The Interplay of Interstitial and Substitutional Copper in Zinc Oxide

Cu impurities are reported to have significant effects on the electrical and optical properties of bulk ZnO. In this work, we study the defect properties of Cu in ZnO using hybrid quantum mechanical/molecular mechanical (QM/MM)–embedded cluster calculations based on a multi-region approach that allows us to model defects at the true dilute limit, with polarization effects described in an accurate and consistent manner. We compute the electronic structure, energetics, and geometries of Cu impurities, including substitutional and interstitial configurations, and analyze their effects on the electronic structure. Under ambient conditions, CuZn is the dominant defect in the d9 state and remains electronically passive. We find that, however, as we approach typical vacuum conditions, the interstitial Cu defect becomes significant and can act as an electron trap.

Atomistic Assessment of Solute-Solute Interactions during Grain Boundary Segregation

Grain boundary solute segregation is becoming increasingly common as a means of stabilizing nanocrystalline alloys. Thermodynamic models for grain boundary segregation have recently revealed the need for spectral information, i.e., the full distribution of environments available at the grain boundary during segregation, in order to capture the essential physics of the problem for complex systems like nanocrystalline materials. However, there has been only one proposed method of extending spectral segregation models beyond the dilute limit, and it is based on simple, fitted parameters that are not atomistically informed. In this work, we present a physically motived atomistic method to measure the full distribution of solute-solute interaction energies at the grain boundaries in a polycrystalline environment. We then cast the results into a simple thermodynamic model, analyze the Al(Mg) system as a case study, and demonstrate strong agreement with physically rigorous hybrid Monte Carlo/molecular statics simulations. This approach provides a means of rapidly measuring key interactions for non-dilute grain boundary segregation for any system with an interatomic potential.

Thermophysical Properties of Mixtures of Thorium and Uranium Nitride

The miscibility, lattice parameter, and thermophysical properties of (Th0.2U0.8)N and (Th0.5U0.5)N have been investigated. It is shown that additions of thorium nitride (ThN) to uranium nitride (UN) increases the thermophysical performance of the mixed nitride fuel form in comparison to reference UN. In the more dilute limit, additions of ThN serve as a burnable neutronic poison and reduces the change in keff over the lifecycle of the fuel. At higher concentrations, additions of ThN serve as a significant fertile source of 233U. Where appropriate, comparisons to previous work on UN + PuN mixtures are made, as this is a comparable fuel form for potential fast reactor concepts, and a suitable point of contrast in the possible design space afforded by mixed (ThxU1 − x)N fuel forms. The data from this work are the input parameters for finite element modeling of the temperature distribution in a compact reactor. The results of modeling and simulation of this core design are shown for the case of steady-state operation and during double, adjacent heat pipe failure.

Thermochemistry of Polonium Evaporation from LBE

Polonium is formed in relatively large quantities in lead-bismuth eutectic (LBE) cooled nuclear systems. Because of its radiotoxicity and volatility, a good understanding of the chemical equilibria governing polonium release from LBE is required. In this work, a set of thermochemical data is derived for the chemical species involved in the equilibrium between a solution of polonium in LBE and its vapor in inert conditions. The data were obtained by matching thermochemical models with experimental vapor pressure measurements and ab initio results. The dilute-limit activity coefficient of dissolved polonium in LBE is estimated, as well as the solubility of solid lead polonide in LBE. The results indicate that polonium evaporates from LBE according to the experimentally determined Henry’s law, up to dissolved polonium concentrations well above that expected in LBE cooled nuclear systems.

Self-diffusion in nanofluids of nonelongated particles in the dilute limit

The dynamic features of a dilute suspension of nanoparticles (nanofluid) are fully modified depending on the dominant particles slip mechanism acting in the suspension. Self-diffusion effects in highly sheared diluted suspensions (entrance conditions and microapplications) can lead to a particles distribution fully different from the bulk one. The reported investigation proposes a model to determine the self-diffusion of three-planes symmetric nonelongated particles inmersed in a sheared Stokes flow. The model is based on the real displacements between any pair of particles and an statistical approach to determine contact kinematic irreversibilities. According to the proposed model, the source of hydrodynamic irreversibility is closely related to the particles shape. This is clearly demonstrated through the application of the model to cubic particles. The main conclusion is that the particles shape plays a significant role in the dynamic behavior of the suspension and, as a result, in the self-diffusion coefficient. The reported results arising from the cubic particles trajectories in a Stokes flow are reasonably close to the ones reported by Brady and Morris (J Fluid Mech, 348:103–139, 1997) for suspensions under high Pe number, and Zarraga and Leighton (Phys Fluids 13(3):565-577, 2001).

The Boltzmann distribution and molecular gases

“The Boltzmann distribution and molecular gases” explains why an “ordinary” gas has its molecules Boltzmann-distributed. The most concentrated Fermi–Dirac gas, helium 3 at its boiling point, is still in a “dilute limit”, dilute enough to be approximately Boltzmann. Similarly, the most concentrated Bose–Einstein gas, helium 4 at its boiling point, is also approximately Boltzmann.

Impact of interstitial impurities on the trapping of dislocation loops in tungsten

Ab initio simulations are employed to assess the interaction of typical interstitial impurities with self-interstitial atoms, dislocation loops and edge dislocation lines in tungsten. These impurities are present in commercial tungsten grades and are also created as a result of neutron transmutation or the plasma in-take process. The relevance of the study is determined by the application of tungsten as first wall material in fusion reactors. For the defects with dislocation character, the following ordering of the interaction strength was established: H < N < C < O < He. The magnitude of the interaction energy was rationalized by decomposing it into elastic (related to the lattice strain) and chemical (related to local electron density) contributions. To account for the combined effect of impurity concentration and pinning strength, the impact of the presence of these impurities on the mobility of isolated dislocation loops was studied for DEMO relevant conditions in the non-elastic and dilute limit.

Accurate Prediction of Deprotonation and pH value of Acids in Aqueous Solutions over the Whole Concentration Range

The pKa of an acid is important for determining the dissociation and thermodynamic properties of solutions containing it. However, the value of pKa is typically determined at dilute limit and cannot be used to describe properties of the solution at high concentrations. In this work, we propose an approach to determine the concentration independent equilibrium constant Keq based on pKa and predicted activity coefficients. The Keq determined is applied to predict the degree of dissociation over whole concentration range for weak to strong acids. The pH of acid aqueous solution is predicted over whole concentration range, showing a good agreement with experiments. Based on this approach, we found that the vapor pressures of acid aqueous solutions strongly depend on the degree of dissociation of acids. The proposed model provides useful insights to link the macroscopic properties of acid aqueous solutions to its microscopic dissociation phenomena over the whole concentration range.

Cyclic dynamics of misfires and partial burns in a dilute spark-ignition engine

This study investigates the cyclic dynamics of cumulative heat release data past the edge of stability in a dilute spark-ignition engine. Emphasis is placed on analyzing the cyclic dynamics near the dilute limit where partial burns and misfires are frequent. These events are often followed by a higher-energy cycle due to the feed-forward mechanism present in the residual gases. These patterns are deterministic and increase the coefficient of variation to undesirable levels. Symbol sequence analysis was used to investigate the cyclic dynamics of these low–high patterns. The heat release was partitioned on an energy basis to give physical meaning to each partition and each sequence created when analyzing the symbol sequence results. This partitioning method provided insight into the differences in the dynamics when operating in the misfire or partial burn regime. These differences could impact the control method used.