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This primer introduces the theory of self-assembly of block polymers, most notably self-consistent field theory (SCFT). Block polymer self-assembly is a fascinating and highly interdisciplinary topic. This primer can be read at several levels, depending on what readers want to get out of it. Readers who want an overview of self-assembly in block polymer and what SCFT says about the process can read Chapters 1-3 and skip to Chapter 7 to see the open questions. If the reader is further interested in the output of SCFT calculations but not how those outputs are generated, they should read Chapter 6 as well. But if the reader wants to learn how to do the SCFT calculations themselves, Chapters 4 and 5 offer an accessible introduction to the theory and numerical methods, providing an excellent entry point into the literature. This primer includes data that the authors have computed using SCFT. All calculations use the open-source software package Polymer Self-Consistent Field (PSCF), developed by David Morse at the University of Minnesota. Take breaks from reading to watch ten “Insider Q&A” videos included throughout, which offer additional insight from experts in the field, such as An-Chang Shi, Chinedum O. Osuji, Frank S. Bates, Christopher M. Bates, Glenn H. Fredrickson, and Lisa Hall. Furthermore, this primer includes multiple features to aid and enhance readers’ learning. “That’s a Wrap” summarizes key concepts at the end of each chapter, while “Read These Next” suggests references that may interest further reading. A pop-up glossary ensures readers have definitions as needed throughout the primer.
It is the belief of the editors of this book that the recognition of block copolymers as being amphiphilic molecules and sharing common features with other well-studied amphiphiles will prove beneficial to both the surfactant and the polymer communities. An aim of this book is to bridge the two communities and cross-fertilise the different fields. To this end, leading researchers in the field of amphiphilic block copolymer self-assembly, some having a background in surfactant chemistry, and others with polymer physics roots, have agreed to join forces and contribute to this book.The book consists of four entities. The first part discusses theoretical considerations behind the block copolymer self-assembly in solution and in the melt. The second part provides case studies of self-assembly in different classes of block copolymers (e.g., polyethers, polyelectrolytes) and in different environments (e.g., in water, in non-aqueous solvents, or in the absence of solvents). The third part presents experimental tools, ranging from static (e.g., small angle neutron scattering) to dynamic (e.g., rheology), which can prove valuable in the characterization of block copolymer self-assemblies. The fourth part offers a sampling of current applications of block copolymers in, e.g., formulations, pharmaceutics, and separations, applications which are based on the unique self-assembly properties of block copolymers.
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.
1 N. Hadjichristidis, M. Pitsikalis, H. Iatrou: Synthesis of Block Copolymers.- 2 V. Abetz: Phase Behaviour and Morphologies of Block Copolymers.-
It is the belief of the editors of this book that the recognition of block copolymers as being amphiphilic molecules and sharing common features with other well-studied amphiphiles will prove beneficial to both the surfactant and the polymer communities. An aim of this book is to bridge the two communities and cross-fertilise the different fields. To this end, leading researchers in the field of amphiphilic block copolymer self-assembly, some having a background in surfactant chemistry, and others with polymer physics roots, have agreed to join forces and contribute to this book. The book consists of four entities. The first part discusses theoretical considerations behind the block copolymer self-assembly in solution and in the melt. The second part provides case studies of self-assembly in different classes of block copolymers (e.g., polyethers, polyelectrolytes) and in different environments (e.g., in water, in non-aqueous solvents, or in the absence of solvents). The third part presents experimental tools, ranging from static (e.g., small angle neutron scattering) to dynamic (e.g., rheology), which can prove valuable in the characterization of block copolymer self-assemblies. The fourth part offers a sampling of current applications of block copolymers in, e.g., formulations, pharmaceutics, and separations, applications which are based on the unique self-assembly properties of block copolymers.
Ch. 1. Block copolymer thin films / J.-Y. Wang, S. Park and T. P. Russell -- ch. 2. Equilibration of block copolymer films on chemically patterned surfaces / G. S. W. Craig, H. Kang and P. F. Nealey -- ch. 3. Structure formation and evolution in confined cylinder-forming block copolymers / G. J. A. Sevink and J. G. E. M. Fraaije -- ch. 4. Block copolymer lithography for magnetic device fabrication / J. Y. Cheng and C. A. Ross -- ch. 5. Hierarchical structuring of polymer nanoparticles by self-organization / M. Shimomura ... [et al.] -- ch. 6. Wrinkling polymers for surface structure control and functionality / E. P. Chan and A. J. Crosby -- ch. 7. Crystallization in polymer thin films: morphology and growth / R. M. Van Horn and S. Z. D. Cheng -- ch. 8. Friction at soft polymer surface / M. K. Chaudhury, K. Vorvolakos and D. Malotky -- ch. 9. Relationship between molecular architecture, large-strain mechanical response and adhesive performance of model, block copolymer-based pressure sensitive adhesives / C. Creton and K. R. Shull -- ch. 10. Stability and dewetting of thin liquid films / K. Jacobs, R. Seemann and S. Herminghaus -- ch. 11. Anomalous dynamics of polymer Films / O. K. C. Tsui.
Block copolymers have been subject of tremendous research interest owing to their capability of undergoing self-assembly which allows them to tailor their electrical, optical, and mechanical properties. Statistical mechanics of flexible block copolymers is well understood. However, there are many unresolved issues with confinement of block copolymers as well as structure formation in block copolymers having non-flexible polymer blocks. We develop mean field theory models to address the issues arising in thermodynamics of such complex block copolymers. Also, we develop theoretical formalisms to understand the link between morphology and macroscopic properties in these block copolymers. We study the stability and ordering in thin films of flexible diblock copolymer in the presence of compressible solvent using a combined polymer mean field theory and lattice gas model for binary fluid mixtures. We utilize mean field theory model to understand the self-assembly behavior in side-chain liquid crystalline block copolymers which involve interplay between microphase separation and liquid crystalline ordering of side chain mesogenic units. We extend the field theoretic models for block copolymer to account for self-assembly in semicrystalline block copolymers. The semicrystalline chain is modeled as a semiflexible chain having non-bonded attractions between parallel bonds. We characterize the structure formation in such block copolymers as a function of the rigidity of the semicrystalline chain. Then we extend the formalism to study semicrystalline triblock and pentablock copolymers and evaluate bridging fractions in different sequences of semicrystalline multiblock copolymers. Rod-coil block copolymers have a flexible polymer covalently linked to rigid polymer. Such polymers have potential applications as organic LEDs and photovoltaic devices. We study the self-assembly of such block copolymer under confinement. To make these block copolymers viable as photovoltaic devices, we performed the photovoltaic modeling of devices based on self-assembly of block copolymers. We characterize the interplay between self-assembly and anisotropy of charge transport (arising due to rigid polymer chains) in determining the eventual photovoltaic properties.
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.
Spontaneous self-assembly of materials is a phenomenon exhibited by different molecular systems. Among many, Block copolymers (BCPs) proved to be particularly interesting due to their ability to microphase separate into periodic domains. Nonetheless, the rising need for arbitrary, complex, 3D nanoscale morphology shows that what is commonly achievable is quite limited. Expanding the range of BCPs morphologies could be attained through the implementation of a host of strategies that could be used concurrently. Using directed self-assembly (DSA), a sphere forming BCP was assembled in a randomly displaced post template to study system resilience towards defect creation. Template shear-like distortion seemed to govern local defect generation. Defect clusters with symmetries compatible with that of the BCP showed enhanced stability. Using 44 and 32434 Archimedean tiling templates that are incompatible with BCP six-fold symmetry created low symmetry patterns with an emergent behavior dependent on pattern size and shape. A variation of DSA is studied using modulated substrates. Layer-by-layer deposition of cylinder forming BCPs was investigated. Self-consistent field theory (SCFT) and strong segregation theory SST were employed to provide the understanding and the conditions under which particular orientations of consecutive layers were produced. Furthermore, deep functionalized trenches were employed to create vertically standing high-[chi] BCP structures. Changing annealing conditions for a self-assembled lamellar structure evolved the assembled pattern to a tubular morphology that is non-native to diblock copolymers. A rather fundamental but challenging strategy to go beyond the standard motifs common to BCPs is to synthesize multiblock molecules with an expanded design space. Triblock copolymers produced bilayer perforated lamellar morphology. SCFT analysis showed a large window of stability of such structures in thin films. In addition, a model for bottlebrush BCPs (BBCPs) was constructed to investigate the characteristics of BBCPs self-assembly. Pre-stacked diblock sidechains showed improved microphase separation while providing domain spacing relevant to lithography applications. A rich phase diagram was constructed at different block concentrations. The ability to explore new strategies to discover potential equilibrium morphologies in BCPs is supported by strong numerical modeling and simulations efforts. Accelerating SCFT performance would greatly benefit BCP phase discovery. Preliminary work discussed the first attempt to Neural Network (NN) assisted SCFT. The use of NN was able to cut on the required calculations steps to reach equilibrium morphology, demonstrating accelerated calculation, and escaping trapped states, with no effect on final structure.