[PDF] Directed Self Organization Of Polymer Grafted Nanoparticles In Polymer Thin Films eBook

Author : Ren Zhang (Chemical engineer)
Publisher :
Page : 157 pages
File Size : 14,91 MB
Release : 2016
Category : Ligands
ISBN :

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The controlled organization of nanoparticle (NP) constituents into superstructures of well-defined shape, composition and connectivity represents a continuing challenge in the development of novel hybrid materials for many technological applications. Surface modification of NPs with grafted polymer ligands has emerged as a versatile means to control the interaction and organization of particle constituents in polymer-matrix composite materials. In this study, by incorporating polymer-grafted nanoparticles (PGNPs) into polymeric thin films, we aim to understand and control the spatial organization of PGNPs through the interactions between polymer brush layer and matrix chains. As model systems, we investigate thermodynamic behaviors of polystyrene-tethered gold nanoparticles (denoted as AuPS) dispersed in polymer thin film matrices with identical and different chemical compositions (PS and PMMA, respectively), and evaluate the influence of external perturbation fields on directed organization of nanofillers.With the presence of unfavorable enthalpic interactions between grafted and free polymer chains (i.e. AuPS/ PMMA blend thin films), phase-separated structures are generated upon thermal annealing, characterized with morphologies ranging from discrete droplets to spinodal structures, which is consistent with composition-dependent classic binary polymer blends phase separation. The phase separation kinetics of AuPS/ PMMA blends exhibit distinct features compared to the parent PS/ PMMA homopolymer blends. We further illustrate phase-separated AuPS-rich domains can be directed into unidirectionally aligned anisotropic structures through soft-shear dynamic zone annealing (DZA-SS) process with tunable domain aspect ratios.To exert exquisite control over the shape, size and location of phase-separated PGNP domains, topographically patterned elastomer confinement is introduced to PGNP/ polymer blend thin films during thermal annealing. When the phase-separated lengthscale coincides with confined pattern dimension, long-range ordered submicron-sized AuPS domains are generated in PMMA matrices with dense and well-dispersed nanoparticle distribution. Furthermore, preferential segregation of AuPS nanoparticles at patterned mesa regions can be induced in PS matrices where enthalpic interactions are absent. This selective segregation is achieved due to the local perturbation of grafted chains when confined in a restricted space. The efficiency of this particle segregation process within patterned mesa-trench films can be tuned by changing the relative entropic confinement effects on grafted and matrix chains. This physical pattern directed PGNP organization strategy is applicable to versatile pattern geometries and nanoparticle compositions.

Author : Xiaoteng Wang
Publisher :
Page : 172 pages
File Size : 28,75 MB
Release : 2019
Category : Nanoimprint lithography
ISBN :

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Controlled dispersion and distribution of functional nanoparticles (NPs) in polymer matrix is prerequisite for improved properties of the composite materials. How to control the distribution of NPs in a facile manner remains to be a recurring challenge in the applications of polymer nanocomposites (PNCs). Surface functionalization of NPs with polymer brushes has emerged as an effective and versatile platform of tuning the interactions between the nanoparticles and the polymer hosts, allowing their integration into polymer nanocomposites. The current work aims to understand the phase behaviors of polymer-grafted nanoparticles (PGNPs) in polymer thin films and further control the spatial distribution of PGNPs through the interactions between the grafted and matrix polymer chains. In particular, polystyrene-grafted titanium dioxide nanoparticles (PS-TiO2) embedded in polystyrene (PS) thin film matrices having an initial film thickness h0 » 90 nm were investigated, where fluctuations in the grafting brush layer enables the formation of self-assembled PGNP clustering structures. Nanoimprinting directed lateral organization of the PGNP clusters in polymer thin films via topographically soft-pattern confinement was demonstrated. The PGNP clusters segregate to thicker film regions where they are less confined during thermal annealing. The partitioning of the PGNP clusters to the patterned regions was quantified by introducing the cluster partition coefficient Kc. It shows that the highly selective segregation of the clusters was driven by entropic driving forces while the film surface homogenization and shape transition of the clusters were induced by geometrical confinement of the nanopatterning. Simultaneously, the stability of the low molecular weight PS thin films is greatly enhanced against dewetting by the addition of PGNPs. The extent of the dewetting suppression depends on the PGNP concentration and can also be altered by nanopatterning. This form of soft pattern-directed self-assembly may boost colligative properties and provide enhanced and anisotropic optical such as UV-Vis, electronic and other material properties associated with organized NP clusters into precise large-scale patterns. With better understanding of the chemically identical blend systems, we further extend our model study to other PGNP/polymer blends where enthalpic interactions also participate in the phase behavior. The hybrid blend system composed of polystyrene-grafted silica nanoparticles in a poly (vinyl methyl ether) (PS-SiO2/PVME) blend thin film (≈100 nm) was studied where the brush and matrix polymers exhibit LCST type of phase behavior. Phase separation between the polymer-grafted nanoparticles (PGNPs) and matrix polymer occurs at a temperature ≈ 40° C lower than the LCST of classic binary linear PS/PVME polymer blends. Spatially organized PGNP domain structures on submicrometer scale were illustrated by introducing the symmetry-breaking soft elastomer pattern. Selective partition of the nanoparticles in both one-phase and two-phase regions can be obtained via nanoimprinting. Thermal cycling of the composite film through the critical temperature allows for thermodynamically reversible formation and dissolution of PGNP-rich domain structures. This nanoimprinting guided assembly of PGNPs in polymer nanocomposites would open pathways of novel hybrid materials for many technological applications such as responsive materials.

Author : Roel Gronheid
Publisher : Woodhead Publishing
Page : 328 pages
File Size : 29,73 MB
Release : 2015-07-17
Category : Technology & Engineering
ISBN : 0081002610

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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 : Ophelia Kwan Chui Tsui
Publisher : World Scientific
Page : 312 pages
File Size : 26,10 MB
Release : 2008
Category : Science
ISBN : 9812818820

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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.

Author : Danielle Grolman
Publisher :
Page : 164 pages
File Size : 36,13 MB
Release : 2017
Category : Cellulose nanocrystals
ISBN :

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Polymer nanocomposites have generated widespread interest towards the development of engineered multifunctional materials and novel hybrid assemblies for high performance applications. The addition of anisotropic nanofillers in a polymer matrix can potentially modify the material's optical, thermal, electrical, or mechanical properties due to the high surface area to volume ratio, with increasing advances and focused efforts toward the development of environmentally friendly, reinforced materials from sustainable resources. In this regard, cellulose nanocrystals (CNCs) are promising nanomaterials derived from the world's most abundant natural polymer. However, one of the key challenges and current barriers towards commercialization is controlling uniform dispersion within the polymer matrix in order to achieve effective reinforcement. The objective of this research aims to gain a fundamental understanding on how to control the dispersion and spatial organization of cellulose nanocrystals in polymer thin films by tailoring the thermodynamic interactions between the host polymer matrix and rod-like nanoparticles.The first part of this dissertation focuses on developing a facile strategy to manipulate the spatial distribution of cellulose nanocrystals in polymer thin films, which are highly susceptible to particle aggregation due to strong hydrogen bonding interactions. A model symmetric diblock copolymer poly(styrene-block-methyl methacrylate) (PS-b-PMMA) was utilized as an ideal nanostructured template to selectively sequester and organize the cellulose nanocrystals via directed self-assembly wherein the CNCs were subjected to a degree of confinement within the multilayered structure. The incorporation of anisotropic nanofillers was observed to perturb the block copolymer (BCP) morphology at relatively low nanofiller concentrations. Surface chemistry modification of the nanoparticle was employed to alter interparticle and particle-polymer interactions and subsequently control nanoparticle distribution. Furthermore, significant enhancement in the mechanical performance of these polymer nanocomposite systems were attributed to the multiscale interfacial interactions between the polymer matrix and fillers. To gain insight into the stabilization and wetting behavior of polymer nanocomposite thin films, the presence of anisotropic nanofillers in a polymer matrix was investigated on non-wetting, low surface energy substrates. Control measurements on the film morphology of homopolymer systems without nanoparticles exhibited immediate film rupture and dewetting due to unfavorable interactions between the substrate and polymer thin film. The addition of cellulose nanocrystals was observed to significantly retard dewetting kinetics and resulted in dewetting suppression where thin film stabilization was achieved at a critical particle threshold. These findings exploit the tunable wettability and nanoparticle-induced stabilization of nanoscale films without any required substrate modification which could have significant ramifications towards the development of novel functional coatings.

Author : Juan Rodríguez-Hernández
Publisher : Elsevier Inc. Chapters
Page : 108 pages
File Size : 21,70 MB
Release : 2013-11-28
Category : Technology & Engineering
ISBN : 012809088X

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The design of polymer blends constitutes an interesting alternative to obtaining micro- and nanostructured surfaces. The cost is reasonable and it is free from time-consuming procedures. Blending of polymers can yield materials with unprecedented properties that cannot be provided otherwise by using a single polymer. The free surface topography of polymer blend films, often related to phase domain structure, is critical to the applications. Two main aspects need to be considered in the preparation of multistructured blends: the interfaces involved and the morphology to be obtained. The control of these two aspects depends further on materials-related parameters involving the composition of the blend, the interfacial tension or viscosity ratio, and the processing conditions related to the temperature, time, or intensity of mixing, among others. Both domain structure and topography of the blend films have garnered increasing interest over the past decade. This chapter describes the nanomicrostructures formed at the polymer surface from polymer blends. Despite the crucial role that surfaces play in the final application of the material, up to now most of the studies concerning polymer blends have been related to the control of the mechanical properties (toughness, stiffness, thermal expansion, etc.), their barrier properties, or the electrical conductivity. This chapter focuses on the analysis of the structured polymer surfaces and thin films, giving an overview of the role of these structures on the final application. The principles of phase separation and the resulting structures formed are briefly discussed, followed by a wide overview of the possibilities of producing stimuli-responsive interfaces by introducing, among other things, pH- or temperature-responsive polymers within the blend. Finally, we look at how using particular preparation conditions and/or self-assembly of block copolymers, the formation of films and surfaces with hierarchical order length-scales can be induced. We also examine the main areas in which multiscale-ordered interfaces obtained from polymer blends have been applied.

Author :
Publisher :
Page : pages
File Size : 12,81 MB
Release : 2015
Category :
ISBN :

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Executive Summary Our work was devoted to understanding the structure and properties of a class of thin film polymer nanocomposites (PNCs). PNCs are composed of polymer hosts into which nanoparticles (metallic nanoparticles, quantum dots, nanorods, C60, nanotubes) are incorporated. PNCs exhibit a diverse range of functional properties (optical, electronic, mechanical, biomedical, structural), determined in part by the chemical composition of the polymer host and the type of nanoparticle. The properties PNCs rely not only on specific functional, size-dependent, behavior of the nanoparticles, but also on the dispersion, and organizational order in some cases, inter-nanoparticle separation distances, and on relative interactions between the nanoparticles and the host. Therefore the scientific challenges associated with understanding the interrelations between the structure and function/properties of PNCs are far more complex than may be understood based only on the knowledge of the compositions of the constituents. The challenges of understanding the structure-function behavior of PNCs are further compounded by the fact that control of the dispersion of the nanoparticles within the polymer hosts is difficult; one must learn how to disperse inorganic particles within an organic host. The goal of this proposal was to develop an understanding of the connection between the structure and the thermal (glass transition), mechanical and optical properties of a specific class of PNCs. Specifically PNCs composed of polymer chain grafted gold nanoparticles within polymer hosts. A major objective was to understand how to develop basic principles that enable the fabrication of functional materials possessing optimized morphologies and combinations of materials properties. Accomplishments: We developed: (1) fundamental principles that enabled the creation of thin film PNCs possessing more complex morphologies of homopolymers and block copolymer micellar systems [1-6]; (2) a new understanding of physical phenomena associated with the structure of PNC systems and the glass transition and dynamics [7-11], including surface dynamics [12, 13]; designed PNCs to understand the connection between structure and specific optical responses of the material [14, 15]; electrorheological phenomena [16-18]; coarsening/aggregation phenomena [19, 20]; directed assembly [21] and elastic mechanical properties of thin supported films [22]. We established procedures to design and control the spatial distribution of gold nanoparticles (Au-NP), onto which polystyrene (PS) chains were end-grafted, within thin film PS hosts.[1-3] We explained how enthalpic and entropic interactions between the grafted layers and the polymer host chains, the nanoparticle (NP) sizes and shapes determine the spatial distribution of NPs within the host (i.e.: the morphology). In brief, the chemistries of the grafted chains and the polymer hosts, the degrees of polymerization of grafted and host chains (N and P, respectively), and the surface grafting densities [Sigma] influence the thermodynamic interactions. Thin films are unique: the external interfaces (substrate and free surface) profoundly influence the spatial distribution of NPs within the PNC. For example, thin films are thermodynamically less stable than their bulk analogs due to the preferential attraction between the brush-coated nanoparticles and the external interfaces (i.e.: the free surface/polymer interface and the polymer/substrate interface). We investigated the organization of the brush-coated nanoparticles within a host composed on block copolymer micelles in a homopolymer [4, 5]. Block copolymers, composed of a polymer of type A that is bonded covalently to another polymer of type B (A-b-B) are known to form micelles within homopolymers A or B.A micelle is composed of an inner core of the A component of the copolymer and an outer corona of the B-component, that resides within homopolymer B, which serves as the host. If t ...

Author : Yue Zhang
Publisher :
Page : 45 pages
File Size : 37,37 MB
Release : 2017
Category : Nanoparticles
ISBN :

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Nowadays, the addition of nanoparticles (NPs) in polymer has attracted intensive attention because nanoparticles can bring some excellent properties to polymer materials. To get better control of the dispersion of NPs, polymer-grafted nanoparticle (PGNP) has been used in this work because the polymer ligands on the surface of NPs can give phase separation in the system. The phase separation behavior of bianary PGNP blend thin films has been investigated in this work. The blend thin film is composed of PS-g-SiO2 and PMMA-g-SiO2 nanoparticles. The phase-separated domain growth was slower than PGNP blends with shorter grafted chain lengths. With the application of capillary force lithography (CFL), more PMMA-g-SiO2 nanoparticles were segregated in imprinted trenches with longer thermal annealing time. In contrast, faster soft-shear cold-zone-annealing (CZA-SS) speed induced selective segregation of PMMA-g-SiO2 particles. The process under CFL is a wetting-driven process and that under CZA-SS is a shear-driven process.

Author : Xiaoteng Wang
Publisher :
Page : 75 pages
File Size : 29,27 MB
Release : 2016
Category : Nanocomposites (Materials)
ISBN :

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Polymer-nanoparticle (NP) composites have been studied extensively as a core material that exhibits advantageous optical, electrical and mechanical properties in nanotechnology. It has been well-established that a specific distribution state of nanoparticles in a polymer matrix is the key issue to optimize a desired polymer nanocomposite (PNC) property. However effective way of controlling the spatial distribution of nanoparticles is still a recurring challenge. Here we demonstrated facile processing approach to fabricate nanocomposite thin films with controlled nanoparticle dispersion state by exploiting the entropic interactions, thereby controlling the macroscopic performance of the material. The interactions of nanoparticles with polymers are mediated by the ligands attached to the nanoparticles. Location and dispersion of polystyrene grafted titanium dioxide (PS-g-TiO2) and hydroxyl-functionalized polyhedral oligomeric silsesquioxanes (DPOSS) molecular nanoparticles in homopolymer matrices under various annealing conditions were investigated. PS-g-TiO2 NP filled low molecular weight polystyrene thin films were thermally annealed under nanoscale pattern confinement, which was fabricated by imprinting digital recording media discs (DVD) pattern onto polydimethylsiloxane (PDMS). The NP dispersion changed from randomly distributed to aggregating at the elevated regions of the imprinted films due to the entropic interaction caused by the size difference between the particles and the matrix chains. DPOSS-PS is a type of giant shape amphiphiles which are built up by covalent bonding of molecular nanoparticles. When added to low molecular weight homopolymer matrices, DPOSS-PS nanoparticles exhibited better dispersion in PMMA than in PS matrix. Additionally, to understand the morphology transition and phase separation kinetics, various loading fraction of DPOSS-PS were incorporated into PMMA matrix. Phase separation at multiple length scales was observed when the composition of DPOSS-PS is in the range of 5% and 70%.

Author : Andreas Heilmann
Publisher : Springer Science & Business Media
Page : 236 pages
File Size : 20,24 MB
Release : 2003
Category : Medical
ISBN : 9783540431510

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This book presents an overview of nanostructure determination and ways to find relationships to the electronic and optical properties. The methods described can be applied to a large number of other granular metal-insulator systems and used as a guideline for characterisation and modelling. In addition, the book describes the manufacture of artificially structured nanomaterials using laser or electron-beam irradiation.