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Polymers
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Nano-Structures of Block Copolymers
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Nano-Structures of Block Copolymers

A special issue of Polymers (ISSN 2073-4360).

Deadline for manuscript submissions: closed (31 August 2010) | Viewed by 127067

Special Issue Editor

Prof. Dr. Alexander Böker

E-Mail Website
Guest Editor
Lehrstuhl für Polymermaterialien und Polymertechnologie, University of Potsdam, 14476 Potsdam-Golm, Germany
Interests: self-assembly of block copolymers and nanoparticles; multi-functional patchy particles; Pickering-Emulsions; protein-polymer conjugates; integration of biological functions into polymeric materials

Special Issue Information

Dear Colleagues,

Block copolymers, their microphase separation as well as their resulting nanoscopic structures have been studied extensively over the past three decades both experimentally and theoretically. Despite considerable efforts and promising results, so far industrially relevant technologies based on block copolymer nanostructures have not yet been developed or at least did not make it to the final product.
This special issue is intended to give the reader an overview over recent cutting edge research and new developments in the field of block copolymer nanotechnology. Here, we would like to place emphasis on work dealing with ways to control and guide the self-assembly of block copolymer systems, the introduction of functionality, block copolymer-based templates, block copolymer hybrid systems, and novel morphologies arising from these hybrid materials. Finally, this issue should also give examples how block copolymer nanostructures can help to meet future requirements in fields like e.g. electronics, data storage as well as energy storage and conversion.

Prof. Dr. Alexander Böker
Guest Editor

Keywords

  • functional block copolymers
  • controlled self-assembly
  • external/internal fields
  • control of order
  • hybrid materials
  • block copolymer-based applications

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Published Papers (9 papers)

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Research

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813 KiB  
Article
Structural and Mechanical Hysteresis at the Order-Order Transition of Block Copolymer Micellar Crystals
by Theresa A. LaFollette and Lynn M. Walker
Polymers 2011, 3(1), 281-298; https://doi.org/10.3390/polym3010281 - 11 Jan 2011
Cited by 15 | Viewed by 9280
Abstract
Concentrated solutions of a water-soluble block copolymer (PEO)20-(PPO)70-(PEO)20 show a thermoreversible transition from a liquid to a gel. Over a range of concentration there also exists an order-order transition (OOT) between cubically-packed spherical micelles and hexagonally-packed cylindrical micelles. [...] Read more.
Concentrated solutions of a water-soluble block copolymer (PEO)20-(PPO)70-(PEO)20 show a thermoreversible transition from a liquid to a gel. Over a range of concentration there also exists an order-order transition (OOT) between cubically-packed spherical micelles and hexagonally-packed cylindrical micelles. This OOT displays a hysteresis between the heating and cooling transitions that is observed at both the macroscale through rheology and nanoscale through small angle neutron scattering (SANS). The hysteresis is caused by the persistence of the cubically-packed spherical micelle phase into the hexagonally-packed cylindrical micelle phase likely due to the hindered realignment of the spherical micelles into cylindrical micelles and then packing of the cylindrical micelles into a hexagonally-packed cylindrical micelle phase. This type of hysteresis must be fully characterized, and possibly avoided, for these block copolymer systems to be used as templates in nanocomposites. Full article
(This article belongs to the Special Issue Nano-Structures of Block Copolymers)
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529 KiB  
Article
Spontaneous Enhancement of Packing Regularity of Spherical Microdomains in the Body-Centered Cubic Lattice upon Uniaxial Stretching of Elastomeric Triblock Copolymers
by Takuya Kota, Kimio Imaizumi, Sono Sasaki and Shinichi Sakurai
Polymers 2011, 3(1), 36-50; https://doi.org/10.3390/polym3010036 - 27 Dec 2010
Cited by 10 | Viewed by 10468
Abstract
Block copolymers forming glassy spheres in the matrix of rubbery chains can exhibit elastomeric properties. It is well known that the spherical microdomains are arranged in the body-center cubic (bcc) lattice. However, recently, we have found packing in the face-centered cubic (fcc) lattice, [...] Read more.
Block copolymers forming glassy spheres in the matrix of rubbery chains can exhibit elastomeric properties. It is well known that the spherical microdomains are arranged in the body-center cubic (bcc) lattice. However, recently, we have found packing in the face-centered cubic (fcc) lattice, which is easily transformed into the bcc lattice upon uniaxial stretching. In the same time, the packing regularity of the spheres in the bcc lattice was found to be enhanced for samples completely recovered from the stretched state. This reminds us that a cycle of stretching-and-releasing plays an important role from analogy of densification of the packing in granules upon shaking. In the current paper, we quantify the enhancement of packing regularity of spherical microdomains in the bcc lattice upon uniaxial stretching of the same elastomeric triblock copolymer as used in our previous work by conducting small-angle X-ray scattering (SAXS) measurements using high brilliant synchrotron radiation. Isotropically circular rings of the lattice peaks observed for the unstretched sample turned into deformed ellipsoidal rings upon the uniaxial stretching, with sharpening of the peaks in the direction parallel to the stretching direction and almost disappearing of the peaks in the perpendicular direction. By quantitatively analyzing the SAXS results, it was found that the packing regularity of the spherical microdomains was enhanced in the parallel direction while it was spoiled in the perpendicular direction under the stretched state. The enhanced regularity of packing was unchanged even if the stretching load was completely removed. Full article
(This article belongs to the Special Issue Nano-Structures of Block Copolymers)
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878 KiB  
Article
Surface Roughening of Polystyrene and Poly(methyl methacrylate) in Ar/O2 Plasma Etching
by Yuk-Hong Ting, Chi-Chun Liu, Sang-Min Park, Hongquan Jiang, Paul F. Nealey and Amy E. Wendt
Polymers 2010, 2(4), 649-663; https://doi.org/10.3390/polym2040649 - 2 Dec 2010
Cited by 69 | Viewed by 15787
Abstract
Selectively plasma-etched polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) diblock copolymer masks present a promising alternative for subsequent nanoscale patterning of underlying films. Because mask roughness can be detrimental to pattern transfer, this study examines roughness formation, with a focus on the role of cross-linking, during plasma [...] Read more.
Selectively plasma-etched polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) diblock copolymer masks present a promising alternative for subsequent nanoscale patterning of underlying films. Because mask roughness can be detrimental to pattern transfer, this study examines roughness formation, with a focus on the role of cross-linking, during plasma etching of PS and PMMA. Variables include ion bombardment energy, polymer molecular weight and etch gas mixture. Roughness data support a proposed model in which surface roughness is attributed to polymer aggregation associated with cross-linking induced by energetic ion bombardment. In this model, RMS roughness peaks when cross-linking rates are comparable to chain scissioning rates, and drop to negligible levels for either very low or very high rates of cross-linking. Aggregation is minimal for very low rates of cross-linking, while very high rates produce a continuous cross-linked surface layer with low roughness. Molecular weight shows a negligible effect on roughness, while the introduction of H and F atoms suppresses roughness, apparently by terminating dangling bonds. For PS etched in Ar/O2 plasmas, roughness decreases with increasing ion energy are tentatively attributed to the formation of a continuous cross-linked layer, while roughness increases with ion energy for PMMA are attributed to increases in cross-linking from negligible to moderate levels. Full article
(This article belongs to the Special Issue Nano-Structures of Block Copolymers)
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1786 KiB  
Article
Enhanced Photophysical Properties of Nanopatterned Titania Nanodots/Nanowires upon Hybridization with Silica via Block Copolymer Templated Sol-Gel Process
by Dinakaran Kannaiyan, Saji Thomas Kochuveedu, Yoon Hee Jang, Yu Jin Jang, Ji Yong Lee, Jieun Lee, Juyon Lee, Jooyong Kim and Dong Ha Kim
Polymers 2010, 2(4), 490-504; https://doi.org/10.3390/polym2040490 - 25 Oct 2010
Cited by 43 | Viewed by 13772
Abstract
We fabricated titanium dioxide (TiO2)-silica (SiO2) nanocomposite structures with controlled morphology by a simple synthetic approach using cooperative sol-gel chemistry and block copolymer (BCP) self-assembly. Mixed TiO2-SiO2 sol-gel precursors were blended with amphiphilic poly(styrene-block-ethylene oxide) (PS- [...] Read more.
We fabricated titanium dioxide (TiO2)-silica (SiO2) nanocomposite structures with controlled morphology by a simple synthetic approach using cooperative sol-gel chemistry and block copolymer (BCP) self-assembly. Mixed TiO2-SiO2 sol-gel precursors were blended with amphiphilic poly(styrene-block-ethylene oxide) (PS-b-PEO) BCPs where the precursors were selectively incorporated into the hydrophilic PEO domains. Changing the volumetric ratio of TiO2-SiO2 sol-gel precursor from 5% to 20%, a stepwise structural inversion occurred from nanodot arrays to discrete nanowires. Template free hybrid inorganic nanostructures were produced after the removal of PS-b-PEO by irradiation of UV light. The morphological evolution and photophysical properties were investigated by microscopic studies, UV-visible absorption and photocatalytic properties. Full article
(This article belongs to the Special Issue Nano-Structures of Block Copolymers)
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Review

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943 KiB  
Review
Routes to Nanoparticle-Polymer Superlattices
by Sara Mehdizadeh Taheri, Steffen Fischer and Stephan Förster
Polymers 2011, 3(2), 662-673; https://doi.org/10.3390/polym3020662 - 24 Mar 2011
Cited by 30 | Viewed by 11187
Abstract
Nanoparticles can self-assemble into highly ordered two- and three-dimensional superlattices. For many practical applications these assemblies need to be integrated into polymeric matrices to provide stability and function. By appropriate co-assembly of nanoparticles and polymers it has become possible to tailor the nanoparticle [...] Read more.
Nanoparticles can self-assemble into highly ordered two- and three-dimensional superlattices. For many practical applications these assemblies need to be integrated into polymeric matrices to provide stability and function. By appropriate co-assembly of nanoparticles and polymers it has become possible to tailor the nanoparticle superlattice structure via the length and stiffness of the polymer chains. The present article outlines and discusses established routes to nanoparticle-polymer superlattices. Recent progress has been remarkable so that the integration into functional devices has become the next challenge. Full article
(This article belongs to the Special Issue Nano-Structures of Block Copolymers)
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1104 KiB  
Review
Functionalization of Block Copolymer Vesicle Surfaces
by Stefan Egli, Helmut Schlaad, Nico Bruns and Wolfgang Meier
Polymers 2011, 3(1), 252-280; https://doi.org/10.3390/polym3010252 - 11 Jan 2011
Cited by 92 | Viewed by 17396
Abstract
In dilute aqueous solutions certain amphiphilic block copolymers self-assemble into vesicles that enclose a small pool of water with a membrane. Such polymersomes have promising applications ranging from targeted drug-delivery devices, to biosensors, and nanoreactors. Interactions between block copolymer membranes and their surroundings [...] Read more.
In dilute aqueous solutions certain amphiphilic block copolymers self-assemble into vesicles that enclose a small pool of water with a membrane. Such polymersomes have promising applications ranging from targeted drug-delivery devices, to biosensors, and nanoreactors. Interactions between block copolymer membranes and their surroundings are important factors that determine their potential biomedical applications. Such interactions are influenced predominantly by the membrane surface. We review methods to functionalize block copolymer vesicle surfaces by chemical means with ligands such as antibodies, adhesion moieties, enzymes, carbohydrates and fluorophores. Furthermore, surface-functionalization can be achieved by self-assembly of polymers that carry ligands at their chain ends or in their hydrophilic blocks. While this review focuses on the strategies to functionalize vesicle surfaces, the applications realized by, and envisioned for, such functional polymersomes are also highlighted. Full article
(This article belongs to the Special Issue Nano-Structures of Block Copolymers)
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1719 KiB  
Review
Phase-Segregated Dendrigraft Copolymer Architectures
by Lorena-Eugenia Sanchez Cadena and Mario Gauthier
Polymers 2010, 2(4), 596-622; https://doi.org/10.3390/polym2040596 - 25 Nov 2010
Cited by 8 | Viewed by 9650
Abstract
Dendrigraft polymers have a multi-level branched architecture resulting from the covalent assembly of macromolecular building blocks. Most of these materials are obtained in divergent (core-first) synthetic procedures whereby the molecule grows outwards in successive grafting reactions or generations. Two main types of dendrigraft [...] Read more.
Dendrigraft polymers have a multi-level branched architecture resulting from the covalent assembly of macromolecular building blocks. Most of these materials are obtained in divergent (core-first) synthetic procedures whereby the molecule grows outwards in successive grafting reactions or generations. Two main types of dendrigraft polymers can be identified depending on the distribution of reactive sites over the grafting substrate: Arborescent polymers have a large and variable number of more or less uniformly distributed sites, while dendrimer-like star polymers have a lower but well-defined number of grafting sites strictly located at the ends of the substrate chains. An overview of the synthesis and the characterization of dendrigraft copolymers with phase-segregated morphologies is provided in this review for both dendrigraft polymer families. The tethering of side-chains with a different composition onto branched substrates confers unusual physical properties to these copolymers, which are highlighted through selected examples. Full article
(This article belongs to the Special Issue Nano-Structures of Block Copolymers)
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880 KiB  
Review
Block Copolymer Nanostructures for Technology
by Yu-Chih Tseng and Seth B. Darling
Polymers 2010, 2(4), 470-489; https://doi.org/10.3390/polym2040470 - 20 Oct 2010
Cited by 131 | Viewed by 23218
Abstract
Nanostructures generated from block copolymer self-assembly enable a variety of potential technological applications. In this article we review recent work and the current status of two major emerging applications of block copolymer (BCP) nanostructures: lithography for microelectronics and photovoltaics. We review the progress [...] Read more.
Nanostructures generated from block copolymer self-assembly enable a variety of potential technological applications. In this article we review recent work and the current status of two major emerging applications of block copolymer (BCP) nanostructures: lithography for microelectronics and photovoltaics. We review the progress in BCP lithography in relation to the requirements of the semiconductor technology roadmap. For photovoltaic applications, we review the current status of the quest to generate ideal nanostructures using BCPs and directions for future research. Full article
(This article belongs to the Special Issue Nano-Structures of Block Copolymers)
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1197 KiB  
Review
Design and Application of Nanoscale Actuators Using Block-Copolymers
by Joshua M. G. Swann and Paul D. Topham
Polymers 2010, 2(4), 454-469; https://doi.org/10.3390/polym2040454 - 15 Oct 2010
Cited by 20 | Viewed by 14916
Abstract
Block copolymers are versatile designer macromolecules where a “bottom-up” approach can be used to create tailored materials with unique properties. These simple building blocks allow us to create actuators that convert energy from a variety of sources (such as chemical, electrical [...] Read more.
Block copolymers are versatile designer macromolecules where a “bottom-up” approach can be used to create tailored materials with unique properties. These simple building blocks allow us to create actuators that convert energy from a variety of sources (such as chemical, electrical and heat) into mechanical energy. In this review we will discuss the advantages and potential pitfalls of using block copolymers to create actuators, putting emphasis on the ways in which these materials can be synthesised and processed. Particular attention will be given to the theoretical background of microphase separation and how the phase diagram can be used during the design process of actuators. Different types of actuation will be discussed throughout. Full article
(This article belongs to the Special Issue Nano-Structures of Block Copolymers)
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