Microstructure,mechanical, tribological,and oxidizing properties of AlCrSiN/AlCrVN/AlCrNbN multilayer coatings with different modulated thicknesses

Multilayer structure design is one of the most promising methods for improving the comprehensive performance of AlCrN-based hard coatings applied to cutting tools. In this study, four types of AlCrSiN/AlCrVN/AlCrNbN multilayer coatings, with different modulated thicknesses, were deposited to investigate their microstructure, mechanical, tribological, and oxidizing properties. All multilayer coatings exhibited grain growth along the crystallographic plane of (200) with a NaCl-type face-centered cubic (FCC) structure. The results show that, as the modulation thickness decreases from ～35 nm to ～10 nm, (1) the grain refinement effect is increasingly evident; (2) all multilayer coatings show a hardness of >30 GPa and an elastic modulus of >300 GPa. Both the ability to resist elastic strain to failure and the plastic deformation of multilayer coatings increase. In addition, their resistance to cracking reduces; (3) the wear rates of these multilayer coatings reduce successively from 1.78 × 10^?16 m³ N^?1 m^?1 to 7.7 × 10^?17 m³ N^?1 m^?1. This is attributed to an increase in self-lubricating VO_x and a decrease in adhesives from the counterparts; (4) the best high-temperature oxidation resistance was obtained for the multilayer coating with a modulated thickness of ～15 nm.     

Essential (Mg,Fe, Zn and Cu) and Non-Essential (Cd and Pb) Elements in Predatory Insects (Vespa crabro and Vespa velutina): A Molecular Perspective

The recent introduction of the Asian yellow-legged hornet, Vespa velutina, into Europe has raised concern regarding the threat to honeybees and the competition with the European hornet, Vespa crabro. The aim of this study was to investigated essential (Mg, Fe, Zn, Cu) and non-essential (Cd and Pb) elements in these two species. Element concentrations were determined in the whole body and separately in the head, thorax and abdomen using atomic absorption spectrometry (AAS). The changes in essential element concentration and speciation during metamorphosis were also studied using size exclusion chromatography followed by AAS and proteomic analysis. In both species, the essential elements were more concentrated in the abdomen due to the presence of fat bodies. Magnesium, Fe and Zn concentrations were significantly higher in V. crabro than in V. velutina and could have been related to the higher aerobic energy demand of the former species required to sustain foraging flight. Low concentrations of Cd and Pb were indicative of low environmental exposure. The concentration and speciation of essential elements, particularly Fe, varied among the developmental stages, indicating a modification of ligand preferences during metamorphosis. Overall, the results in the present study provide a better understanding of the hornet metal metabolism and a foundation for additional studies.     

Fabrication of oxide-based near infrared-shielding coatings for a smart window to prevent infrared-induced photoaging in human skin

Oxide-based near infrared (IR)-shielding coatings consisting of quarter‐wave stacks of oxygen-deficient tantalum oxide (Ta₂O_5?x) and silicon oxide (SiO₂) multilayers and tin-doped indium oxide (In₂O₃) (ITO) films with the thicknesses of 200–600 nm can block the passage of IR-A (wavelength: 760–1400 nm) and IR-B (wavelength: 1400–3000 nm) radiation, respectively. In this study, the optical properties and microstructure of these oxide-based IR-shielding coatings were investigated. Transmission electron microscopy images indicated that amorphous Ta₂O_5?x/amorphous SiO₂ multilayers were uniform and dense. ITO films were found to be highly crystalline and show carrier concentrations of up to 7.1 × 10²⁰ cm^?3, resulting in the strong IR-B optical absorption due to the plasma excitation of the free carriers. Oxide-based IR-shielding coatings with an ITO thickness of 420 nm were found to have near-IR shielding rates of >90% and an average visible light transmittance of >70%. The effects of IR on human keratinocytes were studied to evaluate the IR-induced photoaging in human skin. It was found that the downregulation of cellular proliferation and the enhancement of senescence-associated β-galactosidase activity induced by IR irradiation were significantly inhibited by oxide-based IR-shielding coatings. Thus, this study provides a facile method for the development of coatings for smart windows with high IR-shielding ability and high visible light transmittance.     

Investigation of the changes in physical properties of PES/PVC fabrics after aging

The aim of this work was to investigate the physical and mechanical performance of architectural polyester (PES)–poly(vinyl chloride) (PVC) membranes exposed to different artificial aging conditions. Two commercially available architectural membranes were chosen as research objects. The durability of the PES/PVC fabrics was evaluated by the loss in mechanical performance, scanning electron microscopy, and X-ray diffraction analysis in order to understand the effect of the degradation agents on the surface of the membranes. The mechanical performance of the PES/PVC membranes was unchanged. Scanning electron microscopy images of the tested materials showed initial cracks after aging. The X-ray fluorescence analysis showed that at the time of aging, the amount of Cl and Si decreased slightly, while Ti decreased by half, and Ca by volume increased twice. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47523.     

A Highly Sensitive,Reversible, and Bidirectional Humidity Actuator by Calcium Carbonate Ionic Oligomers Incorporated Poly(Vinylidene Fluoride)

Sensitivity and multi-directional motivation are major two factors for developing optimized humidity-response materials, which are promising for sensing, energy production, etc. Organic functional groups are commonly used as the water sensitive units through hydrogen bond interactions with water molecules in actuators. The multi-coordination ability of inorganic ions implies that the inorganic ionic compounds are potentially superior water sensitive units. However, the particle forms of inorganic ionic compounds produced by classical nucleation limit the number of exposed ions to interact with water. Recent progress on the inorganic ionic oligomers has broken through the limitation of classical nucleation, and realized the molecular-scaled incorporation of inorganic ionic compounds into an organic matrix. Here, the incorporation of hydrophilic calcium carbonate ionic oligomers into hydrophobic poly(vinylidene fluoride) (PVDF) is demonstrated. The ultra-small calcium carbonate oligomers within a PVDF film endow it with an ultra-sensitive, reversible, and bidirectional response. The motivation ability is superior to other bidirectional humidity-actuators at present, which realizes self-motivation on an ice surface, converting the chemical potential energy of the humidity gradient from ice to kinetic energy.     

Note of Caution for the Aqueous Behaviour of Metal-Based Drug Candidates

Poor aqueous solubility is one of the recurrent drawbacks of many compounds in medicinal chemistry. To overcome this limitation, the dilution of drug candidates from stock solutions of an organic solvent is common practice. However, the precise characterisation of these compounds in aqueous solutions is often neglected, leading to some uncertainties regarding the nature of the actual active species. In this communication, we demonstrate that two ruthenium complexes previously reported by our group for their chemotherapeutic potential against cancer, namely [Ru(DIP)₂(sq)](PF₆) and [Ru(DIP)₂(3-methoxysq)](PF₆), where DIP is 4,7-diphenyl-1,10-phenanthroline, sq=semiquinonate and 3-methoxysq=3-methoxysemiquinonate, form colloids in water-DMSO (1 % v/v) mixtures that are invisible to the naked eyes. [Ru(DIP)₂(3-methoxysq)](PF₆) was found to form a highly stable and monodispersed colloid with nanoaggregates of ∼25 nm. In contrast, [Ru(DIP)₂(sq)](PF₆) was found to form large reticulates of mostly spherical aggregates which size was found to increase over time. The difference in size and shape distribution of drug candidates is of tremendous significance as the study of their biological activity might be severely affected. Overall, we strongly believe that these observations should be taken into account by the scientific community working on the development of metal-based drugs with poor water solubility.     

Achieving Rich and Active Alkaline Hydrogen Evolution Heterostructures via Interface Engineering on 2D 1T‐MoS2 Quantum Sheets

Large‐scale production of hydrogen from water‐alkali electrolyzers is impeded by the sluggish kinetics of hydrogen evolution reaction (HER) electrocatalysts. The hybridization of an acid‐active HER catalyst with a cocatalyst at the nanoscale helps boost HER kinetics in alkaline media. Here, it is demonstrated that 1T–MoS₂ nanosheet edges (instead of basal planes) decorated by metal hydroxides form highly active ${\text{edge}}_{{\text{1T‐MoS}}_{\text{2}}}$/ ${\text{edge}}_{\text{Ni}{(\text{OH})}_{\text{2}}}$ heterostructures, which significantly enhance HER performance in alkaline media. Featured with rich ${\text{edge}}_{{\text{1T‐MoS}}_{\text{2}}}$/ ${\text{edge}}_{\text{Ni}{(\text{OH})}_{\text{2}}}$ sites, the fabricated 1T–MoS₂ QS/Ni(OH)₂ hybrid (quantum sized 1T–MoS₂ sheets decorated with Ni(OH)₂ via interface engineering) only requires overpotentials of 57 and 112 mV to drive HER current densities of 10 and 100 mA cm^?2, respectively, and has a low Tafel slope of 30 mV dec^?1 in 1 m KOH. So far, this is the best performance for MoS₂‐based electrocatalysts and the 1T–MoS₂ QS/Ni(OH)₂ hybrid is among the best‐performing non‐Pt alkaline HER electrocatalysts known. The HER process is durable for 100 h at current densities up to 500 mA cm^?2. This work not only provides an active, cost‐effective, and robust alkaline HER electrocatalyst, but also demonstrates a design strategy for preparing high‐performance catalysts based on edge‐rich 2D quantum sheets for other catalytic reactions.