The ability to rapidly screen material performance in the vast space of high entropy alloys is of critical importance to efficiently identify optimal hydride candidates for various use cases. Given the prohibitive complexity of first principles simulations and large-scale sampling required to rigorously predict hydrogen equilibrium in these systems, we turn to compositional machine learning models as the most feasible approach to screen on the order of tens of thousands of candidate equimolar high entropy alloys (HEAs). Critically, we show that machine learning models can predict hydride thermodynamics and capacities with reasonable accuracy (e.g. a mean absolute error in desorption enthalpy prediction of ∼5 kJ molH2−1) and that explainability analyses capture the competing trade-offs that arise from feature interdependence. We can therefore elucidate the multi-dimensional Pareto optimal set of materials, i.e., where two or more competing objective properties can't be simultaneously improved by another material. This provides rapid and efficient down-selection of the highest priority candidates for more time-consuming density functional theory investigations and experimental validation. Various targets were selected from the predicted Pareto front (with saturation capacities approaching two hydrogen per metal and desorption enthalpy less than 60 kJ molH2−1) and were experimentally synthesized, characterized, and tested amongst an international collaboration group to validate the proposed novel hydrides. Additional top-predicted candidates are suggested to the community for future synthesis efforts, and we conclude with an outlook on improving the current approach for the next generation of computational HEA hydride discovery efforts.
The use of an electrochemical dissolution process is shown to remove the recast layer contamination from the surfaces of electrical-discharge-machining cut components, as well as the interior exposed surfaces of the structure. The solution chemistry, cell potential, and exposure time are all relevant interdependent variables. Optimization of the electrode geometry should be made for each type of component. For the case of Cu-Zn recast contamination of 300-series alloy components, surface composition analysis indicates that complete electrochemical dissolution is achieved using a dilute solution of nitric acid (HNO3). For example, electrochemical dissolution of the Cu-Zn recast is accomplished at 1.2 V cell potential using a 20% nitric solution and an exposure time of 4 h. The use of a nitric acid bath was specifically chosen since it’s chemically compatible and will not degrade the host alloy or the component. In sum, an electrochemically driven dissolution process can be tailored to remove of the recast contamination without affecting the integrity of the host component structure and its dimensional tolerances.
Liquid organic hydrogen carriers such as alcohols and polyols are a high-capacity means of transporting and reversibly storing hydrogen that demands effective catalysts to drive the (de)hydrogenation reactions under mild conditions. We employed a combined theory/experiment approach to develop MOF-74 catalysts for alcohol dehydrogenation and examine the performance of the open metal sites (OMS), which have properties analogous to the active sites in high-performance single-site catalysts and homogeneous catalysts. Methanol dehydrogenation was used as a model reaction system for assessing the performance of five monometallic M-MOF-74 variants (M = Co, Cu, Mg, Mn, Ni). Co-MOF-74 and Ni-MOF-74 give the highest H2 productivity. However, Ni-MOF-74 is unstable under reaction conditions and forms metallic nickel particles. To improve catalyst activity and stability, bimetallic (NixMg1-x)-MOF-74 catalysts were developed that stabilize the Ni OMS and promote the dehydrogenation reaction. An optimal composition exists at (Ni0.32Mg0.68)-MOF-74 that gives the greatest H2 productivity, up to 203 mL gcat-1 min-1 at 300 °C, and maintains 100% selectivity to CO and H2 between 225-275 °C. The optimized catalyst is also active for the dehydrogenation of other alcohols. DFT calculations reveal that synergistic interactions between the open metal site and the organic linker lead to lower reaction barriers in the MOF catalysts compared to the open metal site alone. This work expands the suite of hydrogen-related reactions catalyzed by MOF-74 which includes recent work on hydroformulation and our earlier reports of aryl-ether hydrogenolysis. Moreover, it highlights the use of bimetallic frameworks as an effective strategy for stabilizing a high density of catalytically active open metal sites. This journal is
Joint EPRI-123HiMAT International Conference on Advances in High-Temperature Materials - Proceedings from EPRI's 9th International Conference on Advances in Materials Technology for Fossil Power Plants and the 2nd International 123HiMAT Conference on High-Temperature Materials
Structural alloy corrosion is a major concern for the design and operation of supercritical carbon dioxide (sCO2) power cycles. Looking towards the future of sCO2 system development, the ability to measure real-time alloy corrosion would be invaluable to informing operation and maintenance of these systems. Sandia has recently explored methods available for in-situ alloy corrosion monitoring. Electrical resistance (ER) was chosen for initial tests due the operational simplicity and commercial availability. A series of long duration (>1000 hours) experiments have recently been completed at a range of temperatures (400-700oC) using ER probes made from four important structural alloys (C1010 Carbon Steel, 410ss, 304L, 316L) being considered for sCO2 systems. Results from these tests are presented, including correlations between the probe measured corrosion rate to that for witness coupons of the same alloys.
The moisture absorption behavior of two fiber reinforced composite materials was evaluated in a unidirectional manner The flat materials were exposed to varying humidity and temperature conditions inside of an environmental chamber in order to determine their effective moisture equilibrium (M m ) and moisture absorption rate (D z ). Two-ply (thin) and four-ply (thick) materials were utilized to obtain M,,, and Dz, respectively. The results obtained from laboratory work were then compared to modeling data to better understand the material properties. Predictions capabilities were built to forecast the maximum moisture content, time required for saturation, and the moisture content at any given humidity and temperature. A case study was included to demonstrate this capability. Also of interest were cubed samples to investigate directionality preferences in water immersion studies. Several coatings were evaluated for their water permeation properties. Further dissemination authorized to the Department of Energy and DOE contractors only; other requests shall be approved by the originating facility or higher DOE programmatic authority.
Titanium alloys such as Ti-6Al-4V and Ti-6Al-7Nb are widely used in the biomedical industry as structural implant materials. The strain-rate sensitivity of tensile strength is now assessed using a modified Kocks-Mecking formulation for hardening. The operative scale of the microstructural strengthening is designated by the coefficieint cb that can be determined from measurements of plastic strain, yield and ultimate strength. It is found that although that strength varies slightly with strain rate, the scale of the microstructure cb remains nearly constant for each material. Finally, a low cb-value of 14 is computed for Ti-6Al-4V that is consistent with the refined twophase microstructure needed to enhance both ductility beyond yielding and its ultimate strength.
In order to design a thermoelectric (TE) module suitable for long-term elevated temperature use, the Department 8651 has conducted parametric experiments to study material compatibility and thermal aging of TE materials. In addition, a comprehensive material characterization has been preformed to examine thermal stability of P- and N-based alloys and their interaction with interconnect diffusion barrier(s) and solder. At present, we have completed the 7-days aging experiments for 36 tiles, from ambient to 250 C. The thermal behavior of P- and N-based alloys and their thermal interaction with both Ni and Co diffusion barriers and Au-Sn solder were examined. The preliminary results show the microstructure, texture, alloy composition, and hardness of P-(Bi,Sb){sub 2}Te{sub 3} and N-Bi{sub 2}(Te,Se){sub 3} alloys are thermally stable up to 7 days annealing at 250 C. However, metallurgical reactions between the Ni-phosphor barriers and P-type base alloy were evident at temperatures {ge} 175 C. At 250 C, the depth (or distance) of the metallurgical reaction and/or Ni diffusion into P-(Bi,Sb){sub 2}Te{sub 3} is approximately 10-15 {micro}m. This thermal instability makes the Ni-phosphor barrier unsuitable for use at temperatures {ge} 175 C. The Co barrier appeared to be thermally stable and compatible with P(Bi,Sb){sub 2}Te{sub 3} at all annealing temperatures, with the exception of a minor Co diffusion into Au-Sn solder at {ge} 175 C. The effects of Co diffusion on long-term system reliability and/or the thermal stability of the Co barrier are yet to be determined. Te evaporation and its subsequent reaction with Au-Sn solder and Ni and Co barriers on the ends of the tiles at temperatures {ge} 175 C were evident. The Te loss and its effect on the long-term required stoichiometry of P-(Bi, Sb){sub 2}Te{sub 3} are yet to be understood. The aging experiments of 90 days and 180 days are ongoing and scheduled to be completed in 30 days and 150 days, respectively. Material characterization activities are continuing for the remaining tiles.