Effect of molecular architecture on the morphology diversity of the multicompartment micelles: A dissipative particle dynamics simulation study

Dissipative particle dynamics simulation is performed to study the sensitive influence of the molecular architecture and/or segment sequence on the morphology diversity of the multicompartment micelles. The multicompartment micelle morphologies formed by ABC triblock copolymers with various molecular architectures, such as the linear, the pentalinear, the cyclic, the star-like, the tetra-arm, and the π-shape are investigated, and different morphologies of the multicompartment micelles, for example, worm-like, “hamburger”, sheet-like with pores, “sweet potato” with alternating layers, sheet-like with cylinder-inclusion, and three-dimensional network are observed in this work. The density profiles and the radial distribution functions are calculated to characterize the structures of the multicompartment micelles. The preparation of complex multicompartment micelles can be fulfilled by simply changing the segment sequence and molecular architecture such as adding new bonds and grafting points.     

Phase behavior of an amphiphilic molecule in the presence of two solvents by dissipative particle dynamics

We examine the phase behavior of A_mB_n amphiphilic molecules in the presence of two solvents X₂ and Y₂, which are strongly selective for A and B, respectively, by dissipative particle dynamics (DPD). We find that increasing the immiscibility parameter between the two solvents not only drives a macrophase separation into two phases X₂-rich and Y₂-rich for systems at less concentrated regimes, but also expands the ordered microphase region at more concentrated regimes. It even induces a sequential transition of various ordered structures. This is not surprising since increasing the solvent immiscibility parameter enhances the preferentiality of X₂ for A and Y₂ for B, and thus qualitatively varies the degree of molecular asymmetry in the amphiphilic molecules. In general, our current results reveal that the DPD simulation method has successfully captured the phase separation behavior of an amphiphilic molecule in the presence of two solvents. However, we find that the packing order of the spherical micelles is greatly affected by the finite size of the simulation box. As such, it becomes difficult to examine the most stable packing array of spheres via the DPD method. Still, DPD reveals a possible spherical order of A15, which has been observed in some amphiphilic molecule systems.     

Effect of solvent quality on Poiseuille flow of polymer solutions in microchannels: A dissipative particle dynamics study

The Poiseuille flows of polymer solutions for varying quality solvents in microchannels have been simulated using dissipative particle dynamics. In particular, the velocity distributions and the polymer migration across the channel have been investigated for good, athermal, and poor solvents. The velocity profiles for all three kinds of solvent deviate from the parabolic profile, and the velocity profile of the athermal solvent falls in between the good solvent and the poor solvent. For the athermal solvent, a migration away from the wall due to the hydrodynamic interactions between the chains and the wall is observed, and a migration away from the channel center due to the different chain Brownian diffusivities is also observed. For the good solvent, because of the more stretched polymer chains, the migration away from the wall is stronger than that for the athermal solvent. However, the migration away from the channel center is not observed for good solvents. For the poor solvent, the hydrodynamic interaction within the chains is screened, and the polymer chains migrate toward the wall and appear to be absorbed by the wall. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47345.     

Multicompartment micelles formed from star-dendritic triblock copolymers in selective solvents: A dissipative particle dynamics study

Dissipative particle dynamics method was used to study the multicompartment micelles formed from star-dendritic triblock copolymers in selective solvents, in which particular attention was paid to the effects of dendritic structure. The simulations show that the dendritic structure not only influences the morphology and the formation process of multicompartment micelles formed, but also the response of the micelle structure to solvent quality. The information obtained is useful for the future design of multicompartment micelles for practical applications, especially in the field of drug delivery.     

Microphase separation and molecular conformation of AB2 miktoarm star copolymers by dissipative particle dynamics

We simulate the microphase separation behavior and analyze the molecular conformation of AB₂ miktoarm star copolymers via dissipative particle dynamics (DPD). The phase diagram is constructed by varying the composition and interaction parameter. Through a mapping of the interaction parameter for a finite chain length, we find that the phase diagram via DPD is in near quantitative agreement with that predicted by the self-consistent mean-field (SCMF) theory. However, when the B composition is small, AB₂ is not able to form the ordered microstructure as easily as SCMF has predicted. Instead, only a tube-like phase is formed. This aggregated micelle-like phase via DPD, which is ignored in the SCMF study, has been frequently observed in experiments. In the analysis of the radius of gyration (R_g), when the interaction parameter increases, the R_g values of each A and B arm remain relatively unchanged; while the overall radius of gyration of AB₂ significantly increases. Furthermore, the angle between A and B arms shows an increasing trend while the angle between B and B arms shows a decreasing behavior with the interaction parameter. These results reveal that in order to reduce the contacts between A and B, the A and B arms tend to separate from each other, and the two B arms are squeezed onto the same side.     

Dissipative particle dynamics simulation study on complex structure transitions of vesicles formed by comb-like block copolymers

Vesicles are membrane-enclosed capsules that can store or transport substances. Their structures and the corresponding structural transitions are important to fulfill specific functions. Using dissipative particle dynamics method, we study the complex structure transitions of vesicles that are spontaneously formed by A₆(B₂)₃ type comb-like block copolymers. In the simulations, the interaction parameters between different components are tuned to mimic the variations of amphiphilicity of the block copolymers and the selectivity of the solvent which are experimentally tractable by, for example, a temperature quench. Complex vesicle structures are found in this research; their transitions, such as fission and reversal, are studied in detail with this dynamic simulation method. We find that the line tension plays a decisive role on the vesicle fission pathways. Moreover, the tube-like vesicles tend to transform to a special layered micelle structure, whereas the onion-shape vesicles tend to transform to reverse onion-shape vesicles when vesicle reversal takes place due to the variation of solvent selectivity.     

Morphologies of diblock copolymer confined in a slit with patterned surfaces studied by dissipative particle dynamics

Diblock copolymers with ordered mesophase structures have been used as templates for nano-fabrication. Unfortunately, the ordered structure only exists at micromete rscale areas, which precludes its use in many advanced applications. To overcome this disadvantage, the diblock copolymer confined in a restricted system with a patterned surface is proved to be an effective means to prohibit the formation of defects and obtain perfect ordered domains. In this work, the morphologies of a thin film of diblock copolymer confined between patterned and neutral surfaces were studied by dissipative particle dynamics. It is shown that the morphology of the symmetric diblock copolymer is affected by the ratio of the pattern period on the surface to the lamellar period of the symmetric diblock copolymer and by the repulsion parameters between blocks and wall particles. To eliminate the defects in the lamellar phase, the pattern period on the surface must match the lamellar period. The difference in the interface energy of different compartments of the pattern should increase with increasing film thickness. The pattern period on the surface has a scaling relationship with the chain length, which is the same as that between the lamellar period and the chain length. The lamellar period is also affected by the polydispersity of the symmetric diblock copolymer. The total period is the average of the period of each component multiplied by the weight of its volume ratio. The morphologies of asymmetric diblock copolymers are also affected by the pattern on the surface, especially when the matching period of the asymmetric diblock copolymer is equal to the pattern period, which is approximately equal to the lamellar period of a symmetric diblock copolymer with the same chain length.     

复杂物系的介观结构和DPD模拟

耗散粒子动力学(DPD)模拟方法是研究复杂物系介观结构的一种重要手段。首先简要介绍了DPD模拟方法,然后介绍了实际物系与DPD模型映射的2种方法,即Groot和Warren方法以及Pagonabarraga和Frenkel方法。最后对DPD模拟的理论和应用研究进展作了回顾。     

Mesoscale simulation on the shape evolution of polymer drop and initial geometry influence

The process experimentally measuring the interfacial tension of polymers was simulated by means of dissipative particle dynamics (DPD) simulation method in the present study. It is a retraction of ellipsoid drop of a polymer within the other polymer bulk. Effect of the initial geometry of the ellipsoid on the finally obtained interfacial tension was focused, since it was found the ellipsoid might not have the same length for both short axes, which is against original assumption. Simulated results show that different initial short axes of b and c do influence eventual measurement of the tension. However, a smaller deviation between b and c was found to be leading to an acceptable measurement. For this judgment, we found a criterion is γ=(b−c)/a<0.3.     

Interface effect on the mechanical behaviour of rigid particle filled polymer

Glass beads, non‐modified and modified separately with two different coupling agents, were incorporated in high density polyethylene to prepare composite materials with different interfacial adhesion strengths. Tensile tests show that the mechanical behaviour of the materials is sensitive to the strain rates. The strong interfacial adhesion can delay the occurrence of damage and so increase the load‐bearing ability under both monotonic and cyclic loading. In situ tensile tests give damage mechanisms mainly induced by the interfacial debonding. The stronger the interfacial adhesion, the lower the number of glass beads debonded from the matrix under a given stress. The degree of microdamage defined as the percentage of debonded particles is obtained as a function of the applied load. © 2001 Society of Chemical Industry     

Dissipative particle dynamics study on the phase morphologies of the ultrahigh molecular weight polyethylene/polypropylene/poly(ethylene glycol) blends

The dissipative particle dynamics (DPD) simulation method has been used to study mesophase formation of the binary UHMWPE/PP and ternary UHMWPE/PP/PEG blends. The effects of shear rates and volume fractions of each of the blend components on end-to-end distances of UHMWPE, diffusivities and mesoscale morphologies of the blends have been investigated in detail. As compositions of the UHMWPE/PP and UHMWPE/PP/PEG blends vary, the mesoscale simulations have predicted the ordered structures with defined morphologies of lamellas, perforated lamellas, hexagonal spheres, and body-centered-cubic spheres. Micelle-like melted structures between totally disordered and the ordered phases have also been found in the UHMWPE/PP (10/90) blends. Immiscibility property of UHMWPE, PP and PEG induces the phase separation and exhibits different mesoscpic morphologies at different shear rates and volume fractions. Taking the shear rates dependence of mesophase into account, the change in morphology of the UHMWPE/PP/PEG blends with shear rate is also well studied in this work. As a function of PP concentration, the end-to-end distances of UHMWPE are found to decrease with the increase of PP concentration. This effect is more prominent for a high amount of PP.     

双亲纳米颗粒在选择性溶剂中的自组装行为：耗散粒子动力学模拟

接枝聚合物纳米颗粒在构筑多级功能性纳米材料方面具有很大潜力,但其在选择性溶剂中自组装相图却鲜见报道。利用耗散粒子动力学模拟研究了溶剂选择性、接枝聚合物链长度以及亲水、疏水聚合物链比例等因素对双亲纳米颗粒自组装行为的影响,并绘制了自组装形态相图。结果显示,随着浓度的增大,双亲纳米颗粒逐渐自组装成球状、棒状、二维膜、纳米膜孔等丰富纳米结构。不仅如此,溶剂与亲水、疏水聚合物相容性差异较小时（a_S-HL=40k_BT/R_c,a_S-HB=50k_BT/R_c）,双亲纳米颗粒自组装形成层状纳米结构,在较高浓度时,形成规则的多孔网络结构。研究发现,双亲纳米颗粒浓度和接枝聚合物的链长以及亲水、疏水聚合物链比例是调控双亲纳米颗粒自组装形态的关键因素。鉴于双亲纳米颗粒丰富的自组装行为,它在气体分离、检测、载药、催化剂载体等领域有着很大的潜在应用价值。     

温敏性两亲嵌段共聚物相行为的耗散粒子动力学模拟

采用耗散粒子动力学模拟研究了由温敏性聚N-异丙基丙烯酰胺(PNIPAM)与聚己内酯(PCL)构成的两亲嵌段共聚物(PCL-PNIPAM-PCL)在水溶液中自组装的动力学过程及微相分离现象,考察了溶液浓度及温度对其相行为的影响。模拟发现不同体积分数的嵌段共聚物在水溶液中呈现出不同的自组装形貌,如球状胶束、柱状胶束、层状胶束等。温度对其在水溶液中的形貌及相变行为有着显著的影响。当温度较低时,PCL-PNIPAM-PCL于稀溶液中可形成稳定的以PCL为核,PNIPAM为壳的球形核壳胶束;而当温度升高到某一值时,在低温时所形成的球形核壳胶束将因温度的升高而转变为表面由PCL组成的多个不连续微区的多隔段胶束。这种温敏现象在耗散粒子动力学模拟中尚属首次被发现。另外,模拟中所得到的该体系的低临界溶解温度与实验测得的值也符合良好。对这一温敏现象作了较深入和细致的解释。本文工作表明耗散粒子动力学能用来研究温度对温敏性两亲嵌段共聚物相行为的影响并揭示其中的机制和一般规律。     

The application of lateral force microscopy to particle removal in aqueous polymer solutions

Abstraet-An atomic force microscope (AFM) has been used to examine the effect of a typical polymeric dispersant on the adhesion between an iron oxide sphere and a silicon wafer in the presence and absence of shear. Two separate methods for the determination of the lateral spring constant (k₁) of AFM cantilevers were employed. Determination of k₁ allows the absolute, rather than relative, shear force to be extracted from the lateral force output of the AFM. A comparison is made between the pull-off force (no shear) and the lateral force as the dispersant concentration and loading force are varied. While in both cases the magnitude of the forces decrease with increasing dispersant concentration, the effect is much less marked for the lateral force. A linear increase in removal forces with increasing loading force was observed. For a given load, the removal force is typically an order of magnitude smaller in the presence of shear.     

The concentration dependence of diffusion in semi-dilute polymer solutions

Dynamic light-scattering data for polystyrene fractions in a good solvent (benzene) and a theta solvent (cyclopentane, 20.4°C) are presented. They encompass a broad concentration interval in the semi-dilute range. These data are compared with those for the systems poly(ethylene oxide)/water and hydroxyethylcellulose/water. The entanglement network in these systems is reflected in part by the nature of the concentration dependence of the mutual diffusion coefficient and in part by the presence of a slow relaxation, information on which may be derived from the non-exponential autocorrelation function.     

Diffusion of single alkane molecule in carbon nanotube studied by molecular dynamics simulation

Full atomistic molecular dynamics simulations have been used to study the diffusion of alkane molecule in single wall carbon nanotube (SWCNT), with different alkane chain lengths and nanotube diameters. In this paper, we calculated the self-diffusion coefficient, mean-square gyration and bond-orientation order parameter of alkane molecule and the average intermolecular interaction energy per segment between SWCNT and alkane. Furthermore, structure of alkane in SWCNT was characterized through the radial distribution function, with results showing that the self-diffusion coefficient is related to the nanotube diameter. The component of mean-square gyration in z-direction scales with alkane chain length in SWCNT(9,9) like N1.07±0.04, which is in good agreement with the prediction from scaling theory for polymers. The obtained results show that nanotube diameter and alkane chain length are important factors affecting the behavior of one-dimensional confined alkanes.     

Flow of viscoelastic polymer solutions in mixed beds of particles

New extensive pressure drop-flow rate data are reported for the creeping flow of well characterised viscoelastic polymer solutions through packed beds of mixed size spheres and of spheres and cylinders. It is established that the effective mean surface diameter is adequate in correlating the pressure loss data in flow through packed beds of mixed size and shape. A distinct correlation exists between the excess pressure loss observed with viscoelastic fluids and the Weissenberg number.     

均匀电场中液滴变形特性的耗散粒子动力学模拟

基于耗散粒子动力学方法,建立了电场作用下近似的液滴粒子力学模型,对两相不相溶液体中液滴在电场作用下的变形特性进行了模拟。模拟结果与他人的实验结果比较表明,模拟结果对液滴形状随时间的演化预测基本符合实际,仅在液滴变形较大时有一定偏差。模拟结果还表明,当外加场强较小时,液滴变形度随时间呈现振荡状态,变形度不会随时间继续增大。增大外加场强,液滴变形幅度增大,振荡频率变慢。当外加场强增大到一定程度时,液滴变形度不再振荡,而是随时间急剧增大,以至液滴最终破碎。场强越大,液滴破碎所需的时间也越短。     

Molecular dynamics simulation of a flexible polymer network in a liquid crystalline solvent; dynamical properties

Molecular dynamics simulation was performed for the systems consisting of a flexible regular tetrafunctional polymer network and a low molecular liquid crystal (LC) solvent. The LC solvent comprises of anisotropic rod-like semiflexible linear molecules composed of beads bonded by a FENE potential. Rigidity was induced by a bending potential, proportional to the cosine of the angle between neighbouring valence bonds. All interactions between non-bonded beads are described by the repulsive part of the Lennard–Jones potential. For comparison the simulations of the system of flexible polymer chains in a low molecular LC solvent and a system of pure low molecular LC solvent were also carried out. The influence of the network and linear chain polymer on the translational and rotational mobility of low molecular LC solvent was studied. The influence of the LC solvent ordering on the local translational mobility of the polymer chains was also observed.