A thesis submitted to the Faculty of Science, University of the Witwatersrand, Johannesburg, in fulfilment of the requirements for the degree of Doctor of Philosophy. / A comprehensive experimental study on alternating current (AC) electrical transport in the three forms of carbon nanotubes (CNTs) and nanodiamond films is presented. It is termed dynamic electrical transport to differentiate it from direct current measurements, which may be referred as static transport. The results and analysis are based on the scattering parameter measurements of a few horizontally aligned single, double, multi-walled carbon nanotubes and nanodiamond films. Which were measured in the frequency range 10 MHz to 65 GHz, at room and cryogenic temperatures using a vector network analyser. The work is motivated by the fact that AC transport in 1D systems has not been fully studied and is not well understood. From direct current measurements, it is known that one dimensional (1D) electrical transport is very different from its two or three dimensional counterpart. This is because adding an electron to a 1D system tends to affect the whole system in ways which to date cannot be fully explained theoretically. CNTs present an ideal platform to study the AC or dynamic transport behaviour of 1D systems because of the high mobility and electrical conductivity at nano-scale. Therefore from the AC complex impedance and conductance, this work demonstrates quantum effects of collectively excited strongly interacting electrons (Luttinger Liquid), which had been predicted theoretically but not observed experimentally using this technique. Ballistic transport at room temperature is also demonstrated by setting the stimulus frequency higher than the scattering rate in the CNTs. A crossover from capacitive to inductive behaviour in the imaginary component of impedance has been shown by improving the CNT-electrode coupling. Furthermore the effect of metal contacts on microwave/ radio frequency transmission is also demonstrated. The results are consolidated by RF simulations, as strong conclusions are drawn. Studies on the dynamic transport in nanodiamond films revealed a crossover from the insulating to semi-metallic regime by nitrogen incorporation. The crossover is explained by considering the changes of the grain boundary morphology. This work shows that AC transport in polycrystalline nanodiamond films is similar to DC transport.

M.Sc., Faculty of Science, University of the Witwatersrand, 2011 / In this dissertation, the synthesis of nitrogen doped carbon nanotubes (N-CNTs) was performed successfully, using a floating catalyst chemical vapour deposition (CVD) method. Fe(CO)5 was utilized as the catalyst and acetonitrile and toluene as nitrogen and carbon sources respectively. Two different procedures were used to add reagents to the reactor: an injection method and a bubbling method. The effect of nitrogen concentration and physical parameters such as reaction temperature, gas flow rate on the morphology, crystallinity and thermal stability of the tubes was studied. The synthesized materials were characterized by means of Raman spectroscopy, TGA and TEM analyses. The presence of nitrogen was confirmed by the presence of the bamboo formations in the tubes by TEM. A comparison of the data from the numerous reactions revealed that N-CNTs can be made from Fe(CO)5 and acetonitrile. Further the main conclusions achieved using the injection method were: i) the maximum number of tubes with bamboo structure were made using on acetonitrile concentration of 15%, ii) The best growth temperature to make N-CNTs was 850 oC, iii) An increase in acetonitrile concentration decreased the yield of NCNTs and iv) Tubes with the narrowest outer diameters were made using an acetonitrile concentration of 15%.

A dissertation submitted to the Faculty of Science, University of the Witwatersrand, Johannesburg, in fulfilment of the requirements for the Degree of Master of Science. Johannesburg, 2015. / Fly ash is a by-product generated during the combustion of coal for electricity gen- eration. Previous studies have shown that various waste fly-ashes (Japanese, Saudi Arabian, and Australian) contain trace quantities of transition metal elements which can be used in the synthesis of shaped carbon nanomaterials. A survey of the litera- ture has shown that no attempts to correlate the composition of a particular coal fly ash and the type or quantity of carbon nanomaterials (CNMs) that can be synthesized has been made. Neither has the effect of leached fly ash been tested for the synthesis of CNMs. Hence a study on the effect of the chemical composition of South African fly ash (collected from ESKOM’s Duvha power station in Mpumalanga) upon the chemical vapour deposition (CVD) synthesis of carbon nanostructures is justified. Untreated and chemically treated fly ash samples were used as catalysts in the CVD method to synthesize CNMs. In the latter case selective leaching experiments were conducted on the fly ash samples under acidic, basic and neutral conditions. Op- timal CNM synthetic conditions were achieved by initially flowing H2 gas to re- duce the metal oxides within the fly ash catalyst followed by the introduction of the carbon source (C2H2) at a temperature range of 600 - 800 ◦C. All samples were quantitatively and/or qualitatively characterized. Inductively coupled plasma optical emission spectrometry (ICP-OES) and X-ray fluorescence (XRF) techniques were used to quantify the metal ions which were removed from the fly ash samples. Fur- thermore, qualitative studies were conducted with (PXRD, and laser Raman spec- troscopy), morphological and surface area characterization techniques (SEM, TEM and BET) were used to investigate the synthesis of CNMs from the untreated and chemically treated fly ash samples. Results have shown that carbon nanofibers (CNFs) of different geometric morpholo- gies were synthesized at an optimal yield temperature of 700◦C. A combination of smooth, thin, wide, spiral platelet-like, stacked cup, and fishbone morphologies were reported when the untreated fly ash catalyst was used. Fly ash catalysts under acidic, basic and neutral treatments showed CNFs of varying sizes and specific morpholo- gies. Smooth graphitic platelet-like, stacked cup and platelet-like CNFs were re- ported when the fly ash catalyst was leached with neutral, basic and acidic solutions. Carbon nanofibre sizes with the IG ID ratios were reported as follows 115 nm (1.092), 52 nm (0.799), and 200 nm (0.960) under neutral, basic and acidic mediums respec- tively. Surface areas (41, 14 and 7) m2/g for the CNFs that were synthesised from the neutral, basic and acidic treated fly ash catalysts were related to the selective leaching of metals. The quality and quantity of CNFs obtained under acidic medium were associated with the leaching of iron (5.6%), cobalt (1.7%), calcium (20.4%), copper (12.5%), chromium (4.6%), magnesium (23.3%), manganese (15.2%) and nickel (2%) from the fly ash catalyst. Under a basic medium only chromium (0.2%), calcium (0.3%) and copper (7.4%) were removed. Significantly the best quality of CNFs was ob- tained when fly ash was treated under neutral conditions. Metal ions such as: cal- cium (3.7%), copper (3.8%), chromium (0.1%), and magnesium (1.3%) were mod- erately removed from the ash matrix. Therefore, composition and quantity of the fly ash catalyst had an effect on the synthesis of CNFs.

SC-15 epoxy is used in many industrial applications and it is well known that the mechanical and viscoelastic properties of epoxy can be signicantly enhanced when reinforced with nanofillers. In this work, SC-15 epoxy is reinforced by loading with magnetically-active nanofillers and cured in a modest magnetic field. Because of the signicant magnetic response of the nanofillers, this is a low cost and relatively easy technique for imposing a strong magnetic anisotropy to the system without the need of a superconducting magnet. It is also found that this method is an effective way of enhancing the mechanical properties of epoxy. Three systems were prepared and studied. The first is a dilute system of various concentrations of Fe2O3 nanoparticles in SC-15 epoxy. The second system is a combination of Fe2O3 nanoparticles and chemically-functionalized single-walled carbon nanotubes (SWCNT(COOH)s) in SC-15 epoxy. The third is a dilute system of SWCNT(COOH)s decorated with Fe3O4 particles t hrough a sonochemical oxidation process in SC-15 epoxy. Samples have an initial cure of 6 hrs in a magnetic led of 10 kOe followed by an additional 24 hours of post curing at room temperature. These are compared to the control samples that do not have initial field curing. Tensile and compressive stress-strain analysis of the prepared systems shows that mechanical properties such as tensile strength, tensile modulus and compressive strength are enhanced with the inclusion of these nanofillers. It is also found that there is an anisotropic enhancement of these properties with respect to the imposed curing field. An interesting phenomenon is observed with the increase in modulus of toughness and fracture strain with nanotube inclusion. / These parameters are drastically enhanced after curing the systems in a magnetic field. While there is a modest shift in glass transition temperature during viscoelastic analysis, the thermal stability of the created systems is not compromised. Results of these mechanical enhancements will be compared with other nanoloading techniques from literature. / by Olga Malkina. / Thesis (Ph.D.)--Florida Atlantic University, 2011. / Includes bibliography. / Electronic reproduction. Boca Raton, Fla., 2011. Mode of access: World Wide Web.

This thesis investigates the use of nanotechnology in an extensive literature search in the field of cement and concrete. A summary is presented. The research was divided into two categories: (1) nanoparticles and (2) nanofibers and nanotubes. The successes and challenges of each category is documented in this thesis. The data from the literature search is taken and analyzed using statistical prediction by the use of the Monte Carlo and Bayesian methods. It shows how statistical prediction can be used to analyze patterns and trends and also discover optimal additive dosages for concrete mixes. / by Jonathan Glenn. / Thesis (M.S.C.S.)--Florida Atlantic University, 2013. / Includes bibliography. / Mode of access: World Wide Web. / System requirements: Adobe Reader.

Thesis (MTech (Chemistry))--Cape Peninsula University of Technology, 2016. / The subject of this current study concerns highly concentrated emulsions of the explosive grade. A distinguishing characteristic of these systems is a high internal to external phase volume ratio. The volume fraction of the aqueous phase of such an emulsion generally far exceeds the close packing limit. Continuous phase of the system is a supersaturated aqueous solution of ammonium nitrate inorganic salt. In combination with high internal phase concentration, this inevitably leads to the destabilisation of the system. The thermodynamic instability of such systems is attributed to two major factors: 1) crystallisation of dispersed phase and 2) coalescence of the individual droplets within the bulk. This poses a significant problem since destabilisation of the bulk emulsion in turn leads to partial or complete loss of sensitivity to detonation of the final product of which highly concentrated emulsion is the base. Since the invention of such types of bulk explosives, a considerable and on-going effort has targeted the improvement of the stability of these systems, with a scope primarily focused on the use of various surfactant agents with different properties as well as stabilising mixtures containing numerous surfactants. In recent years, a new approach has been explored: the stabilisation of highly concentrated emulsions with the use of solid fumed silica nanoparticles. This is a promising new field of study, already being implemented by manufacturers and actively developing. The focus of this present study is to investigate and lay the ground work for further research in the principally new approach towards the stabilisation of highly concentrated emulsions with the use of the polyhedral oligomeric silsesquiozane nanomolecules. These are unique compounds possessing hybrid inorganic-organic structures and properties, and carrying a range of advantages over currently implemented surfactants. As opposed to silica nanoparticles, these compounds are not solid particles but can be regarded as molecular silica. This investigation will focus on the general possibility of implementation of such compounds as stabiliser agents for emulsions in general, and highly concentrated emulsions of the explosive grade in particular, and the resultant effects on the stability. Effects on stability will be investigated both when used solely and in combination with common surfactants. In addition, stability both on shelf and under stress will be investigated within the framework of the study.

表面等離子體基元共振是自由電子在納米尺寸的集體共振效應，該效應會產生一系列新奇的性質。貴金屬納米結構由於可以產生表面等離子體基元共振而受到各個領域廣泛的關注。在共振激發的情況下，貴金屬納米結構具有極大的散射和吸收截面積以及極強的進場放大效應。這些奇特的性質可以應用於傳感、成像、光學調製、光熱療、光催化和太陽能電池等領域。金和銀納米結構由於其表面等離子體基元共振波長處在可見和近紅外波段而受到廣泛研究。然而，在某些應用中純金或純銀納米結構不能起到很好的作用。例如，金和銀對很多化學反應的催化活性很弱或者沒有催化活性。如果把金和銀與其他金屬複合在一起就可以同時獲得表面等離子基元共振和其他效應。在我的博士研究期間，我製備了Au/Ag 和Au/Pd 複合雙金屬納米結構和研究了該複合結構的表面等離子體基元共振的性質和在氫氣傳感和光催化中的應用。 / 由於在金屬納米結構的製備中晶種起著至關重要的作用，所以我首先研究了晶種的晶體結構和形狀對雙金屬納米結構合成的影響。我研究了銀和鈀分別在相同條件下在單晶金納米棒、多晶金納米棒和納米雙錐種子上的生長過程。研究發現當晶種是單晶金納米棒時，銀和鈀的生長形成長方體雙金屬納米結構。然而，當晶種是多晶的金納米棒和納米雙錐時，銀和鈀的生長生成納米棒雙金屬結構。銀和鈀在多晶金納米棒上的生長由兩端開始，而在多晶金納米雙錐上的生長由臺階面開始。這表明在雙金屬納米結構的生長過程中納米晶種的晶體結構對最終納米結構的形貌具有決定性的作用，而納米晶種的形狀對生長動力學有明顯的影響。 / 在Au/Ag納米晶製備過程中，我發現Au/Ag納米晶具有四個表面等離子體基元共振峰。於是我對這四個共振峰的演變和共振模式進行了實驗和理論研究。電動力學模擬表明能量最低的共振峰是縱向的電偶極共振，能量次低的共振峰是沿橫向的電偶極共振，兩個高能量的共振峰是沿著橫向的電八極共振。遲滯效應和兩個垂直橫向激發的干涉是導致形成兩個電八極共振的關鍵因素。研究發現隨著銀殼厚度的增加，縱向電偶極共振峰藍移，橫向電偶極共振峰先藍移后稍微紅移，兩個電八極共振沒有明顯的峰位移動。四個表面等離子體基元共振的強度都隨著銀殼厚度的增加而增強。 / 鈀被廣泛地應用於氫氣傳感和催化反應中。於是我研究了Au/Pd 雙金屬納米結構的氫氣傳感和光催化性能。在氫氣傳感研究中，我製備了兩種不同結構的Au/Pd 納米結構。一種具有連續的鈀殼層，另一種鈀殼層不連續。對於具有連續鈀殼層的納米結構，氫氣的傳感性能隨著鈀殼層厚度的增加而增加。實驗發現當納米結構暴露在4%的氫氣中時表面等離子體基元共振峰移動高達56 nm。不連續鈀殼層的納米結構的氫氣傳感性能不如連續鈀層的納米結構。我進一步對Au/Pd 雙金屬納米結構的光催化性能進行了研究。所選取的催化反應是Suzuki 偶聯反應。研究結果表明Au/Pd 納米結構可以有效地捕獲光能來促進化學反應。由於Au/Pd 納米結構使表面等離子體基元共振功能和催化功能緊密集成在一個納米結構中，因此表面等離子基元共振部份所捕獲的光能可以有效地傳遞到催化功能部份而實現光催化。研究發現熱電子效應和光熱轉化效應同時加速化學反應。其中光熱轉化在我的實驗中體現為非局部加熱效應，熱電子對化學反應的促進作用依賴于環境溫度。因此，光熱轉化效應可以促進熱電子轉移效應。 / 本論文的研究結果有助於人們瞭解具有表面等離子體基元共振性質的雙金屬納米機構的設計和應用。對Au/Ag雙金屬納米結構表面等離子體基元共振性質的研究不僅加深了人們對雙金屬表面等離子體基元共振的瞭解而且對利用不同共振模式實現特定功能有著指導意義。對Au/Pd雙金屬納米結構在氫氣傳感和催化反應應用中的研究明確表面雙金屬表面等離子體納米結構可以實現單一組成不具備的功能，這在一定程度上有助於擴展表面等離子基元共振在生命科學、能源和環境領域的應用。 / Noble metal nanocrystals have attracted great interest from a wide range of research fields because of their intriguing properties endowed by their localized surface plasmon resonances, which are the collective oscillations of free electrons. Under resonant excitation, metal nanostructures exhibit very large scattering and absorption cross sections and large near-field enhancement. These extraordinary properties can be used in different applications, such as plasmonic sensing and imaging, plasmon-controlled optics, photothermal therapy, photocatalysis, solar cells, and so on. Gold and Silver nanocrystals have plasmon resonances in the visible and near-infrared regions. However, gold and silver are not suitable for some applications. For example, they are generally inactive for catalyzing chemical reactions. The integration of plasmonic metals with other metals can offer superior or new physical/chemical properties. In this thesis, I prepared Au/Ag and Au/Pd bimetallic nanostructures and studied their lasmonic properties and applications in hydrogen sensing and photocatalysis. / Seeds have a crucial importance in the synthesis of bimetallic nanostructures. I therefore first studied the roles of the crystalline structure and shape of seeds on the overgrowth of bimetallic nanostructures. The overgrowth of silver and palladium on single crystalline Au nanorods, multicrystalline Au nanorods, and nanobipyramids were studied under the same conditions for each metal. The growths of silver and palladium on single crystalline Au nanorods gave cuboidal nanostructures, while rod-shaped nanostructures were obtained from the growths of silver and palladium on multicrystalline Au nanorods and nanobipyramids. Moreover, the growths of silver and palladium on multicrystalline Au nanobipyramids started at the stepped side facets, while the growths started at the twin boundaries on multicrystalline Au nanorods. These results unambiguously indicate that the crystalline structure of seeds plays a significant role on the final morphologies of multimetallic nanostructures, while the seed shape has a prominent effect on the growth kinetics. / Four plasmon resonance bands were observed in Au/Ag bimetallic nanocrystals. I then studied the evolution and nature of the four plasmon bands during the silver coating on Au nanorods both experimentally and theoretically. Electrodynamic simulations revealed that the lowest-energy peak belongs to the longitudinal dipolar plasmon mode, the second-lowest-energy peak is the transverse dipolar plasmon mode, and the two highest-energy peaks can be attributed to octupolar plasmon modes. The retardation effect and the interference between two perpendicularly polarized excitations along the edge directions are important for the formation of the distinct highest-energy and second-highest-energy octupolar plasmon modes, respectively. As the Ag shell thickness is increased, the longitudinal plasmon mode blue-shifts, the transverse plasmon mode first blue-shifts and then red-shifts slightly, and the two octupolar plasmon modes stay at nearly constant wavelengths. The extinction intensities of all the four plasmon bands increase with the increase of the overall particle size. / Palladium is widely used in hydrogen sensing and catalysis. I therefore studied the applications of Au/Pd bimetallic nanostructures in hydrogen sensing and photocatalysis. Two types of Au/Pd bimetallic nanostructures, nanostructures with continuous and discontinuous Pd shells, were employed to study their hydrogen sensing performances. For the nanostructures with continuous Pd shell, the hydrogen sensing performances were improved with the increase in the Pd shell thickness. A plasmon shift of 56 nm was observed when the hydrogen concentration was 4%. The nanostructures with discontinuous Pd shell exhibited smaller plasmon shifts compared with those with continuous Pd shell. For the photocatalytic application of Au/Pd bimetallic nanostructures, I studied their photocatalytic performance for Suzuki coupling reactions. The results indicate that plasmonic Au/Pd bimetallic nanostructures can efficiently harvest light energy for chemical reactions. The intimate integration of plasmonic and catalytic components in one nanostructure enables the light energy absorbed by the plasmonic component to be directly transferred to the catalytic component. Both hot electron transfer and photothermal heating contribute to the plasmon-enhanced chemical reactions. The photothermal effect is a nonlocal heating and the contribution of the hot electron transfer effect is dependent on the environmental temperature. Therefore, the photothermal heating effect can promote the hot electron transfer effect. / I believe that my research work will be very helpful for the design and application of plasmonic bimetallic nanostructures. My study on the plasmonic properties of Au/Ag bimetallic nanocrystals has deepened the understanding of the plasmons of Au/Ag nanorods and will be helpful for utilizing the different modes to achieve specific functions. The hydrogen sensing and photocatalysis of Au/Pd bimetallic nanostructures have shown that the integration of functional components with plasmonic nanostructures can achieve unconventional properties, which will flourish the applications of plasmons in life sciences, energy, and environmental areas. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Jiang, Ruibin = 雙金屬納米結構表面等離子體基元共振的研究及其在氫氣傳感和化學反應中的應用 / 江瑞斌. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2013. / Includes bibliographical references. / Abstracts also in Chinese. / Jiang, Ruibin = Shuang jin shu na mi jie gou biao mian deng li zi ti ji yuan gong zhen de yan jiu ji qi zai qing qi chuan gan he hua xue fan ying zhong de ying yong / Jiang Ruibin. / Abstract --- p.I / Acknowledgements --- p.VI / Table of Contents --- p.VIII / List of Figures --- p.X / List of Tables --- p.XIII / Chapter 1 --- Introduction --- p.1 / Chapter 1.1 --- Localized surface plasmon resonances --- p.1 / Chapter 1.2 --- Applications of localized surface plasmon resonances --- p.3 / Chapter 1.3 --- Overview of this thesis --- p.13 / Chapter 2 --- Theory, Simulation, and Experimental Methods for the Investigation of LSPRs --- p.20 / Chapter 2.1 --- Theoretical methods --- p.20 / Chapter 2.2 --- Simulation methods --- p.30 / Chapter 2.3 --- Experimental methods --- p.35 / Chapter 3 --- Preparation of Metal Nanostructures --- p.43 / Chapter 3.1 --- Preparation methods for Au nanocrystals --- p.43 / Chapter 3.2 --- Seed-mediated growth method --- p.46 / Chapter 3.3 --- Metal nanostructure preparations --- p.54 / Chapter 4 --- Crystalline Structure-Determined Growth of Bimetallic Nanocrystals --- p.62 / Chapter 4.1 --- Au nanocrystal seed preparation --- p.64 / Chapter 4.2 --- Au/Ag bimetallic nanocrystals --- p.66 / Chapter 4.3 --- Au/Pd bimetallic nanocrystals --- p.71 / Chapter 4.4 --- Summary --- p.77 / Chapter 5 --- Plasmons of Au/Ag Core/Shell Bimetallic Nanocrystals --- p.83 / Chapter 5.1 --- Variations of plasmons with Ag shell thickness --- p.86 / Chapter 5.2 --- Nature of the different plasmon modes --- p.94 / Chapter 5.3 --- Summary --- p.99 / Chapter 6 --- Au/Pd Bimetallic Nanostructures for Hydrogen Sensing --- p.105 / Chapter 6.1 --- Au nanorods with continuous Pd shell for hydrogen sensing --- p.107 / Chapter 6.2 --- Au nanorods with discontinuous Pd shell for hydrogen sensing --- p.114 / Chapter 6.3 --- Theoretical simulations --- p.117 / Chapter 6.4 --- Summary --- p.119 / Chapter 7 --- Plasmon-Enhanced Chemical Reactions --- p.124 / Chapter 7.1 --- Mechanisms of plasmon enhancement in chemical reactions --- p.125 / Chapter 7.2 --- Plasmon-enhanced Suzuki coupling reactions --- p.129 / Chapter 7.3 --- Summary --- p.149 / Chapter 8 --- Conclusions --- p.156 / Curriculum Vita --- p.160

各種納米結構的光學反應，已成為一被相當關注的課題，在物理理論和應用技術的層面上被廣泛研究。在本文中，我們利用格林函數方法(GFF)，研究了新月形圓柱体和兩接近中的圓柱体的靜電共振。格林函數方法裏涉及一表面積分方程式，我們求該方程的解便可以得出各不同形狀的納米結構的電勢。格林函數方法是一容易使用、高效率的方法，並且在研究納米結構的光學行為的問題上得出準確結果。 / 在論文的第一部分，我們計算了新月形圓柱体和兩接近中的圓柱体的杆光譜，從而研究該兩個結構的靜電共振。然而，當這兩個結構中有接觸點時，系統中便有一奇點，因此我們不能直接使用格林函數方法研究這情況。為了解決這問題，我們首先使用了變換光學的方法，求得該結構的雙極因子，再從中得到其有效介電常數的譜密度。為了比較非接觸情況中離散的杆光譜和接觸情況中的連續杆光譜，我們進一步定義了一累積分佈函數，它是其譜密度的累積分佈函數。我們從而發現當系統由非接觸的情況漸近接觸時，其離散的杆光譜便趨向其相應的連續杆光譜。 / 在論文的第二部分，我們直接研究了新月形圓柱体和兩接近中的圓柱体的勢分佈和電埸分佈。我們發現在新月形圓柱体和兩接近中的圓柱体的系統中，能量會分別將集中於其金屬間隔和空氣間隔附近的區域。當我們適當地選擇系統的參數時，其共振及能量更能進一步增強。我們亦確認了使用格林函數方法和使用保角變換方法兩者得出的結果的是吻合的。我們的研究結果可以幫助設計電漿子捕光裝置。 / The optical responses of various nanostructures have attracted a considerable attention and they have been extensively studied from the theoretical and technological points of view. In this thesis, we have studied the electrostatic resonance of crescent-shaped cylinder and two approaching cylinders by the Green function formalism (GFF). In the GFF, a surface integral equation is formulated for the scalar potential for an arbitrary number of nanostructures of various shapes. GFF is easy to apply and gives accurate results for the optical behaviors of these nanostructures. / In the first part of the thesis, we have studied the electrostatic resonance of crescent-shaped cylinder and two approaching cylinders by calculating the pole spectrum. However, in the touching case, there is a singular point and thus the GFF cannot be applied directly. To circumvent this problem, the spectral density is found from the polarizability of the nanostructure, which can be obtained analytically by the transformation optics approach. To compare the discrete pole spectrum of the non-touching cases with the continuous spectrum of the touching case, we have used the cumulative distribution function of the spectral density. We are then able to show that the discrete pole spectrum approaches to the continuous pole spectrum as the system approaches from non-touching cases to the touching case. / In the second part of the thesis, the electrostatic resonance is investigated by directly finding the local field distributions of crescent and two approaching cylinders under a uniform applied electric field. It is shown that there is an energy concentration within the metal narrow gap and the air narrow gap in the cases of crescent and two approaching cylinders respectively. It is also found that when parameters are carefully chosen, the nanoconcentration of energy will be greatly enhanced. The numerical GFF results are confirmed with the analytic results by conformal transformation. The results are useful in designing plasmonic light-harvesting devices. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Yung, Sai Kit = 電漿子納米結構中的能量集中 : 格林函數方法 / 翁世杰. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2012. / Includes bibliographical references (leaves 71-74). / Abstracts also in Chinese. / Yung, Sai Kit = Dian jiang zi na mi jie gou zhong de neng liang ji zhong : Gelin han shu fang fa / Weng Shijie. / Abstract --- p.i / 摘要 --- p.iii / Acknowledgements --- p.iv / Chapter 1 --- Introduction --- p.1 / Chapter 1.1 --- Optical responses in plasmonic systems --- p.1 / Chapter 1.2 --- Objective of the thesis --- p.5 / Chapter 2 --- Review on Green function formalism --- p.7 / Chapter 2.1 --- Integral equation formalism --- p.7 / Chapter 2.2 --- Periodic corrugated interfaces --- p.11 / Chapter 2.3 --- Solution by mode expansion --- p.16 / Chapter 2.4 --- Numerical solution --- p.18 / Chapter 3 --- Pole spectrums of crescent-shaped cylinder and approaching cylinders --- p.21 / Chapter 3.1 --- Review of Green function formalism on the spectral representation of the effective dielectric constant --- p.22 / Chapter 3.2 --- Numerical results --- p.29 / Chapter 3.2.1 --- Spectral representation of the effective dielectric constant of crescent-shaped cylinders --- p.29 / Chapter 3.2.2 --- Spectral representation of the effective dielectric constant of approaching cylinders --- p.37 / Chapter 4 --- Energy concentration of crescent and approaching cylinders --- p.44 / Chapter 4.1 --- Energy concentration of crescent-shaped cylinder --- p.45 / Chapter 4.2 --- Energy concentration of approaching cylinders --- p.53 / Chapter 5 --- Conclusion --- p.58 / Chapter 5.1 --- Suggestion of future works --- p.60 / Chapter A --- Conformal transformation --- p.61 / Chapter A.1 --- Conformal transformation on crescent-shaped cylinder: nontouching case --- p.61 / Chapter A.2 --- Conformal transformation on approaching crescent-shaped cylinders --- p.66 / Bibliography --- p.71

A series of interesting core/shell silver/phenol formaldehyde resin (PFR) nano/microstructures were also synthesized through an efficient microwave process by self-assembly growth. Various morphologies, including monodispersed nanospheres, nanocables, and microcages were obtained by changing the fundamental experimental parameters, such as the reaction time and the surfactants (Pluronic P123 or CTAB). The results indicated that the presence of triblock copolymer Pluronic P123 would result in hollow silver/PFR microcages, while CTAB would prefer the formation of ultralong silver/PFR coaxial nanocables. In the absence of surfactants, monodispersed core/shell silver/PFR nanospheres could be obtained. The size of the nanospheres can be controlled in the range of 110 to 450 nm by changing the molar ratio of reagents (phenol:hexamine). The morphology and composition of the as-prepared products were characterized. The formation mechanism of the products was discussed based on the obtained results. / Bifunctional mesoporous core/shell Ag FeNi3 nanospheres were synthesized by reducing iron(III) chloride, nickel(II) chloride and silver nitrate with hydrazine in ethylene glycol under microwave irradiation. The efficient microwave-hydrothermal process significantly shortened the synthesis time to one minute. The toxicity of Ag FeNi3 nanospheres were tested by exposing to zebrafish, they were less toxic than silver nanoparticles. In vitro MRI confirmed the effectiveness of the Ag FeNi3 nanospheres as sensitive MRI probes. The interaction of Rhodamine Band nanospheres showed greatly enhanced fluorescence over the FeNi3 nanoparticles. / Finally, a series of ZnO microarchitectures including monodispersed spindles, branches, flowers, paddies, and sphere-like clusters were prepared by an efficient microwave-hydrothermal process. The ZnO mophologies could be effectively controlled by changing the reaction conditions such as the reaction temperature, the reactant concentrations and the solvent system. Simple microspindles, interesting flowers and paddies could be obtained in the presence of hexamine, and the more attractive sphere-like clusters could be synthesized by introducing phenol. The formation mechanisms of different morphologies are discussed in detail. These interesting ZnO structures may have potential applications in electronic and optoelectronic devices. / Inorganic nanostrucured materials have attracted much attention owing to their unique features and important applications in biomedicine. This thesis describes the development of rapid and efficient approaches to synthesize inorganic nanostructures, and introduces some potential applications. / Magnetic nanostructures, such as necklace-like FeNi3 magnetic nanochains and magnetite nanoclusters, were synthesized by an efficient microwave-hydrothermal process. They were used as magnetic resonance imaging (MRI) contrast agents. Magnetic FeNi3 nanochains were synthesized by reducing iron(III) acetylacetonate and nickel(II) acetylacetonate with hydrazine in ethylene glycol solution without any template under microwave irradiation. This was a rapid and economical route based on an efficient microwave-hydrothermal process which significantly shortened the synthesis time to mins. The morphologies and size of the materials could be effectively controlled by adjusting the reaction conditions, such as, the reaction time, temperature and concentrations of reactants. The morphology and composition of the as-prepared products were characterized by field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The size of the aligned nanospheres in the magnetic FeNi 3 chains could be adjusted from 150nm to 550nm by increasing the amounts of the precursors. Magnetic measurements revealed that the FeNi3 nanochains showed enhanced coercivity and saturation magnetization. Toxicity tests by exposure of FeNi3 nanochains to the zebrafish larvae showed that the as-prepared nanochains were biocompatible. In vitro magnetic resonance imaging (MRI) confirms the effectiveness of the FeNi 3 nanochains as sensitive MRI probes. Magnetite nanoclusters were synthesized by reducing iron(III) acetylacetonate with hydrazine in ethylene glycol under microwave irradiation. The nanoclusters showed enhanced T2 relaxivity. In vitro and in vivo MRI confirmed the effectiveness of the magnetite nanoclusters as sensitive MRI probes. We also investigated the biodistribution of the nanoclusters in rat liver and spleen. / Jia, Juncai. / Adviser: Jimmy C. Yu. / Source: Dissertation Abstracts International, Volume: 73-06, Section: B, page: . / Thesis (Ph.D.)--Chinese University of Hong Kong, 2011. / Includes bibliographical references. / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Electronic reproduction. [Ann Arbor, MI] : ProQuest Information and Learning, [201-] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstract also in Chinese.

I believe that my research work will provide an in-depth understanding of the basic chemical and physical properties of plasmonic gold nanorods. These works can inspire future applications of plasmonic nanostructures on biotechnology, optoelectronics and solar energy conversion. - / I will first introduce my studies on high-index-faceted gold nanocrystals. Elongated tetrahexahedral (THH) gold nanocrystals have been prepared in high yields using a seed-mediated growth method. Structural characterizations reveal that they are single crystals enclosed by 24 high-index facets. Electrochemical measurements have proven that these THH Au nanocrystals are more chemically active than octahedral Au nanocrystals that are enclosed by low-index {1111} facets. Next, I will demonstrate the formation of large-area, 3D ordered assemblies of Au nanostructures that have different sizes and shapes, including nanorods, polyhedra, nanocubes, and bipyramids, by droplet evaporation. The nature of the resultant assemblies is strongly dependent on the shape of Au nanostructures for single-component systems; while the assembly of binary nanorod mixtures is dependent on the relative diameters of two nanorod samples for the nanorods used in our experiments. / Most applications of plasmonic nanostructures are based on their interactions with other chemical/physical species. In my research work, gold nanorods interacting with photochromic molecules and fluorophores are extensively studied. For the case of photochromic molecules, I have demonstrated a plasmonic switch on the basis of the resonance coupling between single Au nanorods and photochromic molecules. An individual plasmonic switch is composed of a single nanorod and the surrounding photochromic molecules. Its modulation depth reaches 7.2 dB. The estimated power and energy required for operating such a single-nanorod plasmonic switch are ∼13 pW and ∼39 pJ. For the case of fluorophores, I will give a systematic description of my research on plasmon-fluorophore interactions. Excitation polarization-dependent plasmon-enhanced fluorescence, polarized emission, and modulation of fluorophore emission spectra by localized plasmon resonances will be experimentally demonstrated. The interactions between the plasmonic nanorods and the fluorophore molecules can be temporally separated into plasmon-enhanced excitation and coupled emission processes under unsaturated excitation conditions. Finite-difference time-domain (FDTD) method will be employed to explain the origin of the excitation and emission polarization dependence. A term "plasmophore", which is corned by Lakowicz et al., is quoted to describe the artificially prepared quantum emitters that are composed of plasmonic structure and fluorophore. / Noble metal nanocrystals have drawn great attention in a wide range of research fields due to their extraordinary localized surface plasmon resonances, which are essentially collective charge density oscillations confined in metallic nanostructures. Their applications range from bioimaging, sensing and therapy in life sciences to plasmonic circuits and optical data storage in micro-optoelectronics. More attractively, they can be used to enhance light harvesting in solar energy conversion systems. In this thesis, I will systematically describe the preparation and assembly of gold nanorods and their interactions with fluorophores and photochromic molecules, both experimentally and theoretically. / Ming, Tian = 金納米棒的生長、組裝以及他們與螢光團或光至變色分子的相互作用 / 明天. / Adviser: Jianfang Wang. / Source: Dissertation Abstracts International, Volume: 73-06, Section: B, page: . / Thesis (Ph.D.)--Chinese University of Hong Kong, 2011. / Includes bibliographical references. / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Electronic reproduction. [Ann Arbor, MI] : ProQuest Information and Learning, [201-] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstract also in Chinese. / Ming, Tian = Jin na mi bang de sheng chang, zu zhuang yi ji ta men yu ying guang tuan huo guang zhi bian se fen zi de xiang hu zuo yong / Ming Tian.