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.

Charge induced enhancement of adsorption for hydrogen storage materials

The rising concerns about environmental pollution and global warming have facilitated research interest in hydrogen energy as an alternative energy source. To apply hydrogen for transportations, several issues have to be solved, within which hydrogen storage is the most critical problem. Lots of materials and devices have been developed; however, none is able to meet the DOE storage target. The primary issue for hydrogen physisorption is a weak interaction between hydrogen and the surface of solid materials, resulting negligible adsorption at room temperature. To solve this issue, there is a need to increase the interaction between the hydrogen molecules and adsorbent surface. In this study, intrinsic electric dipole is investigated to enhance the adsorption energy. The results from the computer simulation of single ionic compounds with hydrogen molecules to form hydrogen clusters showed that electrical charge of substances plays an important role in generation of attractive interaction with hydrogen molecules. In order to further examine the effects of static interaction on hydrogen adsorption, activated carbon with a large surface area was impregnated with various ionic salts including LiCl, NaCl, KCl, KBr, and NiCl and their performance for hydrogen storage was evaluated by using a volumetric method. Corresponding computer simulations have been carried out by using DFT (Density Functional Theory) method combined with point charge arrays. Both experimental and computational results prove that the adsorption capacity of hydrogen and its interaction with the solid materials increased with electrical dipole moment. Besides the intrinsic dipole, an externally applied electric field could be another means to enhance hydrogen adsorption. Hydrogen adsorption under an applied electric field was examined by using porous nickel foil as electrodes. Electrical signals showed that adsorption capacity increased with the increasing of gas pressure and external electric voltage. Direct measurement of the amount of hydrogen adsorption was also carried out with porous nickel oxides and magnesium oxides using the piezoelectric material PMN-PT as the charge supplier due to the pressure. The adsorption enhancement from the PMN-PT generated charges is obvious at hydrogen pressure between 0 and 60 bars, where the hydrogen uptake is increased at about 35% for nickel oxide and 25% for magnesium oxide. Computer simulation reveals that under the external electric field, the electron cloud of hydrogen molecules is pulled over to the adsorbent site and can overlap with the adsorbent electrons, which in turn enhances the adsorption energy Experiments were also carried out to examine the effects of hydrogen spillover with charge induced enhancement. The results show that the overall storage capacity in nickel oxide increased remarkably by a factor of 4.

Modeling spontaneous three-dimensional polymerization

For human beings, the origin of life has always been an interesting and mysterious matter, particularly how life arose from inorganic matter through natural processes. Polymerization is always involved in such processes. In this paper we built what we refer to as ideal and physical models to simulate spontaneous polymerization based on certain physical principles. As the modeling confirms, without taking external energy, small and simple inorganic molecules formed bigger and more complicated molecules, which are necessary ingredients of all living organisms. In our simulations, we utilized actual ranges of parameters according to their experimentally observed values. The results from the simulations led to a good agreement with the nature of polymerization. After sorting out through all the models that were built, we arrived at a final model that, it is hoped, can be used to simply and efficiently describe spontaneous polymerization using only three parameters: the dipole moment, the distance between molecules, and the temperature.

OPTIMAL SHAPE IN ELECTROMAGNETIC SCATTERING BY SMALL ASPHERICAL PARTICLES

We consider the question of optimal shapes, e.g., those causing minimal extinction among all shapes of equal volume. Guided by the isoperimetric property of a sphere, relevant in the geometrical optics limit of scattering by large particles, we examine an analogous question in the low frequency (electrostatics) approximation, seeking to disentangle electric and geometric contributions. To that end, we survey the literature on shape functionals and focus on ellipsoids, giving a simple proof of spherical optimality for the coated ellipsoidal particle. Monotonic increase with asphericity in the low frequency regime for orientation-averaged induced dipole moments and scattering cross-sections is also shown. Additional physical insight is obtained from the Rayleigh-Gans (transparent) limit and eccentricity expansions. We propose connecting low and high frequency regime in a single minimum principle valid for all size parameters, provided that reasonable size distributions of randomly oriented aspherical particles wash out the resonances for intermediate size parameters. This proposal is further supported by the sum rule for integrated extinction.

Direction finding in the presence of a more realistic environment model

Direction-of-arrival (DOA) estimation is susceptible to errors introduced by the presence of real-ground and resonant size scatterers in the vicinity of the antenna array. To compensate for these errors pre-calibration and auto-calibration techniques are presented. The effects of real-ground constituent parameters on the mutual coupling (MC) of wire type antenna arrays for DOA estimation are investigated. This is accomplished by pre-calibration of the antenna array over the real-ground using the finite element method (FEM). The mutual impedance matrix is pre-estimated and used to remove the perturbations in the received terminal voltage. The unperturbed terminal voltage is incorporated in MUSIC algorithm to estimate DOAs. First, MC of quarter wave monopole antenna arrays is investigated. This work augments an existing MC compensation technique for ground-based antennas and proposes reduction in MC for antennas over finite ground as compared to the perfect ground. A factor of 4 decrease in both the real and imaginary parts of the MC is observed when considering a poor ground versus a perfectly conducting one for quarter wave monopoles in the receiving mode. A simulated result to show the compensation of errors direction of arrival (DOA) estimation with actual realization of the environment is also presented. Secondly, investigations for the effects on received MC of λ/2 dipole arrays placed near real-earth are carried out. As a rule of thumb, estimation of mutual coupling can be divided in two regions of antenna height that is very near ground 0