No abstract

A profound understanding of the properties of unmodified and saturated fatty acid-modified calcite surfaces is essential for elucidating their resistance and stability in the presence of water droplets. Additional insights can be obtained by also studying the effects of carboxylic acid-saturated aqueous solutions. We elucidate surface wettability, structure, and nanomechanical properties beneath and at the edge of a deposited droplet after its evaporation. When calcite was coated by a highly packed monolayer of stearic acid, a hydrophilic region was found at the three-phase contact line. In atomic force microscopy mapping, this region is characterized by low adhesion and a topographical hillock. The surface that previously was covered by the droplet demonstrated a patchy structure of about 6 nm height, implying stearic acid reorganization into a patchy bilayer-like structure. Our data suggest that during droplet reverse dispensing and droplet evaporation, pinning of the three-phase contact line leads to the transport of dissolved fatty carboxylic acid and possibly calcium bicarbonate Ca(HCO 3 ) 2 molecules to the contact line boundary. Compared to the surface of intrinsically hydrophobic materials, such as polystyrene, the changes in contact angle and base diameter during droplet evaporation on stearic acid-modified calcite are strikingly different. This difference is due to stearic acid reorganization on the surface and transport to the water−air interface of the droplet. An effect of the evaporating droplet is also observed on unmodified calcite due to dissolution and recrystallization of the calcite surface in the presence of water. In the case where a water droplet saturated with octanoic acid is used instead of water, the stearic acid-coated calcite remains considerably more stable. Our findings are discussed in terms of the coffee-ring effect.

Understanding the wear of mineral fillers is crucial for controlling industrial processes, and in the present work, we examine the wear resistance and nanomechanical properties of bare calcite and stearic acid-modified calcite surfaces under dry and humid conditions at the nanoscale. Measurements under different loads allow us to probe the situation in the absence and presence of abrasive wear. The sliding motion is in general characterized by irregular stick-slip events that at higher loads lead to abrasion of the brittle calcite surface. Bare calcite is hydrophilic, and under humid conditions, a thin water layer is present on the surface. This water layer does not affect the friction force. However, it slightly decreases the wear depth and strongly influences the distribution of wear particles. In contrast, stearic acid-modified surfaces are hydrophobic. Nevertheless, humidity affects the wear characteristics by decreasing the binding strength of stearic acid at higher humidity. A complete monolayer coverage of calcite by stearic acid results in a significant reduction in wear but only a moderate reduction in friction forces at low humidity and no reduction at 75% relative humidity (RH). Thus, our data suggest that the wear reduction does not result from a lowering of the friction force but rather from an increased ductility of the surface region as offered by the stearic acid layer. An incomplete monolayer of stearic acid on the calcite surface provides no reduction in wear regardless of the RH investigated. Clearly, the wear properties of modified calcite surfaces depend crucially on the packing density of the surface modifier and also on the air humidity.