Nanostructure Formation of Inorganic Materials from the Self-assembly of Highly Amphiphilic Block Copolymers PDF Download

Author: Ju Ho Song
Publisher:
ISBN:
Category :
Languages : en
Pages : 138

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Book Description
High performance catalysts or energy devices such as solar cells and batteries which involve reactions and transport problems require nanostructured functional materials that are highly ordered mesoporous and crystalline materials. The self-assembly based structure direction of functional inorganic materials by block copolymers (BCPs) is a promising route because it combines mesoporosity at the 2-50 nm length scale, high surface areas and full control over morphology. This work explored solubility design guidelines that facilitate the coassembly of titania and poly(isoprene-b-ethylene oxide) (PI-b-PEO) which is a highly amphiphilic block copolymer. This approach enabled the fabrication of highly ordered crystalline titania. The pore size control of mesoporous crystalline titania was also accomplished by applying different molecular weight PI-bPEOs, and the highly ordered titania with the largest cylindrical pores (>30 nm) was reported without the use of pore-expanders. Nanostructured titania membranes were developed for water purification applications based on the knowledge from the previous part because inorganic membranes have superior thermal and chemical stabilities over polymer membranes. The mesoporous titania membranes with different pore size were successfully fabricated on porous disc substrates from both large and small molar mass PI-b-PEOs and presented an excellent molecular weight cut-off performances with high permeability, which would provide a huge potential to be applied in many ultrafiltration areas due to its self-cleaning characteristics from the photocatalytic activity. Finally, an ABC triblock terpolymer system was studied as an extension of the BCP self-assembly based structure direction of inorganic materials because these terpolymers allow wider composition windows for ordered network structures that have advantages such as 3-D connectivity and enhanced mechanical properties. In this work, the ternary morphology map of PI-b-PS-b-PEO and aluminisolicate sols was successfully constructed, which reveals 10 distinct morphologies along with particularly wide composition windows (2-13 vol%) for ordered network morphologies. This morphology map could be used as a model to predict the structure direction of other functional inorganic materials and a highly ordered network titania composite with core-shell double gyroid structure (cs-GD) was demonstrated as an example.

Author: Massimo Lazzari
Publisher: John Wiley & Sons
ISBN: 3527610561
Category : Technology & Engineering
Languages : en
Pages : 447

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Book Description
This first book to take a detailed look at one of the key focal points where nanotechnology and polymers meet provides both an introductory view for beginners as well as in-depth knowledge for specialists in the various research areas involved. It investigates all types of application for block copolymers: as tools for fabricating other nanomaterials, as structural components in hybrid materials and nanocomposites, and as functional materials. The multidisciplinary approach covers all stages from chemical synthesis and characterization, presenting applications from physics and chemistry to biology and medicine, such as micro- and nanolithography, membranes, optical labeling, drug delivery, as well as sensory and analytical uses.

Author: Gity Mir Mohamad Sadeghi
Publisher: Elsevier Inc. Chapters
ISBN: 0128090847
Category : Technology & Engineering
Languages : en
Pages : 121

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Book Description
Block copolymers (BCPs) consist of two or more chemically different polymers connected covalently, and are polymer alloys. Due to their thermodynamic incompatibility and chain connectivity, the phase separation between two (or more) blocks occurs only in a tens of nanometers range. Nanostructures are based on block copolymer self-assembly. They are functional nanomaterials less than 100nm in size and have received extensive scientific and technological attention due to their potential applications in electronic, biomedical, and optical materials. This chapter examines a variety of different synthetic strategies for preparation of linear diblock copolymers by anionic polymerization. Triblocks can be synthesized according to an appropriate synthetic pathway, depending on the monomers used and their sequence in the triblock chain. Nonlinear block copolymers including star block copolymers, graft copolymers, miktoarm star copolymers, cyclic block copolymers, and other complex architectures are explained. Microphase separation drives BCPs to self-assemble, resulting in ordered nanostructures, including spheres, cylinders, gyroids, and lamellae, depending on the composition of the BCP. In nanotechnology, self-assembly (SA) underlies various types of molecular structures built from nanoparticles, nanotubes, or nanorods. Supramolecular structures generated from amphiphilic block copolymers are characterized by a slow rate of intermicellar chain exchange which makes them interesting for a variety of applications. Basic principles of self-assembly and micellization of block copolymers in dilute solution, methods for stabilization of the macromolecular aggregates, are discussed. Stabilized nanoparticles, the so-called “smart materials,” which show responses to environmental changes (pH, temperature, ionic strength, etc.), are presented with a focus on their applications.

Author: Axel H.E. Müller
Publisher: Springer Science & Business Media
ISBN: 364222296X
Category : Technology & Engineering
Languages : en
Pages : 216

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Book Description
Block Copolymer Surfactant Mixtures in Aqueous Solution: Can we Achieve Size and Shape Control by Co-Micellization?, by Thomas Hellweg; Non-ionic Thermoresponsive Polymers in Water, by Vladimir Aseyev, Heikki Tenhu and Françoise Winnik; From Coordination Polymers to Hierarchical Self-Assembled Structures, by Yun Yan, Arie de Keizer, Martien A. Cohen Stuart and Nicolaas A. M. Besseling; Processes of Ordered Structure Formation in Polypeptide Thin Film Solutions, by Ioan Botiz, Helmut Schlaad and Günter Reiter; Amphiphilic Polymers at Interfaces, by Katarzyna Kita-Tokarczyk, Mathias Junginger, Serena Belegrinou and Andreas Taubert;

Author: Roel Gronheid
Publisher: Woodhead Publishing
ISBN: 0081002610
Category : Technology & Engineering
Languages : en
Pages : 328

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Book Description
The directed self-assembly (DSA) method of patterning for microelectronics uses polymer phase-separation to generate features of less than 20nm, with the positions of self-assembling materials externally guided into the desired pattern. Directed self-assembly of Block Co-polymers for Nano-manufacturing reviews the design, production, applications and future developments needed to facilitate the widescale adoption of this promising technology. Beginning with a solid overview of the physics and chemistry of block copolymer (BCP) materials, Part 1 covers the synthesis of new materials and new processing methods for DSA. Part 2 then goes on to outline the key modelling and characterization principles of DSA, reviewing templates and patterning using topographical and chemically modified surfaces, line edge roughness and dimensional control, x-ray scattering for characterization, and nanoscale driven assembly. Finally, Part 3 discusses application areas and related issues for DSA in nano-manufacturing, including for basic logic circuit design, the inverse DSA problem, design decomposition and the modelling and analysis of large scale, template self-assembly manufacturing techniques. - Authoritative outlining of theoretical principles and modeling techniques to give a thorough introdution to the topic - Discusses a broad range of practical applications for directed self-assembly in nano-manufacturing - Highlights the importance of this technology to both the present and future of nano-manufacturing by exploring its potential use in a range of fields

Author: Axel H. E. Müller
Publisher: Springer Science & Business Media
ISBN: 3642224857
Category : Technology & Engineering
Languages : en
Pages : 263

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Book Description
Conformations and Solution Properties of Star-Branched Polyelectrolytes, by Oleg V. Borisov, Ekaterina B. Zhulina, Frans A. M. Leermakers, Matthias Ballauff and Axel H. E. Müller; Self-Assembled Structures of Amphiphilic Ionic Block Copolymers: Theory, Self-Consistent Field Modeling and Experiment, by Oleg V. Borisov, Ekaternia B. Zhulina, Frans A. M. Leermakers and Axel H. E. Müller; Interpolyelectrolyte Complexes Based on Polyionic Species of Branched Topology, by Dmitry V. Pergushov, Oleg V. Borisov, Alexander B. Zezin and Axel H. E. Müller; Co-assembly of Charged Copolymers as a Novel Pathway Towards Reversible Janus Micelles, by Ilja K. Voets, Frans A. Leermakers, Arie de Keizer, Marat Charlaganov and Martien A. Cohen Stuart; Fluorescence Spectroscopy as a Tool for Investigating the Self-Organized Polyelectrolyte Systems, by Karel Procházka, Zuzana Limpouchová, Filip Uhlík, Peter Košovan, Pavel Matejícek, Miroslav Štepánek, Mariusz Uchman, Jitka Kuldová, Radek Šachl, Jana Humpolícková, and M. Hof

Author: Sheng Zhong
Publisher:
ISBN: 9781124241562
Category : Block copolymers
Languages : en
Pages :

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Book Description
There is always an interest to understand how molecules behave under different conditions. One application of this knowledge is to self-assemble molecules into increasingly complex structures in a simple fashion. Self-assembly of amphiphilic block copolymer in solution has produced a large variety of nanostructures through the manipulation in polymer chemistry, assembly environment, and additives. Moreover, some reports suggest the formation of many polymeric assemblies is driven by kinetic process. The goal of this dissertation is to study the influence of kinetics on the assembly of block copolymer. The study shows kinetic control can be a very effective way to make novel polymeric nanostructures. Two examples discussed here are helical cylindrical micelles and patchy nanoparticles. Helical cylindrical micelles are made from the co-assembly of amphiphilic triblock copolymer poly(acrylic acid)- block -poly(methyl acrylate)- block -polystyrene and organoamine molecules in a mixture of tetrahydrofuran (THF) and water (H 2 O). This system has already shown promise of achieving many assembled structures. The unique aspects about this system are the use of amine molecules to complex with acid groups and the existence of cosolvent system. Application of amine molecules offers a convenient control over assembled morphology and the introduction of PMA-PS selective solvent, THF, promotes the mobility of the polymer chains. In this study, multivalent organoamine molecules, such as diethylenetriamine and triethylenetetramine, are used to interact with block copolymer in THF/water mixture. As expected, the assembled morphologies are dependent on the polymer architecture, selection and quantity of the organoamine molecules, and solution composition. Under the right conditions, unprecedented, multimicrometer-long, supramolecular helical cylindrical micelles are formed. Both single-stranded and double-stranded helices are found in the same system. These helical structures share uniform structural parameters, including the width of the micelles, width of the helix, and the pitch distance. There is no preference to the handedness, and both handednesses are observed, which is understandable since there are no chiral molecules or specific binding effects applied during the assembly. The helical structure is a product of kinetic process. Cryogenic transmission electron microscopy has been employed to monitor the morphological transformation. The study indicates there are two complicated but reproducible kinetic pathways to form the helices. One pathway involves the stacks of bended cylinders at early stages and the subsequent interconnection of these bended cylinders. Spherical micelles bud off of the interconnected nanostructure as the final step towards a defect-free helix. Another kinetic pathway shows very short helices are formed at first and aligned via head-to-tail style in the solution, and the subsequent sequential addition of these short helices results in prolonged mature helices. By using a ninhydrin-staining technique, amine molecules within the micellar corona are visualized and confirmed to preferentially locate in the inner side of the helical turns. The aggregation of amine molecules provides a strong attraction force due to electrostatic association between oppositely charged amine and acid groups and accumulation of hydrogen bonding among amine molecules to coil the cylindrical micelles into helical twisting features which are stabilized by the repulsion forces due to the chain packing frustration within the hydrophobic core, steric hindrance of amine molecules as well as the Coulomb repulsion of the excess charged amine groups. The formation mechanism of the helix offers the feasibility to manipulate the helical pitch distance and formation kinetics. The helical pitch distance can be enlarged or shrunk by varying the type and amount of amine molecules used in assembly, introducing inorganic salts, and changing pH. Luckily, the helical structure can be preserved permanently by inducing the amide reaction between amine and carboxylic acid groups. The kinetics of the helix is also subject to many factors, including used amine molecules, inorganic salts and preparation procedure. The aging time for the helix can be either reduced or prolonged. Furthermore, even though the helical formation is pathway-dependent, helical formation can still be triggered from extended cylindrical micelles or stacks of disklike micelles as long as a right condition is applied. Another strategy for kinetic assembly of block copolymer is presented as well. A novel patchy nanoparticle has been produced following this strategy. The patches are formed on the surface of polymeric colloids due to the phase separation of two chemically unlike segments. Certain level of mobility of the polymer chains is required for the blocks to segregate into patches. More importantly, the number and distribution geometry of the patches are related to the particle size. Future efforts are needed to control the particle size in order to manufacture uniform nanoparticles with desired patch patterns for the applications in nanotechnology, drug delivery and nanodevices.

Author: Ramanathan Nagarajan
Publisher: John Wiley & Sons
ISBN: 1119001366
Category : Science
Languages : en
Pages : 364

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Book Description
An introduction to the state-of-the-art of the diverse self-assembly systems Self-Assembly: From Surfactants to Nanoparticles provides an effective entry for new researchers into this exciting field while also giving the state of the art assessment of the diverse self-assembling systems for those already engaged in this research. Over the last twenty years, self-assembly has emerged as a distinct science/technology field, going well beyond the classical surfactant and block copolymer molecules, and encompassing much larger and complex molecular, biomolecular and nanoparticle systems. Within its ten chapters, each contributed by pioneers of the respective research topics, the book: Discusses the fundamental physical chemical principles that govern the formation and properties of self-assembled systems Describes important experimental techniques to characterize the properties of self-assembled systems, particularly the nature of molecular organization and structure at the nano, meso or micro scales. Provides the first exhaustive accounting of self-assembly derived from various kinds of biomolecules including peptides, DNA and proteins. Outlines methods of synthesis and functionalization of self-assembled nanoparticles and the further self-assembly of the nanoparticles into one, two or three dimensional materials. Explores numerous potential applications of self-assembled structures including nanomedicine applications of drug delivery, imaging, molecular diagnostics and theranostics, and design of materials to specification such as smart responsive materials and self-healing materials. Highlights the unifying as well as contrasting features of self-assembly, as we move from surfactant molecules to nanoparticles. Written for students and academic and industrial scientists and engineers, by pioneers of the research field, Self-Assembly: From Surfactants to Nanoparticles is a comprehensive resource on diverse self-assembly systems, that is simultaneously introductory as well as the state of the art.

Author: Stefan Guldin
Publisher: Springer
ISBN: 9783319032887
Category : Science
Languages : en
Pages : 0

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Book Description
Macromolecular self-assembly - driven by weak, non-covalent, intermolecular forces - is a common principle of structure formation in natural and synthetic organic materials. The variability in material arrangement on the nanometre length scale makes this an ideal way of matching the structure-function demands of photonic and optoelectronic devices. However, suitable soft matter systems typically lack the appropriate photoactivity, conductivity or chemically stability. This thesis explores the implementation of soft matter design principles for inorganic thin film nanoarchitectures. Sacrificial block copolymers and colloids are employed as structure-directing agents for the co-assembly of solution-based inorganic materials, such as TiO_2 and SiO_2. Novel fabrication and characterization methods allow unprecedented control of material formation on the 10 – 500 nm length scale, allowing the design of material architectures with interesting photonic and optoelectronic properties.

Author: Katsuhiko Ariga
Publisher: Elsevier
ISBN: 0323994733
Category : Technology & Engineering
Languages : en
Pages : 648

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Book Description
Materials Nanoarchitectonics: From Integrated Molecular Systems to Advanced Devices provides the latest information on the design and molecular manipulation of self-organized hierarchically structured systems using tailor-made nanoscale materials as structural and functional units. The book is organized into three main sections that focus on molecular design of building blocks and hybrid materials, formation of nanostructures, and applications and devices. Bringing together emerging materials, synthetic aspects, nanostructure strategies, and applications, the book aims to support further progress, by offering different perspectives and a strong interdisciplinary approach to this rapidly growing area of innovation. This is an extremely valuable resource for researchers, advanced students, and scientists in industry, with an interest in nanoarchitectonics, nanostructures, and nanomaterials, or across the areas of nanotechnology, chemistry, surface science, polymer science, electrical engineering, physics, chemical engineering, and materials science. - Offers a nanoarchitectonic perspective on emerging fields, such as metal-organic frameworks, porous polymer materials, or biomimetic nanostructures - Discusses different approaches to utilizing "soft chemistry" as a source for hierarchically organized materials - Offers an interdisciplinary approach to the design and construction of integrated chemical nano systems - Discusses novel approaches towards the creation of complex multiscale architectures