In molecular dynamics (MD) simulations, interactions between water molecules and graphitic surfaces are often modeled as a simple Lennard-Jones potential between oxygen and carbon atoms. A possible method for tuning this parameter consists of simulating a water nanodroplet on a flat graphitic surface, measuring the equilibrium contact angle, extrapolating it to the limit of a macroscopic droplet, and finally matching this quantity to experimental results. Considering recent evidence demonstrating that the contact angle of water on a graphitic plane is much higher than what was previously reported, we estimate the oxygen-carbon interaction for the recent SPC/Fw water model. Results indicate a value of about 0.2 kJ/mol, much lower than previous estimations. We then perform simulations of cylindrical water filaments on graphitic surfaces, in order to compare and correlate contact angles resulting from these two different systems. Results suggest that a modified Young's equation does not describe the relation between contact angle and drop size in the case of extremely small systems and that contributions different from the one deriving from contact line tension should be taken into account.

A hierarchical procedure bridging the gap between atomistic and mesoscopic simulation for polymer-clay nanocomposite (PCN) design is presented. The dissipative particle dynamics (DPD) is adopted as the mesoscopic simulation technique, and the interaction parameters of the mesoscopic model are estimated by mapping the corresponding energy values obtained from atomistic molecular dynamics (MD) simulations. The predicted structure of the nylon 6 PCN system considered is in excellent agreement with previous experimental and atomistic simulation results. IntroductionBlending molten polymer and inorganic clays can result in a class of new materials, in which nanoscale clay particles, generally layered silicates, are molecularly dispersed within the polymeric matrix. Such polymer-clay nanocomposites (or PCNs) exhibit dramatic increases in several properties, including mechanical strength and heat resistance, and a decrease in gas permeability when compared to the polymeric matrix alone. [1][2][3][4][5][6][7] Importantly, the improvement in these properties is achieved at very low loadings of the inorganic component, typically 1-10 wt %, thus rendering PCNs lighter in weight than any other conventionally filled polymer. These unique features make PCNs ideal materials for applications such as high barriers for food or pharmaceutical packaging to strong, heat resistant automotive components, just to name a few. Fabricating these materials in an efficient and cost-effective manner, however, poses significant synthetic challenges. To appreciate these challenges, let us discuss briefly the structure of layered silicates by considering montmorillonite (MMT) as a prime example. This inorganic clay consists of stacked silicate sheets, each approximately 200 nm long and 1 nm thick. The spacing between each sheet (or gallery) is also of the order of 1 nm, and this quantity is clearly smaller than the average radius of gyration of any conventional polymer. Therefore, entropy generally constitutes a large barrier that prevents the polymer from penetrating these galleries and becoming an intercalated material. Accordingly, there is a number of critical issues that need to be addressed in order to optimize the design and production of PCNs. Of foremost importance is the isolation of the conditions that result in a promotion of the polymer penetration into the narrow clay galleries. If, however, the sheets ultimately phase-separate from the polymer matrix, the mixture will not exhibit the improved strength, heat resistance, or barrier properties mentioned above. Accordingly, it is also essential to determine the factors that control the macroscopic phase behavior of the mixture. Finally, the properties of the PCNs commonly depend on the structure of the material; thus, it is of particular interest to establish the morphology of the final composite.

Wetting is a widespread phenomenon, most prominent in a number of cases, both in nature and technology. Droplets of pure water with initial radius ranging from 20 to 80 [Å] spreading on graphitic surfaces are studied by molecular dynamics simulations. The equilibrium contact angle is determined and the transition to the macroscopic limit is discussed using Young equation in its modified form. While the largest droplets are almost perfectly spherical, the profiles of the smallest ones are no more properly described by a circle. For the sake of accuracy, we employ a more general fitting procedure based on local averages. Furthermore, our results reveal that there is a possible transition to the macroscopic limit. The modified Young equation is particularly precise for characteristic lengths (radii and contact-line curvatures) around 40 [Å].

We report on a molecular dynamics investigation of the wetting properties of graphitic surfaces by various solutions at concentrations 1 − 8 wt% of commercially available non-ionic surfactants with long hydrophilic chains, linear or T-shaped. These are surfactants of length up to 160 [Å]. It turns out that molecular dynamics simulations of such systems ask for a number of solvent particles that can be reached without seriously compromising computational efficiency only by employing a coarse-grained model. The MARTINI force field with polarizable water offers a framework particularly suited for the parameterization of our systems. In general, its advantages over other coarse-grained models are the possibility to explore faster long time scales and the wider range of applicability. Although the accuracy is sometimes put under question, the results for the wetting properties by pure water are in good agreement with those for the corresponding atomistic systems and theoretical predictions. On the other hand, the bulk properties of various aqueous surfactant solutions indicate that the micellar formation process is too strong. For this reason, a typical experimental configuration is better approached by preparing the droplets with the surfactants arranged in the initial state in the vicinity of contact line. Cross-comparisons are possible and illuminating, but equilibrium contanct angles as obtained from simulations overestimate the experimental results. Nevertheless, our findings can provide guidelines for the preliminary assessment and screening of surfactants. Most importantly, it is found that the wetting properties mainly depend on the length and apolarity of the hydrophobic tail, for linear surfactants, and the length of the hydrophilic headgroup for T-shaped surfactants. Moreover, the T-shaped topology appears to favor the adsorption of surfactants onto the graphitic surface and faster spreading.

We present an innovative, multiscale computational approach to probe the behaviour of polymer-clay nanocomposites (PCNs). Our modeling recipe is based on 1) quantum/force-field-based atomistic simulation to derive interaction energies among all system components; 2) mapping of these values onto mesoscopic bead-field (MBF) hybrid-method parameters; 3) mesoscopic simulations to determine system density distributions and morphologies (i.e., intercalated versus exfoliated); and 4) simulations at finite-element levels to calculate the relative macroscopic properties. The entire computational procedure has been applied to two well-known PCN systems, namely Nylon 6/Cloisite 20A and Nylon 6/Cloisite 30B, as test materials, and their mechanical properties were predicted in excellent agreement with the available experimental data. Importantly, our methodology is a truly bottom-up approach, and no "learning from experiment" was needed in any step of the entire procedure.