Multivalent counterions diminish the lubricity of polyelectrolyte brushes.

Polyelectrolyte brushes provide wear protection and lubrication in many technical, medical, physiological, and biological applications. Wear resistance and low friction are attributed to counterion osmotic pressure and the hydration layer surrounding the charged polymer segments. However, the presence of multivalent counterions in solution can strongly affect the interchain interactions and structural properties of brush layers. We evaluated the lubrication properties of polystyrene sulfonate brush layers sliding against each other in aqueous solutions containing increasing concentrations of counterions. The presence of multivalent ions (Y3+, Ca2+, Ba2+), even at minute concentrations, markedly increases the friction forces between brush layers owing to electrostatic bridging and brush collapse. Our results suggest that the lubricating properties of polyelectrolyte brushes in multivalent solution are hindered relative to those in monovalent solution.

Friction of polyaromatic thiol monolayers in adhesive and nonadhesive contacts.

We have used friction force microscopy to study the effects of adhesion on the boundary friction of self-assembled monolayers of the aromatic compounds thiophenol, p-phenylthiophenol, p-terphenyl thiol, 2-naphthalenethiol, and benzyl mercaptan on gold. To control the adhesion between the monolayer-covered tip and substrate, the friction measurements were made in dry N(2) gas or in ethanol. At low loads, low adhesion (in ethanol) resulted in a linear dependence of the friction force on load (i.e., F = muL) whereas higher adhesion between the same monolayers (in N(2)) gave an apparent area-dependent friction. The friction in the adhesive systems was well described by F = S(c)A with the contact area, A, calculated for a thin, linearly elastic film confined between rigid substrates using the thin-coating contact mechanics (TCCM) model in a transition regime between its DMT- and JKR-like limits. With increasing packing density of the monolayers, a systematic decrease was found in the friction coefficient (mu) obtained in ethanol and the critical shear stress (S(c)) obtained in N(2). To describe these aromatic monolayers with the extended TCCM model, a higher Young's modulus was neeeded than for fatty acid monolayers of similar packing density.

Effects of unsaturation on film structure and friction of fatty acids in a model base oil.

The normal and friction forces between layers of three fatty acids (stearic, oleic, and linoleic acid) and a rosin acid (dehydroabietic acid) have been measured in n-hexadecane with a surface forces apparatus. Stearic, oleic, and dehydroabietic acid form loose-packed monolayers on mica surfaces when adsorbed from dry n-hexadecane. Linoleic acid forms an additional dimer layer between monolayer-covered surfaces, where it is stabilized by interactions between the double-bond-rich regions of the molecules. The monolayers formed by linoleic and dehydroabietic acid are thinner than the ones formed by stearic and oleic acid, but are not as easily removed from between the mica surfaces when the load or pressure is increased. The friction force increased linearly with load in all systems, and the friction coefficient increased with increasing unsaturation. Linoleic acid showed two regimes of linear friction with increasing load, corresponding to two different film thicknesses. Its friction was sensitive to sliding speed and adsorption time, and the thinner film observed at higher load had a lower friction coefficient. Such features were not observed for stearic and oleic acid, where the monolayers were removed and the friction coefficient changed to that of pure n-hexadecane at a pressure of 3.5 MPa.

Friction of fatty acids in nanometer-sized contacts of different adhesive strength.

The effects of adhesion, contact area, and pressure on the lubricating properties of self-assembled monolayers on steel have been investigated with friction force microscopy. The adsorbed molecules were fatty acids with varying degrees of unsaturation (0-2 double bonds; stearic, oleic, and linoleic acid) and a rosin acid (dehydroabietic acid), adsorbed from n-hexadecane solution. The friction of these loose-packed monolayers was studied in dry N2 gas and in ethanol. Low adhesion (in ethanol) resulted in a linear increase in friction force at low loads, that is, F = muL, whereas higher adhesion (in N2 gas) gave an apparent area-dependence at low loads of the form F = S(c)A, where S(c) is the critical shear stress. A recent model for the contact mechanics of a compliant elastic film confined between stiffer substrates was applied to the data obtained in dry N2. Using this approach, we obtained interfacial energies of the compliant monolayers in good agreement with van der Waals-Lifshitz theory. With a low monolayer elastic modulus of E'(1)=0.2 GPa, we obtained a slightly higher value of Sc for stearic acid than that established for more close-packed stearic acid monolayers. An increase of mu and S(c) was found with increasing degree of unsaturation of the fatty acid.

Friction of mixed and single-component aromatic monolayers in contacts of different adhesive strength.

Friction force microscopy has been used to study single-component and mixed self-assembled monolayers of aminothiophenol and thiophenol on gold. The friction forces and transition pressures of mixed monolayers were intermediate to the ones of single-component monolayers, and varied systematically with composition. The strength of the adhesion was altered by working in dry N2 gas or in ethanol. In all systems studied, low adhesion (in ethanol) resulted in a linear dependence of the friction on load already at low loads, whereas high adhesion (in dry N2) gave an apparent area-dependence. However, for a given monolayer composition, similar transition pressures were observed in dry N2 and in ethanol, suggesting that the overall monolayer structure was not strongly altered by the presence of ethanol. Similar observations were made for very close-packed monolayers of octadecanethiol.

The X-ray Surface Forces Apparatus: Structure of a Thin Smectic Liquid Crystal Film Under Confinement.

An x-ray surface forces apparatus for simultaneously measuring forces and structures of confined complex fluids under static and flow conditions is described. This apparatus, combined with an intense synchrotron x-ray source, allows investigation of molecular orientations within a thin liquid crystal film confined between two shearing mica surfaces 3900 angstroms apart. The layer-forming smectic liquid crystal 8CB (4-cyano-4'-octylbiphenyl) adopted a series of distinct planar layer orientations, including the bulk flow-forbidden b orientation.

Direct visualization of cavitation and damage in ultrathin liquid films.

The Surface Forces Apparatus technique was used to observe, at the nanoscopic level, the rapid growth and disappearance of vapor cavities between two moving solid surfaces while simultaneously monitoring their effects on the deformations and damage produced on the surfaces. Both approach-separation and shear motions were studied. In both geometries, as the relative velocity between the two surfaces increases, they deform 'elastohydrodynamically'; in some regions the surfaces become flattened (corresponding to the build up of positive or compressive pressure in the adjacent liquid) while in other regions the surfaces become pointed (corresponding to negative or tensile pressure). Vapor cavities nucleate at these pointed regions once the relative velocity of the two surfaces exceeds a certain critical value. The sudden nucleation and growth of a cavity in a thin liquid film is seen to be a much more violent event than its subsequent collapse, and surface damage due to cavitation occurs during the inception rather than during the much smoother collapse of cavities. These studies are the first to directly visualize cavity formation and associated damage in ultrathin lubricating films, and provide a fairly detailed picture of both of these mechanisms and the relationship between them. The picture that emerges in complex and different from the currently accepted model, in which damage is caused during the collapse of cavities rather than their growth. The results should have a bearing on all phenomena where cavitation and cavitation damage occur in thin lubricating films.