ABSTRACT
An aqueous electrochemically controlled host-guest encapsulation system demonstrates a large and synthetically tunable redox entropy change. Electrochemical entropy is the basis for thermally regenerative electrochemical cycles (TRECs), which utilize reversible electrochemical processes with large molar entropy changes for thermogalvanic waste-heat harvesting and electrochemical cooling, among other potential applications. A supramolecular host-guest system demonstrates a molar entropy change of 4 times that of the state-of-the-art aqueous TREC electrolyte potassium ferricyanide. Upon encapsulation of a guest, water molecules that structurally resemble amorphous ice are displaced from the host cavity, leveraging a change in the degrees of freedom and ordering of the solvent rather than the solvation of the redox-active species to increase entropy. The synthetic tunability of the host allows rational optimization of the system's ΔS, showing a range of -51 to -101 cal mol-1 K-1 (-2.2 to -4.4 mV K-1) depending on ligand and metal vertex modifications, demonstrating the potential for rational design of high-entropy electrolytes and a new strategy to overcome theoretical limits on ion solvation reorganization entropy.
ABSTRACT
The unique microstructure of the alloy AlSi10Mg produced by the laser-based powder bed fusion of metals (PBF-LB/M) provides high-strength and high-strain-hardening capabilities of the material. The microstructure and mechanical properties of 3D-printed, i.e., additively manufactured, AlSi10Mg are significantly altered by post-building heat-treatment processes applied in order to tailor the final properties of the parts. Using an accurate computational model to predict and improve the mechanical performance of 3D-printed samples considering their microstructural features can accelerate their employment in envisaged applications. The present study aims to investigate the correlation between microstructural features and the mechanical behavior of as-built, direct-aged, and T6 heat-treated samples of PBF-LB/M AlSi10Mg under tensile loading using experiment and microstructure-sensitive modeling approaches. Nanoindentation tests are used to calibrate the parameters of the constitutive models for the Al and Si-rich phases. The experimental investigations revealed that heat treatment significantly changes the sub-grain morphology of the Si-rich phase, and this can have a considerable effect on the mechanical behavior of the components. The effect of the modeling of the Si-rich phase in the representative volume elements on the prediction of mechanical behavior is investigated using the J2 plasticity model. The combination of the crystal plasticity model for Al and the J2 plasticity model for the Si-rich phase is used to predict the tensile properties of the as-built and heat-treated states. The predicted results are in good agreement with the experimental results. This approach can be used to understand the microstructure-property relationship of PBF-LB/M AlSi10Mg and eventually tailor heat treatment for PBF-LB/M AlSi10Mg based on the requirement of the application.
ABSTRACT
We study the thermal conductivity of diameter-modulated Si nanowires to understand the impact of different nanoscale transport mechanisms as a function of nanowire morphology. Our investigation couples transient suspended microbridge measurements of diameter-modulated Si nanowires synthesized via vapor-liquid-solid growth and dopant-selective etching with predictive Boltzmann transport modeling. We show that the presence of a low thermal conductivity phase (i.e., porosity) dominates the reduction in effective thermal conductivity and is supplemented by increased phonon-boundary scattering. The relative contributions of both mechanisms depend on the details of the nanoscale morphology. Our findings provide valuable insights into the factors that govern thermal conduction in complex nanoscale materials.
ABSTRACT
Betavoltaic energy converters (i.e., ß-batteries) are attractive power sources because of their potential for high energy densities (>200 MWh/kg) and long duration continuous discharge (>1 year). However, conversion efficiencies have been historically low (<3%). High efficiency devices can be achieved by matching ß-radiation transport length scales with the device physics length scales. In this work, the efficiency of c-Si devices using high-energy (>1 MeV) electrons emitted from 90Sr as a power source is investigated. We propose a design for a >10% efficient betavoltaic device, which generates 1 W of power. A Varian Clinac iX is used to simulate the high-energy electrons emitted from 90Sr, and a high efficiency c-Si photovoltaic cell is used as the converter. The measured conversion efficiency is 16%. This relatively high value is attributed to proper length scale matching and the generation of secondary electrons in c-Si by the primary ß-particles.
