Formation and thermal stability of two-phase microstructures in Al-containing refractory compositionally complex alloys.

Phase separation into an A2+B2 two-phase microstructure in refractory compositionally complex alloys (RCCA) has been speculated as being spinodal in nature with continuous chemical distribution during the separation. However, these reactions might instead occur as precipitation by nucleation and growth. In order to unequivocally elucidate the distinct nature of phase separation sequence in RCCA from the system Ta-Mo-Ti-Cr-Al, atom probe tomography and electron microscopy techniques were utilized on samples that were annealed over multiple orders of magnitude in time. The composition 82(TaMoTi)-8Cr-10Al (at.%) was chosen, as it exhibits a two-phase microstructure, with a desired A2 matrix and embedded B2 phase. Quenching the samples from 1200°C resulted in a microstructure consisting of ordered clusters (2 nm) of distinct chemical composition. Subsequent annealing at 800°C to 1000°C leads to an increase in the volume fraction of the precipitating phase, which saturates after 10 h. Further annealing leads to the ripening of the microstructure; however, the absolute size of the precipitates stays <100 nm even after 1000 h. For the investigated conditions, the interface between matrix and precipitate can be considered sharp within the resolution of the applied techniques and no significant change in the transition of chemical composition across the interface is observed. Therefore, the phase separation mechanism is confirmed to be phase nucleation and growth in contrast to the possible spinodal decomposition, as hypothesized for other RCCA systems. The impact of precipitation and coarsening on the hardness of the alloy is discussed.

One-step sputtering of MoSSe metastable phase as thin film and predicted thermodynamic stability by computational methods.

We present the fabrication of a MoS2-xSex thin film from a co-sputtering process using MoS2 and MoSe2 commercial targets with 99.9% purity. The sputtering of the MoS2 and MoSe2 was carried out using a straight and low-cost magnetron radio frequency sputtering recipe to achieve a MoS2-xSex phase with x = 1 and sharp interface formation as confirmed by Raman spectroscopy, time-of-flight secondary ion mass spectroscopy, and cross-sectional scanning electron microscopy. The sulfur and selenium atoms prefer to distribute randomly at the octahedral geometry of molybdenum inside the MoS2-xSex thin film, indicated by a blue shift in the A1g and E1g vibrational modes at 355 cm-1 and 255 cm-1, respectively. This work is complemented by computing the thermodynamic stability of a MoS2-xSex phase whereby density functional theory up to a maximum selenium concentration of 33.33 at.% in both a Janus-like and random distribution. Although the Janus-like and the random structures are in the same metastable state, the Janus-like structure is hindered by an energy barrier below selenium concentrations of 8 at.%. This research highlights the potential of transition metal dichalcogenides in mixed phases and the need for further exploration employing low-energy, large-scale methods to improve the materials' fabrication and target latent applications of such structures.

The Piezoresponse in WO3 Thin Films Due to N2-Filled Nanovoids Enrichment by Atom Probe Tomography.

Tungsten trioxide (WO3) is a versatile n-type semiconductor with outstanding chromogenic properties highly used to fabricate sensors and electrochromic devices. We present a comprehensive experimental study related to piezoresponse with piezoelectric coefficient d33 = 35 pmV-1 on WO3 thin films ~200 nm deposited using RF-sputtering onto alumina (Al2O3) substrate with post-deposit annealing treatment of 400 °C in a 3% H2/N2-forming gas environment. X-ray diffraction (XRD) confirms a mixture of orthorhombic and tetragonal phases of WO3 with domains with different polarization orientations and hysteresis behavior as observed by piezoresponse force microscopy (PFM). Furthermore, using atom probe tomography (APT), the microstructure reveals the formation of N2-filled nanovoids that acts as strain centers producing a local deformation of the WO3 lattice into a non-centrosymmetric structure, which is related to piezoresponse observations.

Microstructural changes in CoCrFeMnNi under mild tribological load.

The lack of a principle element in high-entropy alloys (HEA) leads to unique and unexpected material properties. Tribological loading of metallic materials often results in deformed subsurface layers. As the microstructure feedbacks with friction forces, the microstructural evolution is highly dynamic and complex. The concept of HEAs promises high solid solution strengthening, which might decrease these microstructural changes. Here, we experimentally investigated the deformation behavior of CoCrFeMnNi in a dry, reciprocating tribological contact under a mild normal load. After only a single stroke, a surprisingly thick subsurface deformation layer was observed. This layer is characterized by nanocrystalline grains, twins and bands of localized dislocation motion. Twinning was found to be decisive for the overall thickness of this layer, and twin formation within the stress field of the moving sphere is analyzed. The localization of dislocation activity, caused by planar slip, results in a grain rotation. Fragmentation of twins and dislocation rearrangement lead to a nanocrystalline layer underneath the worn surface. In addition, oxide-rich layers were found after several sliding cycles. These oxides intermix with the nanocrystalline layer due to material transfer to the counter body and re-deposition to the wear track. Having revealed these fundamental mechanisms, the evolution of such deformation layers in CoCrFeMnNi under a tribological load might lead to other HEAs with compositions and properties specifically tailored to tribological applications in the future.