Effect of inorganic material surface chemistry on structures and fracture behaviours of epoxy resin.

The mechanisms underlying the influence of the surface chemistry of inorganic materials on polymer structures and fracture behaviours near adhesive interfaces are not fully understood. This study demonstrates the first clear and direct evidence that molecular surface segregation and cross-linking of epoxy resin are driven by intermolecular forces at the inorganic surfaces alone, which can be linked directly to adhesive failure mechanisms. We prepare adhesive interfaces between epoxy resin and silicon substrates with varying surface chemistries (OH and H terminations) with a smoothness below 1 nm, which have different adhesive strengths by ~13 %. The epoxy resins within sub-nanometre distance from the surfaces with different chemistries exhibit distinct amine-to-epoxy ratios, cross-linked network structures, and adhesion energies. The OH- and H-terminated interfaces exhibit cohesive failure and interfacial delamination, respectively. The substrate surface chemistry impacts the cross-linked structures of the epoxy resins within several nanometres of the interfaces and the adsorption structures of molecules at the interfaces, which result in different fracture behaviours and adhesive strengths.

Surface Forces Characterization of Concentrated PMMA Brush Layers under Applied Load and Shear.

Concentrated polymer brushes (CPBs) are known to exhibit excellent lubrication properties. However, the frictional behaviors of CPBs vary, depending on their preparation and operating conditions. In order to understand such complicated properties, it is necessary to determine their structures and correlate them with their properties, during shear motion. In this study, we employed surface forces and resonance shear measurement (RSM) as well as refractive index measurement using fringes of equal chromatic order (FECO) for studying the structure of the CPBs of poly(methyl methacrylate) (PMMA) in toluene. The obtained elastic (ks) and viscous (bs) parameters based on the RSM for the PMMA-PMMA were higher than those obtained for PMMA-silica over the entire distance range. With the increasing shear amplitude on the PMMA-PMMA under an applied load, the bs value first increased and then decreased while the ks value monotonically decreased. These behaviors were consistent with those of the thicker CPBs reported in a previous paper (Soft Matter, 2019). Thus, the dynamics of the CPBs under the applied load and shear were not dependent on the thickness of the polymer brushes in this case. The density distribution of the swollen PMMA brushes along the distance in the thickness direction of the brush layer was estimated by using the measured refractive index values, showing that the fraction of the PMMA brushes in the outer region from the surface (20% in the thickness) was ca. 10%. This lower density region near the surface of the swollen CPBs enabled them to interpenetrate with each other. Changes in the refractive index value under shear were observed, indicating that the interpenetrated PMMA chains were pulled out with increasing shear amplitude. These results demonstrated that broader applications of CPBs are possible by regulating the friction between them under different operating conditions, even for usually lubricious CPBs.

Hypolipidemic and Anti-Inflammatory Effects of Curcuma longa-Derived Bisacurone in High-Fat Diet-Fed Mice.

Turmeric (Curcuma longa) contains various compounds that potentially improve health. Bisacurone is a turmeric-derived compound but has been less studied compared to other compounds, such as curcumin. In this study, we aimed to evaluate the anti-inflammatory and lipid-lowering effects of bisacurone in high-fat diet (HFD)-fed mice. Mice were fed HFD to induce lipidemia and orally administered bisacurone daily for two weeks. Bisacurone reduced liver weight, serum cholesterol and triglyceride levels, and blood viscosity in mice. Splenocytes from bisacurone-treated mice produced lower levels of the pro-inflammatory cytokines IL-6 and TNF-α upon stimulation with a toll-like receptor (TLR) 4 ligand, lipopolysaccharide (LPS), and TLR1/2 ligand, Pam3CSK4, than those from untreated mice. Bisacurone also inhibited LPS-induced IL-6 and TNF-α production in the murine macrophage cell line, RAW264.7. Western blot analysis revealed that bisacurone inhibited the phosphorylation of IKKα/ß and NF-κB p65 subunit, but not of the mitogen-activated protein kinases, p38 kinase and p42/44 kinases, and c-Jun N-terminal kinase in the cells. Collectively, these results suggest that bisacurone has the potential to reduce serum lipid levels and blood viscosity in mice with high-fat diet-induced lipidemia and modulate inflammation via inhibition of NF-κB-mediated pathways.

Viscosity of Nanoconfined Branched-Chain Fatty Acids Studied by Resonance Shear Measurements.

Lubricant performance can be improved using additives such as organic friction modifiers (OFMs) and is influenced by their conformation and properties in the space confined between the substrate surfaces, rendering the detailed property analysis of confined OFMs and lubricants a matter of high practical significance. To date, studies on fatty acids as confined OFMs have mainly focused on linear- and unsaturated-chain molecules, leaving branched-chain structures underexplored. To bridge this gap, we used resonance shear measurements in this study to probe the viscosity of two branched-chain C18 fatty acids (isostearic acid T and isostearic acid) confined between mica surfaces at different applied normal loads (L) and surface separation distances (D). The viscosity parameter (bs) of both acids significantly increased at D < ∼4 nm because of structuring and was lower for isostearic acid than that for isostearic acid T at L > ∼0.6 mN. This reversal of bulk viscosity order under nanoconfinement was ascribed to the ability of the bulky methyl-substituted side chain of isostearic acid to prevent ordering in the nanospace between the mica surfaces and thus preserve fluidlike properties. The obtained results provide fundamental insights into the lubricity of branched-chain fatty acids and are expected to promote the development of novel high-performance OFMs.

Structures of Nanoconfined Liquids Determined by Synchrotron X-ray Diffraction.

We have successfully performed X-ray diffraction measurements of the liquids octamethylcyclotetrasiloxane (OMCTS, a quasi-spherical-shaped molecule) and n-hexadecane (a normal alkane) confined between mica surfaces at surface separation distances (D's) from 500 nm to the hard-wall thickness (1.9 nm for OMCTS and 1.0 nm for hexadecane). At all of the studied D's, we observed diffraction peaks corresponding to their mean intermolecular spacing at q = 8.6 nm-1 (d = 0.73 nm) for OMCTS and q = 13.6 nm-1 (d = 0.45 nm) for n-hexadecane. The peak intensity increased at D < ca. 50 nm for OMCTS even with the decreasing distance and exhibited a local maximum at D = 17-13 nm, indicating the sharp increase in the molecular order in this distance range. The peak intensities normalized by the D and Inormalized values of OMCTS and n-hexadecane were nearly constant at D's greater than 100 nm, though they appeared to increase slightly. The increase then became more significant with decreasing D below 100 nm, and finally the Inormalized values became 120 (for OMCTS) and 160 (for n-hexadecane) at the hard wall. These results clearly demonstrated the significant increase in the structural order of OMCTS and n-hexadecane under nanoconfinement, especially below 100 nm. The fwhm values of the peaks of OMCTS and n-hexadecane showed no significant change until small distances when the confinement effect was significant. These results indicated that the increase in the structural order should be mainly ascribed to the ordering of the molecules in the parallel plane in the enhanced layered structure formed under the confinement. The viscous parameters (b2) of OMCTS and n-hexadecane obtained from the resonance shear measurement showed no increase at D's down to ca. 7 nm. This indicated that a certain ordering of the confined molecules was required for the observable increase in the viscosity.

Effects of surface and shear forces on nano-confined smectic-A liquid crystals studied by X-ray diffraction.

The orientational behavior of a smectic-A liquid crystal (4-cyano-4'-octylbiphenyl, 8CB) confined between mica surfaces as well as between silica surfaces with a nanometer scale thickness was investigated by synchrotron X-ray diffraction measurement. The crystallographic axes of two confining mica sheets were adjusted parallel to each other to induce the preferential orientation of 8CB molecules along their crystallographic axis. The silica surfaces, which were hydrophilic and amorphous and had nanometer level smoothness, were prepared on mica surfaces using a sputtering technique. The X-ray diffraction measurement revealed that the 8CB molecules, confined between mica surfaces (DHW = 1.7 nm) and between silica surfaces (DHW = ca. 2 nm), took a planar orientation (oriented its long axis parallel to the surface) and formed a lamellar structure. However, the in-plane orientation of the confined 8CB changed depending on the confining surfaces. The lamellar axis of the 8CB confined between mica surfaces uniaxially oriented most probably due to the preferential alignment of its long axis along the principal crystallographic a-axis of the mica. On the other hand, 8CB between the silica surfaces formed lamellar domains in which the lamellar axis of 8CB omnidirectionally oriented in-plane. The effect of the shear on the orientation of the nano-confined 8CB was also investigated. The lamellar axis, corresponding to the long axis of the 8CB molecules confined between the mica surfaces, rotated only ca. 3 degrees within the plane parallel to the surface by perpendicularly applying shear to the axis. The lamellar axis of the 8CB molecules between the silica surfaces showed no noticeable change by applying the shear. These results indicated that the effect of shear to align the 8CB molecules was significantly suppressed due to the confinement effect which significantly reduces the mobility of molecules as well as the alignment effect along the crystallographic axis in the case of mica. We also observed a change in the orientation of nano-confined 8CB after shear treatment at large D (= 3.3 µm).

Dynamics of lubricious, concentrated PMMA brush layers studied by surface forces and resonance shear measurements.

We employed surface forces and resonance shear measurement (RSM) for studying the structure and properties of typical concentrated polymer brushes (CPBs) of poly(methylmethacrylate) (PMMA) in toluene, which are known to show very low friction. The surface forces measured between the silica surfaces bearing PMMA brush layers showed a steric repulsive force at distances between the silica surfaces of less than ca. 1050 nm (Donset). Upon retraction after compression of the PMMA brush layers, no adhesive force was observed. This indicated that the interpenetration of the polymer chain was not induced by the normal load. Based on the resonance shear measurement, the elastic (k2) and damping (viscous) (b2) parameters, which represent the dynamic properties, of the PMMA brush layers were obtained by analyzing the resonance curves. At distances below the Donset, the b2 value significantly increased and slightly decreased at the higher normal loads, and the k2 value monotonically increased with increasing load. These k2 and b2 values were greater than those obtained for a PMMA brush layer and a bare silica surface (PMMA-silica). This indicated that the mobility of the polymer chains for the PMMA-PMMA brush layers was more suppressed compared to that for the PMMA-silica, due to the interpenetration of the polymer chains. The interpenetration of the polymer chains, commonly not observed for CPBs, could be most probably induced by the application of both the normal load and oscillating shear motion. With increasing shear amplitude on the compressed PMMA-PMMA brushes (at L = 0.84, 1.34 and 4.28 mN), the b2 value first increased then decreased whilst the k2 value monotonically decreased. These tendencies can be explained by the change from the sticking condition due to interpenetration (high k2), small sliding under interpenetration (increase in b2, decrease in k2), and then smooth sliding by pulling out of interpenetrated polymer chains (decrease in b2 and k2). The obtained results indicated that the operating conditions are quite important for using polymer brush layers as tribological materials because they can exhibit both a high and low friction depending on the conditions such as the load and shear amplitude.

Mechanical model analysis for resonance shear measurement.

Resonance shear measurement (RSM), which we developed based on a surface force apparatus, can investigate the structuring, and rheological and tribological properties of confined liquids as a function of the surface separation distance (D) from several µm to zero with a nanometer resolution. Using RSM, we reported that the nanoconfined liquids, including commercial lubricants, exhibited properties quite different from the bulk phase. Mechanical modeling of the resonance system is necessary to quantitatively evaluate the properties of confined liquids and/or sheared interfaces. In this study, we improved the model for RSM as follows: (1) We directly measured the movements of the upper and lower surfaces in addition to the measurement on the movement of the vertical spring to confirm the model, which could be used to estimate the parameters used in the model; (2) we proposed a modified mechanical model which considers the effect of additional motion. This model could fit the resonance curves using a identical apparatus constant for the entire measurement range, while the characteristic values of the confined liquids are the same as those obtained using our previous model, and (3) we calculated the friction (shear) force using the improved model and obtained the characteristic values (viscous and elastic parameters) of the confined liquids. This study afforded the simplicity and reliability of a mechanical model analysis of resonance curves, and the friction force calculation employing the viscous and elastic terms can be useful for studying the mechanism of friction force.

Deformation of contacting interface between polymer hydrogel and silica sphere studied by resonance shear measurement.

The deformation of the interfaces between a soft material and hard material in contact plays an important role in the friction and lubrication between them. We recently reported that the elastic property of the contact interface dominated the friction of the interface between a flat polymer hydrogel [double network (DN) gel of 2-acrylamide-2-methylpropanesulfonic acid and N,N-dimethylacrylamide] and a silica sphere [Ren et al., Soft Matter 11, 6192-6200 (2015)]. In this study, in order to quantitatively describe the dependence of the elastic response on the geometrical parameters of the deformed interfaces, we employed the resonance shear measurement (RSM) and investigated the deformation of the interfaces between a flat DN gel and silica spheres by varying the curvature radius (R = 18.3, 13.8, 9.2, 6.9 mm). Resonance curves were analyzed using a mechanical model consisting of the elastic (k 2) and viscous (b 2) parameters of the contact interface. The obtained elastic parameter (k 2) increases at higher loads and for smaller silica spheres, while the viscous parameter (b 2) was negligibly low for all the conditions. The relations between the elastic parameter (k 2), geometric parameters of the deformed contact interface, and the applied normal load were investigated. The elastic parameter (k 2) was found to be proportional to the arc length (arc) (radius of contact area, r), i.e., k 2 ∝ arc or k 2 ∝ r. We introduced the term "elastic modulus of the contact interface, E contact" as a proportionality constant to describe the elastic parameter of the deformed interfaces (k 2): k 2 (N/m) = arc (m) × E contact (Pa). Thus, the friction (f) between the DN gel and the silica sphere can be described by the following equation: f = f elastic = arc (m) × E contact (N/m2) × Δx (m) (Δx: shear deformation of the contact interface between the DN gel and silica sphere). The E contact value determined from the slope k 2 vs arc was 493 ± 18 kPa. The RSM measurement and the analysis presented here can be a unique method for characterizing the specific properties of the deformed interfaces between soft and hard materials.

X-Ray diffraction and resonance shear measurement of nano-confined ionic liquids.

X-ray diffraction measurement at the SPring-8 synchrotron was employed to investigate the structures of two types of imidazolium-based ionic liquids (ILs), 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([C4mim][NTF2]) and 1-butyl-3-methylimidazolium tetrafluoroborate ([C4mim][BF4]), confined between silica surfaces by varying the surface separation distances of ca. 500 nm (bulk liquid), ca. 10 nm, and ca. 2 nm (hard wall thickness). The obtained diffraction profiles and intensities were discussed by considering the structures and properties of the nano-confined ILs between the silica surfaces investigated by resonance shear measurement (RSM) and molecular dynamics simulation (MD) in our previous reports. [C4mim][NTf2] showed two diffraction peaks at q = 8.8 nm-1 (spacing d = 0.71 nm) and at q = 14.0 nm-1 (spacing d = 0.45 nm) at the greatest distance (D = ca. 500 nm), which were assigned to the interval between the same ions (anion-anion or cation-cation) within the polar network of [C4mim][NTf2] and the interval between the neighboring anion-cation, respectively. The positions of these two peaks remained the same at D = ca. 10 nm and at the hard wall (D = ca. 2 nm) and their intensity factor increased, indicating that both the cation and anion existed in the same layer. This result was consistent with the checkerboard structure of [C4mim][NTf2] on the silica surface computer simulated in our previous studies. On the other hand, [C4mim][BF4] showed a peak at q = 15.4 nm-1 (spacing d = 0.41 nm) corresponding to the anion-cation interval at the greatest distance (D = ca. 500 nm). This peak became broader and weaker at D = ca. 12 nm and at D = ca. 2 nm.

Preparation of stable silica surfaces for surface forces measurement.

A surface forces apparatus (SFA) measures the forces between two surfaces as a function of the surface separation distance. It is regarded as an essential tool for studying the interactions between two surfaces. However, sample surfaces used for the conventional SFA measurements have been mostly limited to thin (ca. 2-3 µm) micas, which are coated with silver layers (ca. 50 nm) on their back, due to the requirement of the distance determination by transmission mode optical interferometry called FECO (fringes of equal chromatic order). The FECO method has the advantage of determining the absolute distance, so it should be important to increase the availability of samples other than mica, which is chemically nonreactive and also requires significant efforts for cleaving. Recently, silica sheets have been occasionally used in place of mica, which increases the possibility of surface modification. However, in this case, the silver layer side of the sheet is glued on a cylindrical quartz disc using epoxy resin, which is not stable in organic solvents and can be easily swollen or dissolved. The preparation of substrates more stable under severe conditions, such as in organic solvents, is necessary for extending application of the measurement. In this study, we report an easy method for preparing stable silica layers of ca. 2 µm in thickness deposited on gold layers (41 nm)/silica discs by sputtering, then annealed to enhance the stability. The obtained silica layers were stable and showed no swelling in organic solvents such as ethanol and toluene.

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.

Force Estimation on the Contact of Poly(l,l-lactide) and Poly(d,d-lactide) Surfaces Regarding Stereocomplex Formation.

The stereocomplex formation of poly(l,l-lactide) (PLLA) and poly(d,d-lactide) (PDLA) was selected in order to investigate the interaction of the two surfaces including hydrogen bonding and van der Waals interaction. Adhesion force measurement using surface force apparatus (SFA) equipped with an optical microscope was conducted on the PLLA and PDLA spin-coated films. The adhesion forces, Fad, phenomenologically followed the linear relation with the applied normal load, L. For the force Fad between PLLA and PDLA films with low molecular weights (PLLA, Mn = 2800; PDLA, : Mn = 2100), the slope of linear fitting of Fad vs L was significantly larger for the heterointerface (PLLA/PLDA) compared with that for the homointerface (PLLA/PLLA and PDLA/PDLA). However, when polymers with higher molecular weights (PLLA, Mn = 8500; PDLA, Mn = 8300) were measured, the slopes of linear fitting lines were almost the same for hetero- and homointerfaces. This indicated that the mobility of the lower molecular weight PLLA/PDLA films promoted the selective interaction of PLLA and PDLA under the applied normal loads. The adhesion between the outermost PLLA layer and PDLA layer prepared by layer-by-layer (LbL) assembly was also measured. It is interesting that the adhesion force was very weak in this case. This weak adhesion could be explained by the much less mobility of the polymer chain due to the stereocomplex formation within the LbL layers. This study demonstrated that the adhesion force due to the selective interaction of PLLA and PDLA between PLLA/PDLA films could be directly measured, and depended on the mobility of the outermost polymer chains, which reflected the different structures of polymer chains in the organized complex films.

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.

Structural stability and polarisation of ionic liquid films on silica surfaces.

We used molecular dynamics simulations to investigate the effect of disorder of the hydroxylated amorphous silica surface on the structure of 8 nm IL films formed from two ionic liquids featuring the same cation 1-butyl-3-methyl-imidazolium or [BMIM], paired with bis(trifluoromethanesulphonyl)amide [NTF2] and tetrafluoroborate [BF4] anions. Several silica surfaces were modelled to estimate the effect of their atomic-scale configuration on the solid-liquid interface and the results are compared to those simulated on the crystalline cristobalite surface. Using strongly polar surfaces, we could also evaluate the response of the ILs to the electric field externally controlled or generated by charged defects in the silica film. We found that the structure of the liquids becomes weaker away from the interface and more susceptible to electric field. Our simulations show that [BMIM][BF4] has a large intrinsic dipole originating at the interface, resilient to external fields, while the polarisation of [BMIM][NTF2] can be more easily controlled.

Friction of polymer hydrogels studied by resonance shear measurements.

The friction between an elastomer and a hard surface typically has two contributors, i.e., the interfacial and deformation components. The friction of viscoelastic hydrogel materials has been extensively studied between planar gel and planar substrate surfaces from the viewpoint of an interfacial interaction. However, the geometry of the contact in practical applications is much more complex. The contribution of geometric and elastic deformation terms of a gel to friction could not be neglected. In this study, we used resonance shear measurements (RSMs) for characterizing the shear response of a glass sphere on a flat polymer hydrogel, a double network (DN) gel of 2-acrylamide-2-methylpropanesulfonic acid and N,N-dimethylacrylamide. The contact mechanics conformed to the Johnson-Kendall-Roberts theory. The observed resonance curves exhibited rather sharp peaks when the DN gel and the silica sphere were brought into contact, and their intensity and frequency increased with the increase in the normal load. We proposed a simple physical model of the shearing system, and the elastic (k2) and viscous (b2) parameters of the interface between a silica sphere and a flat DN gel were obtained. The friction force from elastic deformation and viscous dissipation terms was then estimated using the obtained parameters. It was revealed that the elastic parameter (k2) increased up to 1780 N m(-1) at a normal load of 524 mN, while the viscous parameter (b2) was zero or quite low (<0.1 N s m(-1)) for a silica sphere (radius of 18.4 mm). Thus, the friction force between a flat DN gel and a silica sphere in air was dominated by the elastic term due to the local deformation by contact with the silica sphere. By adding water, the elastic parameter (k2) remained the same, while the viscous parameter (b2) slightly increased. However, the viscous term fviscous was still much smaller than felastic. To the best of our knowledge, this study was the first quantitative estimation of the contribution of the elastic deformation term to the friction in the case when deformation of non-flat contact regions occurs. The obtained results can be basic knowledge for designing gels for applications such as artificial cartilages and sliding bearings.

Effect of confinement on electric field induced orientation of a nematic liquid crystal.

We report the effect of confinement on the electric field induced orientation of a nematic liquid crystal, 4-cyano-4'-hexylbiphenyl (6CB), between mica surfaces. The resonance shear measurement was employed for monitoring changes in the viscosity of 6CB at various surface separation distances (D) with and without an applied electric field. The viscosity depended on the surface separations, and the behaviour for D < ca. 20 nm was quite different from that at D > ca. 20 nm. For D > ca. 20 nm, the viscosity values obtained in the presence of the electric field (ac 1 kHz, 1.87 kV mm(-1), homeotropic orientation) were ca. 2 times higher than the values obtained without the electric field (0 kV mm(-1), planar orientation) due to the difference in the molecular orientation, and were nearly constant. At D < ca. 20 nm, the viscosity of 6CB both with and without the electric field sharply increased and they merged into an identical value at D = 12.5 ± 1.3 nm (Dc), then exhibited a plateau up to D = 6 nm. With the decreasing distance below 6 nm, the viscosity of confined 6CB both with and without the electric field further increased up to more than 100 N s m(-1) at the hard wall thickness of D = ca. 4.0 nm. These results indicated that 6CB molecules both with and without the electric field had the same orientation at D < Dc. The most likely orientation of 6CB was parallel to the surfaces because 6CB was originally in a planar orientation on the mica surface. These results demonstrated for the first time that the effect of confinement exceeded the electric field, thus 6CB molecules could not change their orientation under the electric field at the surface separation below Dc.

Shear dynamics of nanoconfined ionic liquids.

We used molecular dynamics simulations to study the structure and shear dynamics of two ionic liquids (ILs) featuring the same cation 1-butyl-3-methyl-imidazolium or [BMIM], paired with bis(trifluoromethanesulphonyl)amide [NTF2] and tetrafluoroborate [BF4] anions, confined between two hydroxylated silica surfaces. The results demonstrate how the shape of IL molecules affects their layering structure at hydroxylated silica surfaces and how the layered structure of nanoconfined liquids determines their dynamical properties at the molecular level. When [BMIM][NTF2] is sheared, larger molecular fluctuations in the inner layers are required to stabilise the system, and the resulting dynamics is irregular. The alternating charged layers in [BMIM][BF4] allow the system to stabilise through smaller oscillations, and the layers appear to shear on top of each other in a laminar fashion. The simulated dynamics explains qualitatively the relative change in viscosity that the two ILs exhibit when confined, as has been observed in previous experiments.

Structuring of interfacial water on silica surface in cyclohexane studied by surface forces measurement and sum frequency generation vibrational spectroscopy.

We investigated interfacial water, formed by adsorption or phase separation (prewetting transition), on a silica surface in water-cyclohexane binary liquids using a combination of colloidal probe atomic force microscopy (AFM) and sum frequency generation (SFG) vibrational spectroscopy. At 33 ± 9 ppm water, the long-range attraction extending to 19.4 ± 2.9 nm appeared, which was caused by the contact of water layers formed on silica surfaces. The attraction range increased with increasing water concentration and reached 97 ± 17 nm at the saturation concentration of water in cyclohexane (C*), indicating that the thickness of the water layer formed on silica was ca. 50 nm. The interfacial energy between the water adsorption layer and bulk solution (γ = 79.3 ± 2.0 mN/m) was estimated from the pull-off force, and was significantly larger than the value for the bulk water/cyclohexane interface (γ = 50.1 mN/m). SFG spectroscopy demonstrated that the interfacial water formed an icelike structure at C*. These results indicated that the interfacial water molecules formed an icelike ordered structure induced by the hydrogen bonding with surface silanol groups, resulting in the free OH groups being more exposed to the bulk solution. On the other hand, the water adsorption layer induced by phase separation at water concentrations above C* was found to be less ordered and its structure at the adsorption layer/bulk interface was almost the same as that of bulk water, although its thickness was almost the same as that formed at C*. To our knowledge, this is the first report of the observation of liquid adsorption layers formed by chemical interaction up to saturation and by the wetting transition above saturation, and their differences in the structure and properties at the molecular level.

Resonance shear measurement of nanoconfined ionic liquids.

Two types of imidazolium-based ionic liquid (IL), 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide ([C(4)mim][NTF(2)]) and 1-butyl-3-methylimidazolium tetrafluoroborate ([C(4)mim][BF(4)]), confined between silica surfaces were investigated by surface force apparatus (SFA)-based resonance shear measurements together with surface force measurements. The surface force profiles in the ILs showed oscillatory solvation forces below the characteristic surface separations: 10.0 nm for [C(4)mim][NTf(2)] and 6.9 nm for [C(4)mim][BF(4)]. The more pronounced solvation force found in [C(4)mim][NTf(2)] suggests that the crystal-forming ability of the IL contributes to the stronger layering of the ILs adjacent to the surface. The resonance shear measurement and the physical model analysis revealed that the viscosities of the confined ILs were 1-3 orders of magnitude higher than that of the bulk IL. This paper also focused on the correlation between the resonance shear behaviour and the lubrication property of the ILs, and the suspension rheology in the ILs. An understanding of the solid-IL interface and of ILs confined in nanospace will facilitate the further development of novel applications employing ILs.