Deposition patterns formed by the evaporation of linear diblock copolymer solution nanodroplets on solid surfaces.

The evaporation-induced deposition pattern of the linear diblock copolymer solution has attracted attention in recent years. Given its critical applications, we study deposition patterns of the linear diblock copolymer solution nanodroplet on a solid surface (the wall) by molecular dynamics simulations. This study focuses on the influence of the nonbonded interaction strength, including the interaction between the wall and polymer blocks (ɛAW and ɛBW), the interaction between the solvent and the wall (ɛSW), and the interaction between polymer blocks (ɛAB). Conditions leading to diverse deposition patterns are explored, including the coffee-ring and the volcano-like structures. The formation of the coffee-ring structure is attributed to receding interfaces, the heterogeneity inside the droplet, and the self-assembly of polymer chains. This study contributes to the establishment of guidelines for designing deposition patterns of the linear diblock copolymer solution nanodroplet, which facilitates practical applications such as inkjet printing.

Structural heterogeneity in tetra-armed gels revealed by computer simulation: Evidence from a graph theory assisted characterization.

Designing homogeneous networks is considered one typical strategy for solving the problem of strength and toughness conflict of polymer network materials. Experimentalists have proposed the hypothesis of obtaining a structurally homogeneous hydrogel by crosslinking tetra-armed polymers, whose homogeneity was claimed to be verified by scattering characterization and other methods. Nevertheless, it is highly desirable to further evaluate this issue from other perspectives. In this study, a coarse-grained molecular dynamics simulation coupled with a stochastic reaction model is applied to reveal the topological structure of a polymer network synthesized by tetra-armed monomers as precursors. Two different scenarios, distinguished by whether internal cross-linking is allowed, are considered. We introduce the Dijkstra algorithm from graph theory to precisely characterize the network structure. The microscopic features of the network structure, e.g., loop size, dispersity, and size distribution, are obtained via the Dijkstra algorithm. By comparing the two reaction scenarios, Scenario II exhibits an overall more idealized structure. Our results demonstrate the feasibility of the Dijkstra algorithm for precisely characterizing the polymer network structure. We expect this work will provide a new insight for the evaluation and description of gel networks and further help to reveal the dynamic process of network formation.

The design of highly conductive and stretchable polymer conductors with low-load nanoparticles.

Highly conductive and stretchable polymer conductors fabricated from conductive fillers and stretchable polymers are urgently needed in flexible electronics, implants, soft robotics, etc. However, polymer conductors encounter the conductivity-stretchability dilemma, in which high-load fillers needed for high conductivity always result in the stiffness of materials. Herein, we propose a new design of highly conductive and stretchable polymer conductors with low-load nanoparticles (NPs). The design is achieved by the self-assembly of surface-modified NPs to efficiently form robust conductive pathways. We employ computer simulations to elucidate the self-assembly of the NPs in the polymer matrices under equilibrium and tensile states. The conductive pathways retain 100% percolation probability even though the loading of the NPs is lowered to ∼2% volume. When the tensile strain reaches 400%, the percolation probability of the ∼2% NP system is still greater than 25%. The theoretical prediction suggests a way for advancing flexible conductive materials.

Defect transition of smectic liquid crystals confined in spherical cavities.

The formation and transformation of defects in confined liquid crystals are fascinating fundamental problems in soft matter. Here, we use molecular dynamics (MD) simulations to study ellipsoidal liquid crystals (LCs) confined in a spherical cavity, which significantly affects the orientation and translation of LC molecules near the surface. The liquid-crystal droplet can present the isotropic to smectic-B phase transition through the smectic-A phase, as the number density of the LC molecules increases. We further find the change of LC structure from bipolar to watermelon-striped during the phase transition from smectic-A (SmA) to smectic-B (SmB) phases. Our results reveal the transition from bipolar defects to the inhomogeneous structures with the coexistence of nematic and smectic phases in smectic liquid-crystal droplets. We also study the influence of the sphere size in the range of 10σ0 ≤ Rsphere ≤ 50σ0 on the structural inhomogeneities. It shows a weak dependence on the sphere size. We further focus on how the structures can be affected by the interaction strength εGB-LJ. Interestingly, we find the watermelon-striped structure can be changed into a configuration with four defects at the vertices of a tetrahedron upon increasing the interaction strength. The liquid crystals at a strong interaction strength of εGB-LJ = 10.0ε0 show the two-dimensional nematic phase at the surface. We further present an explanation for the origin of the striped-pattern formation. Our results highlight the potential for using confinement to control these defects and their associated nanostructural heterogeneity.

Helical structures of achiral liquid crystals under cylindrical confinement.

Confined liquid crystals (LCs) exhibit complex and intriguing structures, which are fascinating fundamental problems in soft matter. The helical structure of cylindrical cavities is of great importance in LC studies, particularly for their application in optical devices. In this study, we employ molecular dynamics simulations to explore the behavior of achiral smectic-B LCs confined in narrow cylindrical cavities, where geometric frustration plays an important role. By increasing the cylinder size, LCs exhibit a transition from multi-helical to layered structures. Notably, we observe two stable structures, namely the helical structure and the layered structure, at moderate cylinder size. We also investigate the effects of the arrangement of cylindrical wall particles (hexagonal or square array) and anchoring strength on the LC structure. Our findings reveal that both the hexagonal array and strong anchoring strength promote the formation of helical structures. Our study provides novel insights into the confinement physics of LCs and highlights the potential for achieving helical structures in achiral LCs, which will expand the future applications of LCs.

External field induced defect transformation in circular confined Gay-Berne liquid crystals.

Normally, defects in two-dimensional, circular, confined liquid crystals can be classified into four types based on the position of singularities formed by liquid crystal molecules, i.e., the singularities located inside the circle, at the boundary, outside the circle, and outside the circle at infinity. However, it is considered difficult for small aspect ratio liquid crystals to generate all these four types of defects. In this study, we use molecular dynamics simulation to investigate the defect formed in Gay-Berne, ellipsoidal liquid crystals, with small aspect ratios confined in a circular cavity. As expected, we only find two types of defects (inside the circle and at the boundary) in circular, confined, Gay-Berne ellipsoids under static conditions at various densities, aspect ratios, and interactions between the wall and liquid crystals. However, when introducing an external field to the system, four types of defects can be observed. With increasing the strength of the external field, the singularities in the circular, confined system change from the inside to the boundary and the outside, and the farthest position that the singularities can reach depends on the strength of the external field. We further introduce an alternating, triangular wave, external field to the system to check if we can observe the transformation of different defects within an oscillating period. We find that the position of the singularities greatly depends on the oscillating intensity and oscillating period. By changing the oscillating intensity and oscillating period of the external field, the defect types can be adjusted, and the transformation between different defects can be easily observed. This provides a feasible way to modulate liquid crystal defects and investigate the transformation between different defects.

Exploring mechanical properties and failure mechanisms of aramid and PBO crystals through molecular dynamics simulations.

Molecular dynamics simulations were used to analyze the mechanical properties and failure processes of poly(p-phenylene-terephthalamide) (PPTA), poly(p-phenylene-benzimidazole-terephthalamide) (PBIA), PBIA-PPTA (formed by 1:1 copolymerization of PPTA and PBIA), and poly(p-phenylene-benzobisoxazole) (PBO) crystals at different strain rates and temperatures. The failure stress and strain were found to be linear with the temperature and logarithmic strain rate. Moreover, based on the kinetic theory of fracture and the comprehensive simulation results, we formulated a model that describes the failure stress of the aforementioned crystals under varying strain rates and temperatures. Through the analysis of the failure process, we found that in PPTA, PBIA, and PBIA-PPTA crystals, the bond failure probability is correlated with the strain rate and temperature. The examination of bond lengths and angles unveiled that bonds with larger initial aligning angles are more susceptible to failure during the strain process. Intriguingly, the stretching process induced a conformational change in the PBO molecular chain, leading to a deviation from the linear relation in its stress-strain curve.

Colloidal cubic diamond photonic crystals through cooperative self-assembly.

Colloidal cubic diamond crystals with low-coordinated and staggered structures could display a wide photonic bandgap at low refractive index contrasts, which makes them extremely valuable for photonic applications. However, self-assembly of cubic diamond crystals using simple colloidal building blocks is still considerably challenging, due to their low packing fraction and mechanical instability. Here we propose a new strategy for constructing colloidal cubic diamond crystals through cooperative self-assembly of surface-anisotropic triblock Janus colloids and isotropic colloidal spheres into superlattices. In self-assembly, cooperativity is achieved by tuning the interaction and particle size ratio of colloidal building blocks. The pyrochlore lattice formed by self-assembly of triblock Janus colloids acts as a soft template to direct the packing of colloidal spheres into cubic diamond lattices. Numerical simulations show that this cooperative self-assembly strategy works well in a large range of particle size ratio of these two species. Moreover, photonic band structure calculations reveal that the resulting cubic diamond lattices exhibit wide and complete photonic bandgaps and the width and frequency of the bandgaps can also be easily adjusted by tuning the particle size ratio. Our work will open up a promising avenue toward photonic bandgap materials by cooperative self-assembly employing surface-anisotropic Janus or patchy colloids as a soft template.

A chiral smectic phase induced by an alternating external field.

Using simple achiral building blocks modulated by an external field to achieve chiral liquid crystal phases remains a challenge. In this study, a chiral helix liquid crystal phase is obtained for a simple Gay-Berne ellipsoid model under an alternating external field by using molecular dynamics simulations. Our results show that the chiral helix liquid crystal phase can be observed in a wide range of external field strengths when the oscillation period is smaller than the rotational characteristic diffusion timescale of ellipsoids. In addition, we find that the pitch and tilt angle of the helix structure can also be adjusted by changing the strength and oscillation period of the applied alternating external field. This may provide a feasible route for the regulation of chiral liquid crystal phases by an alternating external field.

Multiple 2D crystal structures in bilayered lamellae from the direct self-assembly of 3D systems of soft Janus particles.

Numerous crystals and Frank-Kasper phases in two-dimensional (2D) systems of soft particles have been presented by theoretical investigations. How to realize 2D crystals or Frank-Kasper phases via the direct self-assembly of three-dimensional (3D) systems remains an important issue. Here, through numerical simulations, we report the surprising finding of multiple 2D crystal structures in bilayered lamellae from the direct self-assembly of 3D systems of soft Janus particles. With varying the patch size and particle density, soft Janus particles, which exhibit very similar self-assembly behavior to giant amphiphiles, spontaneously form ordered bilayered lamellae. Within each layer of the bilayered lamellae, we find abundant highly-ordered 2D crystals including the Frank-Kasper σ phase and open kagome lattice. The kinetic mechanisms of the formation of these 2D crystals within the layers are revealed, and include a classical one-step nucleation mechanism and a two-step nucleation mechanism. Our findings suggest a simple route towards 2D crystals via the direct self-assembly of 3D systems of amphiphilic Janus building blocks.

Long-wavelength fluctuations and anomalous dynamics in 2-dimensional liquids.

In 2-dimensional systems at finite temperature, long-wavelength Mermin-Wagner fluctuations prevent the existence of translational long-range order. Their dynamical signature, which is the divergence of the vibrational amplitude with the system size, also affects disordered solids, and it washes out the transient solid-like response generally exhibited by liquids cooled below their melting temperatures. Through a combined numerical and experimental investigation, here we show that long-wavelength fluctuations are also relevant at high temperature, where the liquid dynamics do not reveal a transient solid-like response. In this regime, these fluctuations induce an unusual but ubiquitous decoupling between long-time diffusion coefficient D and structural relaxation time τ, where [Formula: see text], with [Formula: see text] Long-wavelength fluctuations have a negligible influence on the relaxation dynamics only at extremely high temperatures in molecular liquids or at extremely low densities in colloidal systems.

Mechanism of periodic field driven self-assembly process.

Dissipative self-assembly, a ubiquitous type of self-assembly in biological systems, has attracted a lot of attention in recent years. Inspired by nature, dissipative self-assembly driven by periodic external fields is often adopted to obtain controlled out-of-equilibrium steady structures and materials in experiments. Although the phenomena in dissipative self-assembly have been discovered in the past few decades, fundamental methods to describe dynamical self-assembly processes and responsiveness are still lacking. Here, we develop a theoretical framework based on the equations of motion and Floquet theory to reveal the dynamic behavior changing with frequency in the periodic external field driven self-assembly. Using the dissipative particle dynamics simulation method, we then construct a block copolymer model that can self-assemble in dilute solution to confirm the conclusions from the theory. Our theoretical framework facilitates the understanding of dynamic behavior in a periodically driven process and provides the theoretical guidance for designing the dissipative conditions.

Free energy for inclusion of nanoparticles in solvated polymer brushes from molecular dynamics simulations.

The inclusion of nanoparticles (NPs) into solvated polymer brushes (PBs) provides a path for designing novel nanocomposites and a multifunctional surface for wide applications. Despite intensive study over the years, the correlation between the structural properties of NPs (or PBs) and the NP-PB interactions is still to be well unveiled. Here, we present molecular dynamics simulations with the umbrella sampling method to systematically investigate the interaction between NPs and PBs, via calculating the free energy cost (Uins, associated with the inclusion of NPs into PBs) as a function of a series of factors, such as brush grafting density (ρg), grafted polymer chain architecture, NPs' size, NPs' surface properties, and NPs' shape and surface structure, as well as the solvent quality. Our results show that at a fixed NP size, the inclusion free energy approximately scales with the osmotic pressure (Π) of PBs under good solvent conditions [Uins∼Π(ρg)∼ρg 3/2], regardless of the NPs' shape and surface properties. Once the radius of the NP (RNP) is varied, a scaling law, Uins∼RNP 3, can be obtained for NPs deeply inserted in swollen PBs with a high grafting density. While for shallow inclusions, a surface tension correction of the form ∼RNP 2 plays a role. Further studies reveal that Θ and poor solvents will weaken the osmotic pressure effects of PBs and reversely enhance the surface tension effects due to the increased NP-brush repulsion. Our simulation results verify previous theoretical perspectives that the Uins can be approximated by the sum of the volume and surface contributions from the osmotic pressure Π and surface tension γ (Uins∼ΠRNP 3+γRNP 2). Our work not only helps us to understand the applicability of previous theories on the NP-PB system but also reveals the key factors that impact the NP-PB interaction in a series of probable conditions, which may provide valuable guidelines for designing and engineering novel nanomaterials based on functional NPs and PBs.

Effect of the Self-Assembled Structures of Hydrated Polyzwitterionic and Polyanionic Brushes on Their Self-Cleaning Capabilities.

The capability of polyelectrolyte brushes to spontaneously clean oil fouling via water is determined by factors including water wettability and the self-assembled structures of hydrated polyelectrolytes. Although the charged groups of polyelectrolytes provide the original source of water wettability, the self-assembled structures play a significant role in the self-cleaning performances. Here, we employ coarse-grained molecular dynamics simulations to study the general self-cleaning characteristics of two types of surface-grafted polyelectrolyte brushes (i.e., zwitterionic and anionic polyelectrolytes). It has been found that the high grafting density is favorable to fouling reduction for both polyzwitterions and polyanions. To be specific, the hydrated polyzwitterions form an intermolecular cross-linked network via zwitterionic complexes, resulting in better self-cleaning capabilities than the polyanions at lower grafting densities. However, polyanions form bundles with each consisting of several chains via hydrophobic interactions and electrostatic repulsions presenting better self-cleaning performances than the polyzwitterions at higher grafting densities.

Coupling and decoupling between translational and rotational dynamics in supercooled monodisperse soft Janus particles.

We perform dynamics simulations to investigate the translational and rotational glassy dynamics in a glass-forming liquid of monodisperse soft Janus particles. We find that, with decreasing temperature, the mean-square angular displacement shows no clear plateau in the caging region, in contrast with the apparent caging behavior of translational motion. By defining a reorientational mean-square angular displacement, the caging behavior of rotational motion can be recognized. On approaching the glass transition (decreasing temperature), the coupling between translational and rotational relaxation increases, while the coupling between translational and rotational diffusion decreases, whereas the coupling between translational and reorientational diffusion increases. The strong decoupling between translational and rotational diffusion is due to the suppressed translational mobility but promoted rotational mobility of soft Janus particles. We think that the low-T SE and SED decoupling is mainly attributed to hopping motion of soft Janus particles, whereas the high-T SE and SED decoupling is mainly attributed to collective cage motion of soft Janus particles. Our results demonstrate that interaction anisotropy has a critical effect on the translational and rotational dynamics of soft Janus particles.

Heterogeneous dynamics of unentangled chains in polymer nanocomposites.

We present a systematic investigation on the effect of adding nanoparticles on the dynamics of polymer chains by using coarse-grained molecular dynamics simulation. The dynamics is characterized by three aspects: molecular motion, relaxation at different length scales, and dynamical heterogeneity. It is found that the motion of polymer chains slows down and the deviation from Gaussian distribution becomes more pronounced with increasing nanoparticle volume fractions. For polymer nanocomposites with R ≤ Rg, the relaxation at the wave vector q = 7.0 displays multistep decay, consistent with the previous reports in strongly interacting polymer nanocomposites. Moreover, a qualitatively universal law is established that dynamic heterogeneity at whole chain's scale follows a nonmonotonic increase with increasing nanoparticle loadings, where the volume fraction of the maximum dynamic heterogeneity corresponds to the particle loading when the average distance between nanoparticles is equal to the Kuhn length of polymer chains. We show that the decoupling between whole chain's dynamics and segment dynamics is responsible for the nonmonotonic behavior of dynamic heterogeneity of whole chains.

General patchy ellipsoidal particle model for the aggregation behaviors of shape- and/or surface-anisotropic building blocks.

We present a general patchy ellipsoidal particle model suitable for conducting dynamics simulations of the aggregation behaviors of various shape- and/or surface-anisotropic colloids, especially patchy ellipsoids with continuously variable shape and tunable patchiness. To achieve higher computational efficiency in dynamics simulations, we employ a multi-GPU acceleration technique based on a domain decomposition algorithm. The validation and performance evaluation of this GPU-assisted model are performed by simulating several typical benchmark systems of non-patchy and patchy ellipsoids. Given the generality and efficiency of our GPU-assisted patchy ellipsoidal particle model, it will provide a highly feasible dynamics simulation framework to investigate the aggregation behaviors of anisotropic soft matter systems comprised of shape- and/or surface-anisotropic building blocks.

Improving the productivity of monodisperse polyhedral cages by the rational design of kinetic self-assembly pathways.

Hollow polyhedral cages hold great potential for application in nanotechnological and biomedical fields. Understanding the formation mechanism of these self-assembled structures could provide guidance for the rational design of the desired polyhedral cages. Here, by constructing kinetic network models from extensive coarse-grained molecular dynamics simulations, we elucidated the formation mechanism of the dodecahedral cage, which is formed by the self-assembly of patchy particles. We found that the dodecahedral cage is formed through increasing the aggregate size followed by structure rearrangement. Based on this mechanistic understanding, we improved the productivity of the dodecahedral cage through the rational design of the patch arrangement of patchy particles, which promotes the structural rearrangement process. Our results demonstrate that it should be a feasible strategy to achieve the rational design of the desired nanostructures via the kinetic analysis. We anticipate that this methodology could be extended to other self-assembly systems for the fabrication of functional nanomaterials.

Influence of chain stiffness on the dynamical heterogeneity and fragility of polymer melts.

It is well accepted that stiffer polymers have higher glass transition temperatures. However, the influence of chain stiffness on the slow dynamics and dynamical heterogeneity when approaching the glass transition point is still not well understood. In this work, we investigate the influence of chain stiffness on the dynamic heterogeneity and fragility of supercooled polymer melts by using molecular dynamics simulation. The chain stiffness is tuned by varying the bending strength, and the diffusion and relaxation of polymer segments are studied. We find that the power law relation between the rescaled diffusion coefficient and the structural relaxation time does not change with changing chain stiffness, indicating similarities of glass-forming behavior of polymer melts with different chain stiffness. The dynamical heterogeneities are characterized by the non-Gaussian parameter and dynamic susceptibility, and the string-like cooperative motion is analyzed by the string-length. It is found that the non-Gaussian parameter and dynamic susceptibility characterize a different aspect of dynamical heterogeneities. Though both decreasing temperature and increasing bending strength lead to slower dynamics and growing dynamical heterogeneities, there is no simple superposition between temperature and bending strength. Our work may shed new light on the glass transition behavior of polymers with different chain stiffness.

The relationship between local density and bond-orientational order during crystallization of the Gaussian core model.

Whether nucleation is triggered by density or by bond-orientational order is one of the most hotly debated issues in recent investigations of the crystallization process. Here, we present a numerical study of the relationship between them for soft particles within the isothermal-isobaric ensemble. We compress the system and thus obtain the fluid-solid transition. By investigating locally dense-packed particles and particles with a relatively high bond-orientational order in the compressing process, we find a sharp increase of the spatial correlations for both densely packed particles and highly bond-orientational ordered particles at the phase transition point, which provide new characterization methods for the liquid-crystal transition. We also find that it is the bond-orientational order rather than density that triggers the nucleation process. The relationship between the local density and the bond-orientational order parameter is strongly affected by the characterization methods used. The local bond order parameter (q6) shows clear correlation with the local density (ρ) in the fluid stage, while the coarse-grained form (q[combining macron]6) does not correlate with ρ at all, owing to the comparable spatial scales of q6 and ρ. Nevertheless, q[combining macron]6 shows an obvious advantage in distinguishing between solid and liquid particles in our work. These results may elevate our understanding of the mechanism of the crystallization process.