Ionic liquids at electrified interfaces

Until recently, “room-temperature” (<100–150 °C) liquid-state electrochemistry was mostly electrochemistry of diluted electrolytes(1)–(4) where dissolved salt ions were surrounded by a considerable amount of solvent molecules. Highly concentrated liquid electrolytes were mostly considered in the narrow (albeit important) niche of high-temperature electrochemistry of molten inorganic salts(5-9) and in the even narrower niche of “first-generation” room temperature ionic liquids, RTILs (such as chloro-aluminates and alkylammonium nitrates).(10-14) The situation has changed dramatically in the 2000s after the discovery of new moisture- and temperature-stable RTILs.(15, 16) These days, the “later generation” RTILs attracted wide attention within the electrochemical community.(17-31) Indeed, RTILs, as a class of compounds, possess a unique combination of properties (high charge density, electrochemical stability, low/negligible volatility, tunable polarity, etc.) that make them very attractive substances from fundamental and application points of view.(32-38) Most importantly, they can mix with each other in “cocktails” of one’s choice to acquire the desired properties (e.g., wider temperature range of the liquid phase(39, 40)) and can serve as almost “universal” solvents.(37, 41, 42) It is worth noting here one of the advantages of RTILs as compared to their high-temperature molten salt (HTMS)(43) “sister-systems”.(44) In RTILs the dissolved molecules are not imbedded in a harsh high temperature environment which could be destructive for many classes of fragile (organic) molecules

Silver nanoparticle engineering via oligovaline organogels

L-Valine-based oligopeptides with the chemical structure Z–(L-Val)₃–OMe and Z–(L-Val)₂–L-Cys(S-Bzl)–OMe form stable organogels in butanol. Both peptides are efficient gelators, but Z–(L-Val)₂–L-Cys(S-Bzl)–OMe crystallizes more readily than Z–(L-Val)₃–OMe. The two peptides can form mixed fibers, which also gel butanol. The resulting organogels are very similar to oligovaline organogels reported earlier (Mantion and Taubert, Macromol. Biosci., 2007, 7, 208) as they also form highly ordered peptide fibers with a predominant β-sheet structure and diameters of ca. 100 nm. The fibers can be mineralized with silver nanoparticles using DMF as a reducing agent. The fraction of the sulfur-containing peptide Z–(L-Val)₂–L-Cys(S-Bzl)–OMe controls the shape and size of the resulting nanoparticles. At high Z–(L-Val)₂–L-Cys(S-Bzl)–OMe content, small spherical particles are distributed all over the fiber. Lower contents of Z–(L-Val)₂–L-Cys(S-Bzl)–OMe lead to a size increase of the particles and to more complex shapes like plate-like and raspberry-like silver particles. The interactions between peptide and silver ions or silver particles takes place via a complexation of the silver ions to the sulfur atom of the thioether moiety, and are shown to be the key interaction in controlling particle formation

Non-reactive HiPIMS deposition of NbCx thin films : Effect of the target power density on structure-mechanical properties

The exceptional mechanical properties of transition metal carbide coatings are known to be governed by the carbon content and its morphological distribution. Here, we verify the influence of the target peak power density on the chemical composition, microstructure, and mechanical properties of NbCx coatings grown by non-reactive high-power impulse magnetron sputtering (HiPIMS). By tuning the pulse parameters, the power density can be increased from 0.11 to 1.48 kW/cm2 leading to a decrease in the C/Nb ratio from 1.52 to 0.99 within the films - proven by combined elastic backscattering and time-of-flight elastic recoil detection analysis. This decrease in the C/Nb ratio is accompanied by microstructural changes from nanocomposite morphologies with an average grain size of 6.6 +/- 2.5 nm at 0.13 kW/cm2 into more columnar structures with an average column width of 65.2 +/- 18.7 nm at 1.48 kW/cm2. Independent from the C/Nb ratio, all films exhibit a single face-centered cubic structure. The mechanical properties correlate with the enhanced growth behavior dominated by ions at higher peak power densities and the varied C/Nb ratios. A maximum in hardness and fracture toughness of H = 38.7 +/- 3.6 GPa and KIc = 2.78 +/- 0.13 MPa center dot m1/2 (at 3.2 GPa residual compressive stress), is obtained for the nearly stoichiometric NbC coating exhibiting C/Nb ratio of 1.06

Dynamic Potential Sputtering of Lunar Analog Material by Solar Wind Ions

Pyroxenes ((Ca, Mg, Fe, Mn)2Si2O6) belong to the most abundant rock forming minerals that make up the surface of rocky planets and moons. Therefore, sputtering of pyroxenes by solar wind ions has to be considered as a very important process for modifying the surface of planetary bodies. This is increased due to potential sputtering by multiply charged ions; to quantify this effect, sputtering of wollastonite (CaSiO3) by He2+ ions was investigated. Thin films of CaSiO3 deposited on a quartz crystal microbalance were irradiated, allowing precise, in situ, real time sputtering yield measurements. Experimental results were compared with SDTrimSP simulations, which were improved by adapting the used input parameters. On freshly prepared surfaces, He2+ ions show a significant increase in sputtering, as compared to equally fast He+ ions. However, the yield decreases exponentially with fluence, reaching a lower steady state after sputtering of the first few monolayers. Experiments using Ar8+ ions show a similar behavior, which is qualitatively explained by a preferential depletion of surface oxygen due to potential sputtering. A corresponding quantitative model is applied, and the observed potential sputtering behaviors of both He and Ar are reproduced very well. The results of these calculations support the assumption that mainly O atoms are affected by potential sputtering. Based on our findings, we discuss the importance of potential sputtering for the solar wind eroding the lunar surface. Estimated concentration changes and sputtering yields are both in line with previous modeling for other materials, allowing a consistent perspective on the effects of solar wind potential sputtering