We have used friction force microscopy to probe friction laws for nanoasperities sliding on atomically flat substrates under controlled atmosphere and liquid environment, respectively. A power law relates friction force and normal load in dry air, whereas a linear relationship, i.e., Amontons' law, is observed for junctions fully immersed in model lubricants, namely, octamethylciclotetrasiloxane and squalane. Lubricated contacts display a remarkable friction reduction, with liquid and substrate specific friction coefficients. Comparison with molecular dynamics simulations suggests that load-bearing boundary layers at junction entrance cause the appearance of Amontons' law and impart atomic-scale character to the sliding process; continuum friction models are on the contrary of limited predictive power when applied to lubrication effects. An attempt is done to define general working conditions leading to the manifestation of nanoscale lubricity due to adsorbed boundary layers.
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