This book provides a comprehensive overview of the synthesis and characterization of nanocomposites based on block copolymers. Because of the self-assembly capability of block copolymers for the generation of nanostructures, besides their ability to nanostructure thermosetting matrices such as epoxy and polyester, binary or ternary nanocomposites can be prepared with different nanofillers such as nanoparticles and carbon nanotubes. The book starts with a review on nanocomposites based on block copolymers and nanoparticles synthesized with the use of surfactants, followed by a review on nanocomposites with metallic nanoparticles with polymer brushes and those with carbon nanotubes. A chapter is devoted to binary systems based on block copolymers and nanoparticles synthesized by sol-gel. A review on nanocomposites based on thermosetting matrices nanostructured with block copolymers (amphiphilic or chemically modified) is also presented for both epoxy and polyester resins. The work on ternary systems based on thermosetting matrices, block copolymers, and nanoparticles is presented next. The book concludes with a discussion on nanocomposites based on epoxy and block copolymers with azobenzene groups for optical purposes.

This book provides an overview of polymer nanocomposites and hybrid materials with polyhedral oligomeric silsesquioxanes (POSS). Among inorganic nanoparticles, functionalized POSS are unique nano-building blocks that can be used to create a wide variety of hybrid and composite materials, where precise control of nanostructures and properties is required. This book describes the influence of incorporation of POSS moieties into (organic) polymer matrices on the mechanical, thermal and flammability behavior of composites and hybrid organic-inorganic materials. Importantly, POSS-containing materials can be bio-functionalized by linking e.g. peptides and growth factors through appropriate surface modification in order to enhance the haemo-compatibility of cardiovascular devices made of these materials. This volume includes descriptions of synthesis routes of POSS and POSS-containing polymeric materials (e.g. based on polyolefines, epoxy resins and polyurethanes), presentation of POSS’ role as flame retardants and as biocompatible linker, as well as the depiction of decomposition and ageing processes.

As the conventional nanofabrication methods are reaching their limits of miniaturization, new methods are being studied to overcome this miniaturization challenge. Among the new emerging nanofabrication methods, bottom-up self assembly of Block Copolymers (BCPs) is gaining significant popularity among the researchers and the semiconductor industries. BCP self assembly has many advantages among which, low processing cost, high resolution, and large scale processing are the more prominent ones. Controlling the polymer fraction in the BCP mix leads to variety of different morphologies, these morphologies can be used to create nanofabrication masks and templates. A great amount of research has been conducted on how to control BCP morphologies. However, orientation of these BCP morphologies are very important and crucial to the nanofabrication technologies. Ideally, morphologies with perpendicular orientation to the surface of the substrate with very high aspect ratios are preferred for pattern transfer. To obtain this unique orientation many different methods have been studied, however in this research we employed a unique method to modify the surface energy of the substrate and create perpendicular morphologies for the BCP of PS-b-PMMA. Further, electron beam lithography was used to modify the properties of the PS-b-PMMA block copolymer in order to obtain different morphologies within the same BCP thin film.

Self-assembly of block copolymers (BCPs) is emerging as a promising route for numerous technological applications to fabricate a variety of nanoscopic structures. The resulting feature sizes range from a few to several hundred nanometers, and are readily tunable by varying the molecular weights of block copolymers. Directed self-assembly of block copolymer is an effective way to pattern periodic arrays of features with long-range order, to generate complex patterns, and to multiplicatively increase the pattern density and resolution that are far beyond the limit of conventional lithography. Despite of the significant progress in the area of directed self-assembly in recent years, critical research problems regarding the dimension scalability toward sub-10-nm regime and large feature sizes on hundreds of nanometers scale as well as the capability of generating complex device-oriented patterns remain challenging. In this thesis, BCP systems, including high-v BCPs that are capable of self-assembling into extreme small and large feature sizes as well as those with more complex block architectures, are identified and studied in order to understand how those materials may be processed and directed selfassembly to bridge the patterning size spectrum between nano- and micro-fabrication. Another focus is placed on the scientific exploration of directed self-assembly of triblock terpolymers and the investigation on the mechanisms that regulate the scaling and geometry of self-assembled patterns. A comprehensive understanding about self-assembly of BCP thin films will enable developing device-oriented geometries, manipulating BCPs phase behavior, and incorporating new functional materials for a wider range of applications. In the meanwhile, optimizing the processing condition of self-assembly of various BCPs is essential to confirm viability of the directed self-assembly of block copolymers process in manufacturing.

The "bottom-up" fabrication of functional hybrid material can be achieved by using directed self-assembly of functional nanoparticles (NP) and block copolymers (BCP) as templates. The versatile nanostructures of BCP provide possibilities to precisely control NPs spatial distribution and the resulting hybrid materials exhibit enhanced electrical, mechanical and optical functionalities. Three main topics related to BCP/NP composites are discussed in this dissertation: I) the spatial distribution of large NP in linear BCP; II) the morphology control of BCP templates with new architectures; and III) the magneto-optical properties of hybrid material using magnetic NPs. For well-ordered BCP/NP composite, the ratio of NP core diameter (dcore) and BCP domain width (L) has been generally limited with dcore/L 0.3 when BCP/NP interactions are relatively neutral or weak. By modifying the Au NPs with hydrogen bonding (H-bonding) donor group, the selective spatial distribution of Au NPs ranges in size up to 0.8 times that of the target domain width in symmetric polystyrene-block-poly (2-vinylpyridine) (PS-b-P2VP). In addition, H-bonding meditated 15 nm NPs can be directed by linear BCP of dsubcore/sub/L up to 0.4 at 20wt % loading. The H-bonding interactions between NP and BCP provide favorable enthalpic interaction to overcome the inherent entropy penalties mainly arising from polymer chain stretching upon the sequestration of large particles. On the other hand, the extensive chain entanglements of linear BCP still remain a challenge for hybrid materials with the consequence of long processing duration, many defects and lack of orientation. Bottlebrush BCPs (BBCPs) exhibit much lower degree of chain entanglement due to the highly extended confirmation. A systematic study was conducted to investigate the morphology transitions that occur in polystyrene-block-poly (ethylene oxide) (PS-b-PEO) BBCPs upon varying PEO volume fraction (fsubPEO/sub) from 22 % to 81 %. Either symmetric or asymmetric lamellar morphologies were observed in the BBCPs over an exceptionally wide range of fsubPEO/sub from 28 % to 72 %. A microphase transition temperature TsubMST/sub was observed over a temperature range of 150-180 °C. Finally, enhanced magneto-optical (MO) composites with excellent Faraday rotation (FR) response were fabricated using iron platinum (FePt) NPs and PS-b-P2VP linear BCP. Gallic acid (GA) functionalized FePt NPs with average dsubcore/sub from 1.9 to 9.3 nm were selectively incorporated into a P2VP domain through H-bonding interactions. The use of copolymer template to selectively arrange the magnetic NPs enabled high MO performance with limited trade-off of scattering loss, providing a simple strategy to prepare functional materials for MO applications. Verdet constants of a 10 wt % loaded 4.9 nm FePt NP composite reached absolute magnitudes as high as ~ -6x10sup4

Block copolymers represent an important class of multi-phase material, which have received very widespread attention, particularly since their successful commercial development in the mid-1960s. Much of the interest in these polymers has arisen because of their rather remarkable micro phase morphology and, hence, they have been the subject of extensive microstructural examination. In many respects, the quest for a comprehensive interpretation of their structure, both theoretically and experimentally, has not been generally matched by a corresponding enthusiasm for developing structure/property relationships in the context of their commercial application. Indeed, it has been left largely to the industrial companies involved in the development and utilization of these materials to fulfil this latter role. While it is generally disappointing that a much greater synergism does not exist between science and technology, it is especially sad in the case of block copolymers. Thus these materials offer an almost unique opportunity for the application of fundamental structural and property data to the interpretation of the properties of generally processed artefacts. Accordingly, in this book, the editor has drawn together an eminent group of research workers, with the specific intention of highlighting some of those aspects of the science and technology of block copolymers that are potentially important if further advances are to be made either in material formulation or utilization. For example, special consideration is given to the relationship between the flow properties of block copo lymers and their microstructure.

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.

Many researchers have studied the orientation behavior of block copolymers (BCPs) with the most recent works directed towards nanotechnologies. Self-assembly of block copolymers is very relevant in controlling periodic nanostructures for nanotechnological applications. Nanotechnological applications of BCPs are possible due to their physical properties related to mass and energy transport, as well as mechanical, electrical, and optical properties. These properties provide substantial benefits in nanostructure membranes, nanotemplates, photonic crystals, and high-density information storage media. In many applications, such nanopatterns need to be achieved as ordered and tunable structures. Consequently, the control of orientation of such structures with defect-free ordering on larger length scales still remain as major research challenge in many cases. In addition to their pure block forms, blends of copolymers with other polymers offer productive research areas in relation to nanostructural self-assembly. We prepared well-aligned nanocylinders into block copolymer over the enhanced sample area and scale of height without any external field applications or modification of interaction between the sample and the substrate. Self-assembled 3-dimensional perpendicular cylinder orientation was achieved mainly by blending of minority homopolymer into the blockcopolymer. Thus, this study investigated a spontaneous and simple method for the orientation of perpendicular cylinders in BCP/homopolymer mixtures on a preferential substrate, by increasing the interaction force between the homologous polymer pair at a fixed composition of minority block component. Since the thermodynamical changes have been simply accomplished by the control of incompatibility between the block components, the intrinsic advantages of block copolymer nanopatterning, such as fast and spontaneous 3-dimensional nanopatterning with a high thermodynamic stability and reproducibility, have been completely preserved in this fabrication strategy. By exploiting thermodynamical changes using temperature variation and by blending a homopolymer with well controlled molecular weight, we illustrated that redistribution of homopolymer resulted in a shift of phase boundaries and in the stabilization of well-ordered structures to create new opportunities for nanotechnologies.