Preparation and characterization of ultrathin dual-layer ionic liquid lubrication film assembled on silica surfaces

A novel ultrathin dual-layer film, which contained both bonded and mobile phases in ionic liquids (ILs) layer, was fabricated successfully on a silicon substrate modified by a self-assembled monolayer (SAM). The formation and surface properties of the films were analyzed using ellipsometer, water contact angle meter, attenuated total reflectance Fourier transform infrared spectroscopy, multi-functional X-ray photoelectron spectroscopy, and atomic force microscope. Meanwhile, the adhesive and nanotribological behaviors of the films were evaluated by a homemade colloidal probe. A ball-on-plate tribometer was used to evaluate the microtribological performances of the films. Compared with the single-layer ILs film deposited directly on the silicon surface, the as-prepared dual-layer film shows the improved tribological properties, which is attributed to the special chemical structure and outstanding physical properties of the dual-layer film, i.e., the strong adhesion between bonded phase of ILs and silicon substrate via the chemical bonding with SAM, the interlinked hydrogen bonds among the molecules, and two-phase structure composed of steady bonded phase with load-carrying capacity and flowable mobile phase with self-replenishment property.     

Functionalized imidazolium wear‐resistant ionic liquid ultrathin films for MEMS/NEMS applications

As a kind of new material, ionic liquids (ILs) are considered a new type of lubricant for micro/nanoelectromechanical system (M/NEMS) due to their excellent thermal and electrical conductivity. However, so far, only a few reports have investigated the friction and wear of thin films of these materials at the micro scale. Evaluating the nanoscale tribological performance of ILs when applied as films of a few nanometers thickness on a substrate is a critical step for their application in M/NEMS devices. To achieve this purpose, IL thin films with four kinds of anions were synthesized and prepared on single‐crystal silicon wafers by the dip‐coating method. Film thickness was determined by the ellipsometric method. Their surface morphologies were observed by means of atomic force microscopy (AFM). The nano and micro tribological properties of the IL films were investigated by a friction force microscope (FFM)with a spherical probe and a UMT‐2MT tribotester, respectively. The corresponding morphologies of the wear tracks of the IL films were examined using a three‐dimensional non‐contact interferometric microscope. The impact of temperature on the adhesion behavior was studied, as well as the effect of sliding frequency and load on the friction coefficient, load bearing capacity and anti‐wear durability. It was found that friction, adhesion and durability of IL films were strongly dependent on their anionic molecular structures, wettability and ambient environment. Copyright © 2010 John Wiley & Sons, Ltd.     

Ionic liquids: solvents and sorbents in sample preparation

The applications of ionic liquids (ILs) and IL‐derived sorbents are rapidly expanding. By careful selection of the cation and anion components, the physicochemical properties of ILs can be altered to meet the requirements of specific applications. Reports of IL solvents possessing high selectivity for specific analytes are numerous and continue to motivate the development of new IL‐based sample preparation methods that are faster, more selective, and environmentally benign compared to conventional organic solvents. The advantages of ILs have also been exploited in solid/polymer formats in which ordinarily nonspecific sorbents are functionalized with IL moieties in order to impart selectivity for an analyte or analyte class. Furthermore, new ILs that incorporate a paramagnetic component into the IL structure, known as magnetic ionic liquids (MILs), have emerged as useful solvents for bioanalytical applications. In this rapidly changing field, this Review focuses on the applications of ILs and IL‐based sorbents in sample preparation with a special emphasis on liquid phase extraction techniques using ILs and MILs, IL‐based solid‐phase extraction, ILs in mass spectrometry, and biological applications.     

Superlubricity behaviors of Si3N4/DLC Films under PAO oil with nano boron nitride additive lubrication

The tribological properties of Si₃N₄ ball sliding against diamond‐like carbon (DLC) films were investigated using a ball‐on‐disc tribometer under dry friction and oil lubrications, respectively. The influence of nano boron nitride particle as lubricant additive in poly‐α‐olefin (PAO) oil on the tribological properties of Si₃N₄/DLC films was evaluated. The microstructure of DLC films was measured by Raman spectroscopy and X‐ray photoelectron spectroscopy. The experimental results show coefficient of friction (COF) of Si₃N₄/DLC films was as low as 0.035 due to the formation of graphite‐like transfer films under dry friction condition. It also indicates that the tribological properties of Si₃N₄/DLC films were influenced significantly by the viscosity of oil and the content of nano boron nitride particle in PAO oil. COF increases with the viscosity of PAO oil increasing. Si₃N₄/DLC films exhibit the superlubricity behaviors (μ=0.001 and nonmeasurable wear) under PAO 6 oil with 1.0 wt% nano boron nitride particle lubrication, indicating that the improved boundary lubrication behaviors have indeed been responsible for the significantly reduced friction. Nano boron nitride additive is used as solid lubricant‐like nano scale ball bearing to the pointlike contact and a soft phase bond with the weak van der Waals interaction force on the contact surface to improve the lubrication behaviors of Si₃N₄/DLC films. The potential usefulness of nano boron nitride as lubricant additive in PAO oil for Si₃N₄/DLC films has been demonstrated under oil lubrication conditions. The present work will extend the wide application of nano particle additive and introduce a new approach to superlubricity under boundary lubrication in future technological areas. Copyright © 2013 John Wiley & Sons, Ltd.     

The tribological performance of fullerene‐like hydrogenated carbon films under ionic liquid lubrication

Fullerene‐like hydrogenated carbon films were deposited on Si substrate by plasma‐enhanced chemical vapor deposition. The microstructures of films were characterized by high‐resolution transmission electron microscopy and Raman spectrum. The tribological performance of films was tested by reciprocating ball‐on‐disc tester under 1‐ethyl‐3‐methylimidazolium tetrafluoroborate ionic liquid. The surface morphology and chemical composition of wear tracks and wear rates were investigated by optical microscope, X‐ray photoelectron spectroscopy, and 3D surface profiler. The results indicated that the film with a typical fullerene‐like structure embedded into the amorphous sp² and sp³ carbon networks could be prepared successfully, and the film shows a higher hardness (26.7 GPa) and elastic recovery (89.9%) compared with the amorphous carbon film. Furthermore, the film shows a lower friction coefficient at low contact load and friction frequency, and excellent wear‐resistance performance at high load and frequency under ionic liquid lubrication. Meanwhile, the wear life of fullerene‐like hydrogenated carbon films could be improved significantly using ionic liquid as a lubrication material. Copyright © 2015 John Wiley & Sons, Ltd.     

The high‐temperature tribological properties of Si‐DLC films

The tribological properties of Silicon‐containing diamond‐like‐carbon (Si‐DLC) films, deposited by magnetron sputtering Si target in methane/argon atmosphere, were studied in comparison with diamond‐like‐carbon (DLC) films. The DLC films disappeared because of the oxidation in the air at 500 °C, whereas the Si‐DLC films still remained, implying that the addition of Si improved significantly the thermal stability of DLC films. Retarded hydrogen release from DLC film at high temperature and silicon oxide on the surface might have contributed to lower friction coefficient of the Si‐DLC films both after annealing treatment and in situ high‐temperature environment. Copyright © 2012 John Wiley & Sons, Ltd.     

Thin films of discotic liquid crystals and their applications

ABSTRACT

Discotic liquid crystals (DLCs) are considered as fascinating systems due to their unique property of self-assembly to yield different columnar structures. DLCs are organic semiconductors and create pathways for the development of numerous optical and electrical devices. The thin films of DLCs can be considered as low dimensional system which can exhibit remarkable optical and physical properties. In this article, we present a review on ultrathin films of some interesting DLC molecules at air–water and air–solid interfaces. The Langmuir monolayer and Langmuir–Blodgett films of DLC molecules are extensively studied. The ultrathin films of DLC molecules can yield highly anisotropic layer wherein the molecular orientation and aggregation can have large impact on the physicochemical properties of the film. Different surface phases with different molecular orientations as function of surface density and temperature can be obtained by forming the Langmuir monolayer of the DLC molecules at the air–water interface. The Langmuir monolayer in a particular phase can be deposited onto the active area of a device layer-by-layer by employing a highly controlled Langmuir–Blodgett technique. Here, we report some interesting results related on molecular orientation of the DLC molecules at different interfaces. Such aggregation of DLC molecules in ultrathin films may find applications in thin film-based electro-optical devices.     

Application of ionic liquid in liquid phase microextraction technology

Ionic liquids (ILs) are novel nonmolecular solvents. Their unique properties, such as high thermal stability, tunable viscosity, negligible vapor pressure, nonflammability, and good solubility for inorganic and organic compounds, make them excellent candidates as extraction media for a range of microextraction techniques. Many physical properties of ILs can be varied, and the structural design can be tuned to impart the desired functionality and enhance the analyte extraction selectivity, efficiency, and sensitivity. This paper provides an overview of the applications of ILs in liquid phase microextraction technology, such as single‐drop microextraction, hollow fiber based liquid phase microextraction, and dispersive liquid–liquid microextraction. The sensitivity, linear calibration range, and detection limits for a range of target analytes in the methods were analyzed to determine the advantages of ILs in liquid phase microextraction.     

Reversible Hydrophobic–Hydrophilic Transition of Ionic Liquids Driven by Carbon Dioxide

Ionic liquids (ILs) with a reversible hydrophobic–hydrophilic transition were developed, and they exhibited unique phase behavior with H₂O: monophase in the presence of CO₂, but biphase upon removal of CO₂ at room temperature and atmospheric pressure. Thus, coupling of reaction, separation, and recovery steps in sustainable chemical processes could be realized by a reversible liquid–liquid phase transition of such IL‐H₂O mixtures. Spectroscopic investigations and DFT calculations showed that the mechanism behind hydrophobic–hydrophilic transition involved reversible reaction of CO₂ with anion of the ILs and formation of hydrophilic ammonium salts. These unique IL‐H₂O systems were successfully utilized for facile one‐step synthesis of Au porous films by bubbling CO₂ under ambient conditions. The Au porous films and the ILs were then separated simultaneously from aqueous solutions by bubbling N₂, and recovered ILs could be directly reused in the next process.     

Wettability of Nematic Liquid Crystals

Organic liquids such as nematic liquid crystals should wet solids with high surface energies like mica, yet they generally do not. In the model proposed here, the affinity to wet the solid in form of Hamaker forces is opposed by elastic effects due to nematic order. Results predict correctly that such liquids show small contact angles and the formation of ultrathin liquid films ahead of the bulk drops. Copyright 2001 Academic Press.     

Development of New Efficient Adsorbent by Functionalization of Mg3Al-LDH with Methyl Trialkyl Ammonium Chloride Ionic Liquid

The present paper describes a new way of obtaining an efficient adsorbent material by functionalization of Mg₃Al layered double hydroxides (LDH) with methyl trialkyl ammonium chloride-ionic liquid (IL) using two methods: ultrasound and cosynthesis. Layered double hydroxides are good solid support for the functionalization with ionic liquids due to their well-ordered structure. The immobilization of the ILs in suitable solid supports combine the advantages of the ILs with the properties of the solid supports bringing more benefits such as use of lower quantity of ILs and avoiding of ILs loss in the aqua phase which overall decrease the treatment costs. In case of ultrasound method of functionalization is assured a uniform distribution of IL on the solid surface, but through immobilization by cosynthesis due to the tunable properties of LDH, is assured an intercalation of the ILs between the LDH layers. This fact was highlighted by the X-ray diffraction (RXD), scanning electron microscopy (SEM) analyses and Fourier-transform infrared (FTIR) spectroscopy of the obtained adsorbent. The added value brought by the functionalization of Mg₃Al with the studied IL was underlined by the adsorption studies conducted in the treatment process of water with diclofenac content. Kinetic, thermodynamic, and equilibrium studies were performed. DCF adsorption onto the studied materials correspond to a chemisorption, the pseudo-second-order kinetic model describing the most accurately the experimental data. DCF adsorption onto the studied materials occurs as a heterogeneous process, with the experimental data fitting best with the SIPS isotherm. The sample obtained through cosynthesis developed a maximum adsorption capacity of 648 mg/g.     

Nanoscale structural and electronic properties of ultrathin blends of two polyaromatic molecules: a Kelvin probe force microscopy investigation.

We describe a Kelvin Probe Force Microscopy (KPFM) study on the morphological and electronic properties of complex mono and bi-molecular ultrathin films self-assembled on mica. These architectures are made up from an electron-donor (D), a synthetic all-benzenoid polycyclic aromatic hydrocarbon, and an electron-acceptor (A), perylene-bis-dicarboximide. The former molecule self-assembles into fibers in single component films, while the latter molecule forms discontinuous layers. Taking advantage of the different solubility and self-organizing properties of the A and D molecules, multicomponent ultrathin films characterized by nanoscale phase segregated fibers of D embedded in a discontinuous layer of A are formed. The direct estimation of the surface potential, and consequently the local workfunction from KPFM images allow a comparison of the local electronic properties of the blend with those of the monocomponent films. A change in the average workfunction values of the A and D nanostructures in the blend occurs which is primarily caused by the intimate contact between the two components and the molecular order within the nanostructure self-assembled at the surface. Additional roles can be ascribed to the molecular packing density, to the presence of defects in the film, to the different conformation of the aliphatic peripheral chains that might cover the conjugated core and to the long-range nature of the electrostatic interactions employed to map the surface by KPFM limiting the spatial and potential resolution. The local workfunction studies of heterojunctions can be of help to tune the electronic properties of active multicomponent films, which is crucial for the fabrication of efficient organic electronic devices as solar cells.     

Effect of temperature on friction and wear behaviors of polyimide (PI)‐based solid–liquid lubricating materials

The tribological properties of polyimide (PI) under four oils (including two perfluoropolyether oils and two silicon oils) lubricated conditions were comparatively investigated at room temperature in vacuum and Fomblin M30 and chlorine‐containing silicon oil were selected to study the friction and wear behaviors of PI‐based solid–liquid lubricants against steel at different temperatures in vacuum. Significant improvement in tribological performance of PI was found under oil‐lubricated conditions. The friction coefficient increased as the test temperature decreased for the mobility of liquid lubricant was limited at lower temperatures, while the wear rate exhibited distinct rule. Besides, no tribochemical reaction was detected at the contact surface of PI and chlorine‐containing silicon oil. However, the –CF₃ and fluorinated C? O groups were detected on the worn tracks of PI/Fomblin M30 by X‐ray photoelectron spectroscopy, which indicated that tribochemical reaction happened to PI and Fomblin M30 under high temperature as well as the simulation of friction heat. Copyright © 2015 John Wiley & Sons, Ltd.     

Surface‐Coated Thermally Expandable Microspheres with a Composite of Polydisperse Graphene Oxide Sheets

Surface‐modified thermally expandable microcapsules (TEMs) hold potential for applications in various fields. In this work, we discussed the possible surface coating mechanism and reported the properties of TEMs coated with polyaniline (PANI) and polydisperse graphene oxide sheets (ionic liquid‐graphene oxide hybrid nanomaterial (ILs‐GO)). The surface coating of PANI/ ILs‐GO increased the corresponding particle size and its distribution range. The morphologies analyzed by scanning electron microscopy indicated that no interfacial gap was observed between the microspheres ink and substrate layer during the substrate application. The thermal properties were determined by thermogravimetric and differential thermal analyses. The addition of ILs‐GO to the polyaniline coating significantly improved the thermal expansion and thermal conductivity of the microcapsules. The evaporation of hexane present in the core of TEMs was not prevented by the coating of PANI/ ILs‐GO. The printing application of TEMs showed excellent adaptability to various flexible substrates with great 3D appearance. By incorporating a flame retardant agent into TEMs coated by PANI/ILs‐GO, finally, these TEMs also demonstrated a great flame retardant ability. We expect that these TEM‐coated PANI/ ILs‐GO are likely to have the potential to improve the functional properties for various applications.     

Solid/liquid interfacial tension as a tool to study stability of lysozyme on adsorption to solid surfaces

This work proposes the use of solid/liquid interfacial tension to study the stability of adsorbed lysozyme films on a solid surface using the contact angle of a liquid at the three phase contact line, in the presence of a denaturant, urea.Results suggest a direct correlation between this method with a standard technique like the fluorescence emission spectra and is measured with the same observable error as in the spectral methods. Further the technique provides a simple and direct handle to evaluate the homogeneity and degree of polarity of protein films on solid surfaces.     

Micro/macrotribological properties of several nano‐scale ionic liquid films on modified silicon wafers

Three kinds of alkylimidazolium base room temperature ionic liquids (RTILs) were synthesized and their nano‐scale lubricant films were prepared on modified silicon wafers by dip‐coating method. The thicknesses of these films were measured and their relationship between thickness and solution concentration was obtained. Their surface morphologies were observed and contact angles of water on these films were determined. The adhesions and friction coefficients of these films were detected by contact mode AFM. As comparison, their macrotribological properties were evaluated on a UMT‐2MT tribo‐tester. It was found that, in microscale, 1‐hexyl‐3‐methyl‐imidazolium hexafluorophosphate performed the best tribological properties, while in macroscale, its tribological properties were similar with that of 1‐hexyl‐3‐methyl‐imidazolium tetrafluoroborate and better than that of 1‐hexyl‐3‐methyl‐imidazolium adipate. Copyright © 2009 John Wiley & Sons, Ltd.     

Pd-Pt and Fe-Ni nanoparticles formed by covalent molecular assembly in supercritical carbon dioxide

We report the formation of Pd-Pt nanoparticles within a dendrimer-laden ultrathin film matrix immobilized on a solid support and constructed by covalent layer-by-layer (LbL) assembly using supercritical carbon dioxide (SCCO2) as the processing medium. Particle size distribution and composition were controlled by precursor composition. The precursor compositions are optimized for Pd-Pt nanoparticles and later extended to the formation of Fe-Ni nanoparticles. As an example of the application of nanoparticles in tribology, Fe-Ni nanoparticle-laden films were observed to exhibit better tribological properties than those containing the monometallic species, thereby suggesting that combination of nanoparticles can be used to derive greater benefits.     

Cotton thread modified with ionic liquid copolymerized polymer for online in‐tube solid‐phase microextraction and HPLC analysis of nonsteroidal anti‐inflammatory drugs

Cotton fiber is a biodegradable material that possesses properties such as high specific area, adjustable shape, and hygroscopicity. In this work, organic polymer was directly in situ grown on the surface of cotton thread and packed into a poly(ether ether ketone) tube for online in‐tube solid‐phase microextraction. The novel strategy solves the problems like high backpressure and tedious optimization process of normal monolithic polymer‐based in‐tube solid‐phase microextraction capillary. The quaternary ammonium typed ionic liquid of 1‐allyl‐methylimidazolium chloride, 4‐vinylbiphenyl, and ethylene dimethacrylate were co‐polymerized and in situ grown on the surface of cotton thread as extraction phase. The solid‐phase microextraction tube showed excellent performance for the extraction of three nonsteroidal anti‐inflammatory drugs including ketoprofen, naproxen, and flurbiprofen due to the strong ion exchange and hydrophobic interactions. After online coupling with a high‐performance liquid chromatography system by six‐port valve, the method was applied for the quantitative analysis of nonsteroidal anti‐inflammatory drugs in human plasma samples showing good enrichment performance (enrichment factor between 263 and 279), high sensitivity, good linearity, and good reproducibility.     

Tribological properties of self-assembled monolayers of catecholic imidazolium and the spin-coated films of ionic liquids

A novel compound of an imidazolium type of ionic liquid (IL) containing a biomimetic catecholic functional group normally seen in mussel adhesive proteins was synthesized. The IL can be immobilized on a silicon surface and a variety of other engineering material surfaces via the catecholic anchor, allowing the tribological protection of these substrates for engineering applications. The surface wetting and adhesive properties and the tribological property of the synthesized self-assembled monolayers (SAMs) are successfully modulated by altering the counteranions. The chemical composition and wettability of the IL SAMs were characterized by means of X-ray photoelectron spectroscopy (XPS) and contact angle (CA) measurements. The adhesive and friction forces were measured with an atomic force microscope (AFM) on the nanometer scale. IL composite films were prepared by spin coating thin IL films on top of the SAMs. The macrotribological properties of these IL composite films were investigated with a pin-on-disk tribometer. The results indicate that the presence of IL SAMs on a surface can improve the wettability of spin-coated ionic liquids and thus the film quality and the tribological properties. These films registered a reduced friction coefficient and a significantly enhanced durability and load-carrying capacity. The tribological properties of the composite films are better than those of pure IL films because the presence of the monolayers improves the adhesion and compatibility of spin-coated IL films with substrates.     

Recent developments in the study of ionic liquid interfaces using X-ray photoelectron spectroscopy and potential future directions

A perspective is given on the potential of X-ray photoelectron spectroscopy to investigate ionic liquid (IL) interfaces and related bulk properties. To allow for cross-correlation of different IL properties, the study is restricted to imidazolium-based systems. By systematic variation of alkyl chain lengths, by investigation of different anions, and by introduction of functional groups detailed information on surface orientation, enrichment effects, cation-anion interactions, and the correlation to macroscopic properties such as density and surface tension of ILs are derived. Furthermore, the molecular arrangement and growth behaviour of ultrathin ionic liquid layers on various substrates, in situ monitoring of chemical reactions, and the dissolution of transition metal complexes are addressed.