archives@tulane.edu / A block copolymer (BCP) consists of two or more covalently-bound chemically distinct homopolymer blocks. These macromolecules have emerging applications in energy storage, membrane separations, and nanolithography stemming from their propensity to self-assemble into regular nanoscale structures. For a pure BCP, this self-assembly is dictated entirely by the polymer’s degree of polymerization (N), chemistry (χ), composition (f), and chain architecture. Blending together different types of these polymers provides a simpler, synthesis-free method for tuning nanoscale morphology and feature size. This dissertation describes the use of dissipative particle dynamic (DPD) simulation to develop a fundamental understanding of phase behavior in BCP/homopolymer and cyclic-linear BCP blends. Block copolymer-homopolymer blends offer a simple method for tuning nanostructure sizes to meet application-specific demands. We systematically investigated morphology and feature size in ternary blends of symmetric linear copolymers and their constituent homopolymers (A-b-B/A/B), finding a close match between simulation results and known experimental behavior. Having established DPD simulation as a valid model, we used the simulation results to explore the relationship between polymer chain length, molecular packing, and the degree of lamellar swelling with homopolymer addition in ternary blends. A consensus of theoretical and simulation work suggests that cyclic BCPs form features up to 40% smaller than their linear analogues - while also exhibiting superior thin film stability and assembly dynamics – making them intriguing candidates for nanolithography. However, the complex syntheses required to produce these molecules mean that a need for pure cyclic BCPs would present a challenge to large-scale manufacturing. Thus, we aspired to understand the self-assembly of cyclic-linear copolymer blends. We first combined DPD simulation results and strong segregation theory to develop a scaling prediction for neat BCP feature size based on experimentally-tunable parameters (χ, N, f, and polymer architecture). The resulting Revised Scaling Law quantitatively predicts domain spacings over a wide range of BCP chain lengths, segregation strengths, and compositions and offers an explanation for the significant discrepancies between prior theoretical predictions and experimental results of cyclic BCP feature size. Next, we investigated the dimensions and interfacial roughness of nanofeatures formed by cyclic-linear BCP blends. For mixtures of symmetric cyclic and linear polymers of equivalent N, up to 10% synthetic impurity had minimal impact on cyclic BCP feature dimensions. On the other hand, we found that adding small amounts of cyclic BCP was an effective method for “fine-tuning” linear BCP feature sizes. We also analyzed our simulated blend domain spacings in the context of the revised scaling law, and found deviations between simulation and theory that arose from molecular-level packing motifs not included in theory. Finally, we investigated the impact of blending polymer architectures on the BCP order-disorder transition, finding that a mismatch in molecular size and architecture can strongly inhibit ordering. These insights into blend self-assembly will assist experimentalists in the rational design of BCP materials for advanced nanolithography applications. / 1 / Amy Dubetz Goodson

Attachment of particles to one another due to action of certain inter-particle forces is called as particle agglomeration. It has applications ranging from efficient capture of ultra-fine particles generated in coal-burning boilers to effective discharge of aerosol sprays. Aerosol sprays have their application in asthma relievers, coatings, cleaning agents, air fresheners, personal care products and insecticides. There are several factors that cause particle agglomeration and based on the application, agglomeration or de-agglomeration is desired. These various factors associated with agglomeration include van derWaals forces, capillary forces, electrostatic double-layer forces, effects of turbulence, gravity and brownian motion. It is therefore essential to understand the underlying agglomeration mechanisms involved. It is difficult to perform experiments to quantify certain effects of the inter-particle forces and hence we turn to numerical simulations as an alternative. Simulations can be performed using the various numerical simulation techniques such as molecular dynamics, discrete element method, dissipative particle dynamics or other probabilistic simulation techniques. The main objective of this thesis is to study the geometric characteristics of particle agglomerates using dissipative particle dynamics. In this thesis, agglomeration is simulated using the features of dissipative particle dynamics as the simulation technique. Forces of attraction from the literature are used to modify the form of the conservative force. Agglomeration is simulated and the characteristics of the result ing agglomerates are quantified. Simulations were performed on a sizeable number of particles and we observe agglomeration behavior. A study of the agglomerates resulting from the different types of attractive forces is performed to characterize them methodically. Also as a part of this thesis, a novel, dynamic particle simulation technique was developed by interfacing MATLAB and our computational C program.

Micro-particles are ubiquitous in microsystems. The effective manipulation of micro-particles is often crucial for achieving the desired functionality of microsystems and requires a fundamental understanding of the particle dynamics. In this dissertation, the dynamics of two types of micro-particles, Janus catalytic micromotors (JCMs) and magnetic clusters, in complex environment are studied using numerical simulations. The self-diffusiophoresis of JCMs in a confined environment is studied first. Overall, the translocation of a JCM through a short pore is slowed down by pore walls, although the slowdown is far weaker than the transport of particles through similar pores driven by other mechanisms. A JCM entering a pore with its axis not aligned with the pore axis can execute a self-alignment process and similar phenomenon is found for JCMs already inside the pore. Both hydrodynamic effect and 'chemical effect', i.e., the modification of the concentration of chemical species around JCMs by walls and other JCMs, play a key role in the observed dynamics of JCMs in confined and crowded environment. The dynamics of bubbles and JCMs in liquid films covering solid substrates are studied next. A simple criterion for the formation of bubbles on isolated JCMs is developed and validated. The anomalous bubble growth law (r~t^0.7) is rationalized by considering the relative motion of growing bubbles and their surrounding JCMs. The experimentally observed ultra-fast collapse of bubbles is attributed to the coalescence of the bubble with the liquid film-air interface. It is shown that the collective motion of JCMs toward a bubble growing on a solid substrate is caused by the evaporation-induced Marangoni flow near the bubble. The actuation of magnetic clusters using non-uniform alternating magnetic fields is studied next. It is discovered that the clusters' clockwise, out-of-plane rotation is a synergistic effect of the magnetophoresis force, the externally imposed magnetic torque and the hydrodynamic interactions between the cluster and the substrate. Such a rotation enables the cluster to move as a surface walker and leads to unique dynamics, e.g., the cluster moves away from the magnetic source and its trajectory exhibits a periodic fluctuation with a frequency twice of the field frequency. / Ph. D.

Electrostatic interactions between charged species play a prominent role in determining structures and states of physical system, leading to important technological and biological applications. In coarse-grained simulations, accurate description of electrostatic interactions is crucial in addressing physical phenomena at larger spatial and longer temporal scales. In this thesis, we implement ENUF method, an abbreviation for Ewald summation based on non-uniform fast Fourier transform technique, into dissipative particle dynamics (DPD) scheme. With determined suitable parameters, the computational complexity of ENUF-DPD method is approximately described as O(N logN). The ENUF-DPD method is further validated by investigating dependence of polyelectrolyte conformations on charge fraction of polyelectrolyte and counterion valency of added salts, and studying of specific binding structures of dendrimers on amphiphilic membranes. In coarse-grained simulations, electrostatic interactions are either explicitly calculated with suitable methods, or implicitly included in effective potentials. The effect of treatment fashion of electrostatic interactions on phase behavior of [BMIM][PF6] ionic liquid (IL) is systematically investigated. Our systematic analyses show that electrostatic interactions should be incorporated explicitly in development of effective potentials, as well as in coarse-grained simulations to improve reliability of simulation results. Detailed image of microscopic structures and orientations of [BMIM][PF6] at graphene and vacuum interfaces are investigated by using atomistic simulations. Imidazolium rings and alkyl side chains of [BMIM] lie preferentially flat on graphene surface. At IL-vacuum interface, ionic groups pack closely together to form polar domains, leaving alkyl side chains populated at interface and imparting hydrophobic character. With the increase of IL filmthickness, orientations of [BMIM] change gradually from dominant flat distributions along graphene surface to orientations where imidazolium rings are either parallel or perpendicular to IL-vacuum interface with tilted angles. The interfacial spatial ionic structural heterogeneity formed by ionic groups also contributes to heterogeneous dynamics in interfacial regions.

In order to mitigate the risk of global warming by reducing CO2 emissions, the co-firing technique, burning pulverized coal and granular biomass together in conventional pulverised fuel power station boilers, has been advocated to generate “greener” electricity to satisfy energy demand while continuing to utilize existing rich coal resources. A major problem is controllably distributing fuel mixtures of pulverized coal and granular biomass in a common pipeline, thus saving much investment. This is still under development in many co-firing studies. This research into particle dynamics in pipe flow was undertaken in order to address the problem of controllable distribution in co-firing techniques and gain an improved understanding of pneumatic conveying mechanisms. The objectives of this research were, firstly, to numerically evaluate the influence of various factors on the behaviour of particles of the different materials in a horizontal pipe gas-solid flow, secondly, to develop an extended technique of Laser Doppler Anemometry in order to determine cross-sectional characteristics of the solid phase flow in the horizontal and vertical legs of a pneumatic conveying system, and, thirdly, to develop a novel imaging system for visualizing particle trajectories by using a high definition camcorder on a cross-section illuminated by a white halogen light sheet. Finally, a comparison was made of cross-sectional flow characteristics established by experiments and those simulated by using a commercial Computational Fluid Dynamics code (Fluent) and the coupling calculations of Fluent & EDEM (a commercial code of Discrete Element Method) respectively. Particle dynamic behaviour of the solid phase in a dilute horizontal pipe flow was investigated numerically by using the Discrete Phase Model (DPM) in Fluent 6.2.16. The numerical results indicate that the Saffman force plays an important role in re-suspending particles at the lower pipe boundary and that three critical parameters of the critical air: conveying velocity, the critical particle size and the critical pipe roughness, exist in pneumatic conveying systems. The Stokes number can be used as a similarity criterion to classify the dimensionless mean particle velocity of the different materials in the fully developed region. An extended Laser Doppler Anemometry (LDA) technique has been developed to measure the distributions of particle velocities and particle number over a whole pipe cross section in a dilute pneumatic conveying system. The first extension concentrates on a transform matrix for predicting the refracted laser beams’ crossing point in a pipe according to the shift coordinate of the 3D computer-controlled traverse system on which the probes of the LDA system were mounted. Another part focussed on the proper sampling rate of LDA for measurements on the gas-solid pipe flow with polydispersing particles. A suitable LDA sampling rate should ensure that enough data is recorded in the measurement interval to precisely calculate the particle mean velocity or other statistical values at every sample point. The present study explores the methodology as well as fundamentals of measurements of the local instantaneous density of particles as a primary standard using a laser facility. The extended LDA technique has also been applied to quantitatively investigate particle dynamic behaviour in the horizontal and vertical pipes of a dilute pneumatic conveying system. Three kinds of glass beads were selected to simulate the pulverized coal and biomass pellets transported in a dilute pneumatic conveying system. Detailed information on the cross-sectional spatial distributions of the axial particle velocity and particle number rate is reported. In the horizontal pipe section, experimental data on a series of cross-sections clearly illustrate two uniform fluid patterns of solid phase: an annular structure describing the cross-sectional distribution of the axial particle velocity and a stratified configuration describing particle number rate. In the vertical pipe downstream of an elbow R/D=1.3, a horseshoe-shaped feature, which shows that the axial particle velocity is highest in wall regions of the pipe on the outside of the bend for all three types of glass beads on the section 0D close to the elbow outlet. The developments of cross-sectional distributions of particle number rate indicate that the horseshoe-shaped feature of particle flow pattern is rapidly dispersed for particles with high inertia. A video & image processing system has been built using a high definition camcorder and a light sheet from a source consisting of a halogen lamp. A set of video and image processing algorithms has been developed to extract particle information from each frame in a video. The experimental results suggest that the gas-solid flow in a dilute pneumatic conveying system is always heterogeneous and unsteady. The parameter of particle mass mean size is superior to particle number mean size for statistically describing the unsteady properties of gas-solid pipe flow. It is also demonstrated that the local data of particle number rate or concentration are represented by a stratified structure of the flow pattern over a horizontal pipe cross-section. Finally, comparisons of numerically predicated flow patterns and experimental ones show that there is reasonable agreement at pipe cross-sections located at horizontal positions less than half the product of particle mean velocity and mean free fall time in the pipe from the particle inlet. Further away from the inlet, the numerical results show flow patterns which are increasingly divergent from the experimental results along the pipe in the direction of flow. This discrepancy indicates that particles’ spatial distribution in the pipe is not accurately predicted by the Discrete Phase Model or Fluent coupled with EDEM.

Computer simulation and animation (CSA) has been receiving growing attention and wide application in the engineering education community. The goal of this dissertation research was to improve students' conceptual understanding and procedural skills for solving particle dynamics problems, by developing, implementing and assessing 12 interactive computer simulation and animation learning modules. The developed CSA learning modules integrate visualization with mathematical modeling to help students directly connect engineering dynamics with mathematics. These CSA modules provide a constructivist environment where students can study physical laws, demonstrate mental models, make predictions, derive conclusions, and solve problems. A mixed-method research was conducted in this study: quasi-experimental method (quantitative), and survey questionnaires and interviews (qualitative and quantitative). Quasi-experimental research involving an intervention group and a comparison group was performed to investigate the extent that the developed CSA learning modules improved students' conceptual understanding and procedural skills in solving particle dynamics problems. Surveys and interviews were administrated to examine students' learning attitudes toward and experiences with the developed CSA learning modules. The results of quasi-experimental research show that the 12 CSA learning modules developed for this study increased students' class-average conceptual and procedural learning gains by 29% and 40%, respectively. Therefore, these developed CSA modules significantly improved students' conceptual understanding and procedural skills for solving particle dynamics problems. The survey and interview results show that students had a positive experience with CSA learning.

In this study, the nanocomposite of graphene and PMMA at the different volume fractions was investigated by molecular dynamics and dissipative particle dynamics simulations. The MD simulation can be performed to simulate the nanocomposite system at different weight fractions to obtain the different repulsive parameters. After obtaining the repulsive parameters, the DPD simulation can be utilized to study the equilibrium phase of graphene and PMMA nanocomposite. From our result, all equilibrium phases at different volume fractions are cluster. However, it is difficult to enhance the property for nanocomposite material due to the aggregated graphene (cluster). Hence, we change the interaction repulsive parameters to stand for the different degrees of functionalized graphene. When the interaction repulsive parameter is smaller than 80, the equilibrium phase is dispersion. In addition, the different number of functionalized garphene bead per graphene was studied, and results show that the equilibrium phase is dispersion when all graphene beads per graphene are functionalized.

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In this thesis, molecular dynamics and dissipative particle dynamics simulation methods are adopted to investigate the effects of volume fraction (1:1; 1:4; 1:6; 1:14; 1:20), repulsive interaction parameter (aij) and chain length on the microstructure of (5,5) carbon-nanotube (CNT)/polyethylene (PE) mixture. In order to obtain the information of microstructure for different simulation conditions, we used the radius of gyration and orientational order parameter to explore the polymer conformation. It is found that micro-structures will be very different when different repulsive interaction parameters and volume fractions are used.

In this work we rst study the non-Newtonian effects on the inertial instabilities in shear flows and second the inertial suspensions of finite size rigid particles by means of numerical simulations. In the first part, both inelastic (Carreau) and elastic models (Oldroyd-B and FENE-P) have been employed to examine the main features of the non-Newtonian fluids in several congurations; flow past a circular cylinder, in a lid-driven cavity and in a channel. In the framework of the linear stability analysis, modal, non-modal, energy and sensitivity analysis are used to determine the instability mechanisms of the non-Newtonian flows. Signicant modifications/alterations in the instability of the different flows have been observed under the action of the non-Newtonian effects. In general, shear-thinning/shear-thickening effects destabilize/stabilize the flow around the cylinder and in a lid driven cavity. Viscoelastic effects both stabilize and destabilize the channel flow depending on the ratio between the viscoelastic and flow time scales. The instability mechanism is just slightly modied in the cylinder flow whereas new instability mechanisms arise in the lid-driven cavity flow. In the second part, we employ Direct Numerical Simulation together with an Immersed Boundary Method to simulate the inertial suspensions of rigid spherical neutrally buoyant particles in a channel. A wide range of the bulk Reynolds numbers, 500&lt;Re&lt;5000, and particle volume fractions, 0&lt;\Phi&lt;3, is studied while fixing the ratio between the channel height to particle diameter, 2h/d = 10. Three different inertial regimes are identied by studying the stress budget of two-phase flow. These regimes are laminar, turbulent and inertial shear-thickening where the contribution of the viscous, Reynolds and particle stress to transfer the momentum across the channel is the strongest respectively. In the inertial shear-thickening regime we observe a signicant enhancement in the wall shear stress attributed to an increment in particle stress and not the Reynolds stress. Examining the particle dynamics, particle distribution, dispersion, relative velocities and collision kernel, confirms the existence of the three regimes. We further study the transition and turbulence in the dilute regime of finite size particulate channel flow. We show that the turbulence can sustain in the domain at Reynolds numbers lower than the one of the unladen flow due to the disturbances induced by particles. / <p>QC 20151127</p>