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Droplet coalescence is ubiquitous in nature and, at the same time key to various technologies, such as inkjet printing. Herein, this study reports on the coalescence of polymer droplets with different chain lengths coalescing on substrates of different wettability. By means of molecular dynamics simulations of a coarse‐grained model, it is found that the rate of bridge growth is higher in the case of droplets with smaller contact angles (more wettable substrates) and decreases with the increase of the chain length of the polymers. Different behavior is also identified in the dynamics of the approach of the two droplets during coalescence with the substrate wettability playing a more important role compared to the chain length of the polymers. While the dynamics of the droplet are greatly affected by the latter parameters, the density profile and flow patterns remain the same for the different cases. Thus, this study anticipates that it provides further insights into the coalescence of liquid polymer droplets on solid substrates with implications for relevant technologies. [ABSTRACT FROM AUTHOR]

We use a standard bead-spring model and molecular dynamics simulations to study the static properties of symmetric linear multiblock copolymer chains and their blocks under poor solvent conditions in a dilute solution from the regime close to theta conditions, where the chains adopt a coil-like formation, to the poorer solvent regime where the chains collapse obtaining a globular formation and phase separation between the blocks occurs. We choose interaction parameters as is done for a standard model, i.e., the Lennard-Jones fluid and we consider symmetric chains, i.e., the multiblock copolymer consists of an even number n of alternating chemically different A and B blocks of the same length NA = NB = N. We show how usual static properties of the individual blocks and the whole multiblock chain can reflect the phase behavior of such macromolecules. Also, how parameters, such as the number of blocks n can affect properties of the individual blocks, when chains are in a poor solvent for a certain range of n. A detailed discussion of the static properties of these symmetric multiblock copolymers is also given. Our results in combination with recent simulation results on the behavior of multiblock copolymer chains provide a complete picture for the behavior of these macromolecules under poor solvent conditions, at least for this most symmetrical case. Due to the standard choice of our parameters, our system can be used as a benchmark for related models, which aim at capturing the basic aspects of the behavior of various biological systems. [ABSTRACT FROM AUTHOR]

By molecular dynamics simulation of a coarse-grained bead-spring-type model for a cylindrical molecular brush with a backbone chain of Nb effective monomers to which with grafting density σ side chains with N effective monomers are tethered, several characteristic length scales are studied for variable solvent quality. Side chain lengths are in the range 5 <= N <= 40, backbone chain lengths are in the range 50 <= Nb <= 200, and we perform a comparison to results for the bond fluctuation model on the simple cubic lattice (for which much longer chains are accessible, Nb <= 1027, and which corresponds to an athermal, very good, solvent). We obtain linear dimensions of the side chains and the backbone chain and discuss their N-dependence in terms of power laws and the associated effective exponents. We show that even at the theta point the side chains are considerably stretched, their linear dimension depending on the solvent quality only weakly. Effective persistence lengths are extracted both from the orientational correlations and from the backbone end-to-end distance; it is shown that different measures of the persistence length (which would all agree for Gaussian chains) are not mutually consistent with each other and depend distinctly both on Nb and the solvent quality. A brief discussion of pertinent experiments is given. [ABSTRACT FROM AUTHOR]

When two types of side chains (A,B) are densely grafted to a (stiff) backbone and the resulting bottlebrush polymer is in a solution under poor solvent conditions, an incompatibility between A and B leads to microphase separation in the resulting cylindrical brush. The possible types of ordering are reminiscent of the ordering of block copolymers in cylindrical confinement. Starting from this analogy, Leibler's theory of microphase separation in block copolymer melts is generalized to derive a description of the system in the weak segregation limit. Also molecular dynamics simulation results of a corresponding coarse-grained bead-spring model are presented. Using side chain lengths up to N = 50 effective monomers, the ratio of the Lennard-Jones energy parameter between unlike monomers ([variant_greek_epsilon]AB) and monomers of the same kind ([variant_greek_epsilon]AA = [variant_greek_epsilon]BB) is varied. Various correlation functions are analyzed to study the conditions when (local) Janus-cylinder-type ordering and when (local) microphase separation in the direction along the cylinder axis occurs. Both the analytical theory and the simulations give evidence for short-range order due to a tendency toward microphase separation in the axial direction, with a wavelength proportional to the side chain gyration radius, irrespective of temperature and grafting density, for a wide range of these parameters. [ABSTRACT FROM AUTHOR]

Surface nanobubbles are stable gaseous phases in liquids that form on solid substrates. While their existence has been confirmed, there are many open questions related to their formation and dissolution processes along with their structures and properties, which are difficult to investigate experimentally. To address these issues, we carried out molecular dynamics simulations based on atomistic force fields for systems comprised of water, air (N 2 and O 2 ), and a Highly Oriented Pyrolytic Graphite (HOPG) substrate. Our results provide insights into the formation/dissolution mechanisms of nanobubbles and estimates for their density, contact angle, and surface tension. We found that the formation of nanobubbles is driven by an initial nucleation process of air molecules and the subsequent coalescence of the formed air clusters. The clusters form favorably on the substrate, which provides an enhanced stability to the clusters. In contrast, nanobubbles formed in the bulk either move randomly to the substrate and spread or move to the water–air surface and pop immediately. Moreover, nanobubbles consist of a condensed gaseous phase with a surface tension smaller than that of an equivalent system under atmospheric conditions, and contact angles larger than those in the equivalent nanodroplet case. We anticipate that this study will provide useful insights into the physics of nanobubbles and will stimulate further research in the field by using all-atom simulations. [ABSTRACT FROM AUTHOR]

Theintriguing ability of certain surfactant molecules to drivethe superspreading of liquids to complete wetting on hydrophobic substratesis central to numerous applications that range from coating flow technologyto enhanced oil recovery. Despite significant experimental efforts,the precise mechanisms underlying superspreading remain unknown todate. Here, we isolate these mechanisms by analyzing coarse-grainedmolecular dynamics simulations of surfactant molecules of varyingmolecular architecture and substrate affinity. We observe that forsuperspreading to occur, two key conditions must be simultaneouslysatisfied: the adsorption of surfactants from the liquid–vaporsurface onto the three-phase contact line augmented by local bilayerformation. Crucially, this must be coordinated with the rapid replenishmentof liquid–vapor and solid–liquid interfaces with surfactantsfrom the interior of the droplet. This article also highlights andexplores the differences between superspreading and conventional surfactants,paving the way for the design of molecular architectures tailoredspecifically for applications that rely on the control of wetting. [ABSTRACT FROM AUTHOR]

Recent developments in “superspreading” are highlighted showing this phenomenon to be due to the combined effect of diffusion processes, Marangoni stresses, surfactant, solvent and substrate chemistry, and ambient conditions. The ultimate resolution of the driving mechanisms will involve the application of molecular dynamics simulations together with continuum-scale modeling and multi-scale experimentation. [ABSTRACT FROM AUTHOR]

The surfactant-driven spreading of droplets is an essential process in many applications ranging from coating flow technology to enhanced oil recovery. Despite the significant advancement in describing spreading processes in surfactant-laden droplets, including the exciting phenomena of superspreading, many features of the underlying mechanisms require further understanding. Here, we have carried out molecular dynamics simulations of a coarse-grained model with a force-field obtained from the statistical associating fluid theory to study droplets laden with common and superspreading surfactants. We have confirmed the important elements of the superspreading mechanism, i.e. the adsorption of surfactant at the contact line and the fast replenishment of surfactant from the bulk. Through a detailed comparison of a range of droplets with different surfactants, our analysis has indicated that the ability of surfactant to adsorb at the interfaces is the key feature of the superspreading mechanism. To this end, surfactants that tend to form aggregates and have a strong hydrophobic attraction in the aggregated cores prevent the fast replenishment of the interfaces, resulting in reduced spreading ability. We also show that various surfactant properties, such as diffusion and architecture, play a secondary role in the spreading process. Moreover, we discuss various drop properties such as the height, contact angle, and surfactant surface concentration, highlighting differences between superspreading and common surfactants. We anticipate that our study will provide further insight for applications requiring the control of wetting. [ABSTRACT FROM AUTHOR]

With most of the focus to date having been on the coalescence of freely suspended droplets, much less is known about the coalescence of sessile droplets, especially in the case of droplets laden with surfactant. Here, we employ large-scale molecular dynamics simulations to investigate this phenomenon on substrates with different wettability. In particular, we unravel the mass transport mechanism of surfactant during coalescence, thus explaining the key mechanisms present in the process. Close similarities are found between the coalescence of sessile droplets with equilibrium contact angles above 90° and that of freely suspended droplets, being practically the same when the contact angle of the sessile droplets is above 140°. Here, the initial contact point is an area that creates an initial contact film of surfactant that proceeds to break into engulfed aggregates. A major change in the physics appears below the 90° contact angle, when the initial contact point becomes small and line-like, strongly affecting many aspects of the process and allowing water to take part in the coalescence from the beginning. We find growth exponents consistent with a 2/3 power law on strongly wettable substrates but no evidence of linear growth. Overall bridge growth speed increases with wettability for all surfactant concentrations, but the speeding up effect becomes weaker as surfactant concentration grows, along with a general slowdown of the coalescence compared to pure water. Concurrently, the duration of the initial thermally limited regime increases strongly by almost an order of magnitude for strongly wettable substrates. [ABSTRACT FROM AUTHOR]

As one of the most fascinating confined water/ice phenomena, two-dimensional square ice has been extensively studied and experimentally confirmed in recent years. Apart from the unidirectional homogeneous square icing patterns considered in previous studies, the multidirectional partitioned square icing patterns are discovered in this study and characterized by molecular dynamics (MD) simulations. Square icing parameters are proposed to quantitatively distinguish the partitioned patterns from the homogeneous patterns and the liquid water. The number of graphene monolayers n is varied in this study, and the results show that it is more energetically favorable to form partitioned square icing patterns when the water molecules are confined between graphite sheets (n ≥ 2) compared to graphene (n = 1). This phenomenon is insensitive to n as long as n ≥ 2 because of the short-range nature of the interaction between water molecules and the carbon substrate. Moreover, it is energetically unfavorable to form partitioned square icing patterns for a single layer of water molecules even for n ≥ 2, verifying that the interaction between layers of water molecules is another dominant factor in the formation of partitioned structures. The conversion from partitioned structure to homogeneous square patterns is investigated by changing the pressure and the temperature. Based on the comprehensive MD simulations, this study unveils the formation mechanism of the partitioned square icing patterns. [ABSTRACT FROM AUTHOR]

Droplet coalescence is an important process in nature and various technologies (e.g., inkjet printing). Here, we unveil the surfactant mass transport mechanism and report on several major differences in the coalescence of surfactant-laden droplets as compared to pure water droplets by means of molecular dynamics simulation of a coarse-grained model. Large-scale changes to bridge growth dynamics are identified, such as the lack of multiple thermally excited precursors, attenuated collective excitations after contact, slowing down in the inertial regime due to aggregate-induced rigidity and reduced water flow, and a slowing down in the coalescence rate (deceleration) when surfactant concentration increases, while at the same time, we also confirm the existence of an initial thermal, and a power-law, inertial, regime of the bridge growth dynamics in both the pure and the surfactant-laden droplets. Thus, we unveil the key mechanisms in one of the fundamental topological processes of liquid droplets containing surfactant, which is crucial in relevant technologies. [ABSTRACT FROM AUTHOR]

Droplet evaporation on rough substrates is ubiquitous in nature and has numerous technological applications, such as coating. To study the evaporation characteristics of nanodroplets on substrates with different rough structures, molecular dynamics simulations have been performed. Based on the Wenzel wetting model, three systems with different rough structures were constructed, in which the ratios of contact area (RCA) between substrates and nanodroplets were 33.3%, 50%, and 66.6%, respectively. The results indicate that the evaporation pattern of the nanodroplet in the system with RCA = 33.3% is the mixed mode, the evaporation pattern of the nanodroplet in the system with RCA = 50% is the constant-contact-radius mode, and the evaporation pattern of the nanodroplet in the system with RCA = 66.6% is the constant-contact-angle mode. Meanwhile, when the temperature of substrates (T) is suddenly raised from 0.67 to 0.83 ε/kB, followed by a corresponding rise in the temperature of nanodroplets, we find that temperature and evaporation rates of the nanodroplets increase with the increase in RCA in this period. Changes in RCA that lead to the changes in substrate wettability affect the heat transfer between nanodroplets and substrates. In particular, the more the substrate wettability, the higher the heat transfer efficiency. Moreover, the wettability of the substrate in the systems with RCA = 50% and 66.6% promotes the heat and mass transfer in the three-phase contact line region of the nanodroplets during the evaporation process, while the non-wettability of the substrate in the system with RCA = 33.3% suppresses the local heat and mass transfer. This work offers further knowledge of droplet evaporation on rough substrates, which, in turn, provides a reference for the process optimization of its technological applications. [ABSTRACT FROM AUTHOR]