linoleic-acid and n-hexadecane

Self-assembled monolayers of fatty acids were formed on stainless steel by room-temperature solution deposition. The acids are covalently bound to the surface as carboxylate in a bidentate manner. To explore the effect of saturation in the carbon backbone on friction in sliding tribology, we study the response of saturated stearic acid (SA) and unsaturated linoleic acid (LA) as self-assembled monolayers using lateral force microscopy and nanotribometry and when the molecules are dispersed in hexadecane, using pin-on-disc tribometry. Over a very wide range (10 MPa-2.5 GPa) of contact pressures it is consistently demonstrated that the unsaturated linoleic acid molecules yield friction which is significantly lower than that of the saturated stearic acid. It is argued, using density functional theory predictions and XPS of slid track, that when the molecular backbone of unsaturated fatty acids are tilted and pressed strongly by a probe, in tribological contact, the high charge density of the double bond region of the backbone allows coupling with the steel substrate. The interaction yields a low friction carboxylate soap film on the substrate. The saturated fatty acid does not show this effect.

Topics: Alkanes; Fatty Acids; Friction; Linoleic Acid; Lubrication; Microscopy, Atomic Force; Silicon; Spectrometry, X-Ray Emission; Spectroscopy, Fourier Transform Infrared; Stainless Steel; Stearic Acids

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.

Topics: Abietanes; Adhesiveness; Adsorption; Alkanes; Friction; Linoleic Acid; Microscopy, Atomic Force; Nanostructures; Oleic Acid; Particle Size; Pressure; Stearic Acids; Steel; Surface Properties

Lipid hydroperoxides are important factors in lipid oxidation due to their ability to decompose into free radicals. In oil-in-water emulsions, the physical location of lipid hydroperoxides could impact their ability to interact with prooxidants such as iron. Interfacial tension measurements show that linoleic acid, methyl linoleate, and trilinolein hydroperoxides are more surface-active than their non-peroxidized counterparts. In oil-in-water emulsion containing surfactant (Brij 76) micelles in the continuous phase, linoleic acid, methyl linoleate, and trilinolein hydroperoxides were solubilized out of the lipid droplets into the aqueous phase. Brij 76 solubilization of the different hydroperoxides was in the order of linoleic acid > trilinolein > or = methyl linoleate. Brij 76 micelles inhibited lipid oxidation of corn oil-in-water emulsions with greater inhibition of oxidation occurring in emulsions containing linoleic acid hydroperoxides. Surfactant solubilization of lipid hydroperoxides could be responsible for the ability of surfactant micelles to inhibit lipid oxidation in oil-in-water emulsions.

Topics: Alkanes; Chemical Phenomena; Chemistry, Physical; Emulsions; Kinetics; Linoleic Acid; Linoleic Acids; Lipid Bilayers; Lipid Peroxidation; Lipid Peroxides; Micelles; Surface-Active Agents; Triglycerides; Water