Outstanding radiation resistance of tungsten-based high-entropy alloys (US)

APT analysis of the HEA irradiated to 8 dpa with 3-MeV Cu+ at 1050 K. –  (A) to (D) 3D distribution of Cr, V, Ta, and W. (E) to (H) 2D compositional maps of Cr, V, Ta, and W using a slice of 25 nm by 1 nm by 20 nm. (I) to (L) Top-down view showing the location of three different GBs and the corresponsing elemental segregation. Reconstruction side-view (M) and top-view (N) with 25 at % Cr isocomposition surface showing Cr-V–rich precipitates inside grains. (O) Compositional partitioning between the precipitate and the matrix. ppts, precipitates.

A body-centered cubic W-based refractory high entropy alloy with outstanding radiation resistance has been developed. The alloy was grown as thin films showing a bimodal grain size distribution in the nanocrystalline and ultrafine regimes and a unique 4-nm lamella-like structure revealed by atom probe tomography (APT). Transmission electron microscopy (TEM) and x-ray diffraction show certain black spots appearing after thermal annealing at elevated temperatures. TEM and APT analysis correlated the black spots with second-phase particles rich in Cr and V. No sign of irradiation-created dislocation loops, even after 8 dpa, was observed. Furthermore, nanomechanical testing shows a large hardness of 14 GPa in the as-deposited samples, with near negligible irradiation hardening. Theoretical modeling combining ab initio and Monte Carlo techniques predicts the formation of Cr- and V-rich second-phase particles and points at equal mobilities of point defects as the origin of the exceptional radiation tolerance.


Key components in magnetic fusion reactors, such as the divertor or the plasma-facing materials (PFMs), are required to have stringent properties including low activation, high melting point, good thermomechanical properties, low sputter erosion, and low tritium retention/codeposition. They must operate at high temperature (≥1000 K) for long durations (>107 s), without failure or extensive erosion while exposed to large plasma heat and an intense mixture of ionized and energetic neutral species of hydrogen isotopes (D and T), He ash (fluxes, >1024 m−2 s−1), and neutrons (1). Tungsten (W) is the leading PFM candidate because of its high melting temperature, low erosion rates, and small tritium retention. These advantages are unfortunately coupled with very low fracture toughness characterized by brittle transgranular and intergranular failure regimes, which severely restrict the useful operating temperature window and also create a range of fabrication difficulties. Furthermore, blistering at moderate temperature (<800 K) by D and He (23) and the formation of pits, holes, and bubbles by He at higher temperature (>1600 K) (4) have all been observed. The formation mechanisms that underpin these phenomena are not well understood but have largely been attributed to the accumulation of diffusing D and He in extended defects. In the slightly lower temperature ranging from 1250 to 1600 K, the formation of nanometer-scale bubbles is observed (5) in W exposed to the He plasma. At larger He ion fluences, close to International Thermonuclear Experimental Reactor (ITER) (6) working conditions, exposed surfaces are found to exhibit a nanostructured surface morphology (7), termed as fuzz. The increased surface area and fragility of these nanostructured surfaces raise new concerns for the use of W as a fusion reactor PFM, particularly as a source of high-Z dust that will contaminate the plasma.

Strategies such as adding different alloying elements (e.g., W-Re and W-Ti) or nanostructure-engineered W are being investigated to improve the material processing and working properties. Related to the second strategy, recent work shows that state-of-the-art nanocrystalline W samples exhibit substantial formation of He bubbles at the grain boundaries, which leads to decohesion and poor mechanical properties at operational temperatures (810), reducing its applicability in fusion environments. Therefore, the development of new material systems is paramount to enable fusion as a viable energy source.

In recent years, a set of alloys based on several principal elements has been developed (1114). The configurational entropy of mixing in multicomponent alloys tends to stabilize the solid solution based on simple underlying face-centered cubic (FCC) or body-centered cubic (BCC) crystal structures. Equiatomic compositions maximize this entropic term, promoting random solutions versus intermetallic phases or phase decomposition. Some of the high-entropy alloys (HEAs) show superior mechanical response to traditional materials, which generally links to dislocation properties. These materials can display high hardness values, high yield strengths, large ductility, excellent fatigue resistance, and good fracture toughness. W-based refractory HEAs have been recently developed in the context of high-temperature applications, showing high melting temperature (above 2873 K) and superior mechanical properties at high temperatures compared to Ni-based superalloys and nanocrystalline W (15) samples (1617).

HEAs have been also studied under irradiation, mostly for FCC crystalline structures. Zhang et al. (18) showed how chemical complexity can lead to a variation in the thermodynamic and kinetic properties of defects that might modify the microstructure evolution under irradiation. They linked the amount of irradiation-created defects and defect properties to electron and phonon mean free paths and dissipation mechanisms that could be tuned in these alloys by varying their composition. Granberg et al. (13) combined experiments and modeling to identify the sluggish mobility of dislocation loops as the main mechanism leading to radiation tolerance in Ni-based FCC HEAs. Kumar et al. (19) showed how Ni-based FCC HEAs lead to less radiation-induced segregation and fewer voids, although hardness was observed to increase after irradiation. Other studies show results in the same direction, with HEAs improving radiation tolerance in both FCC and BCC structures (2022). Very recently, W-based quinary HEAs with diverse composition have been synthesized as potential materials for fusion applications. The authors observed the formation of Ti carbides and laves phases at large W concentrations. The authors studied the mechanical response, showing that these materials could lead to twofold improvement in the hardness and strength due to solid solution strengthening and dispersion strengthening (23). However, refractory HEAs have never been tested under irradiation for potential uses as PFMs or structural materials in nuclear fusion environments. In this work, we have developed a quaternary nanocrystalline W-Ta-V-Cr alloy that we have characterized under thermal conditions and after irradiation. Note that the possible combination of elements to synthesize an HEA is exceedingly large. To narrow the possible candidate systems, we have to bear in mind that high-Z materials are generally desirable to minimize sputtering. In addition, low-activation elements must be considered to reduce radiotoxicity, which excludes the use of Ni, Cu, Al, Mo, Co, or Nb. Furthermore, Fe and Mn usually form intermetallics, which might induce a more complex behavior. Thus, W, Ta, V, and Cr were chosen as testing ingredients for the target system. We show how this alloy can be synthesized using a magnetron sputtering deposition system. Both energy dispersive spectroscopy (EDS) analysis, which measures chemical composition, and atom probe tomography (APT) indicate W and Ta enrichment in the deposited films. The EDS mapping on both surface and cross-sectional areas and x-ray diffraction (XRD) results show a single-phase BCC after deposition. The samples were irradiated with 1-MeV Kr+2 in situ at the Intermediate Voltage Electron Microscope (IVEM)–Tandem Facility at Argonne National Laboratory up to 8 displacements per atom (dpa) with no sign of irradiation-created defects. Moreover, nanoindentation tests were also performed, showing hardness of the film on the order of ~15 GPa





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