Nanopartículas de Fe3O4 e Fe2O3 foram sintetizadas a partir da rota de coprecipitação, em atmosfera de N2, mantendo-se o pH entre 9 e 14 na temperatura ambiente e utilizando como precursores o FeCl2 e FeCl3. Após a síntese, as nanopartículas foram tratadas termicamente a 250, 500 e 800 oC. Para obtenção de um sistema híbrido, foram sintetizadas nanopartículas de ouro sobre as nanopartículas de óxido previamente tratadas em diferentes temperaturas. As amostras foram caracterizadas por UV-Vis, difratometria de Raios-X (DRX), microscopia eletrônica de transmissão (MET), microscopia eletrônica de transmissão de alta resolução (MET-AR), espectroscopia no na região do infravermelho (FTIR), magnometria de amostra vibrante (VSM) e espectroscopia Mossbauer (EM), e aplicadas para produção de hidrogênio promovendo a decomposição da hidrazina. Os resultados mostram a síntese de nanopartículas de óxido de ferro com diâmetro médio de cerca de 7 nm. Quando aquecidas a 250 oC o tamanho médio aumentou para ca. de 11 nm e foi observado uma pequena mudança no comportamento óptico e estrutural, mantendo o comportamento superparamagnetico. Quando aquecidas a 500 oC o tamanho médio aumenta para ca. de 50nm e são observadas mudanças significativas nas propriedades ópticas, morfológicas, estruturais. Adicionalmente observa-se transição de comportamento superparamagnetico para paramagnético. Quando aquecidas a 800 oC os efeitos nas propriedades dos materiais são ainda mais significativos; as partículas apresentam tamanho médio de 200 nm, o espectro de absorção no UV-Vis muda significativamente e as partículas passam a ter comportamento pagamagnético. Os resultados obtidos pelas diferentes técnicas e somadas ao Mossbauer sugerem que as amostras sintetizadas são uma mistura de Fe3O4 e -Fe2O3, quando aquecido a 250 e 500 oC uma mistura de -Fe2O3 e -Fe2O3 e a 800 oC somente -Fe2O3. As nanopartículas de ouro sintetizadas sobre as amostras de oxido de ferro apresentaram tamanho médio de 6,0 nm e não afetaram as propriedades magnéticas dos oxidos. As amostras de óxido com nanopartículas de ouro promoveram a decomposição da hidrazina por rota completa, levando a formação de hidrogênio com seletividade de até 33%. / Fe3O4 and Fe2O3 nanoparticles were synthesized by coprecipitation route carried out under N2 atmosphere, maintaining the pH between 9 and 14 at room temperature and using FeCl2 and FeCl3 as precursors. After synthesis the iron oxide nanoparticles were thermally treated at 250, 500 and 800 oC. To obtain a hybrid system, gold nanoparticles were synthesized on the thermally treated oxide nanoparticles. The samples were analyzed by UV-Vis, X-ray diffraction (XRD), transmission electron microscopy (TEM), high resolution transmission electron microscopy (MET-AR), spectroscopy in the region of Infrared (FTIR), vibrating sample magnitude (VSM) and Mossbauer, and applied to produce H2 through hydrazine decomposition. The results show the synthesis of Fe3O4 nanoparticles with average diameter of about 7 nm. When heated to 250 oC the average size increased to about 11 nm and a small change in the optical and structural behavior was observed, while the superparamegnetic behaviour was maintained. When heated to 500 °C, the average particle size increase to ca 51nm, significant changes in the optical, morphological and structural properties are observed, in addition to a transition from superparamegnetic to paramagnetic behaviour. When heated to 800 oC the effects on the properties are even more significant; the nanoparticles increase to ca. 200 nm, the absorption spectrum in UV-Vis changes significantly and the particles present paramagnetic behaviour. The results suggest that when heated to 250 and 500 oC a mixture of -Fe2O3 e -Fe2O3 is obtained, after heating at 800 oC only -Fe2O3 is observed. The gold nanoparticles synthesized on the iron oxides present average size of 6.0 nm, and did not affect the magnetic properties of the oxides. The iron oxides/gold nanoparticle samples were efficiently applied to produce hydrogen, promoting the decomposition of hydrazin. The selectivity to hydrogen reached up to 33%.

Vitrocerâmicas contendo cristais de diopsídio (CaMgSi2O6 = CMS2) têm sido consideradas promissoras para diferentes aplicações. Entretanto, quando tratado termicamente, o vidro de diopsídio exibe somente cristalização superficial. Uma maneira de se obter cristalização no volume neste vidro é através da adição de agentes nucleantes em sua composição. O objetivo inicial desta tese de doutorado foi verificar a eficiência da adição dos compostos TiO2, ZrO2 e Fe2O3, como agentes nucleantes no processo de cristalização volumétrica no vidro de diopsídio. Os vidros foram obtidos pelo método de fusão-resfriamento e, em seguida, foram submetidos a um tratamento térmico de nucleação e crescimento de cristais. Os resultados mostraram que somente a adição de Fe2O3 acima de 7% molar ao vidro CMS2 favorece a cristalização no interior da amostra. O vidro contendo 9 mol% de Fe2O3 apresenta como característica principal uma distribuição homogênea de cristais no volume da amostra vítrea. As fases cristalinas originadas foram caracterizadas por Difratometria de Raios X e o mecanismo de nucleação de cristais foi estudado através do método de Análise Térmica Diferencial (ATD) e análise microestrutural quantitativa de amostras submetidas aos seguintes ciclos de tratamento isotérmico: i) dois estágios (o primeiro de nucleação e o segundo de crescimento de cristais) e ii) um único estágio de nucleação e crescimento de cristais. As amostras contendo 9 mol% de Fe2O3 apresentaram somente a fase cristalina diopsídio com os íons de ferro aparentemente incorporados em sua rede cristalina. Através da análise dos dados de ATD em regime isotérmico da amostra contendo 9 mol% de óxido de ferro foi possível determinar o valor médio do coeficiente de Avrami (n) como sendo próximo a 3,0 para temperaturas de 760, 770, 780 e 790 °C. De acordo com a literatura, estes valores de n indicam que o vidro CMS2 contendo 9 mol% de Fe2O3 exibe um mecanismo de cristalização volumétrica caracterizado pelo aumento e saturação do número de núcleos de cristais tridimensionais de diopsídio férrico e por um mecanismo de crescimento de cristais controlado por interface. Além disso, os resultados do método de microscopia para os dados experimentais correspondentes ao tratamento térmico de simples estágio mostraram que o mecanismo de cristalização volumétrica do vidro CMS2 9F é descrito pelo caso mais geral da equação de KJMAY, onde as taxas de nucleação e de crescimento são dependentes do tempo e podem variar ao longo do processo de cristalização isotérmica. / Glass-ceramics containing diopside crystals (CaMgSi2O6 = CMS2) have been considered promising for different applications. However, when thermally treated, diopside glass exhibits only surface crystallization. One way of obtaining volume crystallization in this glass is by the addition of nucleating agents in its composition. The initial objective of this PhD thesis was to verify the efficiency of the addition of the TiO2, ZrO2 and Fe2O3 compounds as nucleating agents in the process of volume crystallization in diopside glass. Glasses were obtained by the melt-cooling method and were then subjected to a nucleation and crystal growth heat treatment. The results showed that only the addition of Fe2O3 above 7 mol% to the CMS2 glass favors crystallization in the sample volume. Glass containing 9 mol% Fe2O3 has as main characteristics a homogeneous distribution of crystals in the sample volume. The crystalline phases originated were characterized by X-ray diffraction and the crystal nucleation mechanism was studied through the Differential Thermal Analysis (DTA) method and quantitative microstructural analysis of samples submitted to double - and single - stage thermal treatments. The samples containing 9 mol% of Fe2O3 presented only the ferric diopside crystalline phase with the iron atom apparently incorporated in its crystalline network. By analyzing the DTA data in the isothermal regime of the sample containing 9 mol% of iron oxide, it was possible to determine the average value of the Avrami coefficient (n) as being near to 3.0 for temperatures of 760, 770, 780 and 790 oC. According to the literature, these values of n indicate that CMS2 glass containing 9 mol% Fe2O3 exhibits a volume crystallization mechanism characterized by increase and saturation of the number of nuclei and an interface-controlled growth of ferric diopside three-dimensional crystals. In addition, the results of the microscopy method for the experimental data corresponding to the single-stage heat treatment showed that the CMS2 9F glass volume nucleation mechanism is described by the more general case of the KJMAY equation, where the rates of nucleation and growth are time dependent and can vary throughout the isothermal crystallization process.

The recent momentum in energy research has simplified converting solar to electrical energy through photoelectrochemical (PEC) cells. There are numerous benefits to these PEC cells, such as the inexpensive fabrication of thin film, reduction in absorption loss (due to transparent electrolyte), and a substantial increase in the energy conversion efficiency. Alpha-hematite ([U+F061]-Fe2O3) has received considerable attention as a photoanode for water-splitting applications in photoelectrochemical (PEC) devices. The alpha-hematite ([U+F061]-Fe2O3) nanomaterial is attractive due to its bandgap of 2.1eV allowing it to absorb visible light. Other benefits of [U+F061]-Fe2O3 include low cost, chemical stability and availability in nature, and excellent photoelectrochemical (PEC) properties to split water into hydrogen and oxygen. However, [U+F061]-Fe2O3 suffers from low conductivity, slow surface kinetics, and low carrier diffusion that causes degradation of PEC device performance. The low carrier diffusion of [U+F061]-hematite is related to higher resistivity, slow surface kinetics, low electron mobility, and higher electro-hole combinations. All the drawbacks of [U+F061]-Fe2O3, such as low carrier mobility and electronic diffusion properties, can be enhanced by doping, which forms the nanocomposite and nanostructure films. In this study, all nanomaterials were synthesized utilizing the sol-gel technique and investigated using Scanning Electron Microscopy (SEM), X-ray Diffractometer (XRD), UV-Visible Spectrophotometer (UV-Vis), Fourier Transform Infrared Spectroscopy (FTIR), Raman techniques, Particle Analyzer, Cyclic Voltammetry (CV), and Chronoamperometry, respectively. The surface morphology is studied by SEM. X-Ray diffractometer (XRD) is used to identify the crystalline phase and to estimate the crystalline size. FTIR is used to identify the chemical bonds as well as functional groups in the compound. A UV-Vis absorption spectral study may assist in understanding electronic structure of the optical band gap of the material. Cyclic voltammetry and chronoamperometry were used to estimate the diffusion coefficient and study electrochemical activities at the electrode/electrolyte interface. In this investigation, the [U+F061]-Fe2O3 was doped with various materials such as metal oxide (aluminum, Al), dichalcogenide (molybdenum disulfide, MoS2), and co-catalyst (titanium dioxide, TiO2). By doping or composite formation with different percentage ratios (0.5, 10, 20, 30) of aluminum (Al) containing [U+F061]-Fe2O3, the mobility and carrier diffusion properties of [U+F061]-hematite ([U+F061]-Fe2O3) can be enhanced. The new composite, Al-[U+F061]-Fe2O3, improved charge transport properties through strain introduction in the lattice structure, thus increasing light absorption. The increase of Al contents in [U+F061]-Fe2O3 shows clustering due to the denser formation of the Al-[U+F061]-Fe2O3 particle. The presence of aluminum causes the change in structural and optical and morphological properties of Al-[U+F061]-Fe2O3 more than the properties of the [U+F061]-Fe2O3 photocatalyst. There is a marked variation in the bandgap from 2.1 to 2.4 eV. The structure of the composite formation Al-[U+F061]-Fe2O3, due to a high percentage of Al, shows a rhombohedra structure. The photocurrent (35 A/cm2) clearly distinguishes the enhanced hydrogen production of the Al-[U+F061]-Fe2O3 based photocatalyst. This work has been conducted with several percentages (0.1, 0.2, 0.5, 1, 2, 5) of molybdenum disulfide (MoS2) that has shown enhanced photocatalytic activity due to its bonding, chemical composition, and nanoparticle growth on the graphene films. The MoS2 material has a bandgap of 1.8 eV that works in visible light, responding as a photocatalyst. The photocurrent and electrode/electrolyte interface of MoS2-[U+F061]-Fe2O3 nanocomposite films were investigated using electrochemical techniques. The MoS2 material could help to play a central role in charge transfer with its slow recombination of electron-hole pairs created due to photo-energy with the charge transfer rate between surface and electrons. The bandgap of the MoS2 doped [U+F061]-Fe2O3 nanocomposite has been estimated to be vary from 1.94 to 2.17 eV. The nanocomposite MoS2-[U+F061]-Fe2O3 films confirmed to be rhombohedral structure with a lower band gap than Al-[U+F061]-Fe2O3 nanomaterial. The nanocomposite MoS2-[U+F061]-Fe2O3 films revealed a more enhanced photocurrent (180 μA/cm2) than pristine [U+F061]-Fe2O3 and other transition metal doped Al-[U+F061]-Fe2O3 nanostructured films. The p-n configuration has been used because MoS2 can remove the holes from the n-type semiconductor by making a p-n configuration. The photoelectrochemical properties of the p-n configuration of MoS2-α-Fe2O3 as the n-type and ND-RRPHTh as the p-type deposited on both n-type silicon and FTO-coated glass plates. The p-n photoelectrochemical cell is stable and allows for eliminating the photo-corrosion process. Nanomaterial-based electrodes [U+F061]-Fe2O3-MoS2 and ND-RRPHTh have shown an improved hydrogen release compared to [U+F061]-Fe2O3, Al-[U+F061]-Fe2O3 and MoS2-[U+F061]-Fe2O3 nanostructured films in PEC cells. By using p-n configuration, the chronoamperometry results showed that 1% MoS2 in MoS2-[U+F061]-Fe2O3 nanocomposite can be a suitable structure to obtain a higher photocurrent density. The photoelectrochemical properties of the p-n configuration of MoS2-α-Fe2O3 as n-type and ND-RRPHTh as p-type showed 3-4 times higher (450 A/cm2) in current density and energy conversion efficiencies than parent electrode materials in an electrolyte of 1M of NaOH in PEC cells. Titanium dioxide (TiO2) is known as one of the most explored electrode materials due to its physical and chemical stability in aqueous materials and its non-toxicity. TiO2 has been investigated because of the low cost for the fabrication of photoelectrochemical stability and inexpensive material. Incorporation of various percentages (2.5, 5, 16, 25, 50) of TiO2 in Fe2O3 could achieve better efficiencies as the photoanode by enhancing the electron concentration and low combination rate, and both materials can have a wide range of wavelength which could absorb light in both UV and visible spectrum ranges. TiO2 doped with [U+F061]-Fe2O3 film was shown as increasing contacting area with the electrolyte, reducing e-h recombination and shift light absorption along with visible region. The [U+F061]-Fe2O3-TiO2 nanomaterial has shown a more enhanced photocurrent (800 μA/cm2) than metal doped [U+F061]-Fe2O3 photoelectrochemical devices.

Friction stir processing (FSP) was applied to produce aluminum based in situ composites from powder mixtures of Al-Fe, Al-Mo, and Al-Fe2O3. Billet of powder mixtures was prepared by the use of conventional pressing and sintering route. The sintered billet was then subjected to multiple passages of FSP. During FSP, the material has experienced both high temperature and very large plastic strain. The basic idea for fabricating the composites is to combine the hot working nature of friction stir processing (FSP) and the exothermic reaction between aluminum and transition metals (Al-Fe, Al-Mo) or metal oxides (Al-Fe2O3). In the Al-Fe alloy, in situ Al¡VFe reaction can be induced during FSP and form Al-Al13Fe4 composite. The size of reinforcing particles formed by the in-situ reaction is ~100 nm. In Al-Mo alloys, fine Al-Mo intermetallic particles with an average size of ~200 nm were formed and uniformly dispersed in the aluminum matrix by FSP. The Al-Mo intermetallic particles were identified mainly as Al12Mo with minor amount of Al5Mo. The exothermic reaction could result in local melting of Al at the Al/TM interface, and the liquid Al may accelerate the reaction. In addition, it is suggested that the critical mechanism responsible for the rapid reaction and the formation of nanometer sized particles in FSP is the effective removal of the Al-TM intermetallic phase from the Al-TM interface, maintaining an intimate contact between TM and Al. In the Al-Fe2O3 system, the reactions taking place during FSP includes the thermite reaction (2Al +Fe2O3 ¡÷ Al2O3 + 2Fe), and the reaction between the reduced Fe and Al to form Al13Fe4. In the FSPed Al-Fe2O3 specimens, there are two types of second phase particles, Al13Fe4 and Al2O3. The Al2O3 particles (about 10 nm in size) usually appear as a cluster of 100-200 nm in diameter. There are two types of Al2O3 phases existed in the Al matrix after FSP passes, depending on the content of Fe2O3. One is £^-Al2O3 in Al-2Fe2O3 specimens, and the other is £\-Al2O3 in Al-4Fe2O3 specimens. It is suggested that the formation of different type of Al2O3 particles in the Al-Fe2O3 composites may be attributed to different heat release in each system. The lower heat release in Al-2Fe2O3 sample favors the formation of the while the higher heat release in Al-4Fe2O3 sample results in the £\-Al2O3. The Al-Al13Fe4/Al2O3 composite produced by FSP exhibits both high strength and good tensile ductility. The higher strength in Al-Fe2O3 specimen may be due to the presence of fine Al2O3 particles. The flow stress of the Al-4Fe2O3 composite can maintain at 100 MPa even at 773 K. The good thermal stability and high temperature strength of Al-Al13Fe4/Al2O3 composites could be attributed to the fine dispersion of second phase particles in the aluminum matrix, especially the nanometric Al2O3 particles. These Al2O3 particles are very stable at elevated temperatures, even after long time exposure at 873 K. The temperature excursion in FSP is determined by both the FSP parameters and the exothermic reaction involved. The peak temperature in Al-Fe or Al-Fe2O3 system during FSP was calculated as a function of the fraction of Fe or Fe2O3 reacted. Based on calculated results, it is noted that with the in situ reaction, the value of can easily reach the melting point of Al, especially for the Al-Fe2O3 system. The reaction mechanism and microstructure evolution during FSP are discussed.

Th.--Sci.--Metz, 1978.

京都大学 / 新制・課程博士 / 博士(理学) / 甲第23459号 / 理博第4753号 / 新制||理||1681(附属図書館) / 京都大学大学院理学研究科化学専攻 / (主査)教授 倉田 博基, 教授 島川 祐一, 教授 寺西 利治 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

This article presents nano composite TiO2.Fe2O3/laterite materials, which were successfully prepared by hydrometallurgical method. The materials were modified using urea as the nitrogen source. The particles size of the materials is from 20-30 nanometers. The obtained materials can not only absorb arsenic compounds but also enhance the ability of converting As (III) or As (V) into Aso, which is removed from solution. Arsenic removal efficiency of these materials is high. Using sunlight in a hydraulic retention time, about 180 minutes, the arsenic value at the inflow was about 10 mg/L but the outflow was negligible. Covering TiO2.Fe2O3 nano on laterite have brought high economical efficiency, on one hand, it saved material and on the other hand, it can be continuously operated without the centrifugal separation of the nano material. / Bài báo này giới thiệu về phương pháp điều chế vật liệu nano TiO2.Fe2O3 biến tính nitơ được phủtrên đá ong bằng phương pháp thủy luyện. Vật liệu nano thu được có kích thước 20-30 nm. Vật liệu thu được không những có khả năng hấp phụ các hợp chất của asen mà còn có khả năng khử As (III) hoặc As (V) thành Asokhi được chiếu sáng. Sử dụng ánh sáng mặt trời chiếu vào hệ thống xử lý trong thời gian 180 phút có thể loại bỏ được gần như hoàn toàn asen ra khỏi nước mặc dù hàm lượng đầu vào là 10 mg/l. Việc phủ vật liệu TiO2.Fe2O3 nano lên đá ong đã mang lại hiệu quả kinh tế cao, một mặt nó tiết kiệm được vật liệu, mặt khác, vật liệu có thể sử dụng một cách liên tục mà không cần phải tách bằng phương pháp ly tâm.

Πολλοί από τους τομείς της επιστημονικής έρευνας, όπως χημεία, ενέργεια, βιομηχανία και ιατρική χρησιμοποιούν τη νανοτεχνολογία, με στόχο την παρασκευή υλικών, με καλύτερες και πιο εξειδικευμένες ιδιότητες σε σχέση με τα συμβατικά υλικά του μακρόκοσμου. Οι νανοσφαίρες λόγω των ποικίλων ιδιοτήτων που παρουσιάζουν, όπως οπτικές, μηχανικές, ηλεκτρικές κ.α., μπορούν να χρησιμοποιηθούν σε διάφορους τομείς της καθημερινής μας ζωής με μεγαλύτερο ενδιαφέρον στον τομέα της υγείας. Η παρούσα ερευνητική εργασία πραγματοποιήθηκε με στόχο τη σύνθεση και τη μελέτη νανοσφαιρών οξειδίων του σιδήρου. Πιο συγκεκριμένα παρασκευάσθηκαν νανοσφαίρες αιματίτη (α – Fe2O3) και μαγγεμίτη (γ – Fe2O3) και μελετήθηκαν οι μαγνητικές τους ιδιότητες. Στο πρώτο κεφάλαιο παρουσιάζεται μία εισαγωγή – ιστορική αναδρομή στο χώρο της νανοτεχνολογίας και των νανοσφαιρών. Γίνεται επίσης αναφορά στους τρόπους σύνθεσης των νανοσφαιρών και αναφέρονται εν συντομία κάποιες ιδιότητες και εφαρμογές αυτών. Στο δεύτερο κεφάλαιο αναφέρονται κάποιες βασικές έννοιες οι οποίες είναι απαραίτητες για την κατανόηση των ταχνικών που θα χρησιμοποιηθούν. Παρουσιάζονται αναλυτικά οι τρόποι με τους οποίους πραγματοποιείται η σύνθεση των νανοσφαιρών και περιγράφονται αναλυτικά, η μέθοδος λύματος – πηκτής (sol – gel) και η τεχνική του πολυμερισμού. Στο τρίτο κεφάλαιο αναφέρονται τα αντιδραστήρια καθώς επίσης και οι πειραματικές μέθοδοι που χρησιμοποιήθηκαν για το χαρακτηρισμό των νανοσφαιρών και τη μελέτη των ιδιοτήτων τους. Αναφέρονται επίσης τα όργανα που χρησιμοποιήθηκαν καθώς επίσης και οι βασικές αρχές λειτουργίας αυτών. Στο τέταρτο κεφάλαιο περιγράφεται αναλυτικά η πειραματική διαδικασία που πραγματοποιήθηκε και γίνεται συζήτηση των αποτελεσμάτων. Τέλος στο πέμπτο κεφάλαιο ανγράφονται τα συμπεράσματα και αναφέρονται μελλοντικοί στόχοι. / Nanotechnology is the study of the control of matter on an atomic and molecular scale and it’s main objective is the manufacture of new materials with better and more sophisticated properties. Nanotechnology is used in many different sciences like chemistry, physics and most of all in medicine. Nanospheres exhibit many diverse properties (electrical, optical etc) which render them the best solution for application such as drug delivery systems, Magnetic Resonance Imaging (MRI) agents, hyperthermia etc. The present work deals with the synthesis and characterization of magnetic nanospheres and more specifically in the study of magnetic properties of hematite (α – Fe2O3) and maghemite (γ – Fe2O3). The first chapter starts with a short introduction for nanospheres and nanotechnology . It reports also a quick historical review and some lines about new generation nanospheres, it’s properties and it’s applications. In the second chapter, polymerization and sol – gel techniques are described analytically. In the third chapter, reactants and experimental methods are described as well as some basic principles of the methods that were used to characterize the samples. The fourth chapter is the results and discussion session. Finally in the fifth chapter some conclusions and future targets are reported.

Pour mieux comprendre leurs propriétés, diverses nanostructures individuelles ont été étudiées à l’aide d’une technique couplant microscopie à force atomique et spectroscopie Raman confocale. Sous excitation lumineuse polarisée, la composition chimique, la structure et la présence de défauts a pu être précisée dans des nanobâtonnets d’oxydes métalliques (ZnO et α-Fe2O3). Sous irradiation laser résonnante, les spectres de nanotubes de carbone monoparoi enrobés de polymères ont révélé notamment l’absence de transfert de charge polymère-nanotube et un effet de désolvatation. Finalement, des feuillets de graphène oxydé et des ADNs double-brin peignés ont pu être préparés et caractérisés par spectroscopie Raman exaltée par effet de pointe en atteignant une résolution spatiale latérale voisine du rayon de courbure de l’apex de la pointe utilisée (12 nm), bien plus faible que la limite de diffraction, ce qui ouvre la voie à de nouveaux travaux spectroscopiques à l’échelle nanométrique. / To better understand their properties, various nanostructures have been studied using a technique combining atomic force microscopy and confocal Raman spectroscopy. Under polarized light excitation, the chemical composition, the structure and the presence of defects has been described in metal oxides nanorods (ZnO et α-Fe2O3). Under resonant laser excitation, Raman spectra of polymer-wrapped single-walled carbon nanotubes have revealed the absence of polymer-nanotube charge transfer and an effect due to desolvation. Finally, graphene oxide sheets and combed double-stranded DNAs have been prepared and characterized using tip-enhanced Raman spectroscopy with a lateral spatial resolution down to the curvature radius of the apex of the used tip (12 nm), well below the diffraction limit, which opens new opportunities for spectroscopic works at the nanometer scale.

Η παρούσα ειδική ερευνητική εργασία συνιστά μια μελέτη των μη-γραμμικών οπτικών ιδιοτήτων πέντε δειγμάτων νανοσωματιδίων οξειδίων μετάλλων. Κατ’ όνομα πρόκειται για το μονοξείδιο του Κοβαλτίου (CoO), το τετροξείδιο του Μαγγανίου (Mn3O4), το μονοξείδιο του Νικελίου (NiO), τον Αιματίτη (α-Fe2O3) και τον Μαγγεμίτη (γ-Fe2O3). Οι τρίτης τάξης οπτικές μη-γραμμικότητές τους διερευνήθηκαν με την πειραματική τεχνική Z-scan, της οποίας οι βασικές αρχές και οι πειραματικές λεπτομέρειες περιγράφονται στο δεύτερο κεφάλαιο της παρούσης. Ειδικότερα, δίδονται τεχνικές λεπτομέρειες για τις πειραματικές διατάξεις που χρησιμοποιήθηκαν, μελετώνται τα δύο κύρια φαινόμενα που αξιοποιεί η τεχνική, η μη-γραμμική διάθλαση και η μη-γραμμική απορρόφηση και γίνεται σύντομη μαθηματική περιγραφή και παράθεση της διαδικασίας ανάλυσης δεδομένων. Προηγείται των ανωτέρω μια περιεκτική θεωρητική θεμελίωση των βασικών αρχών της μη-γραμμικής οπτικής στο πρώτο κεφάλαιο. Αναπτύσσεται εκ των εξισώσεων Maxwell η μη-γραμμική κυματική εξίσωση. Περιγράφονται οι διεργασίες της γενέσεως δευτέρας αρμονικής, αθροίσματος και διαφοράς συχνοτήτων και διαδοχικά τα βαρύνουσας σημασίας φαινόμενα της αυτό-εστίασης, αυτό-απoεστίασης, κορέσιμης και ανάστροφα κορέσιμης απορρόφησης. Παρατίθεται εν συνεχεία ένας κβαντομηχανικός ορισμός της τρίτης τάξης μη-γραμμικής επιδεκτικότητος και τέλος περιγράφονται αναλυτικά οι μηχανισμοί συνεισφοράς στον μη-γραμμικό δείκτη διάθλασης, από την παραμόρφωση του ηλεκτρονικού νέφους, ως την ηλεκτροσυστολή και τα θερμικά φαινόμενα. Στο τρίτο κεφάλαιο παρουσιάζονται θεωρητικά στοιχεία για τις ιδιότητες των νανοσωματιδίων οξειδίων μετάλλων, την επίδραση του μεγέθους στις εγγενείς ιδιότητες της ύλης και παραδείγματα των πιο ευρέως διαδεδομένων εφαρμογών τους. Εν συντομία δίδονται οι τεχνικές σύνθεσης και οι ενδελεχείς χαρακτηρισμοί που εφαρμόστηκαν με σκοπό να φωτιστούν πλευρές της κρύφιας και ασαφούς φύσης των νανοσωματιδίων. Στο τέταρτο κεφάλαιο παρατίθενται λεπτομερώς οι πειραματικές μετρήσεις, από τα φάσματα απορρόφησης που ελήφθησαν για κάθε παρασκευασθείσα συγκέντρωση διεσπαρμένων νανοσωματιδίων, ως τις γραφικές παραστάσεις που αντιστοιχούν στην τεχνική Z-scan. Συγκεντρώνονται σε πίνακες όλες οι μη-γραμμικές οπτικές παράμετροι που υπολογίστηκαν και λαμβάνει χώρα αναλυτική συζήτηση για τα αποτελέσματα. Τα αποτελέσματα ομαδοποιούνται, εξάγονται ενδιαφέροντα συμπεράσματα και γίνεται σύγκριση με τη βιβλιογραφία. / The present work, a master thesis, is a study of the nonlinear optical properties of five metal oxide nanoparticles, namely Cobalt monoxide (CoO), Manganese tetroxide (Mn3O4), Nickel monoxide (NiO), Hematite (α-Fe2O3) and Maghemite (γ-Fe2O3). Their third ordrer optical nonlinearities were investigated by the means of the Z-scan experimental technique. The basic principles and the experimental details of this technique are described in the second chapter of the present work. Moreover, technical details of the experimental setups used are presented, the two most important phaenomena involved in Z-scan, nonlinear absorption and nonlinear refraction are described, a brief mathematical description and the data analysis details are given. In the first chapter, a comprehensive theoretical basis of the principles of Non-linear Optics is firstly established. Initiating from Maxwell’s equations, the non-linear wave equation is developed step-by-step. The non-linear optical processes of second harmonic generation and sum/difference frequency generation are presented. Consecutively, the very important phaenomena of self-focusing, self-defocusing, saturable and reverse saturable absorption are described. In addition, a quantum-mechanic description of third order nonlinear susceptibility is briefly developed. At last, the contribution mechanisms to the nonlinear refractive index, from the deformation of the electron cloud to the electrostriction and the thermal effects are presented. In the third chapter, some theoretical information about the properties of metal oxides nanoparticles, along with the effects of their size to their behavior and their widely known applications are listed. In brief, the unique details of the synthesis and the assiduous characterization techniques, which were applied in order to illuminate the fringe nature of these nanoscale particles, are given. In the fourth chapter the experimental measurements are apposed in detail, from the UV-Vis-NIR spectra received for every one of the prepared dispersions, to the graphs built on the Z-scan experimental curves. All nonlinear optical parameters deduced, are summed into analytical tables and a lengthy discussion is taking place over all these results. Results are grouped and studied from different perspectives and a bibliographical comparison is done.