Phase behaviors in binary mixture of diblock copolymers confined between two parallel walls

The phase behaviors in binary mixture of diblock copolymers confined between two parallel walls are investigated by using cell dynamics simulation of the time-dependent Ginzburg-Landau theory. The morphological dependence of the wall-block interaction and the distance between walls (confinement degree) has been systematically studied, and the effect of repulsive interactions between different monomers is also discussed. It is interesting that multiple novel morphological transitions are observed by changing these factors, and various multilayered sandwich structures are formed in the mixture. Furthermore, the parametric dependence and physical reasons for the microdomain growth and orientational order transitions are discussed. From the simulation, we find that much richer morphologies can form in binary mixture of diblock copolymers than those in pure diblock copolymer. Our results provide an insight into the phase behaviors under parallel walls confinement and may provide guidance for experimentalists. This model system can also give a simple way to realize orientational order transition in soft materials through confinement.     

Cylindrical-confinement-induced phase behaviours of diblock copolymer melts

The phase behaviours of diblock copolymers under cylindrical confinement are studied in two-dimensional space by using the self-consistent field theory. Several phase parameters are adjusted to investigate the cylindrical-confinement-induced phase behaviours of diblock copolymers. A series of lamella-cylinder mixture phases, such as the mixture of broken-lamellae and cylinders and the mixture of square-lamellae and cylinders, are observed by varying the phase parameters, in which the behaviours of these mixture phases are discussed in the corresponding phase diagrams. Fur-thermore, the free energies of these mixture phases are investigated to illustrate their evolution processes. Our results are compared with the available observations from the experiments and simulations respectively, and they are in good agreement and provide an insight into the phase behaviours under cylindrical confinement.     

Effect of an external field on the structure and the phase transitions of a confined mixture of neutral and dipolar hard spheres

We study by Monte Carlo simulation the model of a binary mixture of neutral and dipolar hard spheres confined between two widely separated planar walls and subjected to a uniform external field. The goal is to investigate the structural response and the phase transitions of a fluid of hard-sphere-like colloids dispersed in a low-permittivity solvent under the combined effect of geometrical confinement and applied field. In a wide slab, the direction of the field, either normal or perpendicular to the walls, remains one of the most important factors that govern the response of the mixture: in normal field, a wide variety of structural effects are evidenced, including partial wetting or drying of the wall; in parallel field, phase separation is favoured with a specific population of the region close to the wall and a clear separation of the two species. These results suggest possible means to modulate the response of the confined fluid for specific needs.     

Confinement-induced novel morphologies of block copolymers

Self-assembly of block copolymers confined in cylindrical nanopores is studied systematically using a simulated annealing technique. For diblock copolymers which form two-dimensional hexagonally packed cylinders with period L0 in the bulk, novel structures such as helices and stacked toroids spontaneously form inside the cylindrical pores. These confinement-induced morphologies have no counterpart in the bulk system and they depend on the pore diameter (D) and the surface-polymer interactions, reflecting the importance of structural frustration and interfacial interactions. On tightening the degree of confinement, transitions from helices to toroids to spheres are observed. Mechanisms of the morphological transitions can be understood based on the degree of structural frustration parametrized by the ratio D/L0.     

Phase behaviour of colloidal assemblies on 2D corrugated substrates

We investigate--using Monte Carlo computer simulations--the phase behaviour of dimeric colloidal molecules on periodic substrates with square symmetry. The molecules are formed in a two-dimensional suspension of like charged colloids subject to periodic external confinement, which can be experimentally realized by optical methods. We study the evolution of positional and orientational order by varying the temperature across the melting transition. We propose and evaluate appropriate order parameters as well as the specific heat capacity and show that the decay of positional correlations belongs to a class of crossover transitions while the orientational melting is a second-order phase transition.     

Phase equilibria of confined liquid crystals

The differences between the phase diagram of the Gay-Berne potential confined by two identical walls versus the corresponding bulk phase diagram have been investigated. A wall-fluid interaction 9-3 Lennard-Jones potential was used. The study was performed in most cases by using the hybrid Monte Carlo method for the μVT ensemble. Several isotherms were analysed where vapour, liquid and smectic phases were observed. The smectic-isotropic coexistence region becomes wider, i.e. the isotropic coexistence line is shifted to lower densities but the smectic coexistence line remains nearly the same. The triple point temperature of the confined system is estimated to be in the vicinity of 0.45 versus 0.40 of the bulk system. For the isotherm at T? = 0.65 an orientational dependence was added to the 9-3 Lennard-Jones potential to model the wall-fluid interaction. For both kinds of walls, 9-3 LJ with and without orientational dependence, confinement was not found to stabilize a nematic phase as found by previous authors.     

Diblock copolymer thin films: Parallel and perpendicular lamellar phases in the weak segregation limit

The European Physical Journal E - We study morphologies of thin-film diblock copolymers between two flat and parallel walls. The study is restricted to the weak segregation regime below the...     

受限导致硬椭球液体的取向有序

Monte Carlo模拟研究了两平行硬墙受限下各向异相的硬椭球液体形成的有序结构. 墙壁对椭球粒子的过量吸附和椭球的长短径之比有关;对于高密度的椭球液体,它在一个临界的长短径之比 a/b=2.9处达到最大值,表明在墙表面附近发生了取向有序. 墙表面附近的密度分布和取向序参量进一步证实这结论. 相同密度条件下体相中的取向序参量计算表明体相结构均为各向同性,这是由于体系的密度依然低于各向同性相向相列向转变的临界密度. 该受限椭球液体中墙表面的取向有序是由墙面的几何受限所导致的.     

Structural changes in block copolymers: coupling of electric field and mobile ions

We argue that the presence of dissociated ions in block copolymers under electric fields can induce strong morphological changes and even lead to phase transitions. We investigate, in particular, diblock copolymers in the body centered cubic (bcc) phase. In pure dielectric materials (no free charges), a dielectric breakdown is expected to occur for large enough electric fields, preempting any structural phase transition. On the other hand, dissociated ions are predicted to induce a phase transition to a hexagonal array of cylinders, at fields of about 10 V/microm or even lower. The strength of this mechanism can be tuned by controlling the amount of free ions present.     

Computer simulations of structure, dynamics, and phase behavior of colloidal fluids in confined geometry and under shear

Using computer simulations, colloidal systems in different external fields are investigated. Colloid-polymer mixtures, described in terms of the Asakura-Oosawa (AO) model, are considered under strong confinement. Both in cylindrical and spherical confinement, the demixing transition of the three-dimensional AO model is rounded and, using Monte Carlo simulations, we analyze in detail the consequences of this rounding (occurrence of multi-domain states in cylindrical geometry, non-equivalence of conjugate ensembles due to different finite-size corrections in spherical geometry etc.). For the case of the AO model confined between two parallel walls, spinodal decomposition is studied using a combination of molecular dynamics simulation and the multiparticle collision dynamics method. This allows us to investigate the influence of hydrodynamic interactions on the domain growth during spinodal decomposition. For a binary glass-forming Yukawa mixture, non-linear active micro-rheology is considered, i.e. a single particle is pulled through a deeply supercooled liquid. The diffusion dynamics of the pulled particle is analyzed in terms of the van Hove correlation function. Finally, the Yukawa mixture in the glass state, confined between walls, is studied under the imposition of a uniform shear stress. Below and around the yield stress, persistent creep in the form of shear-banded structures is observed.     

Surface-field-induced effects on morphologies of lamella-forming diblock copolymers in nanorod arrays

The surface-induced effect on the morphologies of lamella-forming diblock copolymers in nanorod arrays is studied by using the self-consistent field theory.In the simulation study,a rich variety of novel morphologies are observed by variations in the strength of the surface field for the diblock copolymers.Different surface-field-induced effects are examined for the diblock copolymers in the arrays with distinct preferential surfaces.It is observed that the majority-block preferential surfaces have more obvious induced effects than those of minority-block preferential surfaces.The strong surface fields exhibit different behaviours from those observed in the weak surface fields,by which the morphologies possess cylindrical symmetries.Results from this research deepen the knowledge of surface-induced effects in a confinement system,which may aid the fabrication of polymer-based nanomaterials.     

Wetting-driven structure ordering of a copolymer/homopolymer/nanoparticle mixture in the presence of a modulated potential

We investigate pattern formation on a solid substrate of a diblock copolymer-homopolymer mixture containing doping wettable nanoparticles with a preferential attraction for one component of the copolymers, using a three-order-parameter model. The presence of doping nanoparticles under the surface-interaction modulation breaks the isotropy in the process of microphase-separation and macrophase-separation. This leads to the formation of orientational microphase and macrophase structures due to the interplay between the phase separation and wetting particle ordering under a modulated potential at the late stage. Simulations suggest that the microphase morphology and macrophase morphology can be changed through adjustment of the wetting strength, the amplitude as well as the period of the modulated potential. It provides some important insights for changing microphase and macrophase structures in polymer blends by wetting-driven spinodal decomposition.     

两嵌段共聚物软受限自组装行为研究

采用模拟退火算法,系统研究了软受限条件下两嵌段共聚物自组装形貌极其转化机理。共聚物形貌可受到受限程度,组分体积分数,以及溶剂选择性3方面因素的调制。在弱受限条件下,共聚物形貌均为球状呈各向同性。核-壳-笼形貌可以极大的增加组分A和组分B之间的接触粒子数,达到增熵降能的效果,在我们的研究工作中是一种罕见的构型。形成多核结构的条件是： AB复合链末端距与其链长比值小于0.23。此次工作对于纳米颗粒的实验制作以及药品输运方面具有极大的理论指导意义。     

Theory of microphase separation on side-chain liquid-crystalline polymers with flexible spacers

We model a melt of monodisperse side-chain liquid-crystalline polymers as a melt of comb copolymers in which the side groups are rod-coil diblock copolymers. We consider both excluded-volume and Maier-Saupe interactions. The first acts among any pair of segments while the latter acts only between rods. Using a free-energy functional calculated from this microscopic model, we study the spinodal stability of the isotropic phase against density and orientational fluctuations. The phase diagram obtained in this way predicts nematic and smectic instabilities as well as the existence of microphases or phases with modulated wave vector but without nematic ordering. Such microphases are the result of the competition between the incompatibility among the blocks and the connectivity constraints imposed by the spacer and the backbone. Also the effects of the polymerization degree and structural conformation of the monomeric units on the phase behavior of the side-chain liquid-crystalline polymers are studied.     

A possible polar smectic A—Non-polar smectic A transition line in a binary system?

We show the thermal evolution of the orientational order near nematic-smectic A or smectic A-smectic A transitions which we recently revealed in binary mixtures. We compare the experimental behavior to theoretical predictions of a possible smectic A phase with polarized layers.     

Continuous paranematic-to-nematic ordering transitions of liquid crystals in tubular silica nanochannels

The optical birefringence of rodlike nematogens (7CB, 8CB), imbibed in parallel silica channels with 10 nm diameter and 300 microm length, is measured and compared to the thermotropic bulk behavior. The orientational order of the confined liquid crystals, quantified by the uniaxial nematic ordering parameter, evolves continuously between paranematic and nematic states, in contrast to the discontinuous isotropic-to-nematic bulk phase transitions. A Landau-de Gennes model reveals that the strength of the orientational ordering fields, imposed by the silica walls, is beyond a critical threshold, that separates discontinuous from continuous paranematic-to-nematic behavior. Quenched disorder effects, attributable to wall irregularities, leave the transition temperatures affected only marginally, despite the strong ordering fields in the channels.     

Phase Transition Induced by Small Molecules in Confined Copolymer Films

We investigate the phase transition induced by small molecules in confined copolymer films by using density functional theory. It is found that the addition of small molecules can effectively promote the phase separation of copolymers. In a symmetric diblock copolymer film, the affinity and concentration of small molecules play an important role in the structure transitions. The disordered-lamellar transitions, larnellar-lamellar transitions and the re-entrant transitions of the same structures are observed. Our results have potential applications in the fabrication of new functional materials.     

Confinement of columnar diblock copolymers: Simulations, theory and applications

The inherent nanoscale morphologies of self-organizing diblock copolymer melts are now being investigated for a variety of technological applications. To obtain global, well-oriented, regular patterns requires suitably confining and aligning the melt between two flat plates. Here we consider such confinement for an asymmetrical diblock melt, which forms columns of the minority phase in a matrix of the majority phase. We investigate this system with a combination of numerical simulations and strong segregation theory and make suggestions as to when perpendicular orientation should prevail over parallel orientation of the columns. Received 22 May 2001 and Received in final form 14 February 2002     

The formation of biaxial nematic phases in binary mixtures of thermotropic liquid-crystals composed of uniaxial molecules

ABSTRACT

Monte Carlo simulations in the isothermal-isobaric ensemble are used to investigate the formation of an ordered, biaxial nematic phase in a binary mixture of thermotropic liquid crystals. The orientational dependence of the interaction between molecules of each pure component is the same as in the well-known Maier-Saupe model; each pure component of the mixture is therefore capable of forming a uniaxial nematic phase. For the interaction between molecules of different components, we use the same Maier-Saupe model but change the sign of the coupling constant. As a consequence a T-shaped arrangement of these molecules is energetically favoured. The formation of the biaxial phase occurs in two steps. At higher temperatures T, one of the components forms a uniaxial nematic phase whereas the other is in a quasi two-dimensional restricted isotropic liquid state. We develop a simple theoretical model to understand the high degree of (ostensible) nematic order in the latter. At lower T, the second component becomes nematic and then the entire mixture of the two compounds has biaxial symmetry. The biaxial nematic phase does not demix into domains rich in molecules of one or the other species.     

Binary-component micelle and vesicle: Free energy and asymmetric distributions of amphiphiles between monolayers of vesicle

The real-space two-dimensional self-consistent field theory (SCFT) is employed to study the free energies of micelles and vesicles constituted by binary amphiphilic diblock copolymer AB in homopolymer A. With increasing volume fraction of copolymer AB, there are morphological transitions from the circle micelles to oblate circle-like micelles, to compound structure with inverted micelles in the inner center and micelles outer layer, and to vesicles. Special attentions are paid to the role of the copolymer AB in controlling free energies of the micelles and vesicles, by examining the effect of length ratio of A/B with the fixed whole chain length of AB copolymer, the length effect of A or B block with the corresponding fixed length of B or A block, for one component of copolymer, and the effect of different amphiphile compositions for binary-component copolymer system. The quantity η is provided to describe the asymmetric density distribution of amphiphiles between the inner and outer monolayers of vesicles, and to quantify the relative asymmetric extent of the density distribution between two species of copolymers in binary component vesicles.