DIFFUSE-INTERFACE FIELD APPROACH TO MODELING SELF-ASSEMBLY OF HETEROGENEOUS COLLOIDAL SYSTEMS AND RELATED DIPOLE-DIPOLE INTERACTION PHENOMENA

Colloid self-assembly under external control is a new route to fabrication of advanced materials with novel microstructures and appealing functionalities. The kinetic processes of colloidal self-assembly have attracted great interests also because they are similar to many atomic level kinetic processes of materials. In the past decades, rapid technological progresses have been achieved on producing shape-anisotropic, patchy, core-shell structured particles and particles with electric/magnetic charges/dipoles, which greatly enriched the self-assembled structures. Multi-phase carrier liquids offer new route to controlling colloidal self-assembly. Therefore, heterogeneity is the essential characteristics of colloid system, while so far there still lacks a model that is able to efficiently incorporate these possible heterogeneities. This thesis is mainly devoted to development of a model and computational study on the complex colloid system through a diffuse-interface field approach (DIFA), recently developed by Wang et al. This meso-scale model is able to describe arbitrary particle shape and arbitrary charge/dipole distribution on the surface or body of particles. Within the framework of DIFA, a Gibbs-Duhem-type formula is introduced to treat Laplace pressure in multi-liquid-phase colloidal system and it obeys Young-Laplace equation. The model is thus capable to quantitatively study important capillarity related phenomena. Extensive computer simulations are performed to study the fundamental behavior of heterogeneous colloidal system. The role of Laplace pressure is revealed in determining the mechanical equilibrium of shape-anisotropic particles at fluid interfaces. In particular, it is found that the Laplace pressure plays a critical role in maintaining the stability of capillary bridges between close particles, which sheds light on a novel route to in situ firming compact but fragile colloidal microstructures via capillary bridges. Simulation results also show that competition between like-charge repulsion, dipole-dipole interaction and Brownian motion dictates the degree of aggregation of heterogeneously charged particles. Assembly and alignment of particles with magnetic dipoles under external field is studied. Finally, extended studies on the role of dipole-dipole interaction are performed for ferromagnetic and ferroelectric domain phenomena. The results reveal that the internal field generated by dipoles competes with external field to determine the dipole-domain evolution in ferroic materials.

Molecular Modeling of PMR-15 Polyimide

PMR-15 polyimide is a polymer that is used as a matrix in composites. These composites with PMR-15 matrices are called advanced polymer matrix composite that is abundantly used in the aerospace and electronics industries because of its high temperature resistivity. Apart from having high temperature sustainability, PMR-15 composites also display good thermal-oxidative stability, mechanical properties, processability and low costs, which makes it a suitable material for manufacturing aircraft structures. PMR-15 uses the reverse Diels-Alder (RDA) method for crosslinking which provides it with the groundwork for its distinctive thermal stability and a range of 280-300 degree Centigrade use temperature. Regardless of such desirable properties, this material has a number of limitations that compromises its application on a large scale basis. PMR-15 composites has been known to be very vulnerable to micro-cracking at inter and intra-laminar cracking. But the major factor that hinders its demand is PMR-15's carcinogenic constituent, methylene dianilineme (MDA), also a liver toxin. The necessity of providing a safe working environment during its production adds up to the cost of this material. In this study, Molecular Dynamics and Energy Minimization techniques are utilized to simulate a structure of PMR-15 at a given density of 1.324 g/cc and an attempt to recreate the polyimide to reduce the number of experimental testing and hence subdue the health hazards as well as the cost involved in its production. Even though this study does not involve in validating any mechanical properties of the model, it could be used in future for the validation of its properties and further testing for different properties like aging, microcracking, creep etc.

COMPUTATIONAL STUDY OF MICROSTRUCTURE-PROPERTYMECHANISM RELATIONS IN FERROIC COMPOSITES

Ferroic materials, as notable members of smart materials, have been widely used in applications that perform sensing, actuation and control. The macroscopic property change of ferroic materials may become remarkably large during ferroic phase transition, leading to the fact that the macroscopic properties can be tuned by carefully applying a suitable external field (electric, magnetic, stress). To obtain an enhancement in physical and/or mechanical properties, different kinds of ferroic composites have been fabricated. The properties of a ferroic composite are determined not only by the properties and relative amounts of the constituent phases, but also by the microstructure of individual phase such as the phase connectivity, phase size, shape and spatial arrangement. This dissertation mainly focuses on the computational study of microstructure – property – mechanism relations in two representative ferroic composites, i.e., two-phase particulate magnetoelectric (ME) composite and polymer matrix ferroelectric composite. The former is a great example of ferroic composite exhibiting a new property and functionality that neither of the constituent phases possesses individually. The latter well represents the kind of ferroic composites having property combinations that are better than the existing materials. Phase field modeling was employed as the computing tool, and the required models for ferroic composites were developed based on existing models for monolithic materials. Extensive computational simulations were performed to investigate the microstructure-property relations and the underlying mechanism in ferroic composites. In particulate, it is found that for ME composite 0-3 connectivity (isolated magnetostrictive phase) is necessary to exhibit ME effect, and small but finite electrical conductivity of isolated magnetic phase can beneficially enhance ME effect. It is revealed that longitudinal and transverse ME coefficients of isotropic 0-3 particulate composites can be effectively tailored by controlling magnetic domain structures without resort to anisotropic two-phase microstructures. Simulations also show that the macroscopic properties of the ferroelectricpolymer composites critically depend on the ferroelectric phase connectivity while are not sensitive to the sizes and internal grain structures of the ceramic particles. Texturing is found critical to exploit the paraelectric«ferroelectric phase transition and nonlinear polarization behavior in paraelectric polycrystal and its polymer matrix composite. Additionally, a Diffuse Interface Field model was developed to simulate packing and motion in liquid phase which is promising for studying the fabrication of particulatepolymer composites.

Faulted Structures in Li Ion Exchanged NaMO2 (M=Ni(0.25)Mn(0.75))

A family of LiMO2 materials (M=Ni0.25Mn0.75) was prepared from Na1.2-xLixMO∂ precursors (0≤x≤0.6) via ion exchange. The resulting IE products were examined via XRD and compared to simulated XRD patterns produced using DIFFax to determine the defect structures resulting from the IE process. For the 0.1≤x≤0.6 materials, it is observed that there are 3 LiMO2 sub-phases with different Li contents present. As the amount of Li in the precursor increases, the amount of each phase changes resulting in a net shift to higher 2-theta; corresponding to an overall decrease in lattice parameter, approaching the theoretical values for LiMO2. Additionally, as x increases, the probability of O3-type shifting increases, most likely due to an increase in the amount O3-Li2MO3 minority phase which acts to weaken bonds in the TM layer, allowing the O3 shift to occur more easily. For the x=0 IE product, it was seen that the product had an ~O2-type structure, but with lattice parameters closer to those expected for a NaMO2 material.

The Processing of Aluminum Gasarites via Thermal Decomposition of Interstitial Hydrides

Gasarite structures are a unique type of metallic foam containing tubular pores. The original methods for their production limited them to laboratory study despite appealing foam properties. Thermal decomposition processing of gasarites holds the potential to increase the application of gasarite foams in engineering design by removing several barriers to their industrial scale production. The following study characterized thermal decomposition gasarite processing both experimentally and theoretically. It was found that significant variation was inherent to this process therefore several modifications were necessary to produce gasarites using this method. Conventional means to increase porosity and enhance pore morphology were studied. Pore morphology was determined to be more easily replicated if pores were stabilized by alumina additions and powders were dispersed evenly. In order to better characterize processing, high temperature and high ramp rate thermal decomposition data were gathered. It was found that the high ramp rate thermal decomposition behavior of several hydrides was more rapid than hydride kinetics at low ramp rates. This data was then used to estimate the contribution of several pore formation mechanisms to the development of pore structure. It was found that gas-metal eutectic growth can only be a viable pore formation mode if non-equilibrium conditions persist. Bubble capture cannot be a dominant pore growth mode due to high bubble terminal velocities. Direct gas evolution appears to be the most likely pore formation mode due to high gas evolution rate from the decomposing particulate and microstructural pore growth trends. The overall process was evaluated for its economic viability. It was found that thermal decomposition has potential for industrialization, but further refinements are necessary in order for the process to be viable.

PARAMETRIC STUDY OF REAXFF SIMULATION PARAMETERS FOR MOLECULAR DYNAMICS MODELING OF REACTIVE CARBON GASES

Abstract The development of innovative carbon-based materials can be greatly facilitated by molecular modeling techniques. Although the Reax Force Field (ReaxFF) can be used to simulate the chemical behavior of carbon-based systems, the simulation settings required for accurate predictions have not been fully explored. Using the ReaxFF, molecular dynamics (MD) simulations are used to simulate the chemical behavior of pure carbon and hydrocarbon reactive gases that are involved in the formation of carbon structures such as graphite, buckyballs, amorphous carbon, and carbon nanotubes. It is determined that the maximum simulation time step that can be used in MD simulations with the ReaxFF is dependent on the simulated temperature and selected parameter set, as are the predicted reaction rates. It is also determined that different carbon-based reactive gases react at different rates, and that the predicted equilibrium structures are generally the same for the different ReaxFF parameter sets, except in the case of the predicted formation of large graphitic structures with the Chenoweth parameter set under specific conditions.

An Investigation of Waste Glass-Based Geopolymers Supplemented with Alumina

An increased consideration of sustainability throughout society has resulted in a surge of research investigating sustainable alternatives to existing construction materials. A new binder system, called a geopolymer, is being investigated to supplement ordinary portland cement (OPC) concrete, which has come under scrutiny because of the CO2 emissions inherent in its production. Geopolymers are produced from the alkali activation of a powdered aluminosilicate source by an alkaline solution, which results in a dense three-dimensional matrix of tetrahedrally linked aluminosilicates. Geopolymers have shown great potential as a building construction material, offering similar mechanical and durability properties to OPC. Additionally, geopolymers have the added value of a considerably smaller carbon footprint than OPC. This research considered the compressive strength, microstructure and composition of geopolymers made from two types of waste glass with varying aluminum contents. Waste glass shows great potential for mainstream use in geopolymers due to its chemical and physical homogeneity as well as its high content of amorphous silica, which could eliminate the need for sodium silicate. However, the lack of aluminum is thought to negatively affect the mechanical performance and alkali stability of the geopolymer system. Mortars were designed using various combinations of glass and metakaolin or fly ash to supplement the aluminum in the system. Mortar made from the high-Al glass (12% Al2O3) reached over 10,000 psi at six months. Mortar made from the low-Al glass (<1% Al2O3) did not perform as well and remained sticky even after several weeks of curing, most likely due to the lack of Al which is believed to cause hardening in geopolymers. A moderate metakaolin replacement (25-38% by mass) was found to positively affect the compressive strength of mortars made with either type of glass. Though the microstructure of the mortar was quite indicative of mechanical performance, composition was also found to be important. The initial stoichiometry of the bulk mixture was maintained fairly closely, especially in mixtures made with fine glass. This research has shown that glass has great potential for use in geopolymers, when care is given to consider the compositional and physical properties of the glass in mixture design.

MICROWAVE ABSORPTION PROPERTIES OF TIRES

The waste tire is belonging to insoluble high polymer elastic materials. It takes hundreds of years to resolve the macromolecules of waste tire into the standard which does not pollute the environment. More and more waste tires are air stored which causes space occupation and mosquito-breeding in the places that will spread diseases. The disposal methods include landfill, stockpiles, dumping and incising into particles. However, all these methods are not technically and economically efficient. The trend for the development of waste tire treatment processes is low cost, on-site, and high product recovery at high energy efficiency. In this project, microwave energy has been applied for treatment of the waste tire in laboratory scale. Experimental conditions were varied in order to find the optimum processing parameters such as temperature and atmosphere. The microwave absorption capability of waste tire rubber was investigated by measuring its dielectric properties from room temperature to 800°C in stagnant air and pure nitrogen atmospheres, respectively, at both 915 and 2466MHz.The dielectric parameters data increase steadily at temperatures below 400°C. At temperatures above 400°C, the relative dielectric loss factor and relative dielectric constant begin to decrease. This is due to the solid phase of tire rubber begins to transform to gas phase and the release of volatiles. The calculations of microwave half-power depth and penetration depth of waste tire rubber show that the pyrolysis process significantly improves the microwave absorption capability of the waste tire rubber at low temperatures. The calculated reflection loss of the waste tire rubber suggests that its maximum microwave absorption can be obtained when the rubber has a thickness of 25mm at 915MHz. The sample dimension has a significant effect on the overall performance of microwave absorption in waste tire during pyrolysis and thus on the efficiency of microwave waste tire rubber pyrolysis.

ANALYSIS AND VISUALIZATION OF FLOW FIELDS USING INFORMATION-THEORETIC TECHNIQUES AND GRAPH-BASED REPRESENTATIONS

Three-dimensional flow visualization plays an essential role in many areas of science and engineering, such as aero- and hydro-dynamical systems which dominate various physical and natural phenomena. For popular methods such as the streamline visualization to be effective, they should capture the underlying flow features while facilitating user observation and understanding of the flow field in a clear manner. My research mainly focuses on the analysis and visualization of flow fields using various techniques, e.g. information-theoretic techniques and graph-based representations. Since the streamline visualization is a popular technique in flow field visualization, how to select good streamlines to capture flow patterns and how to pick good viewpoints to observe flow fields become critical. We treat streamline selection and viewpoint selection as symmetric problems and solve them simultaneously using the dual information channel [81]. To the best of my knowledge, this is the first attempt in flow visualization to combine these two selection problems in a unified approach. This work selects streamline in a view-independent manner and the selected streamlines will not change for all viewpoints. My another work [56] uses an information-theoretic approach to evaluate the importance of each streamline under various sample viewpoints and presents a solution for view-dependent streamline selection that guarantees coherent streamline update when the view changes gradually. When projecting 3D streamlines to 2D images for viewing, occlusion and clutter become inevitable. To address this challenge, we design FlowGraph [57, 58], a novel compound graph representation that organizes field line clusters and spatiotemporal regions hierarchically for occlusion-free and controllable visual exploration. We enable observation and exploration of the relationships among field line clusters, spatiotemporal regions and their interconnection in the transformed space. Most viewpoint selection methods only consider the external viewpoints outside of the flow field. This will not convey a clear observation when the flow field is clutter on the boundary side. Therefore, we propose a new way to explore flow fields by selecting several internal viewpoints around the flow features inside of the flow field and then generating a B-Spline curve path traversing these viewpoints to provide users with closeup views of the flow field for detailed observation of hidden or occluded internal flow features [54]. This work is also extended to deal with unsteady flow fields. Besides flow field visualization, some other topics relevant to visualization also attract my attention. In iGraph [31], we leverage a distributed system along with a tiled display wall to provide users with high-resolution visual analytics of big image and text collections in real time. Developing pedagogical visualization tools forms my other research focus. Since most cryptography algorithms use sophisticated mathematics, it is difficult for beginners to understand both what the algorithm does and how the algorithm does that. Therefore, we develop a set of visualization tools to provide users with an intuitive way to learn and understand these algorithms.