Behavior of Ionic Liquids Under Nanoconfinement Greatly Affects Actual Friction

Ionic liquids (ILs) are organic salts consisting of anions and cations that exist as liquids at room temperature. ILs exhibit many attractive properties such as negligible volatility, low flammability, and relatively high thermal stability. These properties can be varied in a controlled fashion through systematic changes in the molecular structure of their constituent ions. Some recent studies have aimed to use ILs as new lubricant materials. However, the behavior of ILs as lubricants on the sliding interfaces has not been elucidated. In this chapter, we describe the nano- and macrolubrication properties of some ILs with different types of anions using resonance shear measurement (RSM) and conventional ball-on-plate-type tribotests, respectively. This study reveals that the properties observed by RSM for nanoscale systems can provide important insights for the study of the friction coefficients (macrolubrication properties) obtained by tribotests

Development of Low-Friction Ion Gels for Industrial Applications

Friction reduction is imperative for improving the service life and energy efficiency of mechanical systems. Ion gels using ionic liquids (ILs) as swelling agents are expected to be stable gel lubricants owing to the high thermal stability and negligible volatility of ILs; they can maintain their swollen state even under harsh conditions. Therefore, we investigated two types of ion gels: an IL-substituted double-network gel (DN ion S-gel), in which the water in the DN hydrogel is replaced by the IL 3-ethyl-1-methyl-imidazolium ethylsulfate; and a DN ion gel containing N,N-diethyl-N-(2-methoxyethyl)-N-methyl-ammonium bis(trifluoromethylsulfonyl)imide (DEME-TFSI), where one of the polymer backbones is a network of poly(N,N-diethyl-N-(2-methacryloylethyl)-N-methylammonium bis(trifluoromethylsulfonyl)imide), an IL-type polymer based on our previous synthetic study of IL polymer technology. The DN ion S-gel and DN ion gel achieved compression strengths of 25 and 30 MPa, respectively, and were thermally stable until 196°C and 335°C (10% weight-loss temperature), respectively. The coefficient of friction remained stable and low (0.02) after repeated measurements under harsh conditions (high temperature or vacuum conditions), affirming the durability of the DN ion gel

Measurement of a Phase of a Radio Wave Reflected from Rock Salt and Ice Irradiated by an Electron Beam for Detection of Ultra-High-Energy Neutrinos

We have found a radio-wave-reflection effect in rock salt for the detection of ultra-high energy neutrinos which are expected to be generated in Greisen, Zatsepin, and Kuzmin (GZK) processes in the universe. When an UHE neutrino interacts with rock salt or ice as a detection medium, a shower is generated. That shower is formed by hadronic and electromagnetic avalanche processes. The energy of the UHE neutrino shower converts to thermal energy through ionization processes. Consequently, the temperature rises along the shower produced by the UHE neutrino. The refractive index of the medium rises with temperature. The irregularity of the refractive index in the medium leads to a reflection of radio waves. This reflection effect combined with the long attenuation length of radio waves in rock salt and ice would yield a new method to detect UHE neutrinos. We measured the phase of the reflected radio wave under irradiation with an electron beam on ice and rock salt powder. The measured phase showed excellent consistence with the power reflection fraction which was measured directly. A model taking into account the temperature change explained the phase and the amplitude of the reflected wave. Therefore the reflection mechanism was confirmed. The power reflection fraction was compared with that calculated with the Fresnel equations, the ratio between the measured result and that obtained with the Fresnel equations in ice was larger than that of rock salt.Comment: 6 Pages, 5th International Workshop on Acoustic and Radio EeV Neutrino Detection Activitie

Synthesis of Monodisperse Silica Particles Grafted with Concentrated Ionic Liquid-Type Polymer Brushes by Surface-Initiated Atom Transfer Radical Polymerization for Use as a Solid State Polymer Electrolyte

A polymerizable ionic liquid, N, N-diethyl-N-(2-methacryloylethyl)-N-methylammonium bis(trifluoromethylsulfonyl)imide (DEMM-TFSI), was polymerized via copper-mediated atom transfer radical polymerization (ATRP). The polymerization proceeded in a living manner producing well-defined poly(DEMM-TFSI) of target molecular weight up to about 400 K (including a polycation and an counter anion). The accurate molecular weight as determined by a GPC analysis combined with a light scattering measurement, and the molecular weight values obtained exhibited good agreement with the theoretical values calculated from the initial molar ratio of DEMM-TFSI and the monomer conversion. Surface-initiated ATRP on the surface of monodisperse silica particles (SiPs) with various diameters was successfully performed, producing SiPs grafted with well-defined poly(DEMM-TFSI) with a graft density as high as 0.15 chains/nm2. Since the composite film made from the silica-particle-decorated polymer brush and ionic liquid shows a relatively high ionic conductivity, we have evaluated the relationship between the grafted brush chain length and the ionic conductivity

Tribological Properties of Double-Network Gels Substituted by Ionic Liquids

Since human body joints have a gel-like structure with low friction that persists for several decades, hydrogels have attracted much interest for developing low-friction materials. However, such advantages can hardly be realized in industrial usage because water in the gel evaporates easily and the gel deswells. The substitution of water with an ionic liquid (IL) is one of the effective ways to overcome this problem. In this study, we substituted water in a double network (DN) hydrogel with 3-ethyl-1-methyl-imidazolium ethylsulfate (EMI-EtSulf), a hydrophilic IL, via a simple solvent exchange method to obtain a DN ion gel. A compressive test and thermogravimetric analysis showed that the DN ion gel has a high compression fracture stress and improved thermal properties, with the difference in 10% loss of temperature being ΔT10 = 234 °C. A friction test conducted using a reciprocating tribometer showed that the friction of a glass ball/DN ion gel was relatively higher than that of a glass ball/DN hydrogel. Because the minimum coefficient of friction (COF) value increased after substitution, the increase in polymer adhesion caused by the electrostatic shielding of the surface moieties of glass and poly 2-acrylamidomethylpropanesulfonic acid (PAMPS) was considered the main contributor to the high friction. As the COF value decreased with increasing temperature, the DN ion gel can achieve low friction via the restriction of polymer adhesion at high temperatures, which is difficult in the DN hydrogel owing to drying

Electrical Stimuli-Responsive Decomposition of Layer-by-Layer Films Composed of Polycations and TEMPO-Modified Poly(acrylic acid)

We previously reported that layer-by-layer (LbL) film prepared by a combination of 2,2,6,6-tetramethylpiperidinyl N-oxyl (TEMPO)-modified polyacrylic acid (PAA) and polyethyleneimine (PEI) were decomposed by application of an electric potential. However, there have been no reports yet for other polycationic species. In this study, LbL films were prepared by combining various polycationics (PEI, poly(allylamine hydrochloride) (PAH), poly(diallydimethylammonium chloride) (PDDA), and polyamidoamine (PAMAM) dendrimer) and TEMPO-PAA, and the decomposition of the thin films was evaluated using cyclic voltammetry (CV) and constant potential using an electrochemical quartz crystal microbalance (eQCM). When a potential was applied to an electrode coated on an LbL thin film of polycations and TEMPO-PAA, an oxidation potential peak (Epa) was obtained around +0.6 V vs. Ag/AgCl in CV measurements. EQCM measurements showed the decomposition of the LbL films at voltages near the Epa of the TEMPO residues. Decomposition rate was 82% for the (PEI/TEMPO-PAA)5 film, 52% for the (PAH/TEMPO-PAA)5 film, and 49% for the (PDDA/TEMPO-PAA)5 film. It is considered that the oxoammonium ion has a positive charge, and the LbL films were decomposed due to electrostatic repulsion with the polycations (PEI, PAH, and PDDA). These LbL films may lead to applications in drug release by electrical stimulation. On the other hand, the CV of the (PAMAM/TEMPO-PAA)5 film did not decompose. It is possible that the decomposition of the thin film is not promoted, probably because the amount of TEMPO-PAA absorbed is small

Low Friction, Lubricity, and Durability of Polymer Brush Coatings, Characterized Using the Relaxation Tribometer Technique †

Among the possible solutions for achieving low friction, polymer brushes that are grafted onto surfaces are good candidates. The tribological characterization of such layers becomes more difficult when the friction is lower: the signal-to-noise ratio of the friction force that is measured with conventional tribometers impedes the precise quantification. Therefore, we have applied a new technique that has been developed at the Laboratory of Tribology and System Dynamics (LTDS), called the ‘oscillating relaxation tribometer’. The advantage of this original technique is that it characterizes low friction with unequalled sensitivity. The lower the friction, the better the precision, and it permits obtaining the ‘friction law’ directly from robust and rapid experimental tests. In this study, the samples that have been used are the ionic liquid-type polymer brushes (ILPBs) with different thicknesses, which have been grafted onto silicon wafers and steel coupons. The counter-face is a mirror-polished steel ball. We show that (i) a thick ILPB layer on silicon is very resistant to high contact pressure, up to 555 MPa; (ii) the friction behavior that is obtained is close to that of a Newtonian viscous one, even under maximum normal loads; (iii) poorer results are obtained for the thinner sample; and (iv) the repetition, up to 5000 oscillations on the same surface, does not affect the friction damping of the contact, which demonstrates that this film provides a favorable resistance to friction under severe contact conditions. In addition, the feasibility of grafting onto steel surfaces is demonstrated. The results are then discussed, with respect to friction and dissipation