Hybrid time-dependent Ginzburg-Landau simulations of block copolymer nanocomposites: nanoparticle anisotropy

Block copolymer melts are perfect candidates to template the position of colloidal nanoparticles in the nanoscale, on top of their well-known suitability for lithography applications. This is due to their ability to self-assemble into periodic ordered structures, in which nanoparticles can segregate depending on the polymer-particle interactions, size and shape. The resulting coassembled structure can be highly ordered as a combination of both the polymeric and colloidal properties. The time-dependent Ginzburg-Landau model for the block copolymer was combined with Brownian dynamics for nanoparticles, resulting in an efficient mesoscopic model to study the complex behaviour of block copolymer nanocomposites. This review covers recent developments of the time-dependent Ginzburg-Landau/Brownian dynamics scheme. This includes efforts to parallelise the numerical scheme and applications of the model. The validity of the model is studied by comparing simulation and experimental results for isotropic nanoparticles. Extensions to simulate nonspherical and inhomogeneous nanoparticles are discussed and simulation results are discussed. The time-dependent Ginzburg-Landau/Brownian dynamics scheme is shown to be a flexible method which can account for the relatively large system sizes required to study block copolymer nanocomposite systems, while being easily extensible to simulate nonspherical nanoparticles

Cell dynamics simulations of sphere-forming diblock copolymers in thin films on chemically patterned substrates

The morphology of sphere-forming block copolymers assembled in thin films on patterned surfaces is theoretically analyzed. The patterns on the lower surface are alternating bands of a given width distinctively attracting or repelling a given block. We find that long- range order can be achieved, and it depends on the commensurability of the characteristic length of the block domains with both band periodicity and slit thickness. The comparison of the simulation results with experimental data shows a very good agreement. Furthermore, we show that the proper selection of the band periodicity and, consequently, of the film thickness permits the system to switch from hexagonal packing to body-centered orthohedra. Therefore, we show that it exists a way to control the formation of long-range ordered structures of different types in this kind of system

Mechanisms of electric-field-induced alignment of block copolymer lamellae

We demonstrate that two mechanisms of lamellae reorientation observed experimentally under applied electric field [A. Böker H. Elbs, H. Hänsel, A. Knoll, S. Ludwigs, H. Zettl, V. Urban, V. Abetz, A. H. E. Müller and G. Krausch, Phys. Rev. Lett., 2002, 89, 135502] which have been previously described within dynamic self consistent field theory [A. V. Zvelindovsky and G. J. A. Sevink, Phys. Rev. Lett., 2003, 90, 049601] can be fully explained within a much more simple model using the Ginzburg–Landau Hamiltonian. A third alignment mechanism has been identified which was not previously reported. A more complete picture of reorientation under electric field emerges that clarifies the crucial role of structural defects

The cooperative behaviour of antimicrobial peptides in model membranes

A systematic analysis of the hypothesis of the antimicrobial peptides' (AMPs) cooperative action is performed by means of full atomistic molecular dynamics simulations accompanied by circular dichroism experiments. Several AMPs from the aurein family (2.5,2.6, 3.1), have a similar sequence in the first ten amino acids, are investigated in different environments including aqueous solution, trifluoroethanol (TFE), palmitoyloleoylphosphatidylethanolamine (POPE), and palmitoyloleoylphosphatidylglycerol (POPG) lipid bilayers. It is found that the cooperative effect is stronger in aqueous solution and weaker in TFE. Moreover, in the presence of membranes, the cooperative effect plays an important role in the peptide/lipid bilayer interaction. The action of AMPs is a competition of the hydrophobic interactions between the side chains of the peptides and the hydrophobic region of lipid molecules, as well as the intra peptide interaction. The aureins 2.5-COOH and 2.6-COOH form a hydrophobic aggregate to minimize the interaction between the hydrophobic group and the water. Once that the peptides reach the water/lipid interface the hydrophobic aggregate becomes smaller and the peptides start to penetrate into the membrane. In contrast, aurein 3.1-COOH forms only a transient aggregate which disintegrates once the peptides reached the membrane, and it shows no cooperativity in membrane penetratio

Large scale three dimensional simulations of hybrid block copolymer/nanoparticle systems

Block copolymer melts self-assemble in the bulk into a variety of nanostructures, making them perfect candidates to template the position of nanoparticles. The morphological changes of block copolymers are studied in the presence of a considerable filling fraction of colloids. Furthermore, colloids can be found to assemble into ordered hexagonally close-packed structures in a defined number of layers when softly confined within the phase-separated block copolymer. A high concentration of interface-compatible nanoparticles leads to complex long-lived block copolymer morphologies depending on the polymeric composition. Macrophase separation between the colloids and the block copolymer can be induced if colloids are unsolvable within the matrix. This leads to the formation of ellipsoid-shaped polymer-rich domains elongated along the direction perpendicular to the interface between block copolymer domains

Block copolymer nanoshells

With the help of cell dynamics simulation we investigate morphology of thin block copolymer film around a nanoparticle. The obtained structures include: parallel, perpendicular, mixed and perforated lamellae, parallel and perpendicular cylinders and spheres. Analogy and difference with planar films are discussed. Our simulation suggests that novel porous nanocontainers can be formed by the coating of a sacrificial nano-bead by a block copolymer layer with a well controlled nanostructure

Diblock copolymers in a cylindrical pore

We show that a simple Ginzburg–Landau type theory can predict a tremendous rich “zoo” of diblock copolymer morphologies in cylindrical nanopores. Using the cell dynamics simulation we study in detail lamellar-, cylinder-, and eventually sphere-forming diblock copolymers melts in cylindrical nanopores. A very fast simulation method is proposed to be used as a research precursor for more elaborate computational techniques

Collective behavior of self-propelling particles with kinematic constraints: The relation between the discrete and the continuous description

In two papers we proposed a continuum model for the dynamics of systems of self propelling particles with kinematic constraints on the velocities and discussed some of its properties. The model aims to be analogous to a discrete algorithm used in works by T. Vicsek et al. In this paper we derive the continuous hydrodynamic model from the discrete description. The similarities and differences between the resulting model and the hydrodynamic model postulated in our previous papers are discussed. The results clarify the assumptions used to obtain a continuous description. © 2007 Elsevier B.V. All rights reserved

Nanoparticle anisotropy induces sphere-to-cylinder phase transition in block copolymer melts

Block copolymer nanocomposites including anisotropic nanoparticles have been previously found to co-assemble into complex structures with nanoparticle alignment. Anisotropic nanoparticles with large aspect ratios are found to modify the morphology of block copolymers at modest concentrations, inducing a sphere-to-cylinder phase transition by breaking the local symmetry in the vicinity of a solid particle. This transition takes place over a wide range of NP lengths comparable with the BCP spacing. Controlling the orientation of uniaxial nanoparticles provides additional control over the global orientation of the block copolymer, as previously reported by experiments