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Author: Li Yao Publisher: ISBN: Category : Block copolymers Languages : en Pages : 150
Book Description
This dissertation explores the use of block copolymers which can self-assemble into different morphologies as templates to fabricate nanostructured materials. The first section (Chapters 2-4) reports the formation of mesoporous silica films with spherical, cylindrical and bicontinuous pores up to 40 nm in diameter through replicating the morphologies of the solid block copolymer (BCP) templates, polystyrene-b-poly(tert-butyl acrylate) (PS-b-PtBA), via phase selective condensation of tetraethylorthosilicate in supercritical CO2. Next, directed self-assembly was used to control the orientation of cylindrical domains in PS-b-PtBA templates. Large-area aligned mesochannels in silica films with diameters tunable between 5 and 30 nm were achieved through the replication of oriented templates via scCO2 infusion. The long-range alignment of mesochannels was confirmed through GISAXS with sample stage azimuthal rotation. In the second section (Chapters 5-6), enantiopure tartaric acid was used as an additive to dramatically improve ordering in poly(ethylene oxide-block-tert-butyl acrylate) (PEO-b-PtBA) copolymers. Transmission electron microscopy (TEM), atomic force microscopy (AFM) and X-ray scattering were used to study the phase behavior and morphologies within both bulk and thin films. With the addition of a photo acid generator, photo-induced disorder in the PEO-b-PtBA/tartaric acid composite system was achieved upon UV exposure which deprotected the PtBA block to yield poly(acrylic acid) (PAA), which is phase-miscible with PEO. Area-selective UV exposure using a photo-mask was applied with the assistance of trace amounts of base quencher to achieve high-resolution hierarchical patterns. Helical superstructures were observed by TEM in this BCP/chiral additive system with 3D handedness confirmed by TEM tomography. In the last section (Chapter 7), ultra-high loadings of nanoparticles into target domains of block copolymer composites were achieved by blending the block copolymer hosts with small molecule additives that exhibit strong interactions with one of the polymer chain segments and with the nanoparticle ligands via hydrogen bonding. The addition of 40 wt% D-tartaric acid to poly(ethylene oxide-block-tert-butyl acrylate) (PEO-b-PtBA) enabled the loading of up to 150 wt% of 4-hydroxythiophenol functionalized Au nanoparticles relative to the mass of the target hydrophilic domain. This was equivalent to over 40% Au by mass of the resulting well ordered composite as measured by thermal gravimetric analysis.
Author: Li Yao Publisher: ISBN: Category : Block copolymers Languages : en Pages : 150
Book Description
This dissertation explores the use of block copolymers which can self-assemble into different morphologies as templates to fabricate nanostructured materials. The first section (Chapters 2-4) reports the formation of mesoporous silica films with spherical, cylindrical and bicontinuous pores up to 40 nm in diameter through replicating the morphologies of the solid block copolymer (BCP) templates, polystyrene-b-poly(tert-butyl acrylate) (PS-b-PtBA), via phase selective condensation of tetraethylorthosilicate in supercritical CO2. Next, directed self-assembly was used to control the orientation of cylindrical domains in PS-b-PtBA templates. Large-area aligned mesochannels in silica films with diameters tunable between 5 and 30 nm were achieved through the replication of oriented templates via scCO2 infusion. The long-range alignment of mesochannels was confirmed through GISAXS with sample stage azimuthal rotation. In the second section (Chapters 5-6), enantiopure tartaric acid was used as an additive to dramatically improve ordering in poly(ethylene oxide-block-tert-butyl acrylate) (PEO-b-PtBA) copolymers. Transmission electron microscopy (TEM), atomic force microscopy (AFM) and X-ray scattering were used to study the phase behavior and morphologies within both bulk and thin films. With the addition of a photo acid generator, photo-induced disorder in the PEO-b-PtBA/tartaric acid composite system was achieved upon UV exposure which deprotected the PtBA block to yield poly(acrylic acid) (PAA), which is phase-miscible with PEO. Area-selective UV exposure using a photo-mask was applied with the assistance of trace amounts of base quencher to achieve high-resolution hierarchical patterns. Helical superstructures were observed by TEM in this BCP/chiral additive system with 3D handedness confirmed by TEM tomography. In the last section (Chapter 7), ultra-high loadings of nanoparticles into target domains of block copolymer composites were achieved by blending the block copolymer hosts with small molecule additives that exhibit strong interactions with one of the polymer chain segments and with the nanoparticle ligands via hydrogen bonding. The addition of 40 wt% D-tartaric acid to poly(ethylene oxide-block-tert-butyl acrylate) (PEO-b-PtBA) enabled the loading of up to 150 wt% of 4-hydroxythiophenol functionalized Au nanoparticles relative to the mass of the target hydrophilic domain. This was equivalent to over 40% Au by mass of the resulting well ordered composite as measured by thermal gravimetric analysis.
Author: Massimo Lazzari Publisher: John Wiley & Sons ISBN: 3527610561 Category : Technology & Engineering Languages : en Pages : 447
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: Roel Gronheid Publisher: Woodhead Publishing ISBN: 0081002610 Category : Technology & Engineering Languages : en Pages : 328
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: Gity Mir Mohamad Sadeghi Publisher: Elsevier Inc. Chapters ISBN: 0128090847 Category : Technology & Engineering Languages : en Pages : 121
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: Dmitry Volodkin Publisher: MDPI ISBN: 3039285068 Category : Technology & Engineering Languages : en Pages : 186
Book Description
Nowadays, polymer self-assembly has become extremely attractive for both biological (drug delivery, tissue engineering, scaffolds) and non-biological (packaging, semiconductors) applications. In nature, a number of key biological processes are driven by polymer self-assembly, for instance protein folding. Impressive morphologies can be assembled from polymers thanks to a diverse range of interactions involved, e.g., electrostatics, hydrophobic, hots-guest interactions, etc. Both 2D and 3D tailor-made assemblies can be designed through modern powerful techniques and approaches such as the layer-by-layer and the Langmuir-Blodgett deposition, hard and soft templating. This Special Issue highlights contributions (research papers, short communications, review articles) that focus on recent developments in polymer self-assembly for both fundamental understanding the assembly phenomenon and real applications.
Author: Ramanathan Nagarajan Publisher: John Wiley & Sons ISBN: 1119001366 Category : Science Languages : en Pages : 364
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: Ian W. Hamley Publisher: John Wiley & Sons ISBN: Category : Science Languages : en Pages : 312
Book Description
This unique text discusses the solution self-assembly of block copolymers and covers all aspects from basic physical chemistry to applications in soft nanotechnology. Recent advances have enabled the preparation of new materials with novel self-assembling structures, functionality and responsiveness and there have also been concomitant advances in theory and modelling. The present text covers the principles of self-assembly in both dilute and concentrated solution, for example micellization and mesophase formation, etc., in chapters 2 and 3 respectively. Chapter 4 covers polyelectrolyte block copolymers - these materials are attracting significant attention from researchers and a solid basis for understanding their physical chemistry is emerging, and this is discussed. The next chapter discusses adsorption of block copolymers from solution at liquid and solid interfaces. The concluding chapter presents a discussion of selected applications, focussing on several important new concepts. The book is aimed at researchers in polymer science as well as industrial scientists involved in the polymer and coatings industries. It will also be of interest to scientists working in soft matter self-assembly and self-organizing polymers.
Author: Yi Ding (Ph.D.) Publisher: ISBN: Category : Languages : en Pages : 169
Book Description
Block copolymers (BCPs) are a class of soft materials consisting of two (or more) different chains joint together by covalent bond. This special chemical structure leads to microphase separation and consequently a variety of highly controllable self-assembly patterns. Directed self-assembly (DSA) of BCPs has therefore emerged as one of the most promising technologies to fabricate functional nanostructures and is able to produce patterns with ultra-small resolution (sub-10 nm) while maintaining high throughput and order. However, existing DSA methods depend mostly on carbon or silicon-based BCPs, thus lack functionality for sophisticated applications. This work aims at expanding the capability of DSA techniques by exploring new ways of incorporating functional materials into the BCP matrix and by imposing non-native symmetries on the BCP patterns. First, we focused on constructing nanocomposite thin films composed of BCPs and various types of functional materials (i.e., inorganic ions, inorganic-organic complex, organic compounds and nanoparticles). Based upon this methodology, we developed novel ways of fabricating mesoporous thin film structures with rectangular, triangular and quasicrystalline symmetries by means of graphoepitaxial post array templates. On the other hand, we also examined the limits of DSA by introducing artificial noise to mimic fabrication errors and studied the corresponding responses from BCP. This study demonstrates the potential of DSA of BCP in building thin film nanostructure of unconventional symmetries with functional components.
Author: Li Yao
Author: Li Yao
Author: Massimo Lazzari
Author: Roel Gronheid
Author: Gity Mir Mohamad Sadeghi
Author: Dmitry Volodkin
Author: Xinyu Wang
Author: Le Zhang
Author: Ramanathan Nagarajan
Author: Ian W. Hamley
Author: Yi Ding (Ph.D.)