Microscopic origin of the effect of substrate metallicity on interfacial free energies

We investigate the effect of the metallic character of solid substrates on solid–liquid interfacial thermodynamics using molecular simulations. Building on the recent development of a semiclassical Thomas–Fermi model to tune the metallicity in classical molecular dynamics simulations, we introduce a thermodynamic integration framework to compute the evolution of the interfacial free energy as a function of the Thomas–Fermi screening length. We validate this approach against analytical results for empty capacitors and by comparing the predictions in the presence of an electrolyte with values determined from the contact angle of droplets on the surface. The general expression derived in this work highlights the role of the charge distribution within the metal. We further propose a simple model to interpret the evolution of the interfacial free energy with voltage and Thomas–Fermi length, which allows us to identify the charge correlations within the metal as the microscopic origin of the evolution of the interfacial free energy with the metallic character of the substrate. This methodology opens the door to the molecular-scale study of the effect of the metallic character of the substrate on confinement-induced transitions in ionic systems, as reported in recent atomic force microscopy and surface force apparatus experiments.

Effect of grain size of dental zirconia on shear bond strength of composite resin cement

The effect of grain size of dental zirconia on the shear bond strength of composite resin cement was newly studied. Disc-shaped dental zirconia with small (sample S) and large (sample L) grains were made by sintering of pre-sintered dental zirconia at 1450°C for 0.5 h and 40 h, respectively. After the sintering, the average grain size of sample S was 1.37 ± 0.15 µm, while that of sample L was 3.74 ± 0.50 µm. The sintered discs were successively polished with different grades of diamond and alumina slurries. The interfacial free energies were 63.5 ± 4.2 dyne/cm for sample S and 52.1 ± 5.5 dyne/cm for sample L. Stainless steel cylinders, previously sandblasted with 50 µm alumina powder, were bonded to the zirconia discs using composite resin cement. Next, samples were kept in an oven for 7 d at 36.5°C. The shear bond strength of sample S was 23.0 ± 4.5 MPa while that of sample L was 17.5 ± 4.6 MPa. After the fracture, the areal % values of composite resin cement remaining on the zirconia surfaces were 89.7 ± 5.9% for sample S and 61.6 ± 5.5% for sample L. The results suggest that grain size reduction has a potential to enhance the degree of bonding between a composite resin cement and a dental zirconia due to the increase of interfacial free energy.

Temperature-Dependent Wettability of Water on a Nickel Surface at Pressurized Condition: A Molecular Dynamics Study

Temperature-dependent wettability of water droplets on a metal surface in a pressurized environment is of great theoretical and practical significance. In this paper, molecular dynamic simulation is used to study this problem by relating the temperature-dependent apparent contact angles to the changes in solid-liquid and solid-vapor interfacial free energies and hydrogen bonds in the nano-sized water droplets with increasing the temperature. The temperature range of interest is set from 298 K to 538 K in a 20 K interval under a constant pressure of 7 MPa. The results show that the contact angle in general decreases with raising the temperature and decreasing trend can be divided into two sections with different slopes. The contact angle drops slowly when the temperature is below 458 K as a critical point. Beyond this point, the contact angle shows a much steeper decrease. The difference between solid-vapor and solid-liquid interfacial free energies is found to decrease slightly with temperature. Combining with that the surface tension drops with increasing the temperature, a decreasing trend of the contact angle is expected according to the Young’s equation. As the temperature increases, the number and average energy of the hydrogen bonds both decrease, and the hydrogen bonds tend to aggregate at the bottom of the nano-droplets.