Nanotribological Characterization of Lubricants between Smooth Iron Surfaces.

We performed the resonance shear measurement (RSM) for evaluating the nanorheological and tribological properties of model lubricants, hexadecane and poly(α-olefin) (PAO), confined between iron surfaces. The twin-path surface forces apparatus (SFA) was used for determining the distance between the surfaces. The obtained resonance curves for the confined lubricants showed that the viscosity of the confined hexadecane and PAO increased due to liquid structuring when the surface separation (D) decreased to a value less than 24 and 20 nm, respectively. It was also determined that the iron surfaces were lubricated by the hexadecane when normal load (L) was less than 1.1 mN, while the confined hexadecane behaved almost solid-like and showed poor lubricity when L was greater than 1.1 mN. In contrast, PAO between the iron surfaces showed high lubricity even under the high load (L > 2 mN). The surface separation of hexadecane and PAO at a hard wall contact between the iron surfaces was determined to be 4.6 ± 0.5 and 5.0 ± 0.4 nm by applying the fringes of equal chromatic order (FECO) for half-transparent iron films deposited on mica surfaces as substrates. We also characterized hexadecane and PAO confined between mica surfaces for studying the effect of substrates on the confined lubricants.

Lubrication Properties of Ammonium-Based Ionic Liquids Confined between Silica Surfaces Using Resonance Shear Measurements.

To evaluate the friction properties of new lubrication systems, two types of ammonium-based ionic liquids (ILs), N,N-diethyl-N-methyl-N-(2-methoxyethyl) ammonium tetrafluoroborate ([DEME][BF4]) and N,N-diethyl-N-methyl-N-(2-methoxyethyl) ammonium bis(trifluoromethanesulfonyl) imide ([DEME][TFSI]), were investigated by resonance shear measurements (RSM) and reciprocating type tribotests between silica (glass) surfaces. RSM revealed that an IL layer of ca. 2 nm in thickness was maintained between the silica surfaces under an applied load of 0.40 mN ∼ 1.2 mN. The relative intensity of the RMS signal indicated that the friction of the system was lower for [DEME][BF4], 0.12, than that of [DEME][TFSI], 0.18. On the other hand, the friction coefficients µk obtained from the tribotests of [DEME][BF4] were lower than that of [DEME][TFSI] for sliding velocities in the range of 5.0 × 10(-4) m s(-1) to 3.0 × 10(-2) m s(-1) under applied loads of 196-980 mN. The friction coefficients obtained by the tribotest are discussed with reference to the RSM results.

Self-assembly of double-tail anionic surfactant having cyanobiphenyl terminal groups in water.

This study reports the interfacial properties and lyotropic liquid crystal formation of sodium 1,2-bis{6-[4-(4-cyanophenyl)phenyloxy]hexyloxycarbonyl}ethanesulfonate (SBCPHS), which is a double-tail surfactant with cyanobiphenyl terminal groups, in water. Polarized microscopic observation of water/SBCPHS mixtures revealed the presence of columnar and lamellar phases. In the lamellar phase, myelin figures representing multilamellar tubes were observed, and some of these figures had a double-helix structure. In order to examine these liquid crystal structures in detail, the bilayer thickness of the lamellar tubes and the lattice parameters of the columnar phase were measured by small-angle X-ray scattering analysis. Four scattering peaks that could be ascribed to C2/m symmetry were observed for the columnar phase. The bilayer thickness and one of the lattice parameters were smaller than twice the molecular length of SBCPHS; this showed that the liquid crystal phases had intercalated structures. Comparison of SBCPHS with a typical double-tail hydrocarbon surfactant revealed that the cyanobiphenyl terminal groups in the former helped increase the stability of the liquid crystal formed at low temperatures. The stabilizing effect of the cyanobiphenyl terminal groups on the liquid crystals could have been driven by electrostatic intermolecular interactions between the terminal groups in antiparallel arrangement of the SBCPHS molecules.

Characterization of water/supercritical CO2 microemulsion by UV-visible spectroscopy and dynamic light scattering.

A water/supercritical CO(2) microemulsion (W/scCO(2) microE) with methyl orange (MO) and sodium bis(1H,1H,2H,2H-heptadecafluorodecyl)-2-sulfosuccinate, 8FS(EO)(2), was characterized by means of UV-visible absorption spectral and dynamic light scattering (DLS) measurements. Visual observation of the scCO(2) mixtures revealed transparent and reddish scCO(2) phases with and without separated excess water; they were identified as Winsor-II and Winsor-IV W/scCO(2) microE, respectively. The polarities of the aqueous cores in the Winsor-IV W/scCO(2) microE were examined by observing the spectral shift of the absorbance maximum of MO. It was observed that with an increase in the water-to-surfactant molar ratio (W(0)(c)), the measured absorbance maximum shifted from 418 to 423 nm, which suggests that the polarity of the environment surrounding the MO molecules was methanol-like, and the polarity increased with W(0)(c). The hydrodynamic diameter of Winsor-IV W/scCO(2) microE increased drastically with W(0)(c) but gradually with a decrease in the CO(2) density. The increase in the diameter was a result of the aggregation of the microE droplets and the fusion promoted by the increase in W(0)(c) and the decrease in the CO(2) density, in addition to the swelling of reversed micelles.