Engineering Catalytically Active Sites by Sculpting Artificial Edges on MoS2 Basal Plane for Dinitrogen Reduction at a Low Overpotential

Engineering catalytically active sites have been a challenge so far and often relies on optimization of synthesis routes, which can at most provide quantitative enhancement of active facets, however, cannot provide control over choosing orientation, geometry and spatial distribution of the active sites. Artificially sculpting catalytically active sites via laser-etching technique can provide a new prospect in this field and offer a new species of nanocatalyst for achieving superior selectivity and attaining maximum yield via absolute control over defining their location and geometry of every active site at a nanoscale precision. In this work, a controlled protocol of artificial surface engineering is shown by focused laser irradiation on pristine MoS₂ flakes, which are confirmed as catalytic sites by electrodeposition of AuNPs. The preferential Au deposited catalytic sites are found to be electrochemically active for nitrogen adsorption and its subsequent reduction due to the S-vacancies rather than Mo-vacancy, as advocated by DFT analysis. The catalytic performance of Au-NR/MoS₂ shows a high yield rate of ammonia (11.43 × 10⁻⁸ mol s⁻¹ cm⁻²) at a potential as low as −0.1 V versus RHE and a notable Faradaic efficiency of 13.79% during the electrochemical nitrogen reduction in 0.1 m HCl.     

Numerical investigation of fatigue characteristics of concrete pavement

In concrete pavements, fatigue is one of the major causes of distress. Repeated loads result in the formation of cracks. The propagation of these cracks cause internal progressive damage within the structure, which ultimately leads to failure of the pavement due to fatigue. This paper presents a theoretical investigation of crack propagation within concrete pavement and its fatigue characteristics under cyclic loading. A numerical fatigue performance model has been developed for this purpose. The model is based on fictitious crack approach for the propagation of cracks and stress degradation approach for estimating the bridging stress under cyclic loading. Using the numerical model, a parametric study has been performed for a typical concrete pavement to evaluate its fatigue characteristics for different foundation strengths. The method can be used for prediction of crack propagation in concrete pavement under cyclic loading and gives an estimate of the incremental damage or the entire crack history of the pavement.     

MWCNT reinforced Polyamide-6,6 films: preparation,characterization and properties

Composite films of Polyamide-6,6 (PA66) and multi-walled carbon nanotubes (MWCNTs) were prepared by a combination of solution casting followed by compression molding techniques. Both unfunctionalized (u-MWCNTs) and functionalized nanotubes (f-MWCNTs) were used in this study. The functionalization involved direct solvent-free amination of MWCNTs with hexamethylenediamine. Thermogravimetric analysis was used to observe the changes in the nanotubes upon functionalization and morphological features of the resulting composite films were studied using scanning electron microscopy, transmission electron microscopy, and atomic force microscopy. The crystallinity changes by incorporation of the u-MWCNTs and f-MWCNTs in the PA66 matrix were studied by wide angle X-ray scattering and differential scanning calorimetry. The f-MWCNT/PA66 film showed an improvement of ∼43% in maximum tensile stress (MTS) and ∼32% in Young’s modulus over pristine PA66 film, while at a similar loading of 0.5 wt%, the f-MWCNT/PA66 film showed ∼15% increase in MTS and ∼16% increase in modulus over the u-MWCNT/PA66 film. Dynamic mechanical analysis indicated significant difference in the small-strain mechanical properties between the MWCNT-filled and unfilled PA66 at the very low MWNT loadings that were tested and supported the tensile results. The water absorption trend of the composite films showed dramatic improvement over the neat film.     

Prediction of Arsenic Removal by Electrocoagulation: Model Development by Factorial Design

Model was developed by two-level five-factor full-factorial designed-experiment to predict arsenic removal from contaminated water by electrocoagulation. Five factors, namely arsenic concentration (As), solution volume (V); current (I), electrode area (A), and current processing time (t) were investigated. Among the factors, arsenic concentration (As) and volume (V) have negative effect, and area (A), time (t), and current (I) have positive effect on arsenic removal. Within the studied levels of the factors, variance analysis at 5% significance level indicated that electrode area is not significant in arsenic removal by electrocoagulation. The model predicted reasonably good arsenic removal (error<2%) from low (0.288 mg/L) and high (0.882 mg/L) initial arsenic concentrations in presence of naturally cooccurring solutes in the groundwater. For the range of operating variables studied, optimum removal of arsenic (98.56%) is obtained at higher arsenic concentration (1.18 mg/L), lower volume (1 L), higher current (3 A), and higher current processing time (120 s).     

Restoration of pedicle screw fixation with an in situ setting calcium phosphate cement

STUDY DESIGN: Pedicle screws were pulled out of human cadaveric vertebrae before and after augmentation with polymethylmethacrylate or in situ-setting calcium phosphate cement. The fixation strength of screws augmented with calcium phosphate cement was compared with that of screws augmented with polymethylmethacrylate. OBJECTIVES: To determine whether a new in situ-setting calcium phosphate cement might be suitable for augmenting the fixation of pedicle screws. The principle objective was to compare the pull-out resistance of screws augmented with calcium phosphate cement with the pull-out behavior of screws augmented with polymethylmethacrylate. Polymethylmethacrylate augmentation was chosen as the standard because of its current clinical use. Five types of screws were tested to determine whether screw design had an effect on the efficacy of augmentation. SUMMARY OF BACKGROUND DATA: Although many factors affect the pull-out resistance of pedicle screws, a key determinant of their performance is the strength of their attachment to the spine. In elderly, osteopenic patients, the screw-bone interface is especially at risk for stripping during insertion or pull-out after surgery. In these patients, polymethylmethacrylate has been used to augment pedicle screw fixation, although its use is not without risk. In situ-setting calcium phosphate cements may provide an alternative to polymethylmethacrylate in this application. Like polymethylmethacrylate, calcium phosphate cements can be injected into the prepared screw hole. They have the added advantage of being resorbed and replaced during healing and normal bone remodeling. METHODS: Thirty human lower lumbar vertebrae (L3-L5) were implanted bilaterally with one of five types of pedicle screws (n = 6 for each screw type). The screws were pulled out 3.0 mm at 0.25 mm/sec with a servohydraulic materials testing machine. The 3.0-mm pull-out distance, which was slightly longer than one thread pitch, was designed to strip the screw-bone interface but to leave the pedicle otherwise intact. After the initial testing, the screws in each vertebrae were removed, and the screw tracks were filled with 2.0 cc of polymethylmethacrylate (one side) or calcium phosphate cement (contralateral side). After augmentation, the screws were reinserted, and the cements were allowed to harden for 24 hours. Postaugmentation testing followed the protocols for preaugmentation testing, and the pull-out resistance of screws augmented with calcium phosphate cement was compared with the pull-out resistance of screws augmented with polymethylmethacrylate. RESULTS: Mechanically, calcium phosphate cement compared favorably with polymethylmethacrylate for augmenting pedicle screws. Both restored the strength of the screw-bone interface: across all screw types, the average increase in pull-out strength was 147% with polymethylmethacrylate augmentation and 102% with calcium phosphate cement. There were no significant differences because of screw type with either type of augmentation. CONCLUSIONS: The in situ-setting calcium phosphate cement investigated in this study compared favorably with polymethylmethacrylate in a single-cycle, pull-out test of augmented pedicle screws in senile trabecular bone. With further evaluation, this cement may offer an alternative to polymethylmethacrylate for the enhancement of pedicle screw fixation clinically.     

Factorial Design Approach to Investigate the Effects of Groundwater Cooccurring Solutes on Arsenic Removal by Electrocoagulation

Effects of groundwater cooccurring solutes such as phosphate (PO4), silicate (SiO3), bicarbonate (HCO3), calcium (Ca), and iron (Fe) on arsenic removal were investigated in this study. Investigation by two-level full-factorial designed experiments revealed that PO4 and SiO3 have negative effect on arsenic removal, whereas HCO3 has negligible positive effect. The effects of Ca and Fe present in groundwater have positive effect on arsenic removal by electrocoagulation (EC). Hypothesis testing at 5% significance level suggests that alkalinity (HCO3) is not an important parameter in arsenic removal by EC in naturally occurring pH range of water.     

Aerodynamic heating of ballistic missile including the effects of gravity

The aerodynamic heating of a ballistic missile due to only convection is analysed taking into consideration the effects of gravity. The amount of heat transferred to the wetted area and to the nose region has been separately determined, unlike A Miele’s treatise without consideration of gravity. The peak heating rates to the wetted area and to the nose of the missile are also investigated. Finally four numerical examples are cited to estimate the errors, in heat transfers and heating rates to both wetted area and nose region of the missile, arising out of neglecting the gravitational forces.     

Numerical models of creep and boundary sliding mechanisms in single-phase, dual-phase, and fully lamellar titanium aluminide

Finite element simulations of the high-temperature behavior of single-phase γ, dual-phase α₂+γ, and fully lamellar (FL) α₂+γTiAl intermetallic alloy microstructures have been performed. Nonlinear viscous primary creep deformation is modeled in each phase based on published creep data. Models were also developed that incorporate grain boundary and lath boundary sliding in addition to the dislocation creep flow within each phase. Overall strain rates are compared to gain an understanding of the relative influence each of these localized deformation mechanisms has on the creep strength of the microstructures considered. Facet stress enhancement factors were also determined for the transverse grain facets in each model to examine the relative susceptibility to creep damage. The results indicate that a mechanism for unrestricted sliding of γ lath boundaries theorized by Hazzledine and co-workers leads to unrealistically high strain rates. However, the results also suggest that the greater creep strength observed experimentally for the lamellar microstructure is primarily due to inhibited former grain boundary sliding (GBS) in this microstructure compared to relatively unimpeded GBS in the equiaxed microstructures. The serrated nature of the former grain boundaries generally observed for lamellar TiAl alloys is consistent with this finding.     

Delineation of Groundwater Potential Zones of Coastal Groundwater Basin Using Multi-Criteria Decision Making Technique

Delineation of groundwater potential zones (GWPZ) has been performed for a coastal groundwater basin of eastern India. The groundwater potential zone index (GWPZI) map is generated by using Analytic Hierarchy Process (AHP) from different influencing features, e.g., Land Use/Land Cover (LU/LC), soil (S), geomorphology (GM), hydrogeology (HG), surface geology (SG), recharge rate (RR), drainage density (DD), rainfall (RF), slope (Sl), surface water bodies (SW), lineament density (LD), and Normalized Difference Vegetative Index (NDVI). Recharge rate values are estimated from hydrological water balance model. Overlay weighted sum method is used to integrate all thematic feature maps to generate GWPZ map of the study area. Four zones have been identified for the coastal groundwater basin [very good: 36.39 % (273.53 km², good: 43.57 % (327.47 km²), moderate: 18.27 % (137.30 km²), and poor: 1.77 % (13.27 km²)]. Areas in north to south-west and south-east direction show very good GWPZ due to the presence of low drainage density. GWPZ map and well yield values show good agreement. Sensitivity analysis reveals that exclusion/absence of rainfall and lineament density increases the poor groundwater potential zones. Omission of hydrogeology, soils, surface geology, and NDVI show maximum increase in good GWPZ. Obtained GWPZ map can be utilized effectively for planning of sustainable agriculture. This analysis demonstrates the potential applicability of the methodology for a general coastal groundwater basin.