Highly efficient and stable lead-free cesium copper halide perovskites for optoelectronic applications: A DFT based study.

Recently synthesized industrially significant perovskites Cs3Cu2X5 (X=Cl,Br,I) are subjected to a density functional theory (DFT) investigation utilizing the CASTEP code. This study explores various physical features, including structural, optical, thermodynamic, elastic, mechanical, and electronic properties. There is a strong correlation between the optimized structure parameters and the existing experimental data, which demonstrates the reliability of our DFT-based computations. The band structure and density of states (TDOS and PDOS) analysis revealed that all the studied perovskites are direct band gap semiconductors, and Cs3Cu2Br5 has the smallest band gap (2.092 eV). We also discussed the mechanical and cell stability using the Born stability criterion and formation energy, respectively. The mechanical and dynamic stability of each phase is confirmed by the analysis of the elastic constants. According to the computed values of Pugh's and Poisson's ratios as well as Cauchy's pressure, all of the studied compounds are ductile in nature. The study of density of states, total charge density, and Mulliken atomic populations reveal that all the compounds have complex bonding with both ionic and covalent properties. Finally, utilizing the elastic constant data, the Debye temperatures of Cs3Cu2Cl5, Cs3Cu2Br5, and Cs3Cu2I5 have been determined as 82.90 K, 100.00 K, and 80.70 K, respectively. The analysis of thermodynamics (relatively low values of both ΘD and Kmin) as well as optical properties indicate that all the investigated materials have the potential to serve as thermal barrier coating (TBC) materials.

Exploring the governing transport mechanisms of corrosive agents in a Canadian deep geological repository.

All nuclear energy producing nations face a common challenge associated with the long-term solution for their used nuclear fuel. After decades of research, many nuclear safety agencies worldwide agree that deep geological repositories (DGRs) are appropriate long-term solutions to protect the biosphere. The Canadian DGR is planned in either stable crystalline or sedimentary host rock (depending on the final site location) to house the used nuclear fuel in copper-coated used fuel containers (UFCs) surrounded by highly compacted bentonite. The copper-coating and bentonite provide robust protection against many corrosion processes anticipated in the DGR. However, it is possible that bisulfide (HS-) produced near the host rock-bentonite interface may transport through the bentonite and corrode the UFCs during the DGR design life (i.e., one million years); although container performance assessments typically account for this process, while maintaining container integrity. Because the DGR design life far exceeds those of practical experimentation, there is a need for robust numerical models to forecast HS- transport. In this paper we present the development of a coupled 3D thermal-hydraulic-chemical model to explore the impact of key coupled physics on HS- transport in the proposed Canadian DGR. These simulations reveal that, although saturation delayed and heating accelerated HS- transport over the first 100s and 10,000s of years, respectively, these times of influence were small compared to the long DGR design life. Consequently, the influence from heating only increased total projected HS- corrosion by <20% and the influence from saturation had a negligible impact (<1%). By comparing the corrosion rate results with a simplified model, it was shown that nearly-steady DGR design parameters governed most of the projected HS- corrosion. Therefore, those parameters need to be carefully resolved to reliably forecast the extent of HS- corrosion.

Subsurface transport of carboxymethyl cellulose (CMC)-stabilized nanoscale zero valent iron (nZVI): Numerical and statistical analysis.

Subsurface remediation using nanoscale zero valent iron (nZVI) is a promising in-situ technology that can transform certain groundwater contaminants into non-toxic compounds. However, field scale implementation of nZVI technology has faced major challenges due to poor subsurface mobility, limited longevity and well clogging, all leading to a shorter nZVI travel distance. This distance nZVI travels in the subsurface is an important parameter since it influences the amount of contaminants that can be reached and thereby remediated. There are several factors which may affect nZVI travel distance such as groundwater velocity, injection concentration and rate, lag period (duration when nZVI injection is stopped), solution viscosity, and subsurface heterogeneity. Although various studies have been performed to reveal the effect of different factors on nZVI transport in homogeneous domains, few studies have focused on heterogeneous media, which is more representative of field conditions. In this study, a statistical analysis was performed using a two-dimensional numerical model which simulated carboxymethyl cellulose (CMC) stabilized nZVI transport in randomly distributed soil permeability fields of two aquifers to examine the factors that have the greatest impact on nZVI travel distance. Among all possible factors, field scale solution viscosity and injection rate had a statistically significant effect on nZVI travel distance in both the horizontal and vertical directions, as well as, on the attached mass. Additionally, the lag period between injections had a statistically significant effect on the attached mass, but not the travel distance. These results suggest that having a long injection period followed by a short lag phase during field deployment may result in less nZVI attachment. Lastly, aquifer heterogeneity impacted the nZVI spread while the impact of intrinsic groundwater velocity and injection concentration was found not to be statistically significant. Results from this numerical study can aid in field-scale CMC-nZVI injection by identifying key factors for remediation optimization.