Light-induced ultrafast proton-coupled electron transfer responsible for H2 evolution on silver plasmonics

Light-driven proton-coupled electron transfer (PCET) reactions on nanoplasmonics would bring temporal control of their reactive pathways, in particular, prolong their charge separation state. Using a silver nano-hybrid plasmonic structure, we observed that optical excitation of Ag-localized surface plasmon instigated electron injection into TiO₂ conduction band and oxidation of isopropanol alcoholic functionality. Femtosecond transient infrared absorption studies show that electron transfer from Ag to TiO₂ occurs in ca. 650?fs, while IPA molecules near the Ag surface undergo an ultrafast bidirectional PCET step within 400?fs. Our work demonstrates that ultrafast PCET reaction plays a determinant role in prolonging charge separation state, providing an innovative strategy for visible-light photocatalysis with plasmonic nanostructures.     

New method for controlled synthesis of polylactide block copolymers: organoborane/p-quinone system and reversible-deactivation radical polymerization

We developed a new approach to obtain polylactide hybrid block copolymers with vinyl monomers (styrene, methyl methacrylate, methyl acrylate) through the realization of a reaction sequence using triethylborane and various p-quinones. The method offered includes two stages. In the first stage, a chain-transfer agent was obtained by borylation of the terminal hydroxyl groups of polylactide. The second stage was vinyl monomer radical polymerization in the presence of p-quinone accompanied by S_H2-substitution at the boron atom.1,4-Naphthoquinone, 2,3-dimethyl-1,4-benzoquinone, duroquinone and 2,5-di-tert-butyl-1,4-benzoquinone were used as synthetic polymer chain growth mediators. It is shown that 1,4-naphthoquinone and 2,3-dimethyl-1,4-benzoquinone, similar in their characteristics, are effective agents providing the realization of reversible-deactivation radical polymerization. Realization of reversible-deactivation radical polymerization was proved with the analysis of the kinetics of block copolymerization, molecular weight characteristics and compositional homogeneity of block copolymers as well as its further capability to elongate the polymer chain. Synthesized block copolymers have a high thermal stability compared to the initial borylated polylactide. © 2021 Society of Industrial Chemistry.     

Formation of branched polyethylenes by ethylene homopolymerization using LNiBr2 homo- and heterogeneous precatalysts: Interpretation of the polymer structures in comparison with commercial LLDPE

Comparative data on the micro-structures and properties of branched polyethylenes (BPE) produced via ethylene homopolymerization over homogeneous N,N-α-diimine LNiBr₂ complexes with different ligand composition (AlEt₂Cl as a cocatalyst) and corresponding supported catalysts LNiBr₂/SiO₂(Al) (Al[iso-Bu]₃ as a cocatalyst) are presented. Noticeable differences were observed between micro-structures of BPEs obtained using homo- and heterogeneous LNiBr₂ complexes as catalysts. Supported catalysts produce BPEs with the majority of methyl branches (17–18 CH₃(1000 C)⁻¹ characterized by different molecular masses (1800–210 kg mol⁻¹) and molecular weight distributions (M_w[M_n]⁻¹ = 5.9 and 2.6). Thermal and mechanical properties of these BPE samples obtained over supported Ni catalysts are similar to those of commercial LLDPE samples prepared with metallocene and Ziegler-Natta catalysts.     

Evluation of Strength of Plane Microcracked Structural Elements Via Electrical Resistance Scanning

The paper focuses on experimental verification of a new approach to evaluate strength of structural elements via electrical resistance scanning. The approach utilizes explicit cross-property connections. In the case of multiple parallel cracks, we reconstruct certain characteristics of the microstructure from resistance measurements and evaluate the corresponding strength reduction. The results are compared to actual fracture tests of preconfigured specimens. Experimental strength measurements show strong correlation to the results predicted by the resistance scanning technique.     

Refinement of the Voigt Hypothesis for Copper and Brass

Russian Engineering Research - According to the Voigt hypothesis, the internal frictional coefficient of metals is frequency-independent. Experiments with copper and brass rods show that the...     

Comparative study of different methods for the assessment of print mottle

Print mottle is a print defect that occurs more or less on prints and has a negative influence on the evenness in print. Several methods to assess print mottle have been proposed. In this article, we analyzed three methods for print mottle evaluation: Histogram Mottle Macro, Gray level co‐occurrence matrix (GLCM) and M‐score. The aim was to compare them and to determine their relation to perceived non‐uniformity obtained by visual assessment. In the experimental part, we printed four different substrates with different optical properties with digital printing machine based on electrophotographic process. The surface of papers was characterized by measuring optical paper properties. The results obtained in this study suggest that GLCM method should be used for print mottle assessment. This method has the strongest correlation with the visual experience of print mottle. © 2015 Wiley Periodicals, Inc. Col Res Appl, 41, 493–499, 2016     

Ignition of hydrogen–air mixtures using pulsed nanosecond dielectric barrier plasma discharges in plane-to-plane geometry

Ignition of preheated (400–500 K) H₂–air mixtures at low pressures (80–100 torr) excited by pulsed nanosecond dielectric barrier discharges is investigated through experiments and simulations. Time resolved absolute OH concentration and temperature data are obtained using Laser Induced Fluorescence (LIF) technique. Ignition is achieved in the decaying plasma after a burst of discharge pulses (repetition rate 10–40 kHz), with the time delay inferred from sudden rise in OH^* emission. One-dimensional simulations are performed to obtain information about the plasma generated radicals and heat release across the discharge gap. A plasma fluid formulation is used with ions and neutral species at gas temperature, and electrons in non-equilibrium. An accurate reduced chemistry mechanism is developed through sensitivity analysis to expedite the plasma simulations. The model predictions show excellent agreement with experimental measurements, validating the numerical framework and chemistry data. The input pulse energy and ignition characteristics are found to be highly sensitive to uncertainties in dielectric properties. Ignition delay exhibits a threshold-like dependence on input plasma energy, and increases steeply as the number of pulses in the burst is reduced. The nanosecond plasma assisted ignition is achieved through a two-step process. Firstly, the burst of discharge pulses produce a large pool of radicals and provide an average temperature rise of ∼1–2 K/pulse. In the next step, if the temperature exceeds a threshold value of ∼700 K, significant heat release from partial fuel oxidation is triggered. The process becomes self-sustaining and the temperature continues to rise even after the plasma source is switched off, accelerating the conventional H₂–O₂ chain branching pathways and leading to ignition. We provide conclusive evidence of large volume ignition with nanosecond plasma as opposed to thermal ignition at a hot-spot. Ignition is first observed at the center of the discharge gap, but the kernel expands rapidly to the entire volume, except near walls where heat losses keep the temperature low. It is demonstrated that the ignition occurs independently at different locations due to local plasma chemistry effects and heat transport does not play a significant role.