Stick-Slip Friction Reveals Hydrogel Lubrication Mechanisms.

The lubrication behavior of the hydrated biopolymers that constitute tissues in organisms differs from that outlined by the classical Stribeck curve, and studying hydrogel lubrication is a key pathway to understand the complexity of biolubrication. Here, we have investigated the frictional characteristics of polyacrylamide (PAAm) hydrogels with various acrylamide concentrations, exhibiting Young's moduli (E) that range from 1 to 40 kPa, as a function of applied normal load and sliding velocities by colloid probe lateral force microscopy. The speed-dependence of the friction force shows an initial decrease in friction with increasing velocity, while, above a transition velocity V*, friction increases with speed. This study reveals two different boundary lubrication mechanisms characterized by distinct scaling laws. An unprecedented and comprehensive study of the lateral force loops reveals intermittent friction or stick-slip above and below V*, with characteristics that depend on the hydrogel network, applied load, and sliding velocity. Our work thus provides insight into the closely tied parameters governing hydrogel lubrication mechanisms, and stick-slip friction.

Calcium carbonate with nanogranular microstructure yields enhanced toughness.

The presence of nanogranular microstructures is a widely reported feature of biominerals that form by classical and non-classical mineralization pathways. Inspired by nature, we have synthesized amorphous calcium carbonate nanoparticles with nanogranular microstructures, whose grain size is tuned by varying the polymer concentration. The response to indentation of single calcium carbonate nanoparticles proceeds via an intermittent stick-slip that reflects the characteristics of the nanogranular microstructure. A two-fold mechanism is thus proposed to enhance the toughness of the nanoparticles, namely nanogranular rearrangement and intergranular bridging by an organic phase and/or hydration. This work not only provides a synthesis route to design biologically inspired mineral nanoparticles with nanogranular structure, but also helps in understanding toughening mechanisms of biominerals arising from their nanoscale heterogeneity.

Reconciling DLVO and non-DLVO Forces and Their Implications for Ion Rejection by a Polyamide Membrane.

Recognizing the significance of surface interactions for ion rejection and membrane fouling in nanofiltration, we revise the theories of DLVO (named after Derjaguin, Landau, Verwey, and Overbeek) and non-DLVO forces in the context of polyamide active layers. Using an atomic force microscope, surface forces between polyamide active layers and a micrometer-large and smooth silica colloid were measured in electrolyte solutions of representative monovalent and divalent ions. While the analysis of DLVO forces, accounting for surface roughness, provides how surface charge of the active layer changes with electrolyte concentration, scrutiny of non-DLVO hydration forces gives molecular insight into the composition of the membrane-solution interface. Importantly, we report an expansion of the diffuse layer at high ionic strength, consistent with the recent development of the electrical double layer theory, but in contrast to the widely accepted phenomenon of aggregation in the secondary minimum. Further, the enhanced repulsion acting on modified membranes via polyelectrolyte adsorption can be quantitatively predicted by DLVO and non-DLVO forces. This work serves to solve past misunderstandings about the interaction forces acting on nanofiltration membranes, and it provides guidance for future work on the relation between surface properties and rejection mechanisms and fouling.

Ab Initio Studies of Calcium Carbonate Hydration.

Ab initio simulations of large hydrated calcium carbonate clusters are challenging due to the existence of multiple local energy minima. Extensive conformational searches around hydrated calcium carbonate clusters (CaCO3·nH2O for n = 1-18) were performed to find low-energy hydration structures using an efficient combination of Monte Carlo searches, density-functional tight binding (DFTB+) method, and density-functional theory (DFT) at the B3LYP level, or Møller-Plesset perturbation theory at the MP2 level. This multilevel optimization yields several low-energy structures for hydrated calcium carbonate. Structural and energetics analysis of the hydration of these clusters revealed a first hydration shell composed of 12 water molecules. Bond-length and charge densities were also determined for different cluster sizes. The solvation of calcium carbonate in bulk water was investigated by placing the explicitly solvated CaCO3·nH2O clusters in a polarizable continuum model (PCM). The findings of this study provide new insights into the energetics and structure of hydrated calcium carbonate and contribute to the understanding of mechanisms where calcium carbonate formation or dissolution is of relevance.