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The transport of water and protons in the cathode catalyst layer (CCL) of proton exchange membrane (PEM) fuel cells is critical for cell performance, but the underlying mechanism is still unclear. Herein, the ionomer structure and the distribution/transport characteristics of water and protons in CCLs are investigated via all-atom molecular dynamics simulations. The results show that at low water contents, isolated water clusters form in ionomer pores, while proton transport is mainly via the charged sites of the ionomer side chains and the Grotthuss mechanism. Moreover, with increasing water content, water clusters are interconnected to form continuous water channels, which provide effective paths for proton transfer via the vehicular and Grotthuss mechanisms. Increasing the ionomer mass content can enhance the dense arrangement of the ionomer, which, in turn, increases the density of charge sites and improves the proton transport efficiency. When the ionomer mass content is high, the clustering effect reduces the space for water diffusion, increases the proton transport path, and finally decreases the proton transport efficiency. By providing physics insights into the proton transport mechanism, this study is helpful for the structural design and performance improvement of CCLs of PEM fuel cells. [ABSTRACT FROM AUTHOR]

The breakup of liquid threads into droplets is crucial in various applications, such as nanoprinting, nanomanufacturing, and inkjet printing, where a detailed understanding of the thinning neck dynamics allows for a precise droplet control. Here, the role of surfactant in the breakup process is studied by many-body dissipative particle dynamics, in particular, the various regime transitions and thread profiles, shedding light on molecular-level intricacies of this process hitherto inaccessible to continuum theory and experiments. Moreover, the role of surfactant in the most unstable perturbation, the formed droplet size, and surfactant distributions have been unraveled. As surfactant concentration rises, both the wavelength and time to breakup steadily increase due to the lowering of surface tension below the critical micelle concentration (CMC) and viscous effects introduced by micelles above the CMC. These changes prior to the breakup lead to larger droplets being formed in cases with higher surfactant concentration. We also compared the thinning dynamics to existing theoretical predictions, revealing that the surfactant-laden breakup starts at the inertial regime and transitions into the thermal fluctuation regime when the concentration is increased. Thus, we illuminate the hitherto poorly investigated and intricate breakup process of surfactant-laden liquid threads driven by thermal fluctuations, contributing to a deeper understanding of this process at molecular scales. [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]

The breakup of liquid threads into smaller droplets is a fundamental problem in fluid dynamics. In this study, we estimate the characteristic wavelength of the breakup process by means of many-body dissipative particle dynamics. This wavelength shows a power-law dependence on the Ohnesorge number in line with results from stability analysis. We also discover that the number of satellite droplets exhibits a power-law decay with exponent 0.72 ± 0.04 in the product of the Ohnesorge and thermal capillary numbers, while the overall size of main droplets is larger than that based on the characteristic wavelength thanks to the asynchronous breakup of the thread. Finally, we show that the formation of satellite droplets is the result of the advection of pinching points toward the main droplets in a remaining thinning neck, when the velocity gradient of the fluid exhibits two symmetric maxima. [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]

A decline in natural snow due to global warming increases the reliance of ski resorts on artificial snow. To improve the formation rate and snow amount of artificial snow under any environmental conditions, it is necessary to use atomization technology that maintains the size of liquid drops of the snow-making spray field below a critical size, thus maximizing the number of freezing droplets into ice crystals. Here, we study the effects of the gas–liquid mass-mixing ratio (GLR) and the spacing (d) between two nozzles on the characteristics of the snow-making spray field produced by atomization technology for GLR of 0.05, 0.10, 0.15, and 0.2 and d of 5, 10, 15, and 20 cm. The measurement of the morphology, velocity, and particle-size distribution of the snow-making spray field is conducted by a laser particle-size measuring instrument, particle image velocimetry, and a high-speed camera. Our results show that both the spray cone and the intersection angles increase with the increase in the GLR in a two-nozzle arrangement, while the degree of interference between the nozzles increases with the decrease in spacing, d. We also find that the inward offset of the spray is the main reason for the increase in the intersection angle and the interference area and the deviation of the spray midline. In addition, we compare the characteristics of the spray field produced by the single and the two-nozzle systems. We conclude that the flow-field velocity of the single nozzle is smaller than that of the two nozzles and the velocity gradient of the liquid drops in the two-nozzle flow field varies greatly. The maximum vorticity (Max = 147) in the case of the two-nozzle arrangement is much larger than that of the single nozzle. Moreover, by analyzing the two-nozzle flow field at different spacings, we find that the particle-size distribution is most uniform for GLR = 0.10 and d = 15 cm. Thus, our study elucidates the characteristics of spray fields suitable for snow-making toward achieving higher quality and more efficient snow-making processes. [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]

Atmospheric aerosols can consist of inorganic and organic substances, including surfactants at a significant concentration. Importantly, the latter can reduce the surface tension at the liquid–vapor surfaces, where they preferentially adsorb due to their amphiphilic structure. As a result, processes such as droplet coalescence, development of precipitation, and ultimately cloud lifetime may depend on the presence of surfactants in the aerosols. Here, we present a numerical model for cloud droplet formation, which is based on the Lagrangian particle-based microphysics-scheme superdroplet method and takes into account the presence of the surfactant in the droplets. Our results show that surfactant facilitates cloud formation by increasing the number and size of activated droplets, which concentrate at the bottom of the cloud, while the largest droplets are concentrated at the top of the cloud. This indicates a circulation of droplets that involves activation and growth processes from the bottom of the cloud toward the top. Moreover, our conclusions are independent of the particular approach used for modeling the diffusion of Eulerian variables due to the subgrid-scale turbulence. We anticipate that our results will enrich our understanding of the role of surfactants in the behavior of atmospheric aerosols and, importantly, will pave the way for further developments in the numerical modeling of systems with surfactants at macroscopic scales. [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]

We discuss a coarse-grained model recently proposed by Starr and Sciortino [J. Phys.: Condens. Matter 18, L347 (2006)] for spherical particles functionalized with short single DNA strands. The model incorporates two key aspects of DNA hybridization, i.e., the specificity of binding between DNA bases and the strong directionality of hydrogen bonds. Here, we calculate the effective potential between two DNA-functionalized particles of equal size using a parallel replica protocol. We find that the transition from bonded to unbonded configurations takes place at considerably lower temperatures compared to those that were originally predicted using standard simulations in the canonical ensemble. We put particular focus on DNA-decorations of tetrahedral and octahedral symmetry, as they are promising candidates for the self-assembly into a single-component diamond structure. Increasing colloid size hinders hybridization of the DNA strands, in agreement with experimental findings. [ABSTRACT FROM AUTHOR]

A range of technologies require the directed motion of nanoscale droplets on solid substrates. A way of realizing this effect is durotaxis, whereby a stiffness gradient of a substrate can induce directional motion without requiring an energy source. Here, we report on the results of extensive molecular dynamics investigations of droplets on a surface with varying stiffness. We find that durotaxis is enhanced by increasing the stiffness gradient and, also, by increased wettability of the substrate, in particular, when the droplet size decreases. We anticipate that our study will provide further insights into the mechanisms of nanoscale directional motion.