Tribological Evaluation of Lead-Free MoS2-Based Solid Film Lubricants as Environmentally Friendly Replacements for Aerospace Applications

Solid lubricants, such as MoS2 have been widely used in the aerospace industry with the primary purpose of reducing the friction and wear of tribological interfaces. MoS2 based solid film lubricants are generally doped with other compounds, which can help overcome some of their limitations related to environmental conditions. For instance, compounds like Sb2O3 and Pb have been traditionally used to improve the endurance life of these lubricants. However, with the recent zest in transferring to eco-friendly lubricants, there is a strong push to eliminate Pb based compounds. The main purpose of this work is to better understand the influence of Pb based compounds on the tribological behavior of MoS2 based solid film lubricants as well as to critically evaluate the performance of Pb free lubrication strategies. More specifically, the baseline ‘non-green’ lubricant was doped with Pb compound and Sb2O3 and the Pb compound in the ‘Green’ alternative lubricant was replaced by more Sb2O3. The wear test was done using a ball-on-disk tribometer for specific loads and for 5000 cycles. Ex-situ analysis was conducted using Scanning Electron Microscope (SEM), Atomic Force Microscopy (AFM), and micro-Raman to capture the interfacial processes of these lubricants at different loads. Overall, the non-green lubricant performed better in terms of the tribological behavior (i.e., lower friction and wear), which was attributed to the formation of a dense MoS2-based tribo-/transfer-film with the basal planes oriented in the parallel direction to the sliding. The finding on the interfacial phenomena provided critical insights into the development of novel green alternatives that may have the ability to replace Pb based compounds in the future for a sustainable environment.

Fluorescent Indolo[2,3-b]quinoxalin-2-yl)(Phenyl)methanone Dyes: Photophysical, Aie Activity, Electrochemical, and Theoretical Studies

Herein, we have synthesized four indolo[2,3-b]quinoxalin-2-yl)(phenyl)methanone derivatives 1−4 by cyclocondensation. The photophysical studies of dyes in various solvents and neat solid film exhibit typical electronic spectra with inbuilt intramolecular charge transfer (ICT) (λmax: 397‒490 nm) confirming donor-acceptor architecture. Herein, dyes fluoresce in the blue-orange region (λEmax: 435–614) on excitation at their ICT maxima in toluene, ethyl acetate, chloroform, DMSO, and neat solid film. 1 and 2 which exhibit good emission intensity in all mediums, were studied for aggregation-induced emission (AIE) effect. Electrochemical studies indicate 1−4 possess relatively low lying LUMO (‒3.65 to ‒3.98 eV) comparable to reported n-type/electron-transporting materials. The HOMO and LUMO energy levels in 1−4 were evaluated by DFT and TD-DFT calculations. TGA analysis shows 1−4 exhibit good thermal stability. The characteristic optoelectronic properties and thermal stability signify these dyes are potential candidate for their application in optoelectronics.

Stable and Efficient Red Perovskite Light-Emitting Diodes Based on Ca2+-Doped CsPbI3 Nanocrystals

α-CsPbI3 nanocrystals (NCs) with poor stability prevent their wide applications in optoelectronic fields. Ca2+ (1.00 Å) as a new B-site doping ion can successfully boost CsPbI3 NC performance with both improved phase stability and optoelectronic properties. With a Ca2+/Pb2+ ratio of 0.40%, both phase and photoluminescence (PL) stability could be greatly enhanced. Facilitated by increased tolerance factor, the cubic phase of its solid film could be maintained after 58 days in ambient condition or 4 h accelerated aging process at 120°C. The PL stability of its solution could be preserved to 83% after 147 days in ambient condition. Even using UV light to accelerate aging, the T50 of PL could boost 1.8-folds as compared to CsPbI3 NCs. Because Ca2+ doping can dramatically decrease defect densities of films and reduce hole injection barriers, the red light-emitting diodes (LEDs) exhibited about triple enhancement for maximum the external quantum efficiency (EQE) up to 7.8% and 2.2 times enhancement for half-lifetime of LED up to 85 min. We believe it is promising to further explore high-quality CsPbI3 NC LEDs via a Ca2+-doping strategy.

Long-Term Releasing Kinetics of Chromium from Leather

The release of chromium from leather inevitably results in potential risks and this study is conducted to investigate the long-term releasing behavior. The leaching tests proceed using water at solid to liquid ratio of 1:20 and rotational speed 60 r/min for 240 hours to simulate the release of chrome leather under natural conditions. The experimental data successfully fit with the Pseudo-second-order equation, Elovich equation, and Weber-Morris model, indicating the long-term leaching behavior of chromium in heterogeneous leather is controlled by liquid-solid film, while the interparticle and intraparticle diffusion also play important roles. The leachable chromium accounts for 2.8-4.5% total chromium in leather and increases with temperature. The Three-compartment model depicts the releasing process as rapid, slow, and very slow stages, and temperature mainly affected the very slow stage. The amount of released chromium in rapid and slow stages slightly increases with temperature, which could be used to assess the hazard of chrome leather.

Highly emissive MAPbBr3 perovskite QDs by ligand-assisted reprecipitation: the antisolvent effect

A systematic study of the synthetic procedure to improve quantum efficiency of luminescent hybrid perovskite QDs through ligand-assisted precipitation method is presented. Particularly, the influence of the dielectric constant and dipole moment of the antisolvent on the reaction time and the photophysical properties of the QDs is highlighted. After evaluating the influence of antisolvents and optimizing experimental parameters such as reaction time and Pb excess of the precursor, colloidal crystalline MAPbBr3 QDs with exceptionally high absolute quantum yield up to 97.7% in solution and 69.1% in solid film were obtained. Finally, MAPbBr3 QDs precipitated from anisole were processed like UV-curable nanocomposite as efficient down conversion layer resulting in very narrow green emission LED.

Dissolution and Reprecipitation of Sulfur on Carbon Surface

Further understanding of the redox process of lithium polysulfides (PSs) on carbon surface is helpful to design Li/S batteries with better performance. “Shuttle mechanism” can explain the low coulomb efficiency and self-discharge of a Li/S battery, but it cannot explain the fact that battery performance is closely affected by electrolyte volume and sulfur load. This paper aims to reveal main redox process of PSs on surface of carbon by examining cathodic behavior with different electrolyte volume and sulfur load. SEM photos and Impedance Spectra of cathode before and after 1st discharge were compared, it was found that the discharge process is the continuous dissolution of sulfur composited with carbon into the electrolyte to form PSs, at the same time, PSs re-precipitates sulfur on the surface of cathode through disproportionation reaction to form a solid film. CV curves showed that the solid film passivates electrode, and the electrode is activated only when potential sweeps negatively and Li2S is generated. When lean electrolyte is used, there is fluctuation in CV curves, which proves that the dissolution-reprecipitation of sulfur is the main process of cathode. The discharge-charge curves of cathodes with different sulfur load were compared, it was found that there is wavy fluctuation in the discharge curve with high sulfur load, which proves again that the sulfur reaction dominates the electrode process.

Mobility of Small Molecules in Solid Polymer Film for π-Stacked Crystallization

Crystallization or π-stacked aggregation of small molecules is an extensively observed phenomenon which favors charge transport along the crystal axis and is important for the design of organic optoelectronic devices. Such a process has been reported for N,N’-Bis(1-ethylpropyl)-3,4,9,10-perylenebis(dicarboximide) (EPPTC). However, the π-stacking mechanism requires solution–air or solution–solid interfaces. The crystallization or aggregation of molecules doped in solid films is generally thought to be impossible, since the solid environment surrounding the small molecules does not allow them to aggregate together into π-stacked crystals. In this work, we demonstrate that the movement of the EPPTC molecules becomes possible in a solid polymer film when it is heated to above the glass transition temperature of the polymer. Thus, crystal particles can be produced as a doped matrix in a thin solid film. The crystallization process is found to be strongly dependent on the annealing temperature and the annealing time. Both the microscopic and spectroscopic evaluations verify such discoveries and characterize the related properties of these crystals.

Hydroquinone redox mediator enhances the photovoltaic performances of chlorophyll-based bio-inspired solar cells

Chlorophyll (Chl) derivatives have recently been proposed as photoactive materials in next-generation bio-inspired solar cells, because of their natural abundance, environmental friendliness, excellent photoelectric performance, and biodegradability. However, the intrinsic excitation dynamics of Chl derivatives remain unclear. Here, we show sub-nanosecond pump–probe time-resolved absorption spectroscopy of Chl derivatives both in solution and solid film states. We observe the formation of triplet-excited states of Chl derivatives both in deoxygenated solutions and in film samples by adding all-trans-β-carotene as a triplet scavenger. In addition, radical species of the Chl derivatives in solution were identified by adding hydroquinone as a cation radical scavenger and/or anion radical donor. These radical species (either cations or anions) can become carriers in Chl-derivative-based solar cells. Remarkably, the introduction of hydroquinone to the film samples enhanced the carrier lifetimes and the power conversion efficiency of Chl-based solar cells by 20% (from pristine 1.29% to 1.55%). This enhancement is due to a charge recombination process of Chl-A+/Chl-D–, which is based on the natural Z-scheme process of photosynthesis.

Film-Forming Systems for Dermal Drug Delivery

Film-forming formulations represent a novel form of sustained release dermatic products. They are applied to the skin as a liquid or semi-solid preparation. By evaporation of the volatile solvent on the skin, the polymer contained in the formulation forms a solid film. Various film-forming formulations were tested for their water and abrasion resistance and compared with conventional semi-solid formulations. Penetration and permeation studies of the formulations indicate a potential utility as transdermal therapeutic systems. They can be used as an alternative to patch systems to administer a variety of drugs in a topical way and may provide sustained release characteristics.