Harrison, Mark B. J.
No description available.
Stimuli-Tailored Dispersion State of Aqueous Carbon Nanotube Suspensions and Solid Polymer NanocompositesEtika, Krishna 2010 December 1900 (has links)
Nanoparticles (such as, carbon nanotubes, carbon black, clay etc.) have one or more dimensions of the order of 100 nm or less. Owing to very high van der Waals force of attraction, these nanoparticles exist in a highly aggregated state. It is often required to break these aggregates to truly experience the “nanosize” effect for any required end use. There are several strategies proposed for dispersing/exfoliating nanoparticles but limited progress has been made towards controlling their dispersion state. The ability to tailor nanoparticle dispersion state in liquid and solid media can ultimately provide a powerful method for tailoring the properties of solution processed nanoparticle-filled polymer composites. This dissertation reports the use of a variety of stimuli-responsive polymers to control the dispersion state of single-walled carbon nanotubes. Stimuli-responsive polymers exhibit conformational transitions as a function of applied stimulus (like pH, temp, chemical etc.). These variations in conformations of the polymer can be used tailor nanotube dispersion state in water and solid composites.The use of pH and temperature responsive polymers to stabilize/disperse single walled carbon nanotubes (SWNTs) in water is presented. Non-covalent functionalization of SWNTs using pH and temperature responsive polymer show tailored dispersion state as a function of pH and temperature, respectively. Carbon nanotube microstructure in these aqueous suspensions was characterized using several techniques (cryo-TEM, viscosity measurements, uv-vis spectroscopy, zeta potential measurements and settling behavior). Furthermore, nanotube dispersion state in aqueous suspensions is preserved to a large extent in the composites formed by drying these suspensions as evidenced by SEM images and electrical conductivity measurements. Based on the results obtained a mechanism is proposed to explain the tailored dispersion of SWNTs as a functions of applied external stimulus (i.e., pH, temperature). Such stimuli-controlled dispersion of carbon nanotubes could have a variety of applications in nanoelectronics, sensing, and drug and gene delivery systems. Furthermore, this dissertation also contains a published study focused on controlling the dispersion state of carbon black (CB) in epoxy composites using clay.
Erb, Randall Morgan
<p>This thesis will investigate previously unexplored concepts in magnetic manipulation including controlling the assembly of magnetic and nonmagnetic particles either in bulk fluid or near a substrate. Both uniform glass interfaces and substrates with magnetic microstructures are considered. The main goal of this work is to discuss new strategies for implementing magnetic assembly systems that are capable of exquisitely controlling the positions and orientations of single-component as well as multi-component particle suspensions, including both magnetic and non-magnetic particles. This work primarily focuses on controlling spherical particles; however, there are also several demonstrations of controlling anisotropically shaped particles, such as microrods and Janus colloids. </p><p> Throughout this work, both conventional magnetophoresis and inverse magnetophoresis techniques were employed, the latter relying on ferrofluid, i.e. a suspension of magnetic nanoparticles in a nonmagnetic carrier fluid, which provides a strong magnetic permeability in the surrounding fluid in order to manipulate effectively non-magnetic materials. In each system it was found that the dimensionless ratio between magnetic energy and thermal energy could be successfully used to describe the degree of control over the positions and orientations of the particles. One general conclusion drawn from this work is that the ferrofluid can be modeled with a bulk effective permeability for length scales on the order of 100 nm. This greatly reduces modeling requirements since ferrofluid is a complex collection of discrete nanoparticles, and not a homogenous fluid. It was discovered that the effective magnetic permeability was often much larger than expected, and this effect was attributed to particle aggregation which is inherent in these systems. In nearly all cases, these interactions caused the ferrofluid to behave as though the nanoparticles were clustered with an effective diameter about twice the real diameter.</p><p> The principle purpose of this thesis is to present novel systems which offer the ability to manipulate and orient multi-component spherical or anisotropic particle suspensions near surfaces or in the bulk fluid. First, a novel chip-based technique for transport and separation of magnetic microparticles is discussed. Then, the manipulation of magnetic nanoparticles, for which Brownian diffusion is a significant factor, is explored and modeled. Parallel systems of nonmagnetic particles suspended in ferrofluid are also considered in the context of forming steady state concentration gradients. Next, systems of particles interacting with planar glass interfaces are analyzed, modeled, and a novel application is developed to study the interactions between antigen-antibody pairs by using the self-repulsion of non-magnetic beads away from a ferrofluid/glass interface. This thesis also focuses on studying the ability to manipulate particles in the bulk fluid. First, simple dipole-dipole aggregation phenomenon is studied in suspensions of both nonmagnetic polystyrene particles and endothelial cells. For the sizes of particles considered in these studies, currently accepted diffusion limited aggregation models could not explain the observed behavior, and a new theory was proposed. Next, this thesis analyzed the interactions that exist in multi-component magnetic and nonmagnetic particle suspensions, which led to a variety of novel and interesting colloidal assemblies. This thesis finally discusses the manipulation of anisotropic particles, namely, the ability to control the orientation of particles including both aligning nonmagnetic rods in ferrofluid as well as achieving near-holonomic control of Janus particles with optomagnetic traps. General conclusions of the viability of these techniques are outlined and future studies are proposed in the final chapter.</p> / Dissertation
Cho, Jae Kyu
29 July 2009
The studies of the dynamics, phase behavior, interparticle interactions, and hydrodynamics of stimuli-responsive pNIPAm-co-AAc microgels were described in this thesis. Due to their responsiveness to external stimuli, these colloidal particles serve as excellent model systems to probe the relationship between colloidal interactions and phase behavior. As a first step, we established our core experimental methodology, by demonstrating that particle tracking video microscopy is an effective technique to quantify various parameters in colloidal systems. Then we used the technique in combination with a microfluidic device that provides in situ control over sample pH to probe the phase behavior of pNIPAm-co-AAc microgel suspensions. In essence, the experimental set-up enables changes in effective particle volume fractions by changing pH, which can be used to construct the phase diagram. In order to explain the unique features of the microgel phase diagram, we measured the underlying pairwise interparticle potential of pNIPAm-co-AAc microgels directly in quasi-2D suspension and proved that the interactions are pH dependent and can range from weakly attractive to soft repulsive. Finally, the hindered Brownian diffusion due of colloidal particles confined by hard walls was investigated systematically and striking differences between hard sphere and soft sphere were found, with soft pNIPAm-co-AAc microgels showing surprising mobility even under strong confinement.
Rheology and structure of ceramic suspensions under constraints : a computational study / Rhéologie et structuration des suspensions céramiques sous contraintes : une étude numériqueLaganapan, Aleena Maria 26 November 2015 (has links)
L'enjeu principal de cette thèse est de comprendre et prédire les propriétés structurales et rhéologiques de suspensions colloïdales en tenant compte d'éléments complexes tels que (1) les interactions hydrodynamiques (IHs) et/ou (2) des forces extérieures. Nous employons dans cette thèse deux des techniques numériques les plus rapides de la littérature: la dynamique brownienne standard (BD), pour les systèmes où les IHs peuvent être ignorées; et la technique hybride "stochastic rotation dynamics - molecular dynamics" (SRD-MD), pour les systèmes où les IHs doivent être incorporées.Trois systèmes colloïdaux différents ont été étudiés. Le premier est un système de sphères dures soumis à un cisaillement, où le but a été de vérifier que l'introduction des IHs dans la SRD-MD peut correctement reproduire la relation entre la viscosité et la fraction volumique. Les résultats de viscosité sont en accord avec les résultats connus, qu'ils soient analytiques, numériques et expérimentaux. Le second système consiste en une suspension d'alumine, pour laquelle les interactions sont décrites par la théorie DLVO (Derjaguin-Landau-Verwey-Overbeek). Les simulations montrent que le seuil de percolation (phi_c) diminue lorsque la profondeur du puits de potentiel augmente. De plus, nous observons que la prise en compte des IHs tend à former des structures plus allongées également, par rapport aux structures obtenues sans les IHs. Les valeurs de phi_c obtenues dans les simulations sont en bon accord avec celles estimées par le modèle de la contrainte seuil (YODEL) établi par Flatt et Bowen. Le troisième système comporte deux types de colloïdes qui interagissent par un potentiel de Yukawa. Ce système binaire est soumis à l'influence d'un mur attractif. Nous montrons que la présence d'un mur attractif peut altérer la structure cristalline des agrégats à la surface telle qu'une structure de type CsCl qui se forme au lieu de la structure métastable de type NaCl. Finalement, nous avons réalisé une étude préliminaire par SRD-MD de suspensions soumises à un cisaillement oscillant. Nous montrons que lorsque la suspension est soumise au cisaillement oscillant en même temps que l'agrégation se produit, des structures plus compactes se forment. / The main objective of this thesis is to predict and understand the structural and rheological properties of colloidal suspensions when (1) hydrodynamic interactions (HIs) and/or (2) external forces are present. We employ two of the fastest techniques in literature: Brownian dynamics (BD), for systems without HIs; and the hybrid "stochastic rotation dynamics - molecular dynamics" (SRD-MD) for systems with HIs. Three different systems were studied. The first is a system of hard spheres subjected to shear, where the goal was to ensure that SRD-MD can correctly reproduce the viscosity vs. volume fraction relationship. The results are consistent with known analytical, numerical and experimental data. The second system is an alumina suspension described by the DLVO theory (Derjaguin-Landau-Verwey-Overbeek). The simulations show that the percolation threshold (phi_c) decreases as the depth of the potential well increases. Moreover, we note that HIs tend to form more elongated structures compared to the systems without HIs. The phi_c values obtained are in good agreement with those estimated by Flatt and Bowen's yield stress model (YODEL). The third system consists of binary colloids that interact by Yukawa potential and subjected to the influence of an attractive wall. We show that the presence of an attractive wall may alter the crystalline structures such that CsCl crystals are formed instead of the metastable NaCl crystals. Finally, we conducted a preliminary study of suspensions under an oscillating shear. We show that when the aggregation process suspension coincides with the oscillatory motion, more compact structures are formed.
Droplet-Based Approaches to Probe Complex Behavior in Colloidal Fluids with High Composition ResolutionBleier, Blake J. 01 May 2018 (has links)
In this work, microfluidic and millifluidic droplets are utilized to study and control complex fluid behavior with high composition resolution. Different techniques are used on two length scales to create unique approaches towards the same goal of merging droplet-based experiments with classical colloidal characterization experiments. First, a microfluidic dehydrating droplet device is characterized and a procedure established by concentrating a phase separating organic-inorganic system on chip and using geometric calculations to determine composition. The device is then expanded to a more complex, particle-polymer system to investigate suspension stability and interparticle behavior. A model system containing silica particles and PEO polymer is found to transition from a bridging flocculation mechanism to polymer-coated particle jamming based on the mass ratio of polymer to particle. Lastly, a phase separating particle-polymer system consisting of polystyrene particles and hydroxyethyl cellulose is concentrated on-chip. Interparticle interactions are controlled by varying particle size, polymer size, and polymer type and the effects on phase behavior are examined. Droplet experiments are scaled-up to millifluidic droplets and concentration gradients are used to produce high composition resolution in place of time, used in the dehydrating microfluidic experiments. A novel, millifluidic containment device is created to study aggregation and sedimentation in droplets containing carbon black and OLOA surfactant suspended in dodecane. A slow increase in stabilization behavior is observed as opposed to the previously observed sharp “on-off” effect. The droplet production technique is then improved to achieve more complex composition paths and the device is expanded for a small angle neutron scattering (SANS) application. SANS is performed on flowing droplets with varying concentration to map interparticle interactions and phase behavior of complex particulate systems. Feasibility of device is demonstrated and preliminary model systems of silica particles and polymer, salt, and surfactant are analyzed and characterized.
Theoretical and numerical calculations for the dynamics of colloidal suspensions of molecular particles in flowing solution inside mesoporesAtwi, Ali 02 May 2012 (has links) (PDF)
The purpose of this thesis is to develop a comprehensive model analysis in a three-dimensional spatial frame for the dynamics of molecular particles in dilute colloidal suspensions in solutions flowing inside pores of variable width, subject to hydrodynamic forces, Brownian motion and diffusive collisions at the rough pore boundaries, by using numerical simulations. The approach by simulations is necessary because it is extremely complex to use analytical tools at present to deal with the problem of diffusive collisions of the particles at the solid pore boundaries. The algorithms which we have developed and the corresponding simulations are sufficiently general and refined to be directly applied to the study of the dynamics of a wide variety of polymer and biological particles in dilute solutions under diverse physical and applicable hydrodynamic conditions inside pores. Moreover, the mechanisms leading to the adhesion of particles of nano sizes under what would be non-equilibrium conditions, due to the conflicting influence of the mechanical diffusive collisions and the attractive Hamaker forces at the boundaries, are of major interest. We have hence investigated a theoretical model to calculate the restitution coefficient from basic physical principles. The objective is to quantify the energy balance during the process of a diffusive collision of a nano particle under the influence of the repulsive forces on one hand, and the attractive Hamaker forces acting on the nano particle on the other. This is done by developing a model, based on the JKR and Hertz theories, to account for the energy losses during collisions, and for the energy gains due to the Hamaker interactions. Adhesion becomes an outcome if the energy balance permits this. Our theoretical model is developed by proposing a special analytic approach based on the Hamaker potential. We derive from the theoretical analysis a characteristic nonlinear equation for the restitution coefficient, and analyze its properties which determine under given physical conditions the outcome for adhesion or not.
Nouvelles fonctionnalités de copolymères en brosse dans les suspensions minérales concentrées / New functionalities of bottlebrush copolymers in concentrated mineral suspensionsPellet, Charlotte 30 October 2015 (has links)
La thèse porte sur une nouvelle classe de polymères à architecture en brosse, synthétisés à l'échelle industrielle et utilisés comme additifs dans les suspensions colloïdales pour le couchage du papier. Le polymère en brosse contrôle la déshydratation et le séchage des suspensions ce qui permet d'obtenir des revêtements d'une qualité incomparable. L'objectif est de modéliser sur un plan fondamental le rôle fonctionnel des polymères en relation avec les performances en application. Dans une première partie nous étudions leurs propriétés physicochimiques, structurales et rhéologiques en solution en discutant les spécificités dues à l'architecture en brosse. Dans une seconde partie nous analysons à l'aide d'un dispositif expérimental original les propriétés de rétention d'eau apportées par les polymères. Dans une troisième partie nous étudions le séchage de suspensions de carbonate de calcium sur des substrats solides, qui conduit en général à des motifs hétérogènes dits en " anneau de café ". Nous avons découvert que les polymères en brosse à très faible concentration suppriment ces défauts de séchage de façon remarquable. Le nouveau mécanisme physique à l'¿uvre, que nous appelons effet Marangoni auto-induit, résulte des propriétés interfaciales des polymères et de leurs interactions spécifiques avec les particules de carbonate de calcium. Pour conclure nous établissons un lien entre les propriétés de rétention d'eau et l'inhibition des défauts de séchage. Nous démontrons alors le caractère générique de nos résultats en les transposant à une suspension biologique, le sang, où les polymères pourraient présenter un intérêt dans le traitement de pathologies cardiovasculaires. / This work focuses on a new class of bottlebrush polymers, synthesized on an industrial scale and used as additives in colloidal suspensions for paper coatings. The bottlebrush polymer controls the dehydration and drying of the suspensions, and leads to coatings of outstanding quality. Our aim is to model the functional role of these polymers from a fundamental perspective in relation with applicative performances. In a first part we study their physicochemical, structural and rheological properties in solution, emphasizing the specificities due to the brush architecture. In a second part we implement an original experimental setup to analyze the water retention properties brought by the polymers. In a third part we study the drying of calcium carbonate suspensions on solid substrates, which in general forms to heterogeneous patterns called “coffee-rings”. We discovered that at very low concentration, bottlebrush polymers remarkably suppress these defects. We call auto-induced Marangoni effect the new physical mechanism at work. It results from the interfacial properties of the polymers and their specific interactions with calcium carbonate particles. To conclude, we establish a link between water retention properties and drying defect inhibition. We demonstrate the generic character of our results which can be transposed to a biological suspension, blood, where these polymers could be of interest for cardiovascular disease treatment.
The fabrication of structurally coloured textile materials using uniform spherical silica nanoparticlesGao, Weihong January 2016 (has links)
Natural precious opals consist of silica nanoparticles of uniform diameter organised in a periodic three-dimensional structure. The physical structure of the material produces the perceived colour by a process of light diffraction. The modification of light by the physical structure of the material is also known as structural colour. This is a different process from how most surface colours are produced where light is more usually absorbed by dye and/or pigment molecules. Desirable aesthetic qualities could be achieved if the structural colours produced by natural opals could be replicated in the form of a film or a coating on textile substrates. The work presented investigates how to produce structurally coloured textiles using surface applications of uniform spherical silica nanoparticles (USSNPs). A novel one-step solvent varying (SV) technique has been developed to synthesise USSNPs with particle diameters in a controlled size range. Using suspensions containing USSNPs, structurally coloured artificial opal (AO) films have been fabricated by self-assembly using a process of natural gravity sedimentation. The sedimentation of a particular particle size range of USSNPs (from which a coloured film was produced), onto the surface of fabrics, produced a structurally coloured fabric. By controlling the mean particle diameter a wide range of spectral colours from red to blue was obtained. The light fastness properties of the coloured textiles were investigated. A further surface modification of USSNPs was performed by adding vinyl functional groups to improve the mechanical strength of the structural colour. This work suggested a novel approach to colouring textile materials without using traditional dyes and/or pigments.
03 September 2015
No description available.
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