Elucidating Primary Degradation Mechanisms in High-Cycling-Capacity, Compositionally Tunable High-Entropy Hydrides.

The hydrogen sorption properties of single-phase bcc (TiVNb)100-xCrx alloys (x = 0-35) are reported. All alloys absorb hydrogen quickly at 25 °C, forming fcc hydrides with storage capacity depending on the Cr content. A thermodynamic destabilization of the fcc hydride is observed with increasing Cr concentration, which agrees well with previous compositional machine learning models for metal hydride thermodynamics. The steric effect or repulsive interactions between Cr-H might be responsible for this behavior. The cycling performances of the TiVNbCr alloy show an initial decrease in capacity, which cannot be explained by a structural change. Pair distribution function analysis of the total X-ray scattering on the first and last cycled hydrides demonstrated an average random fcc structure without lattice distortion at short-range order. If the as-cast alloy contains a very low density of defects, the first hydrogen absorption introduces dislocations and vacancies that cumulate into small vacancy clusters, as revealed by positron annihilation spectroscopy. Finally, the main reason for the capacity drop seems to be due to dislocations formed during cycling, while the presence of vacancy clusters might be related to the lattice relaxation. Having identified the major contribution to the capacity loss, compositional modifications to the TiVNbCr system can now be explored that minimize defect formation and maximize material cycling performance.

Relation between Ga Vacancies, Photoluminescence, and Growth Conditions of MOVPE-Prepared GaN Layers.

A set of GaN layers prepared by metalorganic vapor phase epitaxy under different technological conditions (growth temperature carrier gas type and Ga precursor) were investigated using variable energy positron annihilation spectroscopy (VEPAS) to find a link between technological conditions, GaN layer properties, and the concentration of gallium vacancies (VGa). Different correlations between technological parameters and VGa concentration were observed for layers grown from triethyl gallium (TEGa) and trimethyl gallium (TMGa) precursors. In case of TEGa, the formation of VGa was significantly influenced by the type of reactor atmosphere (N2 or H2), while no similar behaviour was observed for growth from TMGa. VGa formation was suppressed with increasing temperature for growth from TEGa. On the contrary, enhancement of VGa concentration was observed for growth from TMGa, with cluster formation for the highest temperature of 1100 °C. From the correlation of photoluminescence results with VGa concentration determined by VEPAS, it can be concluded that yellow band luminescence in GaN is likely not connected with VGa; additionally, increased VGa concentration enhances excitonic luminescence. The probable explanation is that VGa prevent the formation of some other highly efficient nonradiative defects. Possible types of such defects are suggested.

Synthesis of vacant graphitic carbon nitride in argon atmosphere and its utilization for photocatalytic hydrogen generation.

Graphitic carbon nitride (C3N4) was synthesised from melamine at 550 °C for 4 h in the argon atmosphere and then was reheated for 1-3 h at 500 °C in argon. Two band gaps of 2.04 eV and 2.47 eV were observed in all the synthetized materials. Based on the results of elemental and photoluminescence analyses, the lower band gap was found to be caused by the formation of vacancies. Specific surface areas of the synthetized materials were 15-18 m2g-1 indicating that no thermal exfoliation occurred. The photocatalytic activity of these materials was tested for hydrogen generation. The best photocatalyst showed 3 times higher performance (1547 µmol/g) than bulk C3N4 synthetized in the air (547 µmol/g). This higher activity was explained by the presence of carbon (VC) and nitrogen (VN) vacancies grouped in their big complexes 2VC + 2VN (observed by positron annihilation spectroscopy). The effect of an inert gas on the synthesis of C3N4 was demonstrated using Graham´s law of ammonia diffusion. This study showed that the synthesis of C3N4 from nitrogen-rich precursors in the argon atmosphere led to the formation of vacancy complexes beneficial for hydrogen generation, which was not referred so far.

Defect-Engineered Hydroxylated Mesoporous Spinel Oxides as Bifunctional Electrocatalysts for Oxygen Reduction and Evolution Reactions.

In this work, defect-rich ordered mesoporous spinel oxides, including CoCo2O4, NiCo2O4, and ZnCo2O4, were developed as bifunctional electrocatalysts toward oxygen reduction and evolution reactions (ORR and OER, respectively). The materials are synthesized via nanocasting and modified by chemical treatment with 0.1 M NaBH4 solution to enhance the defect concentration. The synthesized samples have metal and oxygen divacancies (VCo + VO) as the primary defect sites, as indicated by positron annihilation lifetime spectroscopy (PALS). Cation substitution in the spinel structure induces a higher number of oxygen vacancies. The increased number of surface defects and the synergistic effect between two incorporated metals provide a high activity in both the OER and ORR in the case of NiCo2O4 and ZnCo2O4. Especially, ZnCo2O4 exhibits the highest OER/ORR activity. The defect engineering with 0.1 M NaBH4 solution results in a metal-hydroxylated surface (M-OH) and enhanced the catalytic activity for the post-treated metal oxides in the ORR and OER. This fundamental investigation of the defective structure of the mixed metal oxides offers some useful insights into further development of highly active electrocatalysts through defect engineering methods.

Vacancy-Hydrogen Interaction in Niobium during Low-Temperature Baking.

A recently discovered modified low-temperature baking leads to reduced surface losses and an increase of the accelerating gradient of superconducting TESLA shape cavities. We will show that the dynamics of vacancy-hydrogen complexes at low-temperature baking lead to a suppression of lossy nanohydrides at 2 K and thus a significant enhancement of accelerator performance. Utilizing Doppler broadening Positron Annihilation Spectroscopy, Positron Annihilation Lifetime Spectroscopy and instrumented nanoindentation, samples made from European XFEL niobium sheets were investigated. We studied the evolution of vacancies in bulk samples and in the sub-surface region and their interaction with hydrogen at different temperature levels during in-situ and ex-situ annealing.

Structure and Properties of High­Strength Ti Grade 4 Prepared by Severe Plastic Deformation and Subsequent Heat Treatment.

Severe plastic deformation represented by three passes in Conform SPD and subsequent rotary swaging was applied on Ti grade 4. This process caused extreme strengthening of material, accompanied by reduction of ductility. Mechanical properties of such material were then tuned by a suitable heat treatment. Measurements of in situ electrical resistance, in situ XRD and hardness indicated the appropriate temperature to be 450 °C for the heat treatment required to obtain desired mechanical properties. The optimal duration of annealing was stated to be 3 h. As was verified by neutron diffraction, SEM and TEM microstructure observation, the material underwent recrystallization during this heat treatment. That was documented by changes of the grain shape and evaluation of crystallite size, as well as of the reduction of internal stresses. In annealed state, the yield stress and ultimate tensile stress decreased form 1205 to 871 MPa and 1224 to 950 MPa, respectively, while the ductility increased from 7.8% to 25.1%. This study also shows that mechanical properties of Ti grade 4 processed by continual industrially applicable process (Conform SPD) are comparable with those obtained by ECAP.

The Effect of Processing Route on Properties of HfNbTaTiZr High Entropy Alloy.

High entropy alloys (HEA) have been one of the most attractive groups of materials for researchers in the last several years. Since HEAs are potential candidates for many (e.g., refractory, cryogenic, medical) applications, their properties are studied intensively. The most frequent method of HEA synthesis is arc or induction melting. Powder metallurgy is a perspective technique of alloy synthesis and therefore in this work the possibilities of synthesis of HfNbTaTiZr HEA from powders were studied. Blended elemental powders were sintered, hot isostatically pressed, and subsequently swaged using a special technique of swaging where the sample is enveloped by a titanium alloy. This method does not result in a full density alloy due to cracking during swaging. Spark plasma sintering (SPS) of mechanically alloyed powders resulted in a fully dense but brittle specimen. The most promising result was obtained by SPS treatment of gas atomized powder with low oxygen content. The microstructure of HfNbTaTiZr specimen prepared this way can be refined by high pressure torsion deformation resulting in a high hardness of 410 HV10 and very fine microstructure with grain size well below 500 nm.

Microstructure and Room Temperature Mechanical Properties of Different 3 and 4 Element Medium Entropy Alloys from HfNbTaTiZr System.

Refractory high entropy alloys (HEA) are promising materials for high temperature applications. This work presents investigations of the room temperature tensile mechanical properties of selected 3 and 4 elements medium entropy alloys (MEA) derived from the HfNbTaTiZr system. Tensile testing was combined with fractographic and microstructure analysis, using scanning electron microscope (SEM), wavelength dispersive spectroscope (WDS) and X-Ray powder diffraction (XRD). The 5 element HEA alloy HfNbTaTiZr exhibits the best combination of strength and elongation while 4 and 3 element MEAs have lower strength. Some of them are ductile, some of them brittle, depending on microstructure. Simultaneous presence of Ta and Zr in the alloy resulted in a significant reduction of ductility caused by reduction of the BCC phase content. Precipitation of Ta rich particles on grain boundaries reduces further the maximum elongation to failure down to zero values.

Insights into Hydrogen Gas Environment-Promoted Nanostructural Changes in Stressed and Relaxed Palladium by Environmental Transmission Electron Microscopy and Variable-Energy Positron Annihilation Spectroscopy.

Environmental transmission electron microscopy (ETEM) and variable-energy positron annihilation spectroscopy (VEPAS) are used to observe hydrogen-induced microstructural changes in stress-free palladium (Pd) foils and stressed Pd thin films grown on rutile TiO2 substrates. The microstructural changes in Pd strongly depend on the hydrogen pressure and on the stress state. At room temperature, enhanced Pd surface atom mobility and surface reconstruction is seen by ETEM already at low hydrogen pressures ( pH < 10 Pa). The observations are consistent with molecular dynamics simulations. A strong increase of the vacancy density was found, and so-called superabundant vacancies were identified by VEPAS. At higher pressures, migration and vanishing of intrinsic defects is observed in Pd free-standing foils. The Pd thin films demonstrate an increased density of dislocations with increase of the H2 pressure. The comparison of the two studied systems demonstrates the influence of the mechanical stress on structural evolution of Pd catalysts.