Effect of molecular branching and surface wettability on solid-liquid surface tension and line-tension of liquid alkane surface nanodroplets.

HYPOTHESIS: Surface nanodroplets have important technological applications. Previous experiments and simulations have shown that their contact angle deviates from Young's equation. A modified version of Young's equation considering the three-phase line tension (τ) has been widely used in literature, and a wide range of values for τ are reported. We have recently shown that molecular branching affects the liquid-vapour surface tension γlv of liquid alkanes. Therefore, the wetting behaviour of surface nanodroplets should be affected by molecular branching. This study conducted molecular dynamics (MD) simulations to gain insight into the wetting behaviour of linear and branched alkane nanodroplets on oleophilic and oleophobic surfaces. We aim to examine the Young equation's validity and branching's effect on fundamental properties, including solid-liquid surface tension γsl and line tension τ. SIMULATIONS: The simulations were performed on a linear alkane, triacontane (C30H62), as well as four of its branched isomers: 2,6,13,17-tetrapropyloctadecane,2,6,9,10,13,17-hexaethyloctadecane, 2,5,7,8,11,12,15-heptaethylhexadecane and 2,3,6,7,10,11-hexapropyldodecane. Nanodroplets with a diameter of approximately 15 nm were released onto the surfaces, and their contact angles were measured. Additionally, using a novel approach, the solid-liquid surface tension (γsl), the validity of Young's equation and line tension for all alkane and surface combinations are determined. FINDINGS: It was discovered that the calculated γsl, deviated from the theoretical γsl,Young predicted from Young's equation for all alkanes on oleophilic surfaces. However, this deviation was minimal for branched alkanes on the oleophobic surfaces but more significant for the linear alkane. The findings indicated that γsl < 0 for oleophilic surfaces and γsl > 0 for oleophobic surfaces. Moreover, it was observed that |γsl| was lower for branched molecules and decreased as branching increased. Line tension values were then determined through a novel method, showing τ was positive for oleophilic surfaces ranging from 1.30 × 10-10 to 6.27 × 10-11N. On an oleophobic surface, linear alkane shows a negative line tension of -1.15 × 10-10N and branched alkanes up to two orders of magnitude lower values ranging from -2.09 × 10-12 to 2.43 × 10-11N. Line tension values between -1.15 × 10-10 and + 1.1 × 10-10N are calculated for various linear alkane and surface combinations. These findings show the dependence of line tension on the contact angle and branching, demonstrating that for linear alkanes, τ is significant, whereas, for branched alkanes, line tension is smaller or negligible for large contact angles.

Tribological and Rheological Properties of Poly(vinyl alcohol)-Gellan Gum Composite Hydrogels.

Polymeric poly(vinyl alcohol) (PVA)-based composite hydrogels are promising materials with various biomedical applications. However, their mechanical and tribological properties should be tailored for such applications. In this study, we report the fabrication of PVA-gellan gum (GG) composite hydrogels and determine the effect of GG content on their rheological and tribological properties. The rheology tests revealed an enhanced storage (elastic) modulus with increased gellan gum (GG) concentration. The results showed up to 89% enhancement of the elastic modulus of PVA by adding 0.5 wt% gellan gum. This elastic modulus (12.1 ± 0.8 kPa) was very close to that of chondrocyte and its surrounding pericellular matrix (12 ± 1 kPa), rendering them ideal for cartilage regeneration applications. Furthermore, the friction coefficient was reduced by up to 80% by adding GG to PVA, demonstrating the increased elastic modulus improved chance of survival under mechanical shear stresses. Examining PVA/GG at different concentrations of 0.1, 0.3, and 0.5 wt% of GG, we demonstrate that at a load of 5 N, the friction coefficient decreases by increasing the GG concentration. However, at higher loads of 10 and 15 N, a 0.3 wt% concentration was sufficient to significantly reduce the friction coefficient. For PVA and PVA/GG composites, we observed a reduction in friction coefficient by increasing the load from 5 to 15 N. We also found the friction to be independent of the sliding velocity. Possible mechanisms of achieving a reduced friction coefficient are discussed.

Anisotropic Wettability on One-Dimensional Nanopatterned Surfaces: The Effects of Intrinsic Surface Wettability and Morphology.

Large-scale molecular dynamic simulations were conducted to study anisotropic wettability on one-dimensional (1D) nanopatterned surfaces. Hexadecane (C16H34) and decane (C10H22) nanodroplets were used as wetting liquids. Initially, surfaces with various intrinsic wettability (oleophobic and oleophilic) were produced using surface lattice size as a control parameter. These surfaces were subsequently patterned with 1D grooves of different sizes, and their anisotropic wettability was examined. The results show that anisotropic wettability strongly depends on intrinsic surface wettability and surface morphology. The results also demonstrate that the anisotropy in the contact angle is negligible for oleophobic surfaces. However, the anisotropy becomes more evident for oleophilic surfaces and increases with the degree of oleophilicity. Results suggest that anisotropy also depends on the surface morphology, including the patterns' width and height. Monitoring the droplet shape showed that more significant droplet distortion was associated with higher anisotropy. A clear association was lacking between the roughness ratio, r, and the degree of anisotropy. The observed average contact angle for 1D patterned oleophilic surfaces disagreed with the predicted values from the Wenzel theory. However, the theory could correctly predict the state of the droplet being Cassie-Baxter or Wenzel.

The Origins of Enhanced and Retarded Crystallization in Nanocomposite Polymers.

Controlling the crystallinity of hybrid polymeric systems has an important impact on their properties and is essential for developing novel functional materials. The crystallization of nanocomposite polymers with gold nanoparticles is shown to be determined by free space between nanoparticles. Results of large-scale molecular dynamics simulations reveal while crystallinity is affected by the nanoparticle size and its volume fraction, their combined effects can only be measured by interparticle free space and characteristic size of the crystals. When interparticle free space becomes smaller than the characteristic extended length of the polymer molecule, nanoparticles impede the crystallization because of the confinement effects. Based on the findings from this work, equations for critical particle size or volume fraction that lead to this confinement-induced retardation of crystallization are proposed. The findings based on these equations are demonstrated to agree with the results reported in experiments for nanocomposite systems. The results of simulations also explain the origin of a two-tier crystallization regime observed in some of the hybrid polymeric systems with planar surfaces where the crystallization is initially enhanced and then retarded by the presence of nanoparticles.

Unravelling the effects of size, volume fraction and shape of nanoparticle additives on crystallization of nanocomposite polymers.

We conducted large scale molecular dynamics simulations to understand the effects of size, shape and volume fraction of additive nanoparticles on the crystallization of nanocomposite polymers. We used spherical and cubic gold nanoparticles of various sizes ranging from 2 to 8 nm to create hexacontane (C60H122)-gold nanocomposites at various volume fractions of 0.84-19.27%. We show that, regardless of the shape, decreasing the size of particles at the same volume fraction results in decreased final crystallinity. Similarly, for the same particle size, increasing the volume fraction causes a decrease in the crystal growth rate and final crystallinity. We demonstrate that this is a confinement induced phenomenon, and the free interparticle space captures the combined effects of particle size and volume fraction. If this free space is smaller than the extended length of the molecule or the characteristic size of the crystal lamella thickness of the polymer, significant slow-down in crystallinity will emerge. In this confinement limit, the interparticle free space controls the crystal growth rate and final crystallinity. We have developed the equations that predict the critical volume fraction (φ cr) for a given size or critical size (D cr) for a given volume fraction. For φ > φ cr or D < D cr, one would expect confinement induced retardation of crystallization. We also show that cubic particles result in a higher growth rate and crystallinity in comparison to spherical particles, purely due to their shape. Furthermore, cubic particles due to flat surfaces lead to distinct two-tier crystallisation kinetics manifested by enhanced crystallization at the early stage of crystallization, followed by slow crystallization due to confinement effects. This two-tier crystallization is more distinct at higher volume fractions. For spherical particles, however, this two-tier crystallization is almost absent and molecular crystallization near the particle is frustrated by the curved shape of the nanoparticle.

Modelling mucosal surface roughness in the human velopharynx: a computational fluid dynamics study of healthy and obstructive sleep apnea airways.

We previously published a unique methodology for quantifying human velopharyngeal mucosal surface topography and found increased mucosal surface roughness in patients with obstructive sleep apnea (OSA). In fluid mechanics, surface roughness is associated with increased frictional pressure losses and resistance. This study used computational fluid dynamics (CFD) to analyze the mechanistic effect of different levels of mucosal surface roughness on velopharyngeal airflow. Reconstructed velopharyngeal models from OSA and control subjects were modified, giving each model three levels of roughness, quantified by the curvature-based surface roughness index (CBSRI0.6) (range 24.8-68.6 mm-1). CFD using the k-ω shear stress transport turbulence model was performed (unidirectional, inspiratory, steady-state, 15l/min volumetric flow rate), and the effects of roughness on flow velocity, intraluminal pressure, wall shear stress, and velopharyngeal resistance (Rv) were examined. Across all models, increasing roughness increased maximum flow velocity, wall shear stress, and flow disruption while decreasing intraluminal pressures. Linear mixed effects modeling demonstrated a log-linear relationship between CBSRI0.6 and Rv, with a common slope (log(Rv)/CBSRI0.6) of 0.0079 [95% confidence interval (CI) 0.0015-0.0143; P = 0.019] for all subjects, equating to a 1.9-fold increase in Rv when roughness increased from control to OSA levels. At any fixed CBSRI0.6, the estimated difference in log(Rv) between OSA and control models was 0.9382 (95% CI 0.0032-1.8732; P = 0.049), equating to an 8.7-fold increase in Rv. This study supports the hypothesis that increasing mucosal surface roughness increases velopharyngeal airway resistance, particularly for anatomically narrower OSA airways, and may thus contribute to increased vulnerability to upper airway collapse in patients with OSA.NEW & NOTEWORTHY Increased mucosal surface roughness in the velopharynx of patients with obstructive sleep apnea (OSA) has recently been identified, but its role in OSA pathogenesis is unknown. This is the first study to model the impact of increased roughness on airflow mechanics in the velopharynx. We report that increasing roughness significantly affects airflow, increasing velopharyngeal resistance and potentially increasing the vulnerability to upper airway collapse, particularly in those patients with an already compromised anatomy.

Surface induced crystallization of polymeric nano-particles: effect of surface roughness.

Molecular dynamics simulations are conducted to study the crystallization of a polymeric system as a drop in an isolated state and on a surface. It is shown that crystallization kinetics for the polymeric system as a particle on a smooth surface is much faster than in the isolated form. We show however that as the surface becomes rough the crystallization rate of the polymeric particle decreases. The effect of roughness was compared for two cases of a polymer drop, partially (Wenzel state) and fully (fully confined) wetting the cavities on a rough surface. In both cases it was observed that crystallization was slower than that on a smooth surface, and crystal growth rate was decreased by increasing the characteristic roughness ratio. The crystallization on rough surfaces was still faster than that of the isolated polymer drop.

Thermostatic and rheological responses of DPD fluid to extreme shear under modified Lees-Edwards boundary condition.

Thermodynamic, hydrodynamic and rheological interactions between velocity-dependent thermostats of Lowe-Andersen (LA) and Nosé-Hoover-Lowe-Andersen (NHLA), and modified Lees-Edwards (M-LEC) boundary condition were studied in the context of Dissipative Particle Dynamics method. Comparisons were made with original Lees-Edwards method to characterise the improvements that M-LEC offers in conserving the induced shear momentum. Different imposed shear velocities, heat bath collision/exchange frequencies and thermostating probabilities were considered. The presented analyses addressed an unusual discontinuity in momentum transfer that appeared in form of nonphysical jumps in velocity and temperature profiles. The usefulness of M-LEC was then quantified by evaluating the enhancements in obtained effective shear velocity, effective shear rate, Péclet number, and dynamic viscosity. System exchange frequency (Γ) with Maxwellian heat bath was found to play an important role, in that its larger values facilitated achieving higher shear rates with proper temperature control at the cost of deviation from an ideal momentum transfer. Similar dynamic viscosities were obtained under both shearing modes between LA and NHLA thermostats up to Γ = 10, whilst about twice the range of viscosity (1 < η < 20) was calculated for M-LEC at larger probabilities (ΓΔt > %). The main benefits of this modification were to facilitate momentum flow from shear boundaries to the system bulk. In addition, it was found that there exist upper thresholds for imposing shear on the system beyond which temperature cannot be controlled properly and nonphysical jumps reappear.

Effect of water on structural and frictional properties of self assembled monolayers.

Self-assembled monolayers (SAMs) of n-alkanethiols [(CH3(CH2)(n-1), n = 14, 15] on Au(111) in the presence of water have been simulated by molecular dynamics simulation. The behavior and effects of compression on structural characteristics and water penetration into monolayers under different ranges of normal pressures have been investigated. Frictional properties of hydrated SAM systems under various sliding velocities, and loading conditions are examined to explore correlation between the amount of water penetration and friction. Simulations for one odd and one even SAM (C14 and C15) systems have revealed interesting odd-even effects in water penetration and frictional properties. We have also compared the frictional and structural properties of hydrated systems to that of dry SAM-Au (one surface of gold is covered by SAM) and SAM-SAM (both gold substrates are covered by SAM) contacts. The results reveal that the even hydrated SAM (C14) shows lower friction coefficient compared with the odd hydrated SAM (C15). We found the presence of water reduces the friction only at lower pressures; and at higher pressures, dry SAM-Au contacts offer lower friction. It was interesting to see that the lubricity effect of water was much stronger for the odd system and persisted to slightly higher pressures (300 MPa for the even SAM and 700 MPa for the odd SAM). At higher pressures, for both odd and even systems, the presence of water increased the friction. We also found that at low sliding velocities and higher pressures apparent water viscosity was enhanced by up to 3 orders of magnitude, indicating possible solidification.

Frictional properties of two alkanethiol self assembled monolayers in sliding contact: odd-even effects.

Using molecular dynamics simulation, we have investigated the structural effects on the frictional properties of self assembled monolayers (SAM) of n-alkanethiols [CH(3)(CH(2))(n-1)SH, n = 12-15] in SAM-SAM contacts attached on Au (111) substrates. We have observed an odd-even effect where friction coefficient for SAM-SAM contacts with n = odd showed consistently higher values than those with n = even. This odd-even effect is independent of the sliding velocity and the relative tilt directions of the SAMs, and persists over a much higher pressure range than that reported before for SAM-Au contacts [L. Ramin and A. Jabbarzadeh, Langmuir 28, 4102-4112 (2012)]. For odd systems higher gauche defects were shown to be the possible source of high friction coefficient. Under the same load and shear rates (comparable sliding velocities), SAM-SAM contacts show mostly higher friction compared to SAM-Au contacts. For SAM-SAM contacts, a more significant increase of friction occurs at higher shear rates due to a shift in the tilt orientation angle. We show SAM-SAM contacts with misaligned relative tilt orientation angle (∼45°-90°) have considerably lower friction compared with those whose tilt orientation angles are almost aligned in the opposite directions and parallel to the shear.

Effect of load on structural and frictional properties of alkanethiol self-assembled monolayers on gold: some odd-even effects.

We have conducted molecular dynamics simulations to study the frictional properties of alkanethiols CH(3)(CH(2))(n-1)SH (Cn, 12 ≤ n ≤ 15) self-assembled monolayers (SAMs) on Au(111) surfaces, under various loading and shearing conditions. For the examined alkanethiols, we found some evidence of the friction coefficient being dependent on the number of carbon atoms in the molecule being odd or even. Alkanethiols with n = odd show consistently higher friction coefficients than those with n = even. Such odd-even effect seems to be independent of the sliding velocity. However, the effect is significant only at lower loads (<700 MPa). The structural origin of this odd-even effect has been discussed. The effect of loading on the structure is also studied. For dodecanethiol (n = 12) we find the film responds to increased loading initially by increasing the tilt and then by deformation of individual molecules. SAM-Au contacts under shear show periodic storage and release of energy and a clear stick-slip pattern in the shear stress, film thickness, and the tilt and tilt orientation angles.

Odd-even effects on the structure, stability, and phase transition of alkanethiol self-assembled monolayers.

Molecular dynamics simulations were conducted to predict the structural properties and phase transition temperatures of n-alkanethiols CH(3)(CH(2))(n-1)SH (Cn, 4 ≤ n ≤ 22) self-assembled monolayers (SAMs) on Au (111) surfaces. We studied the effects of chain length on the structural properties, including tilt and orientation angles, and on phase transition temperature. We found clear dependence of the structural properties, on both the number of carbon atoms, n; and on n being odd or even. Alkanethiols with n ≤ 7 show liquid-like behavior and large rotational mobility, whereas those with n ≥ 12 are well-ordered and stable. For 12 ≤ n ≤ 15, odd-even effects are observed, where for n = odd, larger tilt angles, oriented in the direction of their next next nearest neighbor (NNNN), and for n = even, lower tilt angles, mostly tilted toward next nearest neighbor (NNN), were observed. For 15 ≤ n ≤ 19, we find tilt angle and orientation to be independent of n. For all alkanethiols, a gradual decrease of the tilt angle occurred by increasing the temperature from 300 to 420 K. Order-disorder phase transitions occurred at a certain temperature. This was signified by abrupt instabilities in the tilt orientation angle. This transition temperature showed an enhancement of ∼67-100 °C over the melting point of the corresponding n-alkane bulk system. This enhancement depended on n, and was larger for n = odd. Overall, we found that odd alkanethiols show better structural and thermal stability, and smaller gauche defects.