Applying an Oleophobic/Hydrophobic Fluorinated Polymer Monolayer Coating from Aqueous Solutions.

Despite major advancements in the fabrication of low-surface-energy surfaces, the environmental consequences of their fabrication can be a serious issue, particularly in an industrial context. This is especially the case for fluorine-based coatings, which often require fluorinated solvents for their processing and applications. These solvents are not only detrimental to the ozone layer but also represent a potential workplace hazard because they tend to bioaccumulate. We describe the design, synthesis, and characterization of a new fluorinated-polymer coating that can be simply applied to surfaces from an aqueous environment using a dip-coating technique. This was made possible by copolymerizing three different methacrylate monomers, each serving a specific function. Namely, fluorinated methacrylate providing oleo/hydrophobicity, photocleavable polyethylene glycol (PEG) methacrylate promoting water solubility of the copolymer, and thioether-based methacrylate serving as an anchoring unit to a number of different substrates. This copolymer is initially grafted to the surface as a monolayer from an aqueous solvent, after which the system is treated with ultraviolet (UV) light, cleaving away the protecting PEG moieties to yield an oleo/hydrophobic surface.

Load and Velocity Dependence of Friction Mediated by Dynamics of Interfacial Contacts.

Studying the frictional properties of interfaces with dynamic chemical bonds advances understanding of the mechanism underlying rate and state laws, and offers new pathways for the rational control of frictional response. In this work, we revisit the load dependence of interfacial chemical-bond-induced (ICBI) friction experimentally and find that the velocity dependence of friction can be reversed by changing the normal load. We propose a theoretical model, whose analytical solution allows us to interpret the experimental data on timescales and length scales that are relevant to experimental conditions. Our work provides a promising avenue for exploring the dynamics of ICBI friction.

Effect of the environmental humidity on the bulk, interfacial and nanoconfined properties of an ionic liquid.

With reference to our previous surface-force study on 1-hexyl-3-methylimidazolium ethylsulfate ([HMIM] EtSO4) using an extended surface forces apparatus, which showed an ordered structure within the nanoconfined dry ionic liquid (IL) between mica surfaces that extended up to ∼60 nm from the surface, this work focuses on the influence of the environmental humidity on the bulk, interfacial and nanoconfined structure of [HMIM] EtSO4. Infrared spectroscopy and rheometry reflect the changes in chemical and physical properties of the bulk IL due to the uptake of water when exposed to ambient humidity, while wide-angle X-ray scattering shows a mild swelling of the bulk nanostructure, and the AFM sharp tip reveals an additional surface layer at the mica-IL interface. When the water-containing [HMIM] EtSO4 is nanoconfined between two mica surfaces, no long-range order is detected, in contrast to the results obtained for the dry IL, which demonstrates that the presence of water can prevent the liquid-to-solid transformation of this IL. A combination of techniques and the calculated Bjerrum length indicate that water molecules weaken interionic electrostatic and hydrogen-bonding interactions, which lessens ion-ion correlations. Our work shows that the solid-like behavior of the nanoconfined IL strongly depends on the presence of absorbed water and hence, it has implications with regard to the correct interpretation of laboratory studies and their extension to real applications in lubrication.

Irreversible structural change of a dry ionic liquid under nanoconfinement.

Studies of 1-hexyl-3-methyl-imidazolium ethylsulfate ([HMIM] EtSO4) using an extended surface forces apparatus show, for the first time, an ordered structure within the nanoconfined ionic liquid (IL) between mica surfaces that extends up to ∼60 nm from the surface. Our measurements show the growth of this ordered IL-film upon successive nanoconfinements-the structural changes being irreversible upon removal of the confinement-and the response of the structure to shear. The compressibility of this system is lower than that typically measured for ILs, while creep takes place during shear, both findings supporting a long-range liquid-to-solid transition. AFM (sharp-tip) studies of [HMIM] EtSO4 on mica only reveal ∼2 surface IL-layers, with order extending only ∼3 nm from the surface, indicating that confinement is required for the long-range IL-solidification to occur. WAXS studies of the bulk IL show a more pronounced ordered structure than is the case for [HMIM] with bis(trifluoromethylsulfonyl)imide as anion, but no long-range order is detected, consistent with the results obtained with the sharp AFM tip. These are the first force measurements of nanoconfinement-induced long-range solidification of an IL.

CVD of MoS2 single layer flakes using Na2MoO4 - impact of oxygen and temperature-time-profile.

Two-dimensional (2D) materials are of great interest in many fields due to their astonishing properties at an atomic level thickness. Many fundamentally different methods to synthesize 2D materials, such as exfoliation or chemical vapor deposition (CVD), have been reported. Despite great efforts and progress to investigate and improve each synthesis method, mainly to increase the yield and quality of the synthesized 2D materials, most approaches still involve some compromise. Herein, we systematically investigate a chemical vapor deposition (CVD) process to synthesize molybdenum disulfide (MoS2) single layer flakes using sodium molybdate (Na2MoO4), deposited on a silica (SiO2/Si) substrate by spin-coating its aqueous solution, as the molybdenum source and sulfur powder as sulfur source, respectively. The focus lies on the impact of oxygen (O2) in the gas flow and temperature-time-profile on reaction process and product quality. Atomic force microscopy (AFM), Raman and photoluminescence (PL) spectroscopy, X-ray photoelectron spectroscopy (XPS), and time-of-flight secondary ion mass spectrometry (ToF-SIMS) were used to investigate MoS2 flakes synthesized under different exposure times of O2 and with various temperature-time-profiles. This detailed study shows that the MoS2 flakes are formed within the first few minutes of synthesis and elaborates on the necessity of O2 in the gas flow, as well as drawbacks of its presence. In addition, the applied temperature-time-profile highly affects the ability to detach MoS2 flakes from the growth substrate when immersed in water, but it has no impact on the flake.

Liposomal aggregates sustain the release of rapamycin and protect cartilage from friction.

Liposomes show promise as biolubricants for damaged cartilage, but their small size results in low joint and cartilage retention. We developed a zinc ion-based liposomal drug delivery system for local osteoarthritis therapy, focusing on sustained release and tribological protection from phospholipid lubrication properties. Our strategy involved inducing aggregation of negatively charged liposomes with zinc ions to extend rapamycin (RAPA) release and improve cartilage lubrication. Liposomal aggregation occurred within 10 min and was irreversible, facilitating excess cation removal. The aggregates extended RAPA release beyond free liposomes and displayed irregular morphology influenced by RAPA. At nearly 100 µm, the aggregates were large enough to exceed the previously reported size threshold for increased joint retention. Tribological assessment on silicon surfaces and ex vivo porcine cartilage revealed the system's excellent protective ability against friction at both nano- and macro-scales. Moreover, RAPA was shown to attenuate the fibrotic response in human OA synovial fibroblasts. Our findings suggest the zinc ion-based liposomal drug delivery system has potential to enhance OA therapy through extended release and cartilage tribological protection, while also illustrating the impact of a hydrophobic drug like RAPA on liposome aggregation and morphology.

Functionalized Cellulose Nanocrystals as Active Reinforcements for Light-Actuated 3D-Printed Structures.

Conventional manufacturing techniques allow the production of photoresponsive cellulose nanocrystals (CNC)-based composites that can reversibly modify their optical, mechanical, or chemical properties upon light irradiation. However, such materials are often limited to 2D films or simple shapes and do not benefit from spatial tailoring of mechanical properties resulting from CNC alignment. Herein, we propose the direct ink writing (DIW) of 3D complex structures that combine CNC reinforcement effects with photoinduced responses. After grafting azobenzene photochromes onto the CNC surfaces, up to 15 wt % of modified nanoparticles can be introduced into a polyurethane acrylate matrix. The influence of CNC on rheological properties allows DIW of self-standing 3D structures presenting local shear-induced alignment of the active reinforcements. The printed composites, with longitudinal elastic modulus of 30 MPa, react to visible-light irradiation with 30-50% reversible softening and present a shape memory behavior. The phototunable energy absorption of 3D complex structures is demonstrated by harnessing both geometrical and photoresponsive effects, enabling dynamic mechanical responses to environmental stimuli. Functionalized CNC in 3D printable inks have the potential to allow the rapid prototyping of several devices with tailored mechanical properties, suitable for applications requiring dynamic responses to environmental changes.

Mechanistic insight into the active centers of single/dual-atom Ni/Fe-based oxygen electrocatalysts.

Single-atom catalysts with maximum metal utilization efficiency show great potential for sustainable catalytic applications and fundamental mechanistic studies. We here provide a convenient molecular tailoring strategy based on graphitic carbon nitride as support for the rational design of single-site and dual-site single-atom catalysts. Catalysts with single Fe sites exhibit impressive oxygen reduction reaction activity with a half-wave potential of 0.89 V vs. RHE. We find that the single Ni sites are favorable to promote the key structural reconstruction into bridging Ni-O-Fe bonds in dual-site NiFe SAC. Meanwhile, the newly formed Ni-O-Fe bonds create spin channels for electron transfer, resulting in a significant improvement of the oxygen evolution reaction activity with an overpotential of 270 mV at 10 mA cm-2. We further reveal that the water oxidation reaction follows a dual-site pathway through the deprotonation of *OH at both Ni and Fe sites, leading to the formation of bridging O2 atop the Ni-O-Fe sites.

Influence of Environmental Humidity on the Wear and Friction of a Silica/Silicon Tribopair Lubricated with a Hydrophilic Ionic Liquid.

In this study, the tribological behavior of silica/silicon surfaces lubricated with the ionic liquid 1-ethyl-3-methylimidazolium ethylsulfate ([EMIM] EtSO4) was investigated. Tests were carried out in the presence of either humid air (45-55% relative humidity) or in a nitrogen atmosphere, and the results were compared with those obtained using pure water as a lubricant. The cross-sectional analysis of the contact area performed by focused-ion-beam scanning electron microscopy indicated the presence of cracks in the subsurface region, showing that brittle fracture contributed to wear. Sliding promoted the formation of a third body, the presence of which was indicated by optical and secondary electron microscopy. X-ray photoelectron spectroscopy showed that the third body was mostly composed of silicon oxides. The accumulation of the debris was controlled by the presence of water: in the presence of a nitrogen atmosphere, particles were trapped between the sliding surfaces, whereas in the case of humid air, the debris was progressively removed from the contact. Notably, the presence of trapped particles was associated with higher values of wear coefficients of both disks and pins. In addition, a lower roughness was observed along the direction of sliding in the case of water-containing ionic liquid. The observed trends in wear and the combined results of the various techniques, as well as the comparison with tests carried out in the presence of pure water, all point to the characteristic tribochemical reactions of water with silicon-based materials, namely, the formation of a sacrificial layer of hydrated oxide and the dissociative adsorption of water at crack tips of SiO2. In the absence of water, the lack of a tribochemical mechanism forming a sacrificial layer leads to a microfracture-dominated wear mechanism over the entire duration of the test, thus leading to more severe wear. The possible occurrence of stress-induced phase transformation of silicon during sliding is also discussed.

Layering of ionic liquids on rough surfaces.

Understanding the behavior of ionic liquids (ILs) either confined between rough surfaces or in rough nanoscale pores is of great relevance to extend studies performed on ideally flat surfaces to real applications. In this work we have performed an extensive investigation of the structural forces between two surfaces with well-defined roughness (<9 nm RMS) in 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide by atomic force microscopy. Statistical studies of the measured layer thicknesses, layering force, and layering frequency reveal the ordered structure of the rough IL-solid interface. Our work shows that the equilibrium structure of the interfacial IL strongly depends on the topography of the contact.