Morphology Of Diblock Copolymers Research Articles

Effect of wall potential on morphology of symmetric diblock copolymers in nanotrench

We have investigated the morphology of symmetric poly(styrene-b-methyl methacrylate) (PS-b-PMMA) diblock copolymers in narrow trenches by performing Monte Carlo (MC) simulations. We considered two types of interactions between the PMMA-attractive trench walls and the PS-b-PMMA. First, an exponential-type wall potential was applied to the PMMA segments to attract them to the wall, which has been widely used for the coarse-grained MC model. In the second case, only the PMMA blocks initially located near the trench wall were adsorbed to the wall. In both cases, the number of the PMMA lamellae was step-wisely increased each time the trench was widened by ∼1.0L0 (L0: lamellae period in the bulk). However, due to its considerably thin PMMA layer, the trench width in the second case had ∼0.7L0 offset from that in the first case. These results imply the importance of interfacial characterization between the diblock copolymers and the trench walls.

The crystallinity, thermal properties and microscopic morphology of di-block copolymers ofl-lactide and several acrylates

Di-block copolymers ofl-lactide and (meth)acrylate were synthesized from PLLA macroinitiators, and the microphase separation of copolymers was observed.

Segmental dynamics in lamellar phases of tapered copolymers.

Recent experiments have reported that the lamellar phase of salt-doped tapered copolymers exhibit higher ionic conductivity compared to those seen in similar morphologies of diblock copolymers. Such observations were in turn rationalized by invoking the corresponding glass transition temperature of the segregated copolymers. In this work we report the results of coarse-grained molecular dynamics simulations to identify the mechanisms underlying such characteristics. Explicitly, we probe the combined influences of the degree of segregation and the disparity in mobilities of the segments of the two blocks, upon the local relaxation dynamics of tapered copolymers segregated in lamellar phases. Our results show that the local dynamics of tapered copolymers depend on two independent factors, viz., the degree of segregation of such copolymers relative to their order-disorder transition temperature, and the relative mobilities (glass transition temperatures) of the two blocks. In qualitative correspondence with experiments, we find that for appropriate combinations of mobility ratios and degree of segregation, the lamellar phases of tapered copolymers can exhibit faster local segmental dynamics compared to diblock copolymers.

Frustrated phases under three-dimensional confinement simulated by a set of coupled Cahn-Hilliard equations.

We numerically study a set of coupled Cahn-Hilliard equations as a means to find morphologies of diblock copolymers in three-dimensional spherical confinement. This approach allows us to find a variety of energy minimizers including rings, tennis balls, Janus balls and multipods among several others. Phase diagrams of confined morphologies are presented. We modify the size of the interface between microphases to control the number of holes in multipod morphologies. Comparison to experimental observation by transmission electron microtomography of multipods in polystyrene-polyisoprene diblock copolymers is also presented.

Effect of Tapering on Morphology and Interfacial Behavior of Diblock Copolymers from Molecular Dynamics Simulations

Tapered diblock copolymers are AB diblock copolymers modified by adding a gradient region between the blocks in which composition varies smoothly from one species to the other. This gives additional control parameters, the length of the taper and its direction, to control the microphase separation behavior. Using tapers can also increase the accessibility of the bicontinuous gyroid phase, potentially of interest in transport applications. Recently, the phase diagram of these systems was predicted using self-consistent field theory (SCFT). In this study, we perform coarse-grained molecular dynamics (MD) simulations to investigate both the structural and dynamic properties of tapered diblock copolymers. The MD results are consistent with the SCFT phase diagram, and the density profiles are also similar as a function of taper length and direction. We additionally compute mean-squared displacements and end-to-end relaxation times of lamellar systems and observe individual polymer conformations. Increasing tap...

Self-assembly of semicrystalline PE-b-PS diblock copolymers within AAO nanoporous templates

Strongly segregated polyethylene-b-polystyrene (PE-b-PS) diblock copolymers were infiltrated within anodic aluminum oxide nanoporous templates (AAO) (with 60 nm diameter). After carefully removing the nanofibers from the nanopores, TEM revealed their morphology. This is the first time that the morphology of semi-crystalline diblock copolymers infiltrated within AAO templates is observed. Regardless of their composition, the infiltrated nanofibers are constituted by core–shell or pseudo core–shell self-assembled nanocylinders. The affinity of PE to the AAO walls tailors the morphology towards PE shells with PS cores. The PS cores for some compositions have PE inclusions whose morphology is expected on the basis of previous computer simulation studies. Morphological observations successfully explain the confined crystallization of the PE block within the nanopores and the origin of novel double confinement effects (induced by glassy PS block and rigid AAO walls) on the PE block.

Bulk morphologies of polystyrene-block-polybutadiene-block-poly(tert-butyl methacrylate) triblock terpolymers

The self-assembly of block copolymers in the bulk phase enables the formation of complex nanostructures with sub 100 nm periodicities and long-range order, both relevant for nanotechnology applications. Here, we map the bulk phase behavior of polystyrene-block-polybutadiene-block-poly(tert-butyl methacrylate) (SBT) triblock terpolymers on a series of narrowly distributed polymers with widely different block volume fractions, ϕS, ϕB and ϕT. In dependence of ϕ, we find the lamella–lamella, core-shell cylinder, cylinder-in-lamella and core-shell gyroid morphology, but also a rarely observed cylinder-in-lamella phase. The bulk morphologies are thoroughly characterized by transmission electron microscopy (TEM) and small angle X-ray scattering (SAXS) and display unusually broad stability regions, i.e. morphologies are observed over a broad range of compositions. We attribute this phase behavior to the asymmetric distribution of block–block incompatibilities, along the SBT block sequence, which are relatively large for S/B and S/T interfaces, but small for B/T. The higher enthalpic penalties at the S/B and S/T interface cause B to preferentially spread on the T microdomain thereby adopting its geometry. The morphological behavior of SBT is thus dominated by the volume ratio of the end blocks, ϕS and ϕT, which reduces the number of potential morphologies to only a few, mostly the core-shell analogue of diblock copolymer morphologies. In general, a simplified terpolymer bulk behavior with large stability regions for morphologies offers straightforward synthetic targeting of specific morphologies that usually only appear in a small parameter space as demonstrated here on the core-shell gyroid.

Spontaneous self-assembly of diblock copolymers in nanoconfined geometries by dissipative particle dynamics

We performed dissipative particle dynamics (DPD) simulations to reproduce phase separation morphologies of diblock copolymers for directed self-assembly (DSA) lithography. DSA is a promising technique to overcome the current photolithography resolution limit. The Flory–Huggins χ parameter estimated from a small-angle X-ray scattering experiment was used for the DPD simulations owing to the multiple degrees of coarse-graining. The degree of coarse-graining and the bond parameter for the spring force were optimised to represent the experimental result of the number of lamellar layers formed in a trench guide. The DPD simulations using these parameters can also represent the diameter of the central cylinder domain that is formed by phase separation in the cylindrical hole. It was found that the bond parameter considering the spreading of polymer segments in a coarse-grained particle gives good quantitative agreement between the results of the simulations and the experimental data.

Nano- and Microstructures of Magnetic Field-Guided Maghemite Nanoparticles in Diblock Copolymer Films

The control over the alignment of nanoparticles within a block copolymer matrix was investigated for different external magnetic fields with respect to producing well-aligned, highly oriented metal-oxide-polymer nanopatterns. Hybrid films were prepared by solution casting under a range of external magnetic fields. The nano- and microstructure of maghemite nanoparticles within poly(styrene-b-methyl methacrylate) diblock copolymer films as a function of the nanoparticle concentration was studied using optical microscopy, atomic force microscopy, scanning electron microscopy, and grazing incidence small-angle X-ray scattering. Because of a polystyrene (PS) coating, the nanoparticles are incorporated in the PS domains of the diblock copolymer morphology. At higher nanoparticle concentrations, nanoparticle aggregates perturb the block copolymer structure and accumulate at the films surface into wire-shaped stripes. These wire-shaped nanoparticle aggregates form mainly because of the competition between nanoparticle-polymer friction and magnetic dipolar interaction. The magnetic behavior of the hybrid films was probed at different temperatures for two orthogonal directions (with the line-shaped particle aggregates parallel and perpendicular to the magnetic field). The hybrid film systems show superparamagnetic behavior and remarkable shape anisotropy that render them interesting for magnetic applications.

Morphology of diblock copolymers in porous media

We study the self-assembly of a diblock copolymer melt confined within a porous medium with a prescribed regular two-dimensional geometry using self-consistent field theory. We find that the morphology of the polymer sensitively depends on the characteristic length scales of the porous material and the polymer radius of gyration (Rg). When the pore size is much larger than Rg, the polymer self-assembly is affected only locally close to the contact with the pore surface. However, when the size of the pores and the distance between them is comparable to the diblock characteristic length, novel morphologies appear and the polymer structure changes according to the constraints imposed by the porous material. We develop an interaction potential for the solid particle and copolymer, and show how this provides an understanding of the qualitative feature of the morphologies.

Block Copolymer Morphology Formation on Topographically Complex Surfaces: A Self-Consistent Field Theoretical Study

A self-consistent field theoretic study is performed to study morphological development of lamellae-forming diblock copolymers on substrates with a well-defined roughness, modeled as trenches of varying depth and width engraved into the substrates. There are three possible lamellar orientations observed: horizontal lamellae, vertical lamellae that are parallel to the trench direction, and vertical lamellae that are perpendicular to the trench direction. Which of these three morphologies formed depends upon the trench width and surface affinity; however, trench depth has a relatively insignificant effect on the morphological development. Therefore, tuning trench width, but not trench depth, should allow for a reduction of the morphological defect density in directed self-assembly of lamellar morphology of diblock copolymers.

Self-Assembled Morphologies of Diblock Copolymers Confined in Multiwalled Carbon Nanotubes

Self-assembly of symmetric diblock copolymers (DCP) confined in multiwalled carbon nanotubes (MWCNTs) is studied using coarse-grained molecular dynamic (MD) simulations. The dependence of the self-assembled morphologies on the strength of the surface interactions is examined systematically. A rich variety of novel morphologies under the three-dimensional confinement have been revealed. The adsorption energy and cohesive energy have been discussed qualitatively and used to account for the appearance of the complex morphological transition.

Symmetric Diblock Copolymers Confined by Two Nanopatterned Surfaces

Using Monte Carlo simulations of a coarse-grained model, we explore the equilibrium morphologies of symmetric diblock copolymers between two chemically patterned surfaces. The chemical patterns on the surfaces consist of periodic stripes of width W with a periodicity Ls. The stripes on the two chemical patterns are oriented orthogonally. By systematically varying the width of the stripes, the interaction strength between the patterns and block copolymers, and the thickness of the block copolymer films, we investigate complex three-dimensional morphologies that are not available in the bulk and that could be useful in a wide array of applications. The results of simulations are shown to be in quantitative agreement with experimental observations.

Phase Behavior of Binary Blends of Diblock Copolymer/Homopolymer Confined in Spherical Nanopores

Binary blends of a diblock copolymer (AB) and an incompatible homopolymer (C) confined in spherical cavities are studied using a simulated annealing technique. The phase behavior of the blends is examined for four typical cases, representing the different selectivity of the pore surface to the A, B, and C species. The internal morphology of the spherical polymeric particles is controlled by the homopolymer volume fraction, the degree of confinement, and the composition of the copolymer. Inside a particle, the homopolymers segregate to form one or, under some conditions, two domains; thus, the homopolymers may act as an additional controlling parameter of the shape and symmetry of the copolymer domain. A rich array of confinement-induced novel diblock copolymer morphologies is predicted. In particular, core-shell particles with the copolymers as the shell wrapping around a homopolymer core or a copolymer-homopolymer combined core and Janus-like particles with the copolymers and the homopolymers on different sides are obtained.

Soft Confinement-Induced Morphologies of Diblock Copolymers

The self-assembly of diblock copolymers under soft confinement is studied systematically using a simulated annealing method applied to a lattice model of polymers. The soft confinement is realized by the formation of polymer droplets in a poor solvent environment. Multiple sequences of soft confinement-induced copolymer aggregates with different shapes and self-assembled internal morphologies are predicted as functions of solvent-polymer interaction and the monomer concentration. It is discovered that the self-assembled internal morphology of the aggregates is largely controlled by a competition between the bulk morphology of the copolymer and the solvent-polymer interaction, and the shape of the aggregates can be non-spherical when the internal morphology is anisotropic and the solvent-polymer interaction is weak. These results demonstrate that droplets of diblock copolymers formed in poor solvents can be used as a model system to study the self-assembly of copolymers under soft confinement.

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.

Self-assembly of diblock copolymers under shear flow: A simulation study by combining the self-consistent field and lattice Boltzmann method

In this paper, we study the self-assembly of diblock copolymers under shear flow by combining the self-consistent field (SCF) and lattice Boltzmann (LB) method. We perform LB and SCF simulations in the same lattice, and set SCF simulation results as the input of LB, and then feedback the LB results to SCF simulation. This process is repeated until the system reaches an equilibrium state. This combined simulation method has the advantages of both LB and SCF simulations. It can thus be used to study the self-assembly of a defined copolymer in a real shear flow field. The simulative results imply that the self-assembled morphology of diblock copolymers under shear flow depends on the shear rate and shear frequency. The results correlate well with the experiment.

Morphologies of Charged Diblock Copolymers Simulated with a Neutral Coarse-Grained Model

We present the results of coarse grained molecular dynamics simulation using a charge free model that is able to capture different regions of the morphological phase diagram of charged diblock copolymers. Specifically, we were able to reproduce many phases of the poly(acrylic acid)-(1,4)-polybutadiene (PAA-PBA) diblock copolymer, Ca(2+) and water systems as a function of pH and calcium concentration with short-range LJ type potentials. The morphologies observed range from bilayers to cylinders to spherical micelles. Such polyanionic/cationic amphiphiles in water typically present multiple challenges for molecular simulations, particularly due to the many charge interactions that are long ranged and computationally costly. Further, it is precisely these interactions that are thought to modulate large amphiphile assemblies of interest such as lipid rafts. However, our model is able to reproduce different morphologies due to pH and with or without the addition of Ca(2+) as well as the lateral phase segregation and the domain registration observed in neutral and charged diblock copolymer mixtures. The results suggest that the overall effect of charges is a local structural rearrangement that renormalizes the steric repulsion between the headgroups. This simple model, which is devoid of charges, is able to reproduce the complex phase diagram and can be used to investigate collective phenomena in these charged systems such as domain formation and registration or colocalization of lipid rafts across bilayer leaflets.

Breakdown of Inverse Morphologies in Charged Diblock Copolymers

Brownian Dynamics simulations are carried out to understand the effect of temperature and dielectric constant of the medium on microphase separation of charged-neutral diblock copolymer systems. For different dielectric media, we focus on the effect of temperature on the morphology and dynamics of model charged diblock copolymers. In this study we examine in detail a system with a partially charged block copolymer consisting of 75% neutral blocks and 25% of charged blocks with 50% degree of ionization. Our investigations show that due to the presence of strong electrostatic interactions between the charged block and counterions, the block copolymer morphologies are rather different than those of their neutral counterpart at low dielectric constant, however at high dielectric constant the neutral diblock behaviors are observed. This article highlights the effect of dielectric constant of two different media on different thermodynamic and dynamic quantities. At low dielectric constant, the morphologies are a direct outcome of the ion-counterion multiplet formation. At high dielectric constant, these charged diblocks behavior resembles that of neutral and weakly charged polymers with sustainable long-range order. Similar behavior has been observed in chain swelling, albeit with small changes in swelling ratio for large changes in polarity of the medium. The results of our simulations agree with recent experimental results and are consistent with recent theoretical predictions of counterion adsorption on flexible polyelectrolytes.

Influence of Grafting Density of Diblock Copolymers on Interfacial Assembly Behavior and Interfacial Shear Strength of Glass Fiber/Polystyrene Composites

To investigate the influence of the grafting density and the molecular structure of block copolymers on the interfacial assembly behavior and interfacial shear strength, macromolecular coupling agents, hydroxyl-terminated poly(n-butyl acrylate-b-styrene) (HO-P(BA-b-S)) were synthesized by atom transfer radical polymerization, and then chemically anchored on the glass fiber surfaces to form a well-defined monolayer. The phase separation and 'hemispherical' domain morphologies of diblock copolymer brushes at the polystyrene/glass fiber interface were observed. The interfacial assembly morphology differs with changes in the grafting density of diblock copolymers. When the grafting density is greatest, the highest height difference of the hemispherical domain and the largest surface roughness are achieved, as well as the best interface shear strength. It was also found that the copolymer brush with a PBA block of the polymerization degree (Xn) about 77 is the optimal option for the interfacial adhesion of PS/GF composites. Thus, the grafting density and molecular structure of diblock copolymers determines the interfacial assembly behavior of copolymer brushes, and therefore the interfacial shear strength.