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Interactions between molecules in the synovial fluid and the cartilage surface may play a vital role in the formation of adsorbed films that contribute to the low friction of cartilage boundary lubrication. Osteoarthritis (OA) is the most common degenerative joint disease. Previous studies have shown that in OA-diseased joints, hyaluronan (HA) not only breaks down resulting in a much lower molecular weight (MW), but also its concentration is reduced ten times. Here, we have investigated the structural changes of lipid-HA complexes as a function of HA concentration and MW to simulate the physiologically relevant conditions that exist in healthy and diseased joints. Small angle neutron scattering and dynamic light scattering were used to determine the structure of HA-lipid vesicles in bulk solution, while a combination of atomic force microscopy and quartz crystal microbalance was applied to study their assembly on a gold surface. We infer a significant influence of both MW and HA concentrations on the structure of HA-lipid complexes in bulk and assembled on a gold surface. Our results suggest that low MW HA cannot form an amorphous layer on the gold surface, which is expected to negatively impact the mechanical integrity and longevity of the boundary layer and could contribute to the increased wear of the cartilage that has been reported in joints diseased with OA. [ABSTRACT FROM AUTHOR]

Using neutron reflectivity, the electro-responsive structuring of the non-halogenated ionic liquid (IL) trihexyl(tetradecyl)phosphonium-bis(mandelato)borate, [P6,6,6,14][BMB], has been studied at a gold electrode surface in a polar solvent. For a 20% w/w IL mixture, contrast matched to the gold surface, distinct Kiessig fringes were observed for all potentials studied, indicative of a boundary layer of different composition to that of the bulk IL-solvent mixture. With applied potential, the amplitudes of the fringes from the gold-boundary layer interface varied systematically. These changes are attributable to the differing ratios of cations and anions in the boundary layer, leading to a greater or diminished contrast with the gold electrode, depending on the individual ion scattering length densities. Such electro-responsive changes were also evident in the reflectivities measured for the pure IL and a less concentrated (5% w/w) IL-solvent mixture at the same applied potentials, but gave rise to less pronounced changes. These measurements, therefore, demonstrate the enhanced sensitivity achieved by contrast matching the bulk solution and that the structure of the IL boundary layers formed in mixtures is strongly influenced by the bulk concentration. Together these results represent an important step in characterising IL boundary layers in IL-solvent mixtures and provide clear evidence of electro-responsive structuring of IL ions in their solutions with applied potential. [ABSTRACT FROM AUTHOR]

The effect of electric potential on the lubrication of a non-halogenated phosphonium orthoborate ionic liquid used as an additive in a biodegradable oil was studied. An in-house tribotronic system was built around an instrument designed to measure lubricant film thickness between a rolling steel ball and a rotating silica-coated glass disc. The application of an electric field between the steel ball and a set of customized counter-electrodes clearly induced changes in the thickness of the lubricant film: a marked decrease at negative potentials and an increase at positive potentials. Complementary neutron reflectivity studies demonstrated the intrinsic electroresponsivity of the adsorbate: this was performed on a gold-coated silicon block and made possible in the same lubricant system by deuterating the oil. The results indicate that the anions, acting as anchors for the adsorbed film on the steel surface, are instrumental in the formation of thick and robust lubricating ionic boundary films. The application of a high positive potential, outside the electrochemical window, resulted in an enormous boost to film thickness, implicating the formation of ionic multi-layers and demonstrating the plausibility of remote control of failing contacts in inaccessible machinery, such as offshore wind and wave power installations. [ABSTRACT FROM AUTHOR]

Phosphonium ionic liquids with orthoborate anions have been studied in terms of their interfacial film formation, both physisorbed and sacrificial from chemical breakdown, in sheared contacts of varying harshness. The halogen-free anion architecture was varied through (i) the heteronuclear ring size, (ii) the hybridisation of the constituent atoms, and (iii) the addition of aryl functionalities. Time of Flight-Secondary Ion Mass Spectrometry analysis revealed the extent of sacrificial tribofilm formation allowing the relative stability of the ionic liquids under tribological conditions to be determined and their breakdown mechanisms to be compared to simple thermal decomposition. Overall, ionic liquids outperformed reference oils as lubricants; in some cases, sacrificial films were formed (with anion breakdown a necessary precursor to phosphonium cation decomposition) while in other cases, a protective, self-assembly lubricant layer or hybrid film was formed. The salicylate-based anion was the most chemically stable and decomposed only slightly even under the harshest conditions. It was further found that surface topography influenced the degree of breakdown through enhanced material transport and replenishment. This work thus unveils the relationship between ionic liquid composition and structure, and the ensuing inter- and intra-molecular interactions and chemical stability, and demonstrates the intrinsic tuneability of an ionic liquid lubrication technology. [ABSTRACT FROM AUTHOR]

Improving the tactile aesthetics of products that can be described as touch intensive is an increasing priority within many sectors, including the furniture industry. Understanding which physical characteristics contribute to the haptic experience of a surface, and how, is therefore highly topical. It has earlier been shown that both friction and topography affect tactile perception. Thus, two series of stimuli have been produced using standard coating techniques, with systematic variation in (physical) friction and roughness properties. This was achieved through appropriate selection of matting agents and resins. The stimuli sets were then evaluated perceptually to determine the extent to which discrimination between pairs of surfaces followed the systematic materials variation. In addition to investigating the role of the physical properties in discrimination of the surfaces, their influence on perceived pleasantness and naturalness was also studied. The results indicate that changes in tactile perception can be understood in terms of friction and roughness, and that varying the matting agents (topography) and resins (material properties) in the coatings provide the controlling factors for furniture applications. Perceived pleasantness is associated with low friction and smoother topography, whilst perceived naturalness is found to be described by an interaction between tactile friction and the average maximum peak height of the surface features. [ABSTRACT FROM AUTHOR]

The oft discussed and fretted over environmental influences on hair have led to a popular consensus which suggests that elevated temperature and humidity lead to frizzier, wilder hair. However, few attempts at actually quantifying these effects have been made. Although frizziness is usually perceived visually, here the influence of variations in temperature and humidity on the tactile perception and friction of curly and straight hair were investigated. It is shown that changes in humidity may disproportionately affect perceived frizziness of curly hair by touch due to concurrent changes in the tactile friction. [ABSTRACT FROM AUTHOR]

The effect of water on the electroactive structuring of a tribologically relevant ionic liquid (IL) when dispersed in a polar solvent has been investigated at a gold electrode interface using neutron reflectivity (NR). For all solutions studied, the addition of small amounts of water led to clear changes in electroactive structuring of the IL at the electrode interface, which was largely determined by the bulk IL concentration. At a dilute IL concentration, the presence of water gave rise to a swollen interfacial structuring, which exhibited a greater degree of electroresponsivity with applied potential compared to an equivalent dry solution. Conversely, for a concentrated IL solution, the presence of water led to an overall thinning of the interfacial region and a crowding-like structuring, within which the composition of the inner layer IL layers varied systematically with applied potential. Complementary nanotribotronic atomic force microscopy (AFM) measurements performed for the same IL concentration, in dry and ambient conditions, show that the presence of water reduces the lubricity of the IL boundary layers. However, consistent with the observed changes in the IL layers observed by NR, reversible and systematic control of the friction coefficient with applied potential was still achievable. Combined, these measurements provide valuable insight into the implications of water on the interfacial properties of ILs at electrified interfaces, which inevitably will determine their applicability in tribotronic and electrochemical contexts. [ABSTRACT FROM AUTHOR]

Neutron reflectivity (NR) measurements have been employed to study the interfacial structuring and composition of electroresponsive boundary layers formed by an ionic liquid (IL) lubricant at an electrified gold interface when dispersed in a polar solvent. The results reveal that both the composition and extent of the IL boundary layers intricately depend on the bulk IL concentration and the applied surface potential. At the lowest concentration (5% w/w), a preferential adsorption of the IL cation at the gold electrode is observed, which hinders the ability to electro-induce changes in the boundary layers. In contrast, at higher IL bulk concentrations (10 and 20% w/w), the NR results reveal a significantly larger concentration of the IL ions at the gold interface that exhibit significantly greater electroresponsivity, with clear changes in the layer composition and layer thickness observed for different potentials. In complementary atomic force microscopy (AFM) measurements on an electrified gold surface, such IL boundary layers are demonstrated to provide excellent friction reduction and electroactive friction (known as tribotronics). In agreement with the NR results obtained, clear concentration effects are also observed. Together such results provide valuable molecular insight into the electroactive structuring of ILs in solvent mixtures, as well as provide mechanistic understanding of their tribotronic behaviours. [ABSTRACT FROM AUTHOR]

Humans are extraordinarily skilled in the tactile evaluation of, and differentiation between, surfaces. The chemical and mechanical properties of these surfaces are translated into tactile signals during haptic exploration by mechanoreceptors in our skin, which are specialized to respond to different types of temporal and mechanical stimulation. Describing the effects of measurable physical characteristics on the human response to tactile exploration of surfaces is of great interest to manufacturers of household materials so that the haptic experience can be considered during design, product development and quality control. In this study, methods from psychophysics and materials science are combined to advance current understanding of which physical properties affect tactile perception of a range of furniture surfaces, i.e., foils and coatings, thus creating a tactile map of the furniture product landscape. Participants' responses in a similarity scaling task were analyzed using INDSCAL from which three haptic dimensions were identified. Results show that specific roughness parameters, tactile friction and vibrational information, as characterized by a stylus profilometer, a Forceboard, and a biomimetic synthetic finger, are important for tactile differentiation and preferences of these surface treatments. The obtained dimensions are described as distinct combinations of the surface properties characterized, rather than as 'roughness' or 'friction' independently. Preferences by touch were related to the roughness, friction and thermal properties of the surfaces. The results both complement and advance current understanding of how roughness and friction relate to tactile perception of surfaces. [ABSTRACT FROM AUTHOR]

Control of the interfacial structures of ionic liquids (ILs) at charged interfaces is important to many of their applications, including in energy storage solutions, sensors and advanced lubrication technologies utilising electric fields. In the case of the latter, there is an increasing demand for the study of non-halogenated ILs, as many fluorinated anions have been found to produce corrosive and toxic halides under tribological conditions. Here, the interfacial structuring of a series of four imidazolium ILs ([CnC1Im]) of varying alkyl chain lengths (n = 5, 6, 7, 10), with a non-halogenated borate-based anion ([BOB]), have been studied at charged interfaces using sum frequency generation (SFG) spectroscopy and neutron reflectivity (NR). For all alkyl chain lengths, the SFG spectra show that the cation imidazolium ring responds to the surface charge by modifying its orientation with respect to the surface normal. In addition, the combination of SFG spectra with electrochemical NR measurements reveals that the longest alkyl chain length (n = 10) forms a bilayer structure at all charged interfaces, independent of the ring orientation. These results demonstrate the tunability of IL interfacial layers through the use of surface charge, as well as effect of the cation alkyl chain length, and provide valuable insight into the charge compensation mechanisms of ILs. [ABSTRACT FROM AUTHOR]

Diffusion of EAN confined between polar glass plates separated by a few micrometers is higher by a factor of ca. 2 as compared to bulk values. Formation of a new phase, different to the bulk, was suggested. [ABSTRACT FROM AUTHOR]

It is an honour to be charged with providing the concluding remarks for a Faraday Discussion. As many have remarked before, it is nonetheless a prodigious task, and what follows is necessarily a personal, and probably perverse, view of a watershed event in the Chemical Physics of Electroactive materials. The spirit of the conference was captured in a single sentence during the meeting itself.FOOTNOTE ID="FN1"By Andriy Yaroschuk in commenting on the work of Kelsey Hatzell (DOI: URL URL="HTTP://DX.DOI.ORG/10.1039/C6FD00243A"10.1039/c6fd00243a/URL)./FOOTNOTE“It is the nexus between rheology, electrochemistry, colloid science and energy storage”. The current scientific climate is increasingly dominated by a limited number of global challenges, and there is thus a tendency for research to resemble a football match played by 6 year olds, where everyone on the field chases the (funding) ball instead of playing to their “discipline”. It is thus reassuring to see how the application of rigorous chemical physics is leading to ingenious new solutions for both energy storage and harvesting, via, for example, nanoactuation, electrowetting, ionic materials and nanoplasmonics. In fact, the same language of chemical physics allows seamless transition between applications as diverse as mechano-electric energy generation, active moisture transport and plasmonic shutters – even the origins of life were addressed in the context of electro-autocatalysis! [ABSTRACT FROM AUTHOR]

Atomic force microscopy (AFM) has been used to investigate the potential dependent boundary layer friction at solvate ionic liquid (SIL)–highly ordered pyrolytic graphite (HOPG) and SIL–Au(111) interfaces. Friction trace and retrace loops of lithium tetraglyme bis(trifluoromethylsulfonyl)amide (Li(G4) TFSI) at HOPG present clearer stick-slip events at negative potentials than at positive potentials, indicating that a Li+ cation layer adsorbed to the HOPG lattice at negative potentials which enhances stick-slip events. The boundary layer friction data for Li(G4) TFSI shows that at HOPG, friction forces at all potentials are low. The TFSI− anion rich boundary layer at positive potentials is more lubricating than the Li+ cation rich boundary layer at negative potentials. These results suggest that boundary layers at all potentials are smooth and energy is predominantly dissipated via stick-slip events. In contrast, friction at Au(111) for Li(G4) TFSI is significantly higher at positive potentials than at negative potentials, which is comparable to that at HOPG at the same potential. The similarity of boundary layer friction at negatively charged HOPG and Au(111) surfaces indicates that the boundary layer compositions are similar and rich in Li+ cations for both surfaces at negative potentials. However, at Au(111), the TFSI− rich boundary layer is less lubricating than the Li+ rich boundary layer, which implies that anion reorientations rather than stick-slip events are the predominant energy dissipation pathways. This is confirmed by the boundary friction of Li(G4) NO3 at Au(111), which shows similar friction to Li(G4) TFSI at negative potentials due to the same cation rich boundary layer composition, but even higher friction at positive potentials, due to higher energy dissipation in the NO3− rich boundary layer. [ABSTRACT FROM AUTHOR]

Ionic liquids are pure salts that are liquid under ambient conditions. As liquids composed solely of ions, the scientific consensus has been that ionic liquids have exceedingly high ionic strengths and thus very short Debye screening lengths. However, several recent experiments from laboratories around the world have reported data for the approach of two surfaces separated by ionic liquids which revealed remarkable long range forces that appear to be electrostatic in origin. Evidence has accumulated demonstrating long range surface forces for several different combinations of ionic liquids and electrically charged surfaces, as well as for concentrated mixtures of inorganic salts in solvent. The original interpretation of these forces, that ionic liquids could be envisioned as “dilute electrolytes,” was controversial, and the origin of long range forces in ionic liquids remains the subject of discussion. Here we seek to collate and examine the evidence for long range surface forces in ionic liquids, identify key outstanding questions, and explore possible mechanisms underlying the origin of these long range forces. Long range surface forces in ionic liquids and other highly concentrated electrolytes hold diverse implications from designing ionic liquids for energy storage applications to rationalizing electrostatic correlations in biological self-assembly. [ABSTRACT FROM AUTHOR]

Expansion of (GAA)n repeats in the first intron of the Frataxin gene is associated with reduced mRNA and protein levels and the development of Friedreich’s ataxia. (GAA)n expansions form non-canonical structures, including intramolecular triplex (H-DNA), and R-loops and are associated with epigenetic modifications. With the aim of interfering with higher order H-DNA (like) DNA structures within pathological (GAA)n expansions, we examined sequence-specific interaction of peptide nucleic acid (PNA) with (GAA)n repeats of different lengths (short: n=9, medium: n=75 or long: n=115) by chemical probing of triple helical and single stranded regions. We found that a triplex structure (H-DNA) forms at GAA repeats of different lengths; however, single stranded regions were not detected within the medium size pathological repeat, suggesting the presence of a more complex structure. Furthermore, (GAA)4-PNA binding of the repeat abolished all detectable triplex DNA structures, whereas (CTT)5-PNA did not. We present evidence that (GAA)4-PNA can invade the DNA at the repeat region by binding the DNA CTT strand, thereby preventing non-canonical-DNA formation, and that triplex invasion complexes by (CTT)5-PNA form at the GAA repeats. Locked nucleic acid (LNA) oligonucleotides also inhibited triplex formation at GAA repeat expansions, and atomic force microscopy analysis showed significant relaxation of plasmid morphology in the presence of GAA-LNA. Thus, by inhibiting disease related higher order DNA structures in the Frataxin gene, such PNA and LNA oligomers may have potential for discovery of drugs aiming at recovering Frataxin expression. [ABSTRACT FROM AUTHOR]

According to recent findings, the steady shear viscosity of the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([Emim][Tf2N]) decreases significantly under the influence of electric potential. This implies a causal connection between nanoscale ordering at the electrified interface and a macroscopic change of transport properties. To study this phenomenon in more detail, we reproduced the above-mentioned measurements; however, we find no evidence that the viscosity of [Emim][Tf2N] is a function of electric potential. Additionally, our results show that steady shear measurements can lead to artifacts that, at first glance, may appear to be potential-induced changes in viscosity. We demonstrate that the artifacts result from a sliding electrical contact at the working electrode of the electrochemical cell and we suggest to consider our findings for future viscosity measurements of ionic liquids. [ABSTRACT FROM AUTHOR]

Atomic force microscopy has been used to study the effect of temperature on normal forces and friction for the room temperature ionic liquid (IL) ethylammonium nitrate (EAN), confined between mica and a silica colloid probe at 25 °C, 50 °C, and 80 °C. Force curves revealed a strong fluid dynamic influence at room temperature, which was greatly reduced at elevated temperatures due to the reduced liquid viscosity. A fluid dynamic analysis reveals that bulk viscosity is manifested at large separation but that EAN displays a nonzero slip, indicating a region of different viscosity near the surface. At high temperatures, the reduction in fluid dynamic force reveals step-like force curves, similar to those found at room temperature using much lower scan rates. The ionic liquid boundary layer remains adsorbed to the solid surface even at high temperature, which provides a mechanism for lubrication when fluid dynamic lubrication is strongly reduced. The friction data reveals a decrease in absolute friction force with increasing temperature, which is associated with increased thermal motion and reduced viscosity of the near surface layers but, consistent with the normal force data, boundary layer lubrication was unaffected. The implications for ILs as lubricants are discussed in terms of the behaviour of this well characterised system. [ABSTRACT FROM AUTHOR]

The efficacy of ionic liquids (ILs) as lubricant additives to a model base oil has been probed at the nanoscale and macroscale as a function of IL concentration using the same materials. Silica surfaces lubricated with mixtures of the IL trihexyl(tetradecyl)phosphonium bis(2,4,4-trimethylpentyl)phosphinate and hexadecane are probed using atomic force microscopy (AFM) (nanoscale) and ball-on-disc tribometer (macroscale). At both length scales the pure IL is a much more effective lubricant than hexadecane. At the nanoscale, 2.0 mol% IL (and above) in hexadecane lubricates the silica as well as the pure IL due to the formation of a robust IL boundary layer that separates the sliding surfaces. At the macroscale the lubrication is highly load dependent; at low loads all the mixtures lubricate as effectively as the pure IL, whereas at higher loads rather high concentrations are required to provide IL like lubrication. Wear is also pronounced at high loads, for all cases except the pure IL, and a tribofilm is formed. Together, the nano- and macroscales results reveal that the IL is an effective lubricant additive – it reduces friction – in both the boundary regime at the nanoscale and mixed regime at the macroscale. [ABSTRACT FROM AUTHOR]

The morphology and molecular conformation of Langmuir–Blodgett deposited and floating monolayers of a selection of straight chain (eicosanoic acid, EA), iso (19-methyl eicosanoic acid, 19-MEA), and anteiso (18-methyl eicosanoic acid, 18-MEA) fatty acids have been investigated by Vibrational Sum Frequency Spectroscopy (VSFS), AFM imaging, and the Langmuir trough. While the straight chain fatty acid forms smooth, featureless monolayers, all the branched chain fatty acids display 10–50 nm sized domains (larger for 19-MEA than the 18-MEA) with a homogeneous size distribution. A model is suggested to explain the domain formation and size in terms of the branched fatty acid packing properties and the formation of hemispherical caps at the liquid–air interface. No difference between the chiral (S) form and the racemic mixture of the 18-MEA is observed with any of the utilized techniques. The aliphatic chains of the straight chain fatty acids appear to be oriented perpendicular to the sample surface, based on an orientational analysis of VSFS data and the odd/even effect. In addition, the selection of the subphase (neat water or CdCl2 containing water buffered to pH 6.0) used for the LB-deposition has a profound influence on the monolayer morphology, packing density, compressibility, and conformational order. Finally, the orientation of the 19-MEA dimethyl moiety is estimated, and a strategy for performing an orientational analysis to determine the complete molecular orientation of the aliphatic chains of 19-MEA and 18-MEA is outlined and discussed. [ABSTRACT FROM AUTHOR]

The effect of ionic liquid (IL) molecular structure on nanoscale friction has been investigated using colloidal probe Friction Force Microscopy (FFM). The ILs studied were ethylammonium formate (EAF), ethylammonium nitrate (EAN), propylammonium formate (PAF), propylammonium nitrate (PAN), dimethylethylammonium formate (DMEAF), and ethanolammonium nitrate (EtAN). ILs were confined between a silica colloid probe and a mica surface, and the friction force was measured as a function of normal load for sliding velocities between 10 and 40 μm s−1. At low normal forces, multiple IL layers are found between the probe and the surface, but at higher force, in the boundary layer regime, a single ion layer separates the probe and the surface. In the boundary layer regime energy is dissipated by two main pathways. Firstly, the ionic liquid near the surface, with the exception of the boundary layer, is expelled from the advancing contact made by the probe on the surface. This disruption in the interactions between the boundary layer and the near surface multilayers, leads to energy dissipation and depends on the strength of the attraction between the boundary and near surface layers. The second pathway is via rotations and twists of ions in the boundary layer, primarily associated with the cation terminal methyl group. The friction coefficient did not vary over the limited range of sliding speeds investigated. [ABSTRACT FROM AUTHOR]

Colloid probe atomic force microscopy (AFM) has been employed to investigate the nanotribology of the ionic liquid (IL)–Au(111) interface. Data is presented for four ILs, 1-ethyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate ([EMIM] FAP), 1-butyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate ([BMIM] FAP), 1-hexyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate ([HMIM] FAP) and 1-butyl-3-methylimidazolium iodide ([BMIM] I), at different Au(111) surface potentials. Lateral forces vary as a function of applied surface potential and ion structure because the composition of the confined ion layer changes from cation-enriched (at negative potentials) to mixed (at 0 V), and to anion-enriched (at positive potentials). ILs with FAP− anions all exhibit similar nanotribology: low friction at negative potentials and higher friction at positive potentials. [BMIM] I displays the opposite behaviour, as an I− anion-enriched layer is more lubricating than either the [BMIM]+ or FAP− layers. The effect of cation charged group (charge-delocalised versus charged-localised) was investigated by comparing [BMIM] FAP with 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate ([Py1,4] FAP). [BMIM] FAP is less lubricating at negative potentials, but more lubricating at positive potentials. This indicated that even at positive potentials the cation concentration in the boundary layer is sufficiently high to influence lubricity. The influence of sliding velocity on lateral force was investigated for the [EMIM] FAP–Au(111) system. At neutral potentials the behaviour is consistent with a discontinuous sliding process. When a positive or negative potential bias is applied, this effect is less pronounced as the colloid probe slides along a better defined ion plane. [ABSTRACT FROM AUTHOR]

The aquatic sex pheromone splendipherin (GLVSSIGKALGGLLADVVKSKGQPA-OH) of the male green tree frog Litoria splendida moves across the surface of water to reach the female. Surface pressure and X-ray reflectometry measurements confirm that splendipherin is a surface-active molecule, and are consistent with it having an ordered structure, whereby the hydrophilic portion of the peptide interacts with the underlying water and the hydrophobic region is adjacent to the vapour phase. The movement of splendipherin over the surface of water is caused by a surface pressure gradient. In order to better define the structure of splendipherin at the water/air interface we used 2D NMR studies of the pheromone with the solvent system trifluoroethanol/water (1 : 1 v/v). In this solvent system, splendipherin adopts a bent α helix from residues V3 to K21. The bending of the helix occurs in the centre of the peptide in the vicinity of G11 and G12. The region of splendipherin from V3 to G11 has well-defined amphipathicity, whereas the amphipathicity from G12 to A25 is reduced by K19 and P24 intruding into the hydrophobic and hydrophilic regions respectively. A helical structure is consistent with X-ray reflectometry data. [ABSTRACT FROM AUTHOR]

A number of atomic force microscopy cantilevers have been exhaustively calibrated by a number of techniques to obtain both normal and frictional force constants to evaluate the relative accuracy of the different methods. These were of either direct or indirect character—the latter relies on cantilever resonant frequencies. The so-called Sader [Rev. Sci. Instrum. 70, 3967 (1999)] and Cleveland [Rev. Sci. Instrum. 64, 403 (1993)] techniques are compared for the normal force constant calibration and while agreement was good, a systematic difference was observed. For the torsional force constants, all the techniques displayed a certain scatter but the agreement was highly encouraging. By far the simplest technique is that of Sader, and it is suggested in view of this validation that this method should be generally adopted. The issue of the photodetector calibration is also addressed since this is necessary to obtain the cantilever twist from which the torsional force is calculated. Here a technique of obtaining the torsional photodetector sensitivity by combining the direct and indirect methods is proposed. Direct calibration measurements were conducted in liquid as well as air, and a conversion factor was obtained showing that quantitative friction measurements in liquid are equally feasible provided the correct calibration is performed. [ABSTRACT FROM AUTHOR]

The photodiode sensitivity in the atomic force microscope is calibrated by relating the voltage noise to the thermal fluctuations of the cantilever angle. The method accounts for the ratio of the thermal fluctuations measured in the fundamental vibration mode to the total, and also for the tilt and extended tip of the cantilever. The method is noncontact and is suitable for soft or deformable surfaces where the constant compliance method cannot be used. For hard surfaces, the method can also be used to calibrate the cantilever spring constant. [ABSTRACT FROM AUTHOR]

Presented here is a novel technique for the in situ calibration and measurement of friction with the atomic force microscope that can be applied simultaneously with the normal force measurement. The method exploits the fact that the cantilever sits at an angle of about 10° to the horizontal, which causes the tip (or probe) to slide horizontally over the substrate as a normal force run is performed. This sliding gives rise to an axial friction force (in the axial direction of the cantilever), which is measured through the difference in the constant compliance slopes of the inward and outward traces. Traditionally, friction is measured through lateral scanning of the substrate, which is time consuming, and requires an ex situ calibration of both the torsional spring constant and the lateral sensitivity of the photodiode detector. The present method requires no calibration other than the normal spring constant and the vertical sensitivity of the detector, which is routinely done in the force analysis. The present protocol can also be applied to preexisting force curves, and, in addition, it provides the means to correct force data for cantilevers with large probes. [ABSTRACT FROM AUTHOR]

The effect of relative humidity (RH) on the interactions of AFM tips and colloidal probes with hydrophilic silica substrates is investigated. Both friction and adhesion are studied. For the case of a colloidal probe the interaction is characteristic of a multiasperity contact, the adhesion increased with increasing RH and above a certain threshold relative humidity a large increase in adhesion was measured. This behaviour is explained in terms of a recent model where the Kelvin radius of the condensate becomes larger than some characteristic roughness on the surface. The interaction between the tip and the substrate also exhibited an increase in adhesion above a threshold RH although the increase was much less marked than with the colloid probe. The friction decreased with increasing humidity for both tip and colloid probe although the friction force was much less sensitive than adhesion to changes in RH. Stick-slip behaviour was observed between tip and substrate for all humidities at high loads, but only at the lowest RH (about 5%) it was observed at all loads. At higher humidity the behaviour became increasingly continuum on the experimental timescale, presumably due to viscous contributions from the water. Stick-slip was not observed for the colloidal probe friction measurements. [ABSTRACT FROM AUTHOR]

A protocol for measuring the interaction, deformation and adhesion of soft polymeric substrates with the atomic force microscope (AFM) is described. The technique obtains the photodiode response of the AFM (constant compliance factor) by independent calibration against the rigid substrate adjacent to the deformable particle or patchy film. The zero of separation is taken as the end-point of the jump into contact. A method is given for correcting the velocity dependence of the piezodrive expansion factor, the neglect of which will cause artefacts in dynamic viscoelastic measurements. It is emphasised that conventional force curve analysis, which uses the apparently linear large force region for calibration, will generate erroneous results for deformable substrates. Results are obtained for cellulose particles and for polystyrene films, and their Young's moduli are found to be 22 MPa and 100 MPa, respectively. The latter is about a factor of 30 less than for bulk polystyrene, which indicates that the polystyrene surface is in a less glassy state than the bulk. [ABSTRACT FROM AUTHOR]

The role of saliva in the oral cavity is manifold; an important function is to serve as lubricant between hard (enamel) and soft (mucosal) tissues. Intraoral lubrication is of crucial importance in order to maintain functions such as deglutition, mastication and the faculty of speech. A large number of people suffer from impaired salivary functions, displaying symptoms such as 'dry mouth'. This results in a need for methods to assess the lubricating properties of both native saliva and potential artificial saliva formulations. Here, normal as well as lateral forces, acting between adsorbed salivary films, have been measured for the first time by means of colloidal probe atomic force microscopy (AFM). It was found that the presence of salivary pellicles between hard surfaces reduces the friction coefficient by a factor of 20. This reduction of friction is consistent with the long-range purely repulsive nature of the normal forces acting between the salivary films. The lubricating mechanism is presumably based on a full separation of the sliding surfaces by the salivary films. The friction between salivary films has been investigated at normal loads that cover the clinical jaw closing forces, and it can be concluded that the lubricating properties are maintained within this load interval. The present study indicates the usefulness of colloidal probe AFM, which offers a direct and quantitative measure of lubrication at a molecular level, in the study of biotribological phenomena. In particular, the results obtained here may have implications for the development of saliva substitutes. [ABSTRACT FROM AUTHOR]

Part I. Measures the dynamic surface force using the van der Waals collisions. Effect of cantilever deflection on speed and magnitude of surface force; Details on the collision-induced elastic vibrations in the solids; Factors attributing the surface separation at high accelerations.

Atomic force microscopy measurements reveal that superlubricity can be "switched" on and off in situ when an ionic liquid is used to lubricate the silica-graphite interface. Applying a potential to the graphite surface changes the ion composition of the boundary layer and thus the lubricity. At positive potentials, when the interfacial ion layer is anion rich, friction falls to ultra-low levels. [ABSTRACT FROM AUTHOR]

Surface-adsorbed and near-surface ion layer structure controls nanotribology in the silica–propylammonium nitrate (PAN)–mica system. Atomic Force Microscopy (AFM) imaging and normal force curves reveal that the normal load dictates the number of interfacial ion layers and the lateral layer structure. Shear force measurements show the lubricity of the interface changes with the number, and lateral structure, of the confined ion layer(s). [ABSTRACT FROM AUTHOR]

The aim of this study was to evaluate whether smooth surfaces varying in surface chemistry could be perceptually distinguished with the sense of touch. A set of ten glass surfaces was prepared which varied systematically in terms of the molecular composition of a thin coating of low topography. The contact angle, contact angle hysteresis, and surface energy were evaluated as objective physical parameters characterizing each coating. Additionally, the interaction forces between a human finger and the different coatings were quantified and compared in terms of tactile friction coefficients. The surfaces were evaluated psychophysically in terms of perceived similarities and were then ranked according to pleasantness. The participants could perceptually distinguish between surfaces varying in surface chemistry and a primary and secondary perceptual dimension were identified as sufficient to distinguish them. The primary dimension correlates with surface free energy, but both tactile friction and surface energy contribute to this dimension depending on whether the coatings are organic or inorganic. The secondary dimension could not be identified explicitly in terms of a physical quantity but is discussed in terms of recent developments in the literature. Coated glass is characterized by high friction coefficient upon interaction with a human finger as well as significant hysteresis in the stroking directions (lower applied load and higher friction in the backward stroke). Despite the complexity of the tribology, pleasantness can be clearly linked to it, where low friction (high contact angle) materials receive a higher ranking. [ABSTRACT FROM AUTHOR]

A correction to the article "A novel technique for the in situ calibration and measurement of friction with the atomic force microscope" that was published in number 76, 2005 issue is presented.