Thesis advisor: Chia-kuang Frank Tsung / Pt-based alloy and core-shell nanoparticles have been intensively studied to regulate its size and shape. It has known that these nanoparticles show enhanced catalytic activity in various important fields such as heterogeneous catalysis, and electrochemical energy storage including fuel cells and metal-air batteries. Here, we report a facile hydrothermal synthesis of sub-10 nm PdPt alloy and sub-20 nm Au@PdPt core-shell structures. By using a mild reducing agent in aqueous solution, metal precursors are co-reduced. Specific gases are introduced during the synthesis to optimize the reaction conditions. The PdPt alloy and Au@PdPt core-shell nanostructures were characterized and confirmed by TEM, HRTEM, EDS, ICP-OES and XRD. The resulting PdPt and Au@PdPt particles are monodispersed single crystalline and octahedral shape enclosed by (111) facets. The electrocatalytic activity for the oxidation of formic acid was tested. It was found that the catalytic activity toward the formic acid oxidation of Au@PdPt core-shell particles were much higher than those of PdPt alloy particles. In addition, Pt-rich compositions were the most active in both PdPt alloy and Au@PdPt core-shell nanoparticles. Further studies on thinner alloy-shell core-shell nanoparticles reveal that there is a volcano-curve relationship between the lattice strain strength related to alloy-shell thickness and the catalytic performance. It is proposed that there are three key parameters that can determine the catalytic activity: the alloy composition, the presence of the gold core, and the thickness of alloy-shell. / Thesis (MS) — Boston College, 2012. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

Synthesis and characterization of anisotropic micro- and nanoparticles, either in suspension or localized on a surface, are current areas of intense scientific interest because of their shape-tunable material properties with potential applications in catalysis, microelectronics, data storage and pharmaceutics. Electrochemical deposition represents a facile and versatile route to fabricate anisotropic particles since it offers a high degree of freedom in monitoring and manipulating particle growth processes. The first part of my dissertation presents an additive-mediated electrochemical approach to fabricate anisotropic copper micro- and nanoparticles. This work explores the possibility of using anisotropic copper particles as novel non-noble metal alternatives to expensive anode electrocatalysts (platinum and palladium) used in direct methanol fuel cells (DMFCs). Characterization using SEM, EDS, XRD and TEM confirms the anisotropic morphology and crystal structure of synthesized copper particles. A possible mechanism for anisotropic crystal growth is proposed based on preferential adsorption of additive ions onto selective crystal faces. Methanol oxidation is chosen as model experiment to test the electrocatalytic property of copper particles towards DMFC applications. Characterization using cyclic voltammetry demonstrates shape dependent enhancement in electrocatalytic activity of anisotropic copper particles for methanol oxidation. Chronoamperometry and thermal stability measurements indicate good catalyst stability and durability under steady-state conditions. The second part of my dissertation presents a novel electrochemical fabrication route to generate randomly rough surfaces over large areas. Surface roughness directly affects a material's performance at its functional interface. This work shows that by simple tuning of electrochemical deposition potential for a metal onto an electrode, island nucleation density can be systematically varied. Changes in nucleation density results in generation of thin films with different nanoscale surface roughness. Characterization using AFM illustrates the change in surface topography with applied potential. The fabricated roughness is successfully replicated onto other moldable soft materials (polystyrene and polyurethane) through an embossing and curing step. Roughness gradients were also generated by introducing a controlled mechanical retraction step to the process. Gradient surfaces serve as an effective probing tool for investigating a range of surface parameters in quick time using single experiment, enabling a cost-effective and high-throughput screening method. / acase@tulane.edu

Shape control of a structure with distributed piezoelectric actuators can be achieved through optimally selecting the loci, shapes and sizes of the piezoelectric actuators and choosing the electric fields applied to the actuators. Shape control can be categorised as either static or dynamic shape control. Whether it is a transient or gradual change, static or dynamic shape control, both aim to determine the loci, sizes, and shapes of piezoelectric actuators, and the applied voltages such that a desired structural shape is achieved effectively. This thesis is primarily concerned with establishing a finite element formulation for the general smart laminated composite plate structure, which is capable to analyse static and dynamic deformation using non-rectangular elements. The mechanical deformation of the smart composite plate is modelled using a third order plate theory, while the electric field is simulated based on a layer-wise theory. The finite element formulation for static and dynamics analysis is verified by comparing with available numerical results. Selected experiments have also been conducted to measure structural deformation and the experimental results are used to correlate with those of the finite element formulation for static analysis. In addition, the Linear Least Square (LLS) method is employed to study the effect of different piezoelectric actuator patch pattern on the results of error function, which is the least square error between the calculated and desired structural shapes in static structural shape control. The second issue of this thesis deals with piezoelectric actuator design optimisation (PADO) for quasi-static shape control by finding the applied voltage and the configuration of piezoelectric actuator patch to minimise error function, whereas the piezoelectric actuator configuration is defined based on the optimisation technique of altering nodal coordinates (size/shape optimisation) or eliminating inefficient elements in a structural mesh (topology optimisation). Several shape control algorithms are developed to improve the structural shape control by reducing the error function. Further development of the GA-based voltage and piezoelectric actuator design optimisation method includes the constraint handling, where the error function can be optimised subjected to energy consumption or other way around. The numerical examples are presented in order to verify that the proposed algorithms are applicable to quasi-static shape control based on voltage and piezoelectric actuator design optimisation (PADO) in terms of minimising the error function. The third issue is to use the present finite element formulation for a modal shape control and for controlling resonant vibration of smart composite plate structures. The controlled resonant vibration formulation is developed. Modal analysis and LLS methods are also employed to optimise the applied voltage to piezoelectric actuators for achieving the modal shapes. The Newmark direct time integration method is used to study harmonic excitation of smart structures. Numerical results are presented to induce harmonic vibration of structure with controlled magnitude via adjusting the damping and to verify the controlled resonant vibration formulation.

A dehydrogen is an ‘under-wrapped’ hydrogen bond in a protein that is purported to be a hot spot for binding due to the favorable replacement of water with hydrocarbon upon binding of another protein. A model at the level of dielectric constants is used to test the validity of the claim that moving a hydrogen bond from high dielectric (i.e. a dehydron) to low dielectric (i.e. after binding of another protein) is actually a thermodynamically favorable process. In simulation, several proteins have been shown to undergo a dewetting transition when fixed components are separated a small distance. A new atomic-level hydrophobicity scale is combined with topographical information to characterize protein interfaces. The relationship between hydrophobicity and topography for protein surfaces known to be involved in binding is examined. This framework is then applied to identify surface characteristics likely to have an affect on the occurrence of a dewetting transition. Cadmium selenide (CdSe) nanoparticles form nanospheres or nanorods when grown in solutions of varying concentrations of the surfactants hexylphosphonic acid (HPA) and trioctylphosphine oxide (TOPO). Relative binding free energies are calculated for HPA and TOPO to the solvent-accessible faces of CdSe crystals. Binding free energies calculated with a Molecular Mechanics-Generalized Born model are used to identify a set of low free energy structures for which the solvation free energy is refined with the solution to the Poisson equation. These relative binding free energies provide information about the relative growth rates of these crystal faces in the presence of surfactants. Relative growth rates are then used to help understand why nanoparticles form certain shapes in the presence of specific surfactants. / text

Shape control of a structure with distributed piezoelectric actuators can be achieved through optimally selecting the loci, shapes and sizes of the piezoelectric actuators and choosing the electric fields applied to the actuators. Shape control can be categorised as either static or dynamic shape control. Whether it is a transient or gradual change, static or dynamic shape control, both aim to determine the loci, sizes, and shapes of piezoelectric actuators, and the applied voltages such that a desired structural shape is achieved effectively. This thesis is primarily concerned with establishing a finite element formulation for the general smart laminated composite plate structure, which is capable to analyse static and dynamic deformation using non-rectangular elements. The mechanical deformation of the smart composite plate is modelled using a third order plate theory, while the electric field is simulated based on a layer-wise theory. The finite element formulation for static and dynamics analysis is verified by comparing with available numerical results. Selected experiments have also been conducted to measure structural deformation and the experimental results are used to correlate with those of the finite element formulation for static analysis. In addition, the Linear Least Square (LLS) method is employed to study the effect of different piezoelectric actuator patch pattern on the results of error function, which is the least square error between the calculated and desired structural shapes in static structural shape control. The second issue of this thesis deals with piezoelectric actuator design optimisation (PADO) for quasi-static shape control by finding the applied voltage and the configuration of piezoelectric actuator patch to minimise error function, whereas the piezoelectric actuator configuration is defined based on the optimisation technique of altering nodal coordinates (size/shape optimisation) or eliminating inefficient elements in a structural mesh (topology optimisation). Several shape control algorithms are developed to improve the structural shape control by reducing the error function. Further development of the GA-based voltage and piezoelectric actuator design optimisation method includes the constraint handling, where the error function can be optimised subjected to energy consumption or other way around. The numerical examples are presented in order to verify that the proposed algorithms are applicable to quasi-static shape control based on voltage and piezoelectric actuator design optimisation (PADO) in terms of minimising the error function. The third issue is to use the present finite element formulation for a modal shape control and for controlling resonant vibration of smart composite plate structures. The controlled resonant vibration formulation is developed. Modal analysis and LLS methods are also employed to optimise the applied voltage to piezoelectric actuators for achieving the modal shapes. The Newmark direct time integration method is used to study harmonic excitation of smart structures. Numerical results are presented to induce harmonic vibration of structure with controlled magnitude via adjusting the damping and to verify the controlled resonant vibration formulation.

Crystallization is a key unit operation used for obtaining purified products by many process industries. The key properties of the crystalline products, such as size and shape distribution, purity and polymorphic form are controlled by the crystallization process. All these properties impact significantly the downstream operations such as drying or filtration. Therefore, monitoring and controlling this process is fundamental to ensure the quality of the final product. Process analytical technology (PAT) brings numerous new methods and opportunities in the process analytics and real time process monitoring systems, which can be integrated into the control algorithm and provide high level optimal control strategies as well as deeper understanding of the process. Process monitoring helps develop mathematical models which can, in one hand, help in better understanding the processes and consecvently the development and application of advanced control methods in order to achieve better product quality. In this work, image processing and image analysis based direct nucleation control (IA-DNC) is developed in order to investigate the evolution of the crystal properties, such as crystal size, and crystal shape distribution. The IA-DNC approach is also compared to alternative DNC techniques, in which particle number were measured by Focused Beam Reflectance Measurement (FBRM) in order to control crystal size. A control approach is introduced that control the nucleation and disappearance of crystals during cooling and heating segments related to the changes of the number of counts (measured by Particle Vision Measurment, so called PVM or combination of FBRM and PVM). The approach was applied to investigate crystallization of compounds with different behavior: potassium dihydrogen phosphate (KDP) water, contaminated KDP -water and Ascorbic acid water systems. The results demonstrate the application of imaging technique for model-free feedback control for tailoring crystal product properties. The second main aim of the thesis is to investigate and control crystallization processes in impure media in the presence of multiple impurities, with an impact on the crystal shape via growth kinetics. The broad impact of the crystal growth modifiers (impurities) on the growth kinetics is observed in real time by using in situ video imaging probe and real-time image analysis. A morphological population balance model is developed, which incorporates a multi-site, competitive adsorption mechanism of the impurities on the crystal faces. The kinetic parameters of primary nucleation, growth and impurity adsorption for a model system of potassium dihydrogen phosphate crystallization in water in the presence of two impurities, were estimated and validated with experimental results. It was demonstrated that the model can be used to describe the dynamic evolution of crystal properties, such as size and aspect ratio during crystallization for different impurity profiles in the system. Manual, feedback and hybrid feedback-feedforward control techniques are developed and investigated numerically for continuous processes, while model-based and model-free control approach for crystal shape are developed for batch processes. The developed morphological population balance model is implemented and applied in the model-based control approaches, which are suitable to describe multicomponent adsorption processes and their influence on the crystal shape. Case studies show the effectiveness of crystal growth modifiers based shape control techniques. Comparison of different control approaches shows the effectiveness of the techniques. The third part of the thesis deals with purification of crystals when adsorption of impurities on crystal surfaces and its incorporation into crystals are considered. A purification method, called competitive purity control (CPC) is proposed and investigated. A morphological population balance model, including nucleation, growth and competitive impurity adsorption kinetics is developed to describe the case when multiple impurities can adsorb competitively on the crystal surface. The model is also combined with liquid phase chemical reaction model, in order to investigate the purity control case when an additive is introduced in the system that reacts with the impurity forming a non-adsorbing reaction product. Both competitive purity control approaches proposed: the adsorption based competitive purity control (A-CPC) and the reaction based competitive purity control (R-CPC); are investigated using detailed numerical simulations then compared with the alternative widely used purification method, called recrystallization. In the last contribution chapter, an integrated process optimization of a continuous chemical reactor and crystallizer is performed and studied numerically. The purpose of this study is to show the way in which the byproduct produced in the chemical reactor may affect the crystallization process and how its negative effect can be reduced by applying integrated process optimization. Sensitivity analysis of the system was performed by considering the flow rate and the concentration of substances in the input stream of the chemical reactor as manipulated process variables. Model based integrated process optimization and the sensitivity analysis in order to obtain improved quality product in terms of crystal size, shape and purity.

Observing and studying how life forms behave, i.e., their movement, adaptability, and so on, have enabled human beings to develop new technologies or optimize existing ones. One of the more noticeable phenomena in Nature is morphogenesis. Morphogenetic processes exist in different stages of biological development, from cellular division to tissue and organ formation. It is easy to observe shape development during mophogenesis due to emerging imaging techniques. However, it is hard to understand this process due to its complex organization, and the morphogenetic responses can be induced by a variety of chemicals or mechanical stresses and are subject to the stochastic fluctuation of the environment, making it even more difficult to acquire a fundamental understanding. It is natural to think of mimicking the complex biological process using simplified synthetic approaches. Endowing synthetic protocells with the ability to control their shape and motion autonomously would enable them to perform more like a biological system, but with less complexity. Creating synthetic morphogenesis would potentially further our understanding in biological morphogenetic processes. Moreover, we can borrow some of the morphogenetic functions in engineered materials to achieve a variety of applications, including artificial tissues, self-healing materials, controlled drug delivery, manipulation of soft robots, among others. In this dissertation, we used a synthetic cellular system controlled by a reaction regulated network that imitates the genetic control as a minimal model to understand the potential mechanisms of morphogenesis. Different simulation methods were used depending on the length scales of interest in each problem. We studied the following aspects of the minimal model system: (a) catalytic reaction induced local morphological control of amphiphilic diblock copolymer vesicles; (b) non-equilibrium control over the self-assembled structures of amphiphilic surfactants; and (c) diffusiophoretic/self-diffusiophoretic motion of colloidal particles in response to the concentration gradient field. The results obtained in this thesis work will provide a valuable road-map to guide future experiments.

No / Surface blending with tangential continuity is most widely applied in computer-aided design, manufacturing systems, and geometric modeling. In this paper, we propose a new blending method to effectively control the shape of blending surfaces, which can also satisfy the blending constraints of tangent continuity exactly. This new blending method is based on the concept of swept surfaces controlled by a vector-valued fourth order ordinary differential equation (ODE). It creates blending surfaces by sweeping a generator along two trimlines and making the generator exactly satisfy the tangential constraints at the trimlines. The shape of blending surfaces is controlled by manipulating the generator with the solution to a vector-valued fourth order ODE. This new blending methods have the following advantages: (1) exact satisfaction of C1C1 continuous blending boundary constraints, (2) effective shape control of blending surfaces, (3) high computing efficiency due to explicit mathematical representation of blending surfaces, and (4) ability to blend multiple (more than two) primary surfaces.

The optical and chemical properties of the materials used in catalytic and sensing applications directly determine the characteristics of the resultant catalyst or sensor. It is well known that a catalyst needs to have high activity, selectivity, and stability to be viable in an industrial setting. The hydrogenation activity of palladium catalysts is known to be excellent, but the industrial applications are limited by the cost of obtaining catalyst in amounts large enough to make their use economical. As a result, alloying palladium with a cheaper, more widely available metal while maintaining the high catalytic activity seen in monometallic catalysts is, therefore, an attractive option. Similarly, the optical properties of nanoscale materials used for sensing must be attuned to their application. By adjusting the shape and composition of nanoparticles used in such applications, very fine changes can be made to the frequency of light that they absorb most efficiently. The design, synthesis, and characterization of (i) size controlled monometallic palladium nanoparticles for catalytic applications, (ii) nickel-palladium bimetallic nanoparticles and (iii) silver-palladium nanoparticles with applications in drug detection and biosensing through surface plasmon resonance, respectively, will be discussed. The composition, size, and shape of the nanoparticles formed were controlled through the use of wet chemistry techniques. After synthesis, the nanoparticles were analyzed using physical and chemical characterization techniques such as X-Ray Diffraction (XRD), Transmission Electron Microscopy (TEM), and Scanning Transmission Electron Microscopy- Energy-Dispersive Spectrometry (STEM-EDX). The Pd and Ni-Pd nanoparticles were then supported on silica for catalytic testing using mass spectrometry. The optical properties of the Ag-Pd nanoparticles in suspension were further investigated using ultraviolet-visible spectrometry (UV-Vis). Monometallic palladium particles have been synthesized and characterized to establish the effects of nanoparticle size on catalytic activity in methanol decomposition. The physicochemical properties of the synthesized palladium-nickel nanoparticles will be discussed, as a function of the synthesis parameters. The optical characteristics of the Ag and Pd nanoparticles will be determined, with a view toward tuning the response of the nanoparticles for incorporation in sensors. Analysis of the monometallic palladium particles revealed a dependence of syngas production on nanoparticle size. The peak and steady state TOFs increased roughly linearly with the average nanoparticle diameter. The amount of coke deposited on the particle surfaces was found to be independent on the size of the nanoparticles. Shape control of the nickel-palladium nanoparticles with a high selectivity for (100) and (110) facets (≤ 80%) has been demonstrated. The resulting alloy nanoparticles were found to have homogeneous composition throughout their volume and maintain FCC crystal structure. Substitution of Ni atoms in the Pd lattice at a 1:3 molar ratio was found to induce lattice strains of ~1%. The Ag nanocubes synthesized exhibited behavior very similar to literature values, when taken on their own, exhibiting a pair of distinct absorbance peaks at 350 nm and 455 nm. In physical mixtures with the Pd nanoparticles synthesized, their behavior showed that the peak position of the Ag nanocubes' absorbance in UV-Vis could be tuned based on the relative proportions of the Ag and Pd nanoparticles present in the suspension analysed. The Ag polyhedra synthesized for comparison showed a broad doublet peak throughout the majority of the visible range before testing as a component in a physical mixture with the Pd nanoparticles. The addition of Pd nanoparticles to form a physical mixture resulted in some damping of the doublet peak observed as well as a corresponding shift in the baseline absorbance proportional to the amount of Pd added to the mixture.

Ces travaux de thèse sont basés principalement sur le phénomène de multistabilité des structures minces de type plaques et coques ainsi que quelques applications associées. Les travaux sont divisés en deux parties. La première partie a pour objet l’étude théorique, numérique et expérimentale de la multistabilité des coques minces orthotropes peu profondes à courbures uniformes. On montre notamment qu’une telle coque, lorsqu’elle est soumise à la combinaison d’une courbure initiale et d’une précontrainte suffisamment élevées, possède jusqu’à trois configurations stables vis-à-vis des propriétés matériaux. Dans un premier temps, nous proposons des critères de conception et fabrication de coques multistables allant jusqu’à la tristabilité, validés numériquement et expérimentalement. Ensuite, nous appliquons ces critères à la conception et à la fabrication de coques multistables cylindriques dont la différence de niveau énergétique entre les deux états stables est minime. Sur ce support, la deuxième partie est consacrée à des applications exploitant la bistabilité des coques cylindriques minces à faible différence énergétique. Nous effectuons tout d’abord une application au contrôle de forme via l’utilisation de matériaux actifs que l’on attache à la structure. Cela comprend une première phase théorique de conception de la structure et de la loi d’actionnement, et une seconde phase de mise en œuvre expérimentale. Ensuite, nous étudions théoriquement et expérimentalement les propriétés de dynamique non-linéaire de ce type de coques dans le but de mettre en évidence les modes d’oscillations intrinsèques à une source d’excitation externe. Enfin, nous proposons une application à la récupération d’énergie vibratoire non-linéaire de coques multistables cylindriques métalliques par voie piézoélectrique. / This work is essentially based on the phenomenon of multistability of thin structures as plates and shells and some associated applications. The work is divided in two parts. The first part aims to study theoretically, numerically and experimentally the multistability of thin orthotropic shallow shells with uniform curvature. We show notably that such a shell, when submitted to the combination of initial curvature and pre-stresses sufficiently high, possesses up to three stable states towards the choice of the material. First, we propose criteria to design and manufacture multistable shells up to tristability ; this work is validated by finit element simulations and experiments. After, we apply those criteria to the design and manufacture ofcylindrical multistable shells for which the energetic gap between stable states is minimal. The second part is dedicated to direct applications of bistability of thin cylindrical bistable shells with low energetic gap. We first propose an application on shape control via the use of active materials which we bond on the structure. This includes a first phase of theoretical design of both the structure and the actuation law, and a second phase of experimental demonstration. After, we study both theoretically and experimentally the non-linear dynamic properties of such structures with the aim to highlight the different modes of oscillations intrinsic to an external excitation source. Finally, we propose an application to non-linear broadband energy harvesting from vibrations based on multistable piezoelectric excited shells.