La thèse est consacrée à la synthèse et à l’étude des propriétés des matériaux hybrides inorganique-organique à base de polyaniline (PANI) et de polypyrrole (PPy) avec des nanoparticules TiO2 (rutile et anatase) et SnO2 applicables à détection l'ammoniac et aux amines. La croissance directe du polymère sur la surface des nanoparticules a permis l’obtention de matériaux nanocomposites avec une structure “core-shell” qui diffère du mélange mécanique simple par une distribution plus uniforme des polymères et une interaction plus forte entre les composants source. L’objet de la recherche est le processus de formation de nanocomposites de polyaniline et de polypyrrole avec des oxydes métalliques. L’objectif de la recherche est de révéler les particularités de la formation et les propriétés des matériaux composites nanostructurés à base de polymères conducteurs et nanoparticules d’oxydes métalliques sensibles à l’ammoniac et aux amines. Les méthodes de recherche incluent le RedOx et la surveillance du pH, FTIR et UV-spectroscopie, SEM, TEM, thermogravimétrie, chromatographie liquide, mesures de conductivité et tests de capteurs. La nouvelle approche d’étude de la cinétique du processus de polymérisation de l'aniline par la surveillance simultané du RedOx et du pH du milieu réactionnel a été proposée. Pour la première fois, on a montré l’influence des acides sulfoniques et des oxydes métalliques sur le procédé de polymérisation de l’aniline et les caractéristiques moléculaires du polymère obtenu. En outre, une corrélation linéaire entre le contenu en nanoparticules et la durée réciproque des stades séparés de la polymérisation a été démontrée. Les nanocomposites “core-shell” formés ont une sensibilité à l’ammoniac et aux amines environ 2 fois supérieure à celle du polymère pur. Les nouveaux matériaux développés peuvent être utilisés dans la fabrication de couches actives des capteurs chimiorésistifs. / The thesis is devoted to the synthesis and investigation of properties of inorganic-organic polyaniline (PANI) and polypyrrole (PPy) based hybrid materials with TiO2 (rutile and anatase) and SnO2 nanoparticles applicable for ammonia and amines detection. The direct polymer growth on the surface of nanoparticles allowed obtaining of nanocomposite materials with a “core-shell” structure which differs from simple mechanical mixture by more uniform polymer distribution and stronger interaction between source components.The object of research is the process of formation of polyaniline and polypyrrole nanocomposites with metal oxides. The research goal is to reveal formation peculiarities and properties of nanostructured composite materials based on conducting polymers and metal oxides nanoparticles that are sensitive to ammonia and amines. Research methods include RedOx and pH monitoring, FTIR and UV-spectroscopy, SEM, TEM, thermogravimetry, liquid chromatography, conductivity measurements and sensor tests.The new approach to study kinetics of aniline polymerization process by simultaneous RedOx and pH monitoring of reaction medium was proposed. For the first time the influence of sulfonic acids and metal oxides on the aniline polymerization process and molecular characteristics of the obtained polymer was shown. For the first time a linear correlation between the nanoparticles content and reciprocal duration of separate stages of polymerization was shown. Formed "core-shell" nanocomposites have sensitivity to ammonia and amines of about 2 times higher than the pure polymer. Developed new materials can be used in the manufacturing of chemoresistive sensors' active layers.

The ability to grow materials in the nanometric size regime with controlled shape and size provide a fundamental synthetic challenge, while allowing for evaluation of such unique nanostructures in multiple applications. In this dissertation, colloidal sodium lanthanide fluoride (NaLnF4) nanocrystals are described with an overall emphasis on i) size control, ii) surface chemistry related towards their applications as nano-bioprobes, and iii) the synthesis and fundamental aspects of epitaxial layer growth generally referred as core-shell nanocrystals. Chapter 1 provides a brief overview on the basic aspects of colloidal nanocrystals. In Chapter 2, synthesis and surface modification of colloidal sodium lanthanide fluoride nanocrystals, epitaxial growth, and their applications in optical and magnetic resonance imaging is reviewed. Chapter 3 describes a phase transfer protocol utilizing polyvinylpyrrolidone and subsequent silica coating of initially hydrophobic upconverting nanocrystals. This protocol is extended in Chapter 4 using end-group functionalized polyvinylpyrrolidone and demonstrates tunability of surface charge and functional groups on upconverting nanocrystals for targeted labeling of human prostate cancer cells. The synthesis of size-tunable NaGdF4 nanocrystals below 10 nm is described in Chapter 5. These nanocrystals are evaluated for their efficacy in magnetic resonance imaging (MRI), and a fundamental insight into the effect of surface gadolinium ions in T1 MRI contrast enhancement is presented. Chapter 6 demonstrates the synthesis of tunable, epitaxial layers on upconverting (core) nanocrystals. A novel synthetic strategy is demonstrated, by deliberate defocusing and self-focusing of differently sized nanocrystals driven by the common physical phenomenon of Ostwald ripening. Utilizing the contraction of lanthanide ions along the series, a fundamental investigation on the effect of compressive/tensile strain epitaxial layer growth is presented in Chapter 7. The fundamental rule of minimal lattice mismatch for epitaxial growth takes into account only the magnitude of mismatch and not the sign of mismatch caused by a compressive/tensile strained layer. A strong asymmetric effect between the compressive/tensile layer growth given the same magnitude of lattice mismatch is observed, demonstrating the necessity of including the sign of mismatch to generate isotropic (conformal)/ pseudomorphic (coherent) epitaxial growth. Finally, in Chapter 8 conclusions and possible future work are discussed. / Graduate / 0494

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There have been many applications of cerium oxide in oxidation catalysis but the understanding of its role in catalysis is rather limited. This research is concerned with the use of nano-size cerium oxide in methane steam reforming reaction. It is found that addition of cerium oxide to the commercial supported Ni catalysts can dramatically reduce the undesirable carbon deposition (through surface oxidation), which is thermodynamically favorable under low steam conditions. In order to understanding the fundamental role of oxidation activity of the cerium oxide, different sizes of nano-crystallined cerium oxides have been carefully prepared by micro-emulsion technique. Their reactivity is clearly shown to be size dependent. We found that ceria particle sizes of lower than 5.1 nm are able to activate molecular oxygen, which accounts for the unprecedentedly reported critical size effect on oxidation. Characterizations by EPR, XPS, TPR suggest that a substantially large quantity of adsorbed oxygen species (O₂ ^-) is preferentially formed in the small size ceria from air. Also, it is found that the oxygen vacancies are formed in the interface of metal and oxide, and the strength of the metal oxide interaction may influence the formation of the efficient oxygen vacancies, which are responsible for the adsorbed surface oxygen.

This thesis focuses on core/shell nanoparticle catalysts including preparation, characterization and testing performance using direct methanol fuel cell. Core/shell were prepared using noble and non-noble metals. Also some core/ shell nanoparticles supported on silica and different types of carbon were prepared as well in this thesis. Non-noble core/shell nanoparticles including novel Co/Ni, SiO2/Ni using three types of silica and novel SiO2/CoFe were prepared by a new modified sol-gel method using hydrazine in alkali media as the reducing agent to reduce metal chloride through two steps process. Parameters such as temperature, pH of solution and reducing agents, were seen to be of great importance in deciding the morphology of the final product as well as the structure of the core/shell catalyst. Core/shell nanoparticles have been successfully prepared for Co/Ni and SiO2/CoFe for first time by choosing the right parameters. This study presents the unique structure which has not been obtained previously for SiO2/Ni catalyst using commercial silica as core. A novel halo shaped structure was the common feature in the catalysts prepared as indicated by TEM. This study presents as well noble Ru/Pt core/shell nanoparticles supported on three types of carbon by a new modified polyol method for first time. The author of this work is not aware of any studies that have prepared Ru/Pt on carbon powder smaller or equal to 50 nm and Ru/Pt on CMWNT previously. This work presents special structure (crown- jewel shaped) for Ru/Pt on Vulcan XC-72 carbon which was not obtained previously for the same catalyst. Selected catalysts were tested using a direct methanol fuel cell. SiO2/Pt core/shell nanoparticles were prepared for the first time by two different methods, namely a new modified sol-gel and polyol methods with novelty structures halo and crown- jewel shaped respectively. Based on the particles size obtained from TEM images, the modified polyol method seems to have a much greater impact on the particles size than the modified sol-gel method. Based on these findings Ru/Pt, Ru/Pt supported on three different types of carbon and Pt supported on CMWNT were prepared using the new modified polyol method. Pt on CMWNT catalyst was synthesized for the first time successfully by a new modified polyol method and all the particles were found to be well dispersed with a narrow size distribution of an average particles size of 3nm. This catalyst gave promising results on DMFC. Pt supported on CMWNT and Ru/Pt supported on Vulcan and CMWNT were used for the first time as electro-catalysts in DMFC to study the effect of the support on the catalytic activity of catalysts. The results show that Ru/Pt on CMWNT gives better performance than the unsupported Ru/Pt and Ru/Pt on Vulcan XC-72. Using Ru/Pt on CMWNT with higher methanol concentration (anode feed) improved the fuel cell power density when compared with the RuPt commercial catalyst.

Core-shell nanohybrids have wide applications in pollutant degradation. In this study, core-shell nanohybrid was formed through heteroaggregation between neutral nanoparticles (i.e., hematite nanoparticles or HemNPs) and charged nanoparticles (i.e., carboxylated polystyrene nanoparticles or PSNPs). In the dispersant solution of 1 mM NaCl at pH 6.3, HemNPs were neutral and underwent favorable homoaggregation, whereas PSNPs were negatively charged and underwent no homoaggregation. When the two types of particles were mixed, homoaggregation of HemNPs and heteroaggregation between HemNPs and PSNPs took place simultaneously, forming HemNPs-PSNPs heteroaggregates. The transmission electron microscopy images of heteroaggregates show that HemNPs and PSNPs formed core-shell structure in which HemNPs were the cores and PSNPs were the shells. The size of the core-shell nanohybrids can be controlled by varying the concentration ratio of HemNPs to PSNPs. The increase of the size of charged nanoparticles resulted in larger nanohybrids. This new method has lower energy footprint than existing ones. / Includes bibliography. / Thesis (M.S.)--Florida Atlantic University, 2019. / FAU Electronic Theses and Dissertations Collection

Thesis advisor: Udayan Mohanty / The high surface area and atomic-level tunability offered by nanoparticles has defined their promise as heterogeneous catalysts. While initial studies began with nanoparticles of a single metal assuming thermodynamic shapes, modern work has focused on using nanoparticle composition and geometry to optimize nanocatalysts for a wide variety of reactions. Further optimization of these refined nanocatalysts remains difficult, however, as the factors that determine catalytic activity are intertwined and a fundamental understanding of each remains elusive. In this work, precise synthetic methods are used to tune a number of factors, including composition, strain, metal-to-metal charge transfer, atomic order, and surface faceting, and understand their impact on catalysis. The first chapter focuses on current achievements and challenges in the synthesis of intermetallic nanocatalysts, which offer long-range order that allows for total control of surface structure. A particular focus is given to the impact of the synthetic approach on the activity of the resulting nanoparticles. In the second chapter, multilayered Pd-(Ni-Pt)x nanoparticles serve as a controlled arena for the study of metallic mixing and order formation on the nanoscale. The third chapter controls the shell thickness of Au@PdPt core-alloyed shell nanoparticles on a nanometer scale to isolate strain at the nanoparticle surface. In the fourth chapter, the synthetic approaches of chapters two and three are applied to catalysis. In totality, the work presented here represents a brick in the foundation of understanding and exploiting structure-function relationships on the nanoscale, with an eye toward the rational design of tailored nanocatalysts. / Thesis (PhD) — Boston College, 2020. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

The industrial demand for high strength-to-weight ratio materials is increasing due to the need for high performance components. Epoxy polymers, although often used in fiber-reinforced polymeric composites, have an inherent low toughness that further decreases with decreasing temperatures. Second-phase additives have been effective in increasing the toughness of epoxies at room temperature; however, the mechanisms at low temperatures are still not understood. In this study, the deformation mechanisms of a DGEBA epoxy modified with MX960 core-shell rubber (CSR) particles were investigated under quasi-static tensile and impact loads at room temperature (RT) and liquid nitrogen (LN2) temperature. Overall, the CSR had little effect on the tensile properties at RT and LN2 temperature. The impact strength decreased from neat to 3 wt% but increased from neat to 5 wt% at RT and LN2 temperature, with a higher impact strength at RT at all CSR loadings. The CSR particles debonded in front of the crack tip, inducing voids into the matrix. It was found that an increase in shear deformation and void growth likely accounted for the higher impact strength at 5 wt% CSR loading at RT while the thermal stress fields due to the coefficient of thermal expansion mismatch between rubber and epoxy and an increase in secondary cracking is likely responsible for the higher impact strength at 5 wt% tested at LN2 temperature. While a large toughening effect was not seen in this study, the mechanisms analyzed herein will likely be of use for further material investigations at cryogenic temperatures.

Precipitation polymerization is a unique method that produces narrow-disperse, uniform polymer particles with clean surfaces. In this research, internally structured poly(divinylbenzene-co-chloromethylstyrene) polymer microspheres were prepared by thermal imprinting precipitation polymerization. The influence of thermal profiles and the monomer/crosslinker feed ratio on the resulting core-shell microspheres were explored by optical and transmission electron microscopy, and potential route to extend this technique to other polymer system was discussed. Further surface functionalization of this type of particles was demonstrated by substitution of chlorine with cysteine, a good and hydrophilic nucleophile. Narrow-disperse, hydrophilic particles may in future serve as components of synthetic extracellular matrices used in exploring cell-matrix interactions in a 3D context. / Thesis / Master of Science (MSc)

Piezoelectric material based sensors are widely used in applications such as automobiles, aircraft, and industrial systems. In past decade, attention has been focused on synthesizing composites that can provide multifunctional properties, i.e., same material exhibits two or more properties. In this group of composites, magnetoelectric materials are particularly interesting as they provide the opportunity of coupling magnetic and electric field. Another class of composite materials that are being actively pursued is piezoresistive materials. Piezoresistivity refers to change in resistance with applied stress and these materials are promising for enhancing the sensitivity of current generation pressure sensors based on silicon. In this study, we focus on two composites systems: ferrite / Terfenol-D / nickel — lead zirconate titanate (magnetoelectric); and lanthanum strontium manganate (LSMO) — carbon nanotube (CNT) – silicon carbonitride (SiCN) (piezoresistive). Recently, Islam et al. have reported a magnetic field sensor based on a piezoelectric transformer with a ring- dot electrode pattern. In this thesis, this design was further investigated by synthesizing Terfenol-D / PZT laminate. The fabricated sensor design consists of a ring-dot piezoelectric transformer laminated to a magnetostrictive disc and its working principle is as follows: When a constant voltage is applied to the ring section of the piezoelectric layer at resonance, a stress is induced in the dot section. Then, if an external magnetic object is introduced in the vicinity of the dot section, the effective elastic stiffness is increased, altering the resonance frequency (fr). The variation of resonance frequency and magnitude of output voltage with applied magnetic field was characterized and analyzed to determine the sensitivity. The sensor showed a shift of ~1.36Hz/Oe over the frequency range of 137.4<fr<144.2 kHz with increasing magnetic bias from 1<Hdc<6kOe. Next, in order to overcome the need of magnetic DC bias in current magnetoelectric composites, a metal – ceramic core-shell composite structure was investigated. Metal-ceramic composite particles were synthesized at room temperature and their magnetic properties were investigated. The particles constitute a core-shell structure where the core is nickel-metal, while the shell is manganese zinc ferrite (MZF). Coprecipitation was used for synthesis of MZF nanoparticles comprising the shell, whereas nickel was synthesized by hydrazine assisted reduction of nickel ions in aqueous media. A core shell structure was then obtained by hetero-coagulation to form a shell of MZF around the nickel particles. Electron microscopy and x-ray diffraction confirmed nickel cores coated by MZF shells. Magnetization studies of MZF nano-particles revealed that they were not super-paramagnetic at room temperature, as expected for such particle sizes of 20nm in size. Sintered composites of metal-ceramic particles core-shell exhibited a magnetostriction of 5ppm. Lastly, the thesis investigates the piezoresistive properties of LSMO – CNT – SiCN composites that were synthesized by the conventional ceramic sintering technique. Recent investigations have shown that CNTs and SiCN have high piezoresistive coefficient. DSC/TGA results showed that pure CNTs decompose at temperatures of ~600°C, however, SiCN was found to sustain the sintering temperature of 1300°C. Thus, LSMO – SiCN composites were used for the final analysis. A fractional resistivity change of 4% was found for LSMO — 12.5 vol% SiCN composites which is much higher compared to that of unmodified LSMO. / Master of Science