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- Title
- Piezoresistive Behavior of Carbon Nanopaper Polymer Composites for Strain Sensing.
- Creator
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Beyrooti, Jayden, Kwok, Kawai, Gou, Jihua, Kauffman, Jeffrey L., University of Central Florida
- Abstract / Description
-
Carbon nanopapers made of carbon nanotubes (CNTs) or carbon nanofibers (CNFs), possess unique electrical, thermal and mechanical properties and when integrated with a polymer matrix, can become a multifunctional composite capable of strain sensing and heat actuation. Smart structures such as these can be used in many applications including deployable space structures, human motion detection, and structural health monitoring as flexible, sensitive and stable strain sensors in addition to...
Show moreCarbon nanopapers made of carbon nanotubes (CNTs) or carbon nanofibers (CNFs), possess unique electrical, thermal and mechanical properties and when integrated with a polymer matrix, can become a multifunctional composite capable of strain sensing and heat actuation. Smart structures such as these can be used in many applications including deployable space structures, human motion detection, and structural health monitoring as flexible, sensitive and stable strain sensors in addition to providing electrical heat actuation for the shape memory effect in polymers. This study focuses on strain sensing capabilities by developing a numerical model to predict piezoresistive behavior. The piezoresistive effect is a change in resistivity of a conductive network when a deformation is applied. This allows strain to be determined by simply measuring the electrical resistance. An equivalent resistor network can be formed to represent the fiber network. The proposed 2D model generates randomly oriented fibers inside a unit cell, determines their intersection points, and creates a mesh of the network for finite element analysis. Electrical conductivity is found for the initial and deformed fiber states by determining the current through the network for a known voltage. A piezoresistivity experimental study is conducted to investigate the strain sensing abilities of this material and validate model results. This simple model provides an initial framework that can be developed in future work. Despite its 2D nature, the model captures the governing mechanisms of piezoresistivity to a certain extent.
Show less - Date Issued
- 2019
- Identifier
- CFE0007788, ucf:52353
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0007788
- Title
- Mechanochemistry for Solid-State Syntheses and Catalysis.
- Creator
-
Restrepo, David, Blair, Richard, Kuebler, Stephen, Miles, Delbert, Clausen, Christian, Orlovskaya, Nina, University of Central Florida
- Abstract / Description
-
Traditional methods of synthesizing inorganic materials, such as hydrothermal, sol-gel, calcination and grinding steps, can typically require use of high temperatures, expensive precursors or use of solvents. Because of the energy-intensive nature or environmental impact these techniques, there is a push, especially from an industrial perspective, to move towards greener approaches. Mechanochemistry is a solvent-free alternative technique that can be used to synthesize a variety of materials...
Show moreTraditional methods of synthesizing inorganic materials, such as hydrothermal, sol-gel, calcination and grinding steps, can typically require use of high temperatures, expensive precursors or use of solvents. Because of the energy-intensive nature or environmental impact these techniques, there is a push, especially from an industrial perspective, to move towards greener approaches. Mechanochemistry is a solvent-free alternative technique that can be used to synthesize a variety of materials under ambient conditions. Due to this, there is an increase in attention towards the use of this approach in both solid-state inorganic and organic chemistry.This dissertation reports the mechanochemical synthesis of a few inorganic materials without the need of using high temperatures or solvents. Additionally, examples are presented in which mechanochemistry is used in conjunction with a secondary technique. This mechanical activation of the precursors lead to a decrease in calcination temperature and reactions times, as well as alteration of properties or unique reaction products. The synthesis of kaolinite, vanadia nanostructures, and spinels were carried out in this fashion. Mechanical activation of the precursors allowed for reduced hydrothermal treatment times in case of both kaolinite and vanadia nanostructures and the spinels are calcined at lower temperature for shorter periods of time. In addition, we report alternative template agents than previously reported for the formation of vanadia nanotubes, and report the formation of nanorods. Choosing the appropriate amine template can alter the structure and size of the material.Isomorphously substituted mixed oxides, kaolinite and spinels (MgAl2O4 and ZnAl2O4) were synthesized through a mechanically assisted process. Kaolinites are treated hydrothermally for 1 week at 250 (&)#186;C to produce an X-ray pure crystalline material. The spinels undergo calcination as low as 500 (&)#186;C to produce a nanocrystalline material. Rare-earth metals and transition metals were used as the substitutional atom. The substituted kaolinites exhibit strong order along the c axis, but less ordering along the a and b axes. Trivalent chromium and trivalent rare-earth metals, such as La, Ce, Pr, Nd, Eu, Gd, Ho, and Er, are used to replace aluminum in the structure. Likewise, divalent and trivalent transition, such as Mn, Ni, Cu and Cr, are used as the substitutional atoms in MgAl2O4 and ZnAl2O4. Cathodoluminescence studies on the substituted Spinel structure show that Mn2+ ions can occupy both the tetrahedral or octahedral holes to give a green and red emission, respectively. On the other hand, Cr3+ ions only occupy the octahedral holes to yield a red emission, similar to that in ruby. These isomorphously substituted materials may have potential applications in catalysis or glaze materials in ceramics.Oxidized graphite, an alternative to graphite oxide and graphene, can be synthesized rapidly by mechanochemical means. Grinding urea hydrogen peroxide adduct with graphite without the need of a solvent produces a product with an oxygen content of 5-15 wt%. The byproducts of this reaction are urea and water. This material is oxidized along the edges of the sheets, allowing it to be hydrophilic while retaining the conductivity. The material can suspend in water and processing allows for films of resistivities between 50 ? cm-2 and 10 k? cm-2. It was determined that the edges are fully oxidized to yield (-)COOH groups. This process offers a scalable, environmentally benign route to large quantities of oxidized graphite.An alternative method for the synthesis of nanostructured vanadia is reported. This process involves mechanical grinding of vanadium pentoxide, V2O5, with an amine template, such as diphenylamine, theophylline, rhodamine 6G and rhodamine, prior to hydrothermal treatment. This allows for the synthesis of VOx nanotubes and nanorods dependent on which template is used. Diphenylamine, theophylline, and rhodamine B produce nanorods. Use of rhodamine 6G produces asymmetric VOx nanorods.In addition to the mixed metals oxides mentioned above, sodium and calcium tantalates are synthesized mechanically. This route does not require the need of elevated temperatures or expensive and hazardous materials. X-ray diffraction analysis of NaTaO3, Ca2Ta2O7, Ca4Ta2O9 and CaTa2O6 shows that these are the only phases detected after 4 h, 10 h, 27 h and 10 h of milling, respectively. During the synthesis of Ca2Ta2O7, an intermediate phase, Ca4Ta2O9, forms within 1 h, which reacts after 5 h to form the desired product. Reference Intensity Ratio analysis shows that the material synthesized mechanically is nanocrystalline Ca2Ta2O7.Nanocrystalline ZrSi2 can also be obtained through mechanochemical synthesis. This method allows for size control and results in crystallites ranging from 9 to 30 nm. Dilution with CaCl2 enables the size control process. A linear relationship exists between the concentration of CaCl2 and the crystallite size. Contrary to a typical self-propagating metathesis reaction, this process does not allow for self-propagation and requires continuous input of mechanical energy to continue. However, this method allows for non-passivated nanoparticles of ZrSi2, which can be incorporated into composites as a reinforcement material for several applications.Hard and ultra-compressible borides, such as ReB2 and OsB2, can be synthesized mechanically. The traditional synthesis of ReB2 requires excess boron due to treatment at high temperatures. This can lead to amorphous boron aggregating at the grain boundaries, which in turn, this would degrade the properties of the material. The mechanochemical approach requires mechanical treatment of Re and B powders in stoichiometric quantities for 80 h. Mechanical synthesis of OsB2 powders requires a 1:3 ratio of Os and B powders. After 12 h of milling time, h-OsB2 begins to form, and is the major phase present after 18 h. The lattice parameters corresponding to the hexagonal OsB2 were determined to be a = b = 2.9047 (&)#197;, c = 7.4500 (&)#197;, ? = ? = 90(&)#186;, ? = 120(&)#186;. Treatment of the OsB2 powder at 1050 (&)#186;C under vacuum for 6 days did not induce a phase change, suggesting the hexagonal phase is very stable.Mechanocatalysis of the depolymerization of cellulose and hydrogenation of olefins over BN are reported as well. Heterogeneous catalysis is difficult to apply to solids, such as cellulose. However, mechanical grinding of kaolin and cellulose allows for the catalysis to occur in the solid state. This process allows for a variety of different biomasses to be used as feedstock without inhibition. Kaolinite was found to be the best acid catalyst due to high surface acidity and its layered structure, allowing for up to 84% conversion of the cellulose to water-soluble compounds. This process allows for reduction of waste, insensitivity of feedstock, multiple product pathways and scalability.Hydrogenation reactions are carried out using transition-metals catalysts. These metals have desirable catalytic properties not seen in main group elements, but there is growing concern over their use. A metal-free heterogeneous hydrogenation catalyst based on frustrated Lewis pairs would significantly reduce the health, environmental, and economic concerns associated with these metal-based catalysts. We report the first metal-free heterogeneous hydrogenation catalyst. Hydrogenation of trans-cinnamic acid is carried out over defect-laden h-BN. The reactor we use is designed to maximize the defects produced in BN sheets. The introduction of defects in BN creates frustrated Lewis pairs. DFT calculations show that the carbon double bond is weakened over boron substitution for nitrogen sites, vacancies of both boron and nitrogen, and Stone-Wales defects.A new method for crystalline germanium deposition occurring at lower temperatures (210-260 (&)#186;C) is reported. This method involves mechanical treatment of the precursors to reduce the particle size. A ground mixture of Ge and CuI are heated under vacuum to synthesize GeI2. In situ disproportionation of this compound at 210 (&)#186;C allows for the deposition of polycrystalline Ge films onto a both glass and polymer substrates. The rate of deposition is found to be 25 ng min-1. The byproducts of this process are GeI2, GeI4 and Cu3Ge, which are valuable precursors for the synthesis of germanium nanostructures and organogermanium compounds.Mechanochemistry is also utilized for the synthesis of trisubstituted pnictides. Mechanochemical treatment of bromobenzene with either Na3Sb or Na3Bi allows for the formation of triphenylstibine or triphenylbismuthine, respectively. The synthesis of the alkali metals pnictide precursors is reported as well. The synthesis of triphenylstibine produces SbPh3 as the major product from the reaction. The synthesis of triphenylbismuthine produces more Wurtz-type coupling products, which are due to the BiPh3 acting as a catalyst. Tributyl and triphenyl analogues are reported as well. The trialkylated analogues for both Sb and Bi produce more Wurtz type coupling products. This would allow for a more cost effective and scalable, alternative methods than what is currently in use today.
Show less - Date Issued
- 2013
- Identifier
- CFE0004741, ucf:49785
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0004741
- Title
- UNDERSTANDING THE LOW TEMPERATURE ELECTRICAL PROPERTIESOF NANOCRYSTALLINE SNO2 FOR GAS SENSOR APPLICATIONS.
- Creator
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Drake, Christina, Seal, Sudipta, University of Central Florida
- Abstract / Description
-
Nanocrystalline metal/metal oxide is an important class of transparent and electronic materials due to its potential use in many applications, including gas sensors. At the nanoscale, many of the phenomena observed that give nanocrystalline semiconducting oxide enhanced performance as a gas sensor material over other conventional engineering materials is still poorly understood. This study is aimed at understanding the low temperature electrical and chemical properties of nanocrystalline SnO2...
Show moreNanocrystalline metal/metal oxide is an important class of transparent and electronic materials due to its potential use in many applications, including gas sensors. At the nanoscale, many of the phenomena observed that give nanocrystalline semiconducting oxide enhanced performance as a gas sensor material over other conventional engineering materials is still poorly understood. This study is aimed at understanding the low temperature electrical and chemical properties of nanocrystalline SnO2 that makes it suitable for room temperature gas detectors. Studies were carried out in order to understand how various synthesis methods affect the surfaces on the nano-oxides, interactions of a target gas (in this study hydrogen) with different surface species, and changes in the electrical properties as a function of dopants and grain size. A correlation between the surface reactions and the electrical response of doped nanocrystalline metal-oxide-semiconductors exposed to a reducing gas is established using Fourier Transform Infrared (FTIR) Spectroscopy attached to a specially built custom designed catalytic cell. First principle calculations of oxygen vacancy concentrations from absorbance spectra are presented. FTIR is used for effectively screening of these nanostructures for gas sensing applications. The effect of processing temperature on the microstructural evolution and on the electronic properties of nanocrystalline trivalent dopedSnO2 is also presented. This study includes the effect of dopants (In and Ce) on the growth of nano-SnO2, as well as their effects on the electronic properties and gas sensor behavior of the nanomaterial at room temperature. Band bending affects are also investigated for this system and are related to enhanced low temperature gas sensing. The role and importance of oxygen vacancies in the electronic and chemical behavior of surface modified nanocrystalline SnO2 are explored in this study. A generalized explanation for the low temperature gas sensor behavior of nanocrystalline oxide is presented that can be generalized to other nano-oxide systems and be useful in specific engineering of other nanomaterials. Deeper understanding of how nano-oxides react chemically and electronically would be extremely beneficial to issues present in current low cost, low temperature sensor technology. Ability to exactly monitor and then engineer the chemistry of nanostructures in the space charge region as well as the surface is also of great significance. Knowledge of the mechanisms responsible for enhanced sensor response in this material system could viably be applied to other material systems for sensor applications.
Show less - Date Issued
- 2007
- Identifier
- CFE0001668, ucf:47214
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0001668
- Title
- A Complete Approach to Predict Biodistribution of Nanomaterials Within Animal Species from In-vitro Data.
- Creator
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Price, Edward, Gesquiere, Andre, Huo, Qun, Kolpashchikov, Dmitry, Rex, Matthew, Ebert, Steven, University of Central Florida
- Abstract / Description
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Smart drug-design for antibody and nanomaterial-based therapies allows for optimization of drug efficacy and more efficient early-stage pre-clinical trials. The ideal drug must display maximum efficacy at target tissue sites, but to track and predict distribution to these sites, one must have a mechanistic understanding of the kinetics involved with the individual cells of the tissue itself. This process can be tracked through biological simulations coupled with in-vitro approaches, which...
Show moreSmart drug-design for antibody and nanomaterial-based therapies allows for optimization of drug efficacy and more efficient early-stage pre-clinical trials. The ideal drug must display maximum efficacy at target tissue sites, but to track and predict distribution to these sites, one must have a mechanistic understanding of the kinetics involved with the individual cells of the tissue itself. This process can be tracked through biological simulations coupled with in-vitro approaches, which result in a rapid and efficient in-depth understanding of drug transport within tissue vasculature and cellular environment. As a result, it becomes possible to predict drug biodistribution within live animal tissue cells without the need for animal studies. Herein, we use in-vitro assays to translate transport kinetics to whole-body animal simulations to predict drug distribution from vasculature into individual tissue cells for the first time. Our approach is based on rate constants obtained from an in-vitro assay that accounts for cell-induced degradation, which are translated to a complete animal simulation to predict nanomedicine biodistribution at the single cell level. This approach delivers predictions for therapies of varying size and type for multiple species of animals solely from in-vitro data. Thus, we expect this work to assist in refining, reducing, and replacing animal testing, while at the same time, giving scientists a new perspective during early stages of drug development.
Show less - Date Issued
- 2019
- Identifier
- CFE0007900, ucf:52747
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0007900
- Title
- Nano and nanostructured materials for optical applications.
- Creator
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Chantharasupawong, Panit, Thomas, Jayan, Hagan, David, Kik, Pieter, Gaume, Romain, Chanda, Debashis, University of Central Florida
- Abstract / Description
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Nano and nanostructured materials offer unique physical and chemical properties that differ considerably from their bulk counterparts. For decades, due to their fascinating properties, they have been extensively explored and found to be beneficial in numerous applications. These materials are key components in many cutting-edge optic and photonic technologies, including photovoltaics, waveguides and sensors. In this dissertation, the uses of nano and nanostructured materials for optical...
Show moreNano and nanostructured materials offer unique physical and chemical properties that differ considerably from their bulk counterparts. For decades, due to their fascinating properties, they have been extensively explored and found to be beneficial in numerous applications. These materials are key components in many cutting-edge optic and photonic technologies, including photovoltaics, waveguides and sensors. In this dissertation, the uses of nano and nanostructured materials for optical applications are investigated in the context of optical limiting, three dimensional displays, and optical sensing. Nanomaterials with nonlinear optical responses are promising candidates for self-activating optical limiters. In the first part of this study, optical limiting properties of unexplored nanomaterials are investigated. A photoacoustic detection technique is developed as an alternative characterization method for studying optical nonlinearities. This was done with an indigenously developed setup for measuring the photoacoustic signals generated from samples excited with a pulse laser. A theoretical model for understanding the experimental observations is presented. In addition, the advantages of this newly developed technique over the existing methods are demonstrated. Blending optical sensitizers with photoconducting polymers and chromophores results in a polymer composite that is able to record a light grating. This composite can be used as recording media in 3D holographic display technology. Here, 2D nano materials, like graphenes, are used as optical sensitizers to improve the response time of a photorefractive polymer. The addition of graphenes to a PATPD/ECZ/7-DCST composite results in a three-fold enhancement in response time and therefore faster recording speed of the medium. The faster build-up time is attributed to better charge generation and mobility due to the presence of graphenes in the composite. Lastly, a facile nanofabrication technique is developed to produce metallic nanostructures with a tunable plasmonic response. The enhancement of the light-matter interactions due to these nanostructures in sensing an analyte is demonstrated.
Show less - Date Issued
- 2015
- Identifier
- CFE0006029, ucf:51016
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0006029
- Title
- ARC-DISCHARGE IN SOLUTION: A NOVEL SYNTHESIS METHOD FOR CARBON NANOTUBES AND IN SITU DECORATION OF CARBON NANOTUBES WITH NANOPARTICLES.
- Creator
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Bera, Debasis, Seal, Sudipta, University of Central Florida
- Abstract / Description
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Nanotechnology has reached the status of the 21st century's leading science and technology based on fundamental and applied research during the last two decades. An important feature of nanotechnology is to bridge the crucial dimensional gap between the atomic and molecular fundamental sciences and microstructural scale of engineering. Accordingly, it is very important to have an in-depth understanding of the synthesis of nanomaterials for the use of state-of-the-art high technological...
Show moreNanotechnology has reached the status of the 21st century's leading science and technology based on fundamental and applied research during the last two decades. An important feature of nanotechnology is to bridge the crucial dimensional gap between the atomic and molecular fundamental sciences and microstructural scale of engineering. Accordingly, it is very important to have an in-depth understanding of the synthesis of nanomaterials for the use of state-of-the-art high technological devices with enhanced properties. Recently, the 'bottom-up' approach for the fabrication of nanomaterials has received a great deal of attention for its simplicity and cost effectiveness. Tailoring the various parameters during synthesis of selected nanoparticles can be used to fabricate technologically important components. During the last decade, carbon nanotubes (CNTs) have been envisioned for a host of different new applications. Although carbon nanotubes can be synthesized using a variety of techniques, large-scale synthesis is still a great challenge to the researchers. Three methods are commonly used for commercial and bulk productions of carbon nanotubes: arc-discharge, chemical vapor deposition and laser ablation. However, low-cost, large-scale production of high-quality carbon nanotubes is yet to be reported. One of the objectives of the present research is to develop a simplified synthesis method for the production of large-scale, low-cost carbon nanotubes with functionality. Herein, a unique, simple, inexpensive and one-step synthesis route of CNTs and CNTs decorated with nanoparticles is reported. The method is simple arc-discharge in solution (ADS). For this new method, a full-fledged optoelectronically controlled instrumen is reported here to achieve high efficiency and continuous bulk production of CNTs. In this system, a constant gap between the two electrodes is maintained using a photosensor which allows a continuous synthesis of the carbon nanostructures. The system operates in a feedback loop consisting of an electrode-gap detector and an analogue electronic unit, as controller. This computerized feed system was also used in single process step to produce in situ-decorated CNTs with a variety of industrially important nanoparticles. To name a few, we have successfully synthesized CNTs decorated with 3-4 nm ceria, silica and palladium nanoparticles for many industrially relevant applications. This process can be extended to synthesize decorated CNTs with other oxide and metallic nanoparticles. Sixty experimental runs were carried out for parametric analysis varying process parameters including voltage, current and precursors. The amount of yield with time, rate of erosion of the anode, and rate of deposition of carbonaceous materials on the cathode electrode were investigated. Normalized kinetic parameters were evaluated for different amperes from the sets of runs. The production rate of pristine CNT at 75 A is as high as 5.89 ± 0.28 g.min-1. In this study, major emphasis was given on the characterizations of CNTs with and without nanoparticles using various techniques for surface and bulk analysis of the nanostructures. The nanostructures were characterized using transmission electron microscopy, high resolution transmission electron microscopy, scanning transmission electron microscopy, energy dispersive spectroscopy and scanning electron microscopy, x-ray photo electron spectroscopy, x-ray diffraction studies, and surface area analysis. Electron microscopy investigations show that the CNTs, collected from the water and solutions, are highly pure except the presence of some amorphous carbon. Thermogravimetric analysis and chemical oxidation data of CNTs show the good agreement with electron microscopy analysis. The surface area analysis depicts very high surface area. For pristine multi-walled carbon nanotubes, the BET surface area is approximately 80 m2.g-1. X-ray diffraction studies on carbon nanotubes shows that the products are clean. Nano-sized palladium decorated carbon nanotubes are supposed to be very efficient for hydrogen storage. The synthesis for in-situ decoration of palladium nanoparticles on carbon nanotubes using the arc discharge in solution process has been extensively carried out for possible hydrogen storage applications and electronic device fabrication. Palladium nanoparticles were found to form during the reduction of palladium tetra-chloro-square planar complex. The formation of such a complex was investigated using ultraviolet-visible spectroscopic method. Pd-nanoparticles were simultaneously decorated on carbon nanotubes during the rolling of graphene sheets in the arc-discharge process. Zero-loss energy filtered transmission electron microscopy and scanning transmission electron microscopy confirm the presence of 3 nm palladium nanoparticles. The deconvoluted X-ray photoelectron spectroscopy envelope shows the presence of palladium. Surface area measurements using BET method show a surface area of 28 m2.g-1. The discrepancy with pristine CNTs can be explained considering the density of palladium (12023 kg.m-3). Energy dispersive spectroscopy suggests no functionalization of chlorine to the sidewall of carbon nanotubes. The presence of dislodged graphene sheets with wavy morphology as observed with high-resolution transmission electron microscopy supports the formation of CNTs through the 'scroll mechanism'.
Show less - Date Issued
- 2005
- Identifier
- CFE0000450, ucf:46388
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0000450
- Title
- DEVELOPMENT OF THERMALLY PROCESSED NANOCOMPOSITES WITH CONTROLLED SURFACES.
- Creator
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Georgieva, Petya, Seal, Sudipta, University of Central Florida
- Abstract / Description
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The ever increasing need for technology development requires the integration of inexpensive, light weight and high strength materials which are able to meet the high standards and specifications for various engineering applications. The intention of this work is to show that the suitable material selection and the utilization of plasma spray processing can be of potential interest to a large number of industrial, biomedical and everyday life applications. This research demonstrates also that...
Show moreThe ever increasing need for technology development requires the integration of inexpensive, light weight and high strength materials which are able to meet the high standards and specifications for various engineering applications. The intention of this work is to show that the suitable material selection and the utilization of plasma spray processing can be of potential interest to a large number of industrial, biomedical and everyday life applications. This research demonstrates also that plasma processing is a promising engineering tool for multifunctional coatings and near-net-shape manufacturing. Further, the theoretical and experimental results are combined in order to explain the mechanisms behind nanostructure retention and enhanced properties. Proper design of experiments, an appropriate material selection and experimental methodology are discussed herein. The experimental conditions were optimized in order to achieve the best materials properties according to their explicit properties and functions. Specific materials were consolidated according to their prospective performance and applications: 1) Plasma spraying of nano-Ceria-stabilized Zirconia free form part for stem cells scaffolds, 2) Plasma spraying of FeCrAlY on Ti-alloy plate, additionally coated with nano-size Hydroxyapatite for bone tissue engineering, 3) Wire-arc spraying of nano-based steel wires for aerospace and automotive applications. The performance and characteristics of all of the developed coatings and free-form-parts are evaluated using state-of-the art characterization techniques.
Show less - Date Issued
- 2006
- Identifier
- CFE0001153, ucf:46871
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0001153
- Title
- Electrode Integration of Nanostructured Metal and Metal Oxide Materials Based on in-situ Growth Methods for Environmental Sensors.
- Creator
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Wang, Xiaochen, Cho, Hyoung Jin, Fang, Jiyu, Chen, Quanfang, Lee, Woo Hyoung, University of Central Florida
- Abstract / Description
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In the past decades, increased human population and activities have introduced a large amount of pollutants into the environment. Various types of conventional analytical instruments were used for monitoring the emitted chemicals with low detection limit, high accuracy, and discrimination power. However, many of these methods are laboratory-based owing to sample collection, transportation, extraction, and purification steps. To make real-time on-site monitoring possible, miniaturized sensors...
Show moreIn the past decades, increased human population and activities have introduced a large amount of pollutants into the environment. Various types of conventional analytical instruments were used for monitoring the emitted chemicals with low detection limit, high accuracy, and discrimination power. However, many of these methods are laboratory-based owing to sample collection, transportation, extraction, and purification steps. To make real-time on-site monitoring possible, miniaturized sensors with various integrated elements were developed. One of the most well-known strategies is to utilize nanostructured materials with enhanced sensing properties for those devices. For a majority of the current state of art devices, the synthesis of nanostructured materials and device integration are done separately, that is, (")synthesis first and then integration(") approach which involves two separate process steps. However, this approach comes with some disadvantages such as misalignment, contamination, as well as disconnection between nanomaterials and electrodes.To overcome the aforementioned technical challenge, several synthesis methods were developed and validated for in-situ integration of nanostructured metal and metal oxide materials for environmental sensors in this work. The electroplating technique combined with photolithography was used to make the predefined metal electrodes. Then, with subsequent post-treatments, nanostructured metals and metal oxides could be produced in-situ and directly integrated in the electrodes without any extra transfer process steps.In the process of developing a phosphate sensor, nanofibrous Co electrodes were fabricated by pulsed electroplating of Co-Cu alloy and dealloying the Cu component. A linear potentiometric response to phosphate in the 10-5 to 10-2 M concentration range was obtained which validated the sensor's function. A mechanism based on mixed potential response was proposed to elucidate the Co electrode behavior in aqueous solutions with varying pH conditions and optimum pH ranges for working devices were proposed.In addition to the alloying and dealloying method, the template assisted electroplating method was also investigated. A nanoporous Co-Cu electrode fabricated by electroplating through a sacrificial glass fiber template was obtained. A linear amperometric response to phosphate with suppressed oxygen interference was achieved in a 10-5 to 10-2 M concentration range of phosphate. An analysis of the cyclic voltammetry characterization results provided a direction for further exploring an optimized electrode polarization potential range for suppressing oxygen interference while maintaining a good sensitivity to phosphate. Based on this result, we improved the fabrication process with another template: in-situ hydrothermally grown ZnO nanoflakes on the electrode surface, as a template for uniform nanostructured Co electroplating. The cyclic voltammetry characterization of the fabricated electrode showed an amperometric response in the range of 10-6 to 10-2 M of phosphate where the limit of detection (LOD) was enhanced compared with the previous work.For the flammable gas sensor development, the in-situ oxidation of Cu was utilized to form nanowires for sensing electrode fabrication. Multiple CuO nanowires were synthesized in-situ on the electroplated interdigitated Cu electrodes on a hotplate at 500 ? in air. The nanowires were successfully integrated as a sensing element into the device, forming bridges between two electrodes. The sensor's behavior was characterized by a current-voltage measurement. Simple processing parameters could be utilized for controlling the electrode morphologies and determining the characteristics of contacts - Schottky or Ohmic - at the electrode interface. A hypothesis was proposed to explain the transition phenomenon between Schottky and Ohmic contact modes, providing an important baseline for future device design and fabrication. Finally, the fabricated sensor was tested for a flammable gas detection using saturated ethanol vapor at room temperature, which implicates a low power consumption gas sensor without elevating the sensor temperature unlike traditional gas sensors.
Show less - Date Issued
- 2017
- Identifier
- CFE0007139, ucf:52312
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0007139
- Title
- Direct measurement of thicknesses, volumes or compositions of nanomaterials by quantitative atomic number contrast in high-angle annular dark-field scanning transmission electron microscopy.
- Creator
-
Yuan, Biao, Heinrich, Helge, Sohn, Yongho, Coffey, Kevin, Fang, Jiyu, Roldan Cuenya, Beatriz, University of Central Florida
- Abstract / Description
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The sizes, shapes, volumes and compositions of nanoparticles are very important parameters determining many of their properties. Efforts to measure these parameters for individual nanoparticles and to obtain reliable statistics for a large number of nanoparticles require a fast and reliable method for 3-D characterization. In this dissertation, a direct measurement method for thicknesses, volumes or compositions of nanomaterials by quantitative atomic number contrast in High-Angle Annular...
Show moreThe sizes, shapes, volumes and compositions of nanoparticles are very important parameters determining many of their properties. Efforts to measure these parameters for individual nanoparticles and to obtain reliable statistics for a large number of nanoparticles require a fast and reliable method for 3-D characterization. In this dissertation, a direct measurement method for thicknesses, volumes or compositions of nanomaterials by quantitative atomic number contrast in High-Angle Annular Dark-Field (HAADF) Scanning Transmission Electron Microscopy (STEM) is presented. A HAADF detector collects electrons scattered incoherently to high angles. The HAADF signal intensity is in first-order approximation proportional to the sample thickness and increases with atomic number. However, for larger sample thicknesses this approach fails. A simple description for the thickness dependence of the HAADF-STEM contrast has been developed in this dissertation. A new method for the calibration of the sensitivity of the HAADF detector for a FEI F30 transmission electron microscope (TEM) is developed in this dissertation. A nearly linear relationship of the HAADF signal with the electron current is confirmed. Cross sections of multilayered samples provided by TriQuint Semiconductors in Apopka, FL, for contrast calibration were obtained by focused ion-beam (FIB) preparation yielding data on the interaction cross section per atom.To obtain an absolute intensity calibration of the HAADF-STEM intensity, Convergent Beam Electron Diffraction (CBED) was performed on Si single crystals. However, for samples prepared by the focused ion beam technique, CBED often significantly underestimates the sample thickness. Multislice simulations from Dr. Kirkland's C codes are used for comparison with experimental results. TEM offers high lateral resolution, but contains little or no information on the thickness of samples. Thickness maps in energy-filtered TEM (EFTEM), CBED and tilt series are so far the only methods to determine thicknesses of particles in TEM. In this work I have introduced the use of wedge-shaped multilayer samples prepared by FIB for the calibration of HAADF-STEM contrasts. This method yields quantitative contrast data as a function of sample thickness. A database with several pure elements and compounds has been compiled, containing experimental data on the fraction of electrons scattered onto the HAADF detector for each nanometer of sample thickness. The use of thick samples reveals an increased signal at the interfaces of high- and low-density materials. This effect can be explained by the transfer of scattered electrons from the high density material across the interface into the less-absorbing low-density material. The calibrations were used to determine concentration gradients in nanoscale Fe-Pt multilayers as well as thicknesses and volumes of individual Au-Fe, Pt, and Ag nanoparticles. Volumes of nanoparticles with known composition can be determined with accuracy better than 15%. Porosity determination of materials becomes available with this method as shown in an example of porous Silicon.?
Show less - Date Issued
- 2012
- Identifier
- CFE0004464, ucf:49355
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0004464
- Title
- TUNING THE PROPERTIES OF NANOMATERIALS AS FUNCTION OF SURFACE AND ENVIRONMENT.
- Creator
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Karakoti, Ajay, Seal, Sudipta, University of Central Florida
- Abstract / Description
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Nanotechnology has shaped the research and development in various disciplines of science and technology by redefining the interdisciplinary research. It has put the materials science at the forefront of technology by allowing the researchers to engineer materials with properties ranging from electronics to biomedical by using materials as diverse as ceramics to just plain carbon. These exceptional properties are achieved by minimizing the dimension of particles in such smaller domains that...
Show moreNanotechnology has shaped the research and development in various disciplines of science and technology by redefining the interdisciplinary research. It has put the materials science at the forefront of technology by allowing the researchers to engineer materials with properties ranging from electronics to biomedical by using materials as diverse as ceramics to just plain carbon. These exceptional properties are achieved by minimizing the dimension of particles in such smaller domains that the boundary between the individual atoms, ions or cluster of particles is very small. This results in a change in conventional properties of particles from continuum physics to quantum physics and hence the properties of nanoparticles can be tuned based upon their size, shape and dimensionality. One of the most apparent changes upon decreasing the particle size is the increase in surface area to volume ratio. Thus nanoparticles possess greater tendency to interact with the environment in which they are present and similarly the environment can affect the properties of nanomaterials. The environment here is described as the immediate solid, liquid or gaseous material in immediate contact with the external surface of the nanoparticles. In order to control the physico-chemical properties of nanoparticles it is important to control the surface characteristics of nanoparticles and its immediate environment. The current thesis emphasizes the role of tuning the surface of nanoparticles and/or the environment around the nanoparticles to control their properties. The current approach in literature uses nanoparticles as a platform that can be used for a myriad of applications by just changing the surface species which can tune the properties of nanoparticles. Such surface modification can provide nanomaterials with hydrophilic, hydrophobic, biocompatible, sensing, fluorescence and/or electron transfer properties. The current thesis demonstrates the interaction between nanoparticles and the environment by changing the surface characteristics of nanomaterials through the use of oxide nanoparticles as examples. The first part of the thesis discusses the synthesis, modification and properties of cerium oxide nanoparticles (CNPs), a versatile material used in wide range of applications from catalysis to glass polishing, for their potential use in biomedical applications as a function of medium. The thesis starts by projecting the effect of environment on the properties of nanomaterials wherein it is shown that simple medium, such as, water can influence the optical properties of nanoparticles. It was shown that the strong polarizing effect of water on the non-bonding f electrons can cause a blue shift in the optical properties of CNPs as a function of increase in trivalent oxidation state of cerium in CNPs. This phenomenon, contradictory to existing literature in solid state where a red shift is observed upon increasing the trivalent oxidation state of cerium in CNPs, is purely attributed to the medium-inflicted change in properties of nanoparticles. This concept is built upon in the first half of thesis by increasing the colloidal stability of nanoparticles by surface and/or medium modification. It is shown that the narrow range of pH in which the colloidal CNPs are stable can be extended by changing the medium from water to polyhydroxy compounds such as glucose and dextran. The synthesis was designed specially to avoid the traditional precipitation and re-dispersion strategy of synthesis of nanoparticles to preserve the surface activity. The complex forming ability of cerium with polysaccharides was employed to synthesize the CNPs in a one step process and the pH stability of the NPs was extended between 2.0 to 9.5. The difference in the complexing ability of the monomer - glucose and its anhydro glucose polymer - dextran is reflected in the ability of cerium to form super-agglomerates with the monomer while anhydro gluco polymer forms extremely disperse 3-5 nm nanoparticles through steric modification. It is shown that the antioxidant activity of nanoparticles remain unchanged by surface modification by demonstrating the cycling of the oxidation state of cerium in CNPs, with time, through hydrogen peroxide mediated transition of oxidation states of cerium. It is demonstrated that the polymeric coatings, generally considered as passive surface coatings, can also play an active role in tuning the properties of nanomaterials and increasing their biocompatibility as well as bio-catalytic activity. It is demonstrated that the antioxidant activity of CNPs can be increased as a function of polyethylene glycol (PEG) while the biocompatibility is unaltered due to the biocompatible nature of PEG. The antioxidant activity of CNPs involves an electron transfer (ET) from the CNPs to the reactive oxygen species or vice versa. This heterogeneous ET system is further complicated by the presence of surface adsorbed species. Interfacial charge/electron transfer (ET) between a particle and adsorbed (or covalently bonded) molecule presents significant complexity as it involves a solid state electron transfer over long distance. Unlike a free ion, in solid state, the conducting electrons can be temporarily trapped by the coupling lattice sites. Adsorption/attachment of surface species to nanoparticle can disturb the electronic levels by further polarizing the electron cloud thereby localizing the electron and facilitating the charge transfer. Such an interfacial electron transfer between NPs and adsorbed organic species can be compared to the single electron transfer carried by organometallic systems with a metal ion core modified with electron delocalizing porphyrin ligands. It is demonstrated that in this PEGyltaed CNPs system, the PEG essentially forms a complex with CNPs in the presence of hydrogen peroxide to facilitate this electron transfer process. The superoxide dismutase (SOD) and catalase mimetic ability of CNPs is described and special emphasis is given to its biocompatibility. The second half of the thesis emphasizes the role of synthesis and surface modification in influencing the catalytic performance of cerium oxide modified titanium dioxide catalysts for decomposition of methanol. Noble metals supported on oxide nanoparticles have been an area of active research in catalysis. It is demonstrated that the modification of surface of the oxide nanoparticles by noble metals is a function of the synthesis process. By keeping the size of the nanoparticles constant, it was demonstrated that the differences in the oxidation state of noble metals can lead to change in the activity of noble metals. This contribution adds to the already existing controversy in the open literature about the role of the oxidation state of platinum in catalysis. The core level shifts in the binding energy of the 4f electrons of platinum was used as a guide to the gauge the oxidation state. Results from an in-house built catalytic reactor coupled to mass spectrometer and in-situ diffuse reflectance infra-red spectroscopy are used to quantify the catalytic performance and identify the mechanism of reaction as well as products of methanol decomposition.
Show less - Date Issued
- 2010
- Identifier
- CFE0003189, ucf:48590
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0003189
- Title
- Advanced Nanoscale Characterization of Plants and Plant-derived Materials for Sustainable Agriculture and Renewable Energy.
- Creator
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Soliman, Mikhael, Tetard, Laurene, Vaidyanathan, Raj, Kang, Hyeran, Santra, Swadeshmukul, Zhai, Lei, Chumbimuni Torres, Karin, University of Central Florida
- Abstract / Description
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The need for nanoscale, non-invasive functional characterization has become more significant with advances in nano-biotechnology and related fields. Exploring the ultrastructure of plant cell walls and plant-derived materials is necessary to access a more profound understanding of the molecular interactions in the systems, in view of a rational design for sustainable applications. This, in turn, relates to the pressing requirements for food, energy and water sustainability experienced...
Show moreThe need for nanoscale, non-invasive functional characterization has become more significant with advances in nano-biotechnology and related fields. Exploring the ultrastructure of plant cell walls and plant-derived materials is necessary to access a more profound understanding of the molecular interactions in the systems, in view of a rational design for sustainable applications. This, in turn, relates to the pressing requirements for food, energy and water sustainability experienced worldwide.Here we will present our advanced characterization approach to study the effects of external stresses on plants, and resulting opportunities for biomass valorization with an impact on the food-energy-water nexus.First, the adaption of plants to the pressure imposed by gravity in poplar reaction wood will be discussed. We will show that a multiscale characterization approach is necessary to reach a better understanding of the chemical and physical properties of cell walls across a transverse section of poplar stem. Our Raman spectroscopy and statistical analysis reveals intricate variations in the cellulose and lignin properties. Further, we will present evidence that advanced atomic force microscopy can reveal nanoscale variations within the individual cell wall layers, not attainable with common analytical tools. Next, chemical stresses, in particular the effect of Zinc-based pesticides on citrus plants, will be considered. We will show how multiscale characterization can support the development of new disease management methods for systemic bacterial diseases, such as citrus greening, of great importance for sustainable agriculture. In particular, we will focus on the study of new formulations, their uptake and translocation in the plants following different application methods. Lastly, we will consider how plant reactions to mechanical and chemical stresses can be controlled to engineer biomass for valorization applications. We will present our characterization of two examples: the production of carbon films derived from woody lignocellulosic biomass and the development of nanoscale growth promoters for food crop. A perspective of the work and discussion of the broader impact will conclude the presentation.
Show less - Date Issued
- 2018
- Identifier
- CFE0007415, ucf:52717
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0007415
- Title
- Tuning chemical and optical properties of nanomaterials: From extended surfaces to finite nanoclusters.
- Creator
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Hooshmand Gharehbagh, Zahra, Rahman, Talat, Kara, Abdelkader, Kaden, William, Uribe Romo, Fernando, University of Central Florida
- Abstract / Description
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Modifying the electronic and optical properties of surfaces and nanostructures are in the forefront of surface science. This dissertation's focus is on this problem. The first part is on the adsorption of functionalized naphthalene molecules on Cu(111) surface. The results show that changing the functional group results in modification of charge redistribution at the interface of molecule and surface and the electronic structure of Cu changes. The second part discusses the new Moir(&)#233;...
Show moreModifying the electronic and optical properties of surfaces and nanostructures are in the forefront of surface science. This dissertation's focus is on this problem. The first part is on the adsorption of functionalized naphthalene molecules on Cu(111) surface. The results show that changing the functional group results in modification of charge redistribution at the interface of molecule and surface and the electronic structure of Cu changes. The second part discusses the new Moir(&)#233; structure of h-BN on Rh(111) induced by intrinsic carbon impurities of Rh single crystals. We found that these impurities intercalate between h-BN and Rh(111) with new local properties such as charge transfer from Rh and C atoms to h-BN such as appearance of new states in the BN. The third part is about the study of CO super lattice structure at 1/2ML when adsorbed on Pd(111). By considering all the possible overlayer structures and using several different functionals, we found that two structures can be made by CO adsorbents and all the other structures convert to one of these two. The fourth part is on the electronic and optical properties of ligated Ag44 nanoclusters. Using DFT and TDDFT calculations we show that when the pH level of a solvent is changed, the protecting ligands deprotonate and their interaction with each other as well as the metal core varies and the new peaks in absorption spectrum arise from electron rich deprotonated ligands. The final part is on the adsorption of planar molecules on MoS2. We found that the isomers of di-iodobenzene adsorb with same strength on MoS2 and it is the symmetry of frontier orbitals that identifies their different behavior. Also the adsorption and dissociation of benzenethiol on MoS2 was studied and the results show that benzenethiol dissociates only in the presence of defects and heals the structure.
Show less - Date Issued
- 2018
- Identifier
- CFE0007337, ucf:52138
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0007337