAlx high entropy alloys

For (CoCrFeMn)$_{100-x}$Al$_{x}$ high-entropy alloys, we investigate the phase evolution with increasing Al-content (0 $\le$ x $\le$ 20 at.%). From first-principles theory, the Al-doping drives the alloy structurally from FCC to BCC separated by a narrow two-phase region (FCC+BCC), which is well supported by our experiments. We highlight the effect of Al-doping on the formation enthalpy and electronic structure of (CoCrFeMn)$_{100-x}$Al$_{x}$ alloys. As chemical short-range order (SRO) in multicomponent alloys indicates the nascent local order (and entropy changes), as well as expected low-temperature ordering behavior, we use thermodynamic linear-response within density-functional theory to predict SRO and ordering transformation and temperatures inherent in (CoCrFeMn)$_{100-x}$Al$_{x}$. The predictions agree with our present experimental findings, and other reported ones.Comment: 27 pages, 9 figures, 1 tabl

Tuning phase-stability and short-range order through AI-doping in (CoCrFeMn)100-xAIx high entropy alloys

For (CoCrFeMn)100−xAlx high-entropy alloys, we investigate the phase evolution with increasing Al content (0≤x≤20 at.%). From first-principles theory, aluminum doping drives the alloy structurally from fcc to bcc separated by a narrow two-phase region (fcc+bcc), which is well supported by our experiments. Using KKR-CPA electronic-structure calculations, we highlight the effect of Al doping on the formation enthalpy (alloy stability) and electronic dispersion of (CoCrFeMn)100−xAlx alloys. As chemical short-range order indicates the nascent local order, and entropy changes, as well as expected low-temperature ordering behavior, we use KKR-CPA-based thermodynamic linear response to predict the chemical ordering behavior of arbitrary complex solid-solution alloys—an ideal approach for predictive design of high-entropy alloys. The predictions agree with our present experimental findings and other reported ones

On the interplay between microstructure, residual stress and fracture toughness of (Hf-Nb-Ta-Zr)C multi-metal carbide hard coatings

The development of sputtered coatings with improved hardness-toughness property combination is widely sought after. Multi-element ceramic carbide (Hf-Nb-Ta-Zr)C coatings with excess carbon, synthesized by DC co-sputtering is presented in this study as a promising candidate to achieve this objective. The specific roles of microstructure and residual stress are decoupled in order to understand their influence on the mechanical properties. Extensive mechanical characterization through in situ testing of focused ion beam fabricated microcantilevers and nanoindentation based approaches are adopted to quantitatively separate the effect of residual stresses on the fracture toughness of the (Hf-Nb-Ta-Zr)C coatings. Residual stress free, microcantilever testing in notched and unnotched conditions, in combination with microstructural characterization unambiguously reveals the intrinsic mechanical behavior of coatings, which solely depend on the microstructure. On the other hand, nanoindentation based testing techniques probe the influence of residual stress and microstructure on the measured mechanical properties. The segregation and thickening of carbon-rich clusters, especially to the grain boundaries with increasing deposition temperatures is speculated to lead to substantial degradation in all mechanical properties measured. An easier fracture path through grain boundaries leads to a reduction in fracture resistance, which is possibly related to carbon enrichment

Compatibility of Zr2AlCZr_{2}AlC MAX phase-based ceramics with oxygen-poor, static liquid lead-bismuth eutectic

This work investigates the compatibility of $Zr_{2}AlC$ MAX phase-based ceramics with liquid LBE, and proposes a mechanism to explain the observed local $Zr_{2}AlC$/LBE interaction. The ceramics were exposed to oxygen-poor ($C_{O}\le2.2 \cdot10^{-10}$ mass%), static liquid LBE at 500{\deg}C for 1000 h. A new $Zr_{2}(Al,Bi,Pb)C$ MAX phase solid solution formed in-situ in the LBE-affected $Zr_{2}AlC$ grains. Out-of-plane ordering was favorable in the new solid solution, whereby $\textit{A}$-layers with high and low-Bi/Pb contents alternated in the crystal structure, in agreement with first-principles calculations. Bulk $Zr_{2}(Al,Bi,Pb)C$ was synthesized by reactive hot pressing to study the crystal structure of the solid solution by neutron diffraction

Design, synthesis and properties of multi-component alloy thin films

A novel, FeMnCoCrAl high entropy alloy synthesized by combinatorial sputtering and casting is introduced in the first part of the thesis. The synthesized thin film library, exhibiting concentration gradients of Al from 0 to 54 at.%, is characterized using X-ray diffraction, electron diffraction, atom probe tomography, nano-indentation and magnetometry to elucidate the impact of Al concentration on phase formation, elastic and magnetic properties. Al additions to FeMnCoCr crystallizing in the alpha-Mn structure cause the formation of the body centered cubic (BCC) structure. This is consistent with density functional theory predictions as Al additions give rise to a larger stability for the BCC phase compared to the face centered cubic phase (FCC) which can be rationalized by the formation of a pseudogap at the Fermi level indicating the stabilization of the BCC phase over the FCC phase. This underlines the ability of the FeMnCoCrAl high entropy alloy family to form single phase solid solutions at non-equiatomic compositions and hence with varying configurational entropy contributions. Nano-indentation elastic modulus of the equiatomic FeMnCoCrAl bulk and thin film samples exhibit good agreement. The experimental values are also comparable to the DFT calculated modulus with deviations less than 6 % between theory and experiment. Regarding magnetic properties, Al additions to paramagnetic FeMnCoCr induce ferromagnetism. The largest saturation magnetization was measured for the film containing 8 at.% of Al. As the concentration of non-ferromagnetic Al is increased beyond 8 at.%, the number density of the ferromagnetic species is decreased causing a concomitant decrease in magnetization. This trend is consistent with ab initio predictions of the Al concentration induced changes in the magnetic moment. Based on the experimental and theoretical results presented here the effect of the Al concentration on the phase formation and the magnetic properties of FeMnCoCrAl thin film library can be rationalized. In the second part of the thesis, the synthesis temperature dependent phase formation of Ni10Ti10Al25Fe35Cr20 compositionally complex alloy thin films is compared to a bulk processed sample of identical composition. The as-cast alloy exhibits a dual-phase microstructure which is composed of a disordered BCC phase and AlNiTi-based B2- and/or L21-ordered phase(s). Formation of the BCC phase as well as an ordered AlNi-based B2 phase is observed for a thin film synthesized at 500 °C (ratio of synthesis temperature of thin film to melting temperature of bulk alloy: T/Tm = 0.49), which is attributed to both surface and bulk diffusion mediated growth. Post deposition annealing at 900 °C (T/Tm = 0.75) of a thin film deposited without intentional heating results in the formation of NiAlTi-based B2 and/or L21-phase(s) similar to the bulk sample, which is attributed to bulk diffusion. Depositions conducted at room temperature without intentional substrate heating (T/Tm = 0.20) resulted in the formation of an X-ray amorphous phase, while a substrate temperature increase to 175 °C (T/Tm = 0.28) causes the formation of a BCC phase. Atom probe tomography of the thin films deposited without intentional substrate heating and at 175 °C indicates the formation of ~5 nm and ~10 nm FeAl-rich domains, respectively. This can be rationalized based on the activation energy for surface diffusion, as Ti and Ni exhibit 2.5 to 4 times larger activation energy barriers than Al, Fe and Cr. It is evident from the homologous temperature that the phase formation observed at 500 °C (T/Tm = 0.49) is a result of both surface and bulk diffusion. As the temperature is reduced, the formation of FeAl-rich domains can be understood based on the differences in activation energy for surface diffusion and is consistent with kinetically limited thin film growth

Combinatorial evaluation of phase formation and magnetic properties of FeMnCoCrAl high entropy alloy thin film library

We report on the influence of the Al content (from 3.5 to 54 at.%) on phase formation and magnetic properties in FeMnCoCrAl high entropy alloy thin film libraries. Al additions to FeMnCoCr crystallizing in the alpha-Mn structure cause the formation of the body centered cubic (BCC) structure. This is consistent with density functional theory predictions as Al additions give rise to a larger stability for the BCC phase compared to the face centered cubic phase (FCC) which can be rationalized by the formation of a pseudogap at the Fermi level indicating the stabilization of the BCC phase over the FCC phase. Al additions to paramagnetic FeMnCoCr induce ferromagnetism. The largest saturation magnetization was measured for the film containing 8 at.% of Al. As the concentration of non-ferromagnetic Al is increased beyond 8 at.%, the number density of the ferromagnetic species is decreased causing a concomitant decrease in magnetization. This trend is consistent with ab initio predictions of the Al concentration induced changes in the magnetic moment. Based on the experimental and theoretical results presented here the effect of the Al concentration on the phase formation and the magnetic properties of FeMnCoCrAl thin film library can be rationalized

Elemental segregation in an AlCoCrFeNi high-entropy alloy - A comparison between selective laser melting and induction melting

Additive manufacturing of a high-entropy alloy, AlCoCrFeNi, was studied with selective laser melting from gas atomized powder. A wide process parameter window in the SLM process was investigated but it was impossible to produce crack-free samples, attributed to stresses that originate during the building processes. The microstructure and elemental segregation in the SLM samples were compared with induction-melted AlCoCrFeNi. The induction-melted sample crystallizes in randomly oriented large grains (several hundred microns). Dendritic and inter-dendritic areas with slightly different chemical composition can be observed. Within these areas a spinodal decomposition occurs with a separation into FeCr- and NiAl-rich domains. Further spinodal decomposition within the FeCr-rich regions into Cr- and Fe-rich domains was observed by atom probe tomography.In contrast, the SLM-samples crystallizes in much smaller grains (less than 20 μm) with a dendrite-like substructure. These dendrite-like features exhibit distinct chemical fluctuations on the nm-scale. During annealing more pronounced chemical fluctuations and the formation of Cr-rich and Cr-poor regions can be observed. The difference in microstructure and spinodal decomposition between the induction-melted and SLM samples is attributed to the significantly higher cooling rate for SLM. This study shows that, by using different synthesis pathways, it is possible to modify the microstructure and segregation of element within alloys. This can be used to tune the materials properties, if the cracking behavior is handled e.g. by change of alloy composition to minimize phase transformations or use of a heating stage