Enhanced Solar‐to‐Hydrogen Generation with Broadband Epsilon‐Near‐Zero Nanostructured Photocatalysts

The direct conversion of solar energy into fuels or feedstock is an attractive approach to address increasing demand of renewable energy sources. Photocatalytic systems relying on the direct photoexcitation of metals have been explored to this end, a strategy that exploits the decay of plasmonic resonances into hot carriers. An efficient hot carrier generation and collection requires, ideally, their generation to be enclosed within few tens of nanometers at the metal interface, but it is challenging to achieve this across the broadband solar spectrum. Here the authors demonstrate a new photocatalyst for hydrogen evolution based on metal epsilon‐near‐zero metamaterials. The authors have designed these to achieve broadband strong light confinement at the metal interface across the entire solar spectrum. Using electron energy loss spectroscopy, the authors prove that hot carriers are generated in a broadband fashion within 10 nm in this system. The resulting photocatalyst achieves a hydrogen production rate of 9.5 µmol h^?1 cm^?2 that exceeds, by a factor of 3.2, that of the best previously reported plasmonic‐based photocatalysts for the dissociation of H₂ with 50 h stable operation.     

Influence of matrix material on flexural fatigue performance of unidirectional composites

A deflection-controlled flexural fatigue study of unidirectional glass fiber reinforced epoxy and vinyl ester composites was undertaken. Damage initiation and growth for various deflection levels were evaluated. Also, quantitative assessment of damage was made by monitoring stiffness loss in the composites as a function of fatigue cycles. Results show that the glass/epoxy composite has better performance compared with the glass/vinyl ester composite, especially at low deflection amplitudes. Fatigue behavior of the composites at low deflection amplitudes is found to be primarily influenced by matric and fiber-matrix interfacial damage in the form of longitudinal splitting.     

A novel infinite 1D covalent chain of end-to-end thiocyanato bridged heptacoordinated cadmium(II)Schiff base: π…π interaction and weak C–H…S hydrogen bonded supramolecule

A new Schiff base, N,N′-(bis(pyridin-2-yl)formylidene)ethane-1,2-diamine (bpfd) is prepared and used to synthesize a novel end-to-end thiocyanato bridged infinite 1D polymeric heptacoordinated cadmium(II) chain [Cd(bpfd)(μ_1,3-NCS)(NCS)]_n (1) which forms a 3D supramolecule through weak C–H…S hydrogen bonding and π…π interaction.     

Analysis of interfacial cracks in a TBC/superalloy system under thermal loading

Thermal barrier coatings (TBCs) provide thermal insulation to high temperature superalloys. Residual stresses develop in TBCs during cool down from processing temperatures and subsequent thermal cyclic loading due to the thermal expansion mismatch between the different layers (substrate, bond coat, and TBC). These residual stresses can initiate microcracks at the bond coat/TBC interface and can lead to debonding at the bond coat/TBC interface. The highest residual stresses occur at the interfaces. The effect of voids or crack like flaws at the interface can be responsible for initiating debonding and accelerate the oxidation process. The effect of interfacial microcracks has been investigated using the fracture mechanics approach. In particular, J-integral and the energy release rate G, for both mode I and mode II using the virtual crack extension method were evaluated. Two types of specimens were studied. The specimens were cooled down from processing temperature of 1000°C to 0°C. The variation of the properties as a function of temperature were used for the analysis. It was found that the use of temperature dependent properties in contrast to constant properties provide significantly different values of J-integral and G. For the stepped-disc specimen with an edge crack, crack growth is only due to mode II, while for the cylinder specimen with an internal crack, crack growth is due to mixed-mode loading. An important implication of this result is that edge delaminations in a disk specimen may only grow due to mode II conditions under pure thermal loading. Shear fracture characteristics of interfacial crack thus become important in the failure of the TBC.     

Himalayan waters at the crossroads: issues and challenges

The Hindu Kush Himalayas are called the water towers of Asia as they are the source of 10 major rivers and have the largest snow and ice deposits outside the two poles. Water emanating from the HKH provides food, energy and ecosystem services to up to 1.3 billion people. Climate change and socio-economic and demographic changes have put unprecedented pressure on these water resources, leading to uncertain supplies, increased demands and higher risks of extreme events like floods and droughts. The eight articles in this special issue highlight various dimensions of the Himalayan water resources by focusing on both physical and social science aspects of water management.     

Time-dependent behavior of adhesively bonded composite–composite beams under flexural loading

Abstract

Time-dependent behavior is characteristic of adhesively bonded structureswhen put under constant load (creep). In this study, adhesively bonded beam specimens prepared by adhesively bonding two unidirectional carbon fiber laminated beams were subjected to accelerated three-point bending creep tests. A three-point bending test was selected because of its simplicity and the fact that bending stresses tend to develop in structures under load even if not subjected to direct flexural load. The aim of this study is to predict the long-term behavior and to investigate the long-term creep response of the adhesively bonded composite system. The long-term creep behavior was predicted by time–temperature superposition principle (TTSP) and construction of the master curve at a reference temperature.     

Plant Regeneration and Somatic Embryogenesis from Immature Embryos Derived through Interspecific Hybridization among Different Carica Species

Plant regeneration and somatic embryogenesis through interspecific hybridization among different Carica species were studied for the development of a papaya ringspot virus-resistant variety. The maximum fruit sets were recorded from the cross of the native variety C. papaya cv. Shahi with the wild species C. cauliflora. The highest hybrid embryos were recorded at 90 days after pollination and the embryos were aborted at 150 days after pollination. The immature hybrid embryos were used for plant regeneration and somatic embryogenesis. The 90-day-old hybrid embryos from the cross of C. papaya cv. Shahi × C. cauliflora showed the highest percentage of germination, as well as plant regeneration on growth regulators free culture medium after 7 days pre-incubation on half-strength MS medium supplemented with 0.2 mg/L BAP, 0.5 mg/L NAA and 60 g/L sucrose. The 90-day-old hybrid embryos from the cross of C. papaya cv. Shahi × C. cauliflora produced maximum callus, as well as somatic embryos when cultured on half-strength MS medium containing 5 mg/L 2,4-D, 100 mg/L glutamine, 100 mg/L casein hydrolysate and 60 g/L sucrose. The somatic embryos were transferred into half-strength MS medium containing 0.5 mg/L BAP and 0.2 mg/L NAA and 60 g/L sucrose for maturation. The highest number of regenerated plants per hybrid embryo (10.33) was recorded from the cross of C. papaya cv. Shahi × C. cauliflora. Isoenzyme and dendrogram cluster analysis using UPGMA of the regenerated F₁ plantlets confirmed the presence of the hybrid plantlets.     

Characterization of Failed Surface of Ti and Imidex (PI) Film for Different Inter-layer Thicknesses of Ti Film

For miniaturized biomedical devices, laser joining of dissimilar materials offers excellent potential to make precise joints. An important system for consideration is titanium (Ti) coated glass joined with biocompatible imidex polyimide (PI). Metallic Ti with various thicknesses was deposited on top of pyrex 7740 borosilicate glass by using DC-magnetron sputtering deposition method. Effect of bond strength between Ti coated glass and imidex polyimide (PI), due to thickness variation of sputtered Ti coating was studied. Three different Ti inter-layer thicknesses were considered, 50, 200, and 400?nm. Tests results indicated that the thinner film produced lower shear strength and higher thickness produced higher shear strength. It has been observed that thicker film (200 and 400?nm) enhanced considerably the bond strength with enhancing the film roughness as well. Higher roughness resulted in more contact area at the interface, results higher number of chemical bonds and increased mechanical interlocking; which in turn increase the laser joint strength. For stronger bond with higher thickness, mixed mode failure was observed which included cohesive failure of polymer, interface failure of Ti/glass and failure on the glass itself. On the other hand, for weak bond with thinner film, mostly interface failure was observed for this system of Ti coated glass/imidex. For thicker film, chemical bond of Ti-C and Ti-O were observed. The role of both surface characteristics and chemical bonding for laser joints were investigated by using advanced techniques such as X-ray photoelectron spectroscopy, scanning electron microscopy, and energy dispersive spectroscopy.     

Regioselective Synthesis of Phenols and Halophenols from Arylboronic Acids Using Solid Poly(N‐vinylpyrrolidone)/ Hydrogen Peroxide and Poly(4‐vinylpyridine)/Hydrogen Peroxide Complexes

Solid hydrogen peroxide complexes based on poly(N‐vinylpyrrolidone) and poly(4‐vinylpyridine) were prepared and used as solid hydroxylating reagents. These solid hydrogen peroxide equivalents are found to be much safer, convenient and efficient reagent systems for the ipso‐hydroxylation of arylboronic acids to the corresponding phenols in high yields at a faster rate. The versatility of the reagents has been further expanded for the one‐pot synthesis of halophenols. Density functional theory calculations were carried out on hydrogen peroxide complexes of N‐ethylpyrrolidone and 4‐ethylpyridine as models to get a better understanding of structure and behavior of hydrogen peroxide complexes of the polymers poly(N‐vinylpyrrolidone) and poly(4‐vinylpyridine) compared to aqueous hydrogen peroxide.