Em aproveitamentos hídricos, onde podem estar envolvidas elevadas alturas de água armazenada, o vertedouro é a estrutura hidráulica responsável por conduzir com segurança o escoamento que excede a capacidade de armazenamento do reservatório. Neste aspecto, é necessário considerar o processo de dissipação de energia a fim de proteger o pé da barragem e a própria estrutura do vertedouro contra a ação erosiva da água. Este fluxo que é descarregado é usualmente amortecido por um colchão d’água, o qual é delimitado em uma bacia de dissipação projetada com intuito de resistir aos esforços impostos pelo escoamento. Em grandes barramentos, a utilização de um vertedouro tipo salto esqui, que é caracterizado por um defletor de fluxo no final de sua calha, possibilita que não haja necessidade de revestir o leito próximo do pé da barragem, pois a incidência do jato lançado ocorre distante deste local. Desta maneira, a dissipação da energia é efetuada sobre o próprio leito do rio, sendo formada uma fossa de erosão, contudo, dependendo da resistência do leito e de suas características anisotrópicas, os padrões de recirculação do fluxo podem fazer a fossa evoluir para uma situação nociva. Por isso, desde a fase de projeto desse tipo de vertedouro, monitoramento e previsões da progressão da fossa são essenciais. Então, conforme proposta deste trabalho, abordou-se cada fenômeno que influencia no potencial erosivo do jato, como a turbulência em sua emissão e o grau de difusão do mesmo no colchão d’água. Assim, com ensaios sobre modelo físico, foi possível desenvolver duas metodologias, aplicáveis tanto para a verificação da erosão de material granular na superfície de leitos, quanto para o interior de leitos rochosos fissurados, cujas forças atuantes em um bloco de rocha isolado, podem vencer seu peso submerso e o destacar da matriz. / In hydroelectric plants, which may be involved elevated heights of stored water, the dam spillway is responsible for safely flow the water that exceeds the storage capacity of the reservoir. In this respect, it is necessary to consider the process of energy dissipation in order to protect the base of the dam and the spillway structure itself against the erosive action of the water. This stream discharged is usually cushioned by a waterbed, which is bounded into a stilling basin designed with the purpose of resist the efforts imposed by the flow. In large dams, the use of a ski jump spillway type, which is characterized by a flow deflector at the end of its chute, allows no need lining the bed near the foot of the dam, since the impact of the jet is launched away this location. Thus, the energy dissipation is performed on the riverbed itself, generating a scour hole, however, depending on the resistance of the bed and its anisotropic features, patterns of flow recirculation can evolve the pit into a harmful state. For this reason, since the design phase of this type of spillway, monitoring and predicting the progression of the pit are essential. Then, according to the proposal of this work, it was dealt with each phenomenon that influences the erosive potential of the jet, as the turbulence at its issue on the air, and the level of its diffusion of on waterbed. Based on physical model tests, it was possible to develop two methodologies, applicable both for verifying erosion of granular material from the surface of the bottom, as for analyze the interior of a fissured bedrock, which the forces acting on an isolated block of rock can overcome its submerged weight and uplift it off the matrix.

Em aproveitamentos hídricos, onde podem estar envolvidas elevadas alturas de água armazenada, o vertedouro é a estrutura hidráulica responsável por conduzir com segurança o escoamento que excede a capacidade de armazenamento do reservatório. Neste aspecto, é necessário considerar o processo de dissipação de energia a fim de proteger o pé da barragem e a própria estrutura do vertedouro contra a ação erosiva da água. Este fluxo que é descarregado é usualmente amortecido por um colchão d’água, o qual é delimitado em uma bacia de dissipação projetada com intuito de resistir aos esforços impostos pelo escoamento. Em grandes barramentos, a utilização de um vertedouro tipo salto esqui, que é caracterizado por um defletor de fluxo no final de sua calha, possibilita que não haja necessidade de revestir o leito próximo do pé da barragem, pois a incidência do jato lançado ocorre distante deste local. Desta maneira, a dissipação da energia é efetuada sobre o próprio leito do rio, sendo formada uma fossa de erosão, contudo, dependendo da resistência do leito e de suas características anisotrópicas, os padrões de recirculação do fluxo podem fazer a fossa evoluir para uma situação nociva. Por isso, desde a fase de projeto desse tipo de vertedouro, monitoramento e previsões da progressão da fossa são essenciais. Então, conforme proposta deste trabalho, abordou-se cada fenômeno que influencia no potencial erosivo do jato, como a turbulência em sua emissão e o grau de difusão do mesmo no colchão d’água. Assim, com ensaios sobre modelo físico, foi possível desenvolver duas metodologias, aplicáveis tanto para a verificação da erosão de material granular na superfície de leitos, quanto para o interior de leitos rochosos fissurados, cujas forças atuantes em um bloco de rocha isolado, podem vencer seu peso submerso e o destacar da matriz. / In hydroelectric plants, which may be involved elevated heights of stored water, the dam spillway is responsible for safely flow the water that exceeds the storage capacity of the reservoir. In this respect, it is necessary to consider the process of energy dissipation in order to protect the base of the dam and the spillway structure itself against the erosive action of the water. This stream discharged is usually cushioned by a waterbed, which is bounded into a stilling basin designed with the purpose of resist the efforts imposed by the flow. In large dams, the use of a ski jump spillway type, which is characterized by a flow deflector at the end of its chute, allows no need lining the bed near the foot of the dam, since the impact of the jet is launched away this location. Thus, the energy dissipation is performed on the riverbed itself, generating a scour hole, however, depending on the resistance of the bed and its anisotropic features, patterns of flow recirculation can evolve the pit into a harmful state. For this reason, since the design phase of this type of spillway, monitoring and predicting the progression of the pit are essential. Then, according to the proposal of this work, it was dealt with each phenomenon that influences the erosive potential of the jet, as the turbulence at its issue on the air, and the level of its diffusion of on waterbed. Based on physical model tests, it was possible to develop two methodologies, applicable both for verifying erosion of granular material from the surface of the bottom, as for analyze the interior of a fissured bedrock, which the forces acting on an isolated block of rock can overcome its submerged weight and uplift it off the matrix.

The work presented here pertains to investigations on gas-on-liquid type of impinging injectors with a generic approach with prospective applications in several areas, and at places with particular emphasis on cryogenic or semi-cryogenic liquid propellant rockets. In such rockets, one of the components arrives at the injector in a gaseous phase after passing through the regenerative coolant passages or a preceding combustion stage. Most often, the injectors in such systems are of shear coaxial type. The shear coaxial injectors suffer from several disadvantages like complexity in design, manufacture and quality control. Adoption of impinging jet configuration can alleviate these problems in addition to providing further benefits in terms of cost, robustness in high temperature environment and manifolding. However, there is very little literature on gas-on-liquid injectors either in this context or in any other Even for the simplest form of impinging injectors such as like-on-like doublets, literature provides no conclusive direction at describing a spray from the theoretical models of physical mechanisms. Empirical approach is still the prime mode of obtaining a proper understanding of the phenomena. Steady state spray characterization includes mainly of describing the spatial distribution of liquid mass and drop size distribution as a function of geometric and injection parameters. The parameters that are likely to have an impact on spray characteristics are orifice diameter, ratio of orifice length to diameter, pre-impingement length of individual jets, inter orifice distance, impingement angle, jet velocity and condition of the jet just before impingement. The gas-on- liquid configuration is likely to experience some qualitative changes because of the expansion of the gas jet. The degree to which each one of the above variables influences the drop size and mass distribution having implication to combustion performance forms the core theme of the thesis. A dedicated experimental facility has been built, calibrated and deployed exhaustively. While spray drop size measurement is done largely by a laser diffraction instrument, some of the cases warranted an image processing technique. Two different image processing algorithms are developed in-house for this purpose. The granulometric image processing method developed earlier in the group for cryogenic sprays is modified and its applicability to gas-on-liquid impinging sprays are verified. Another technique based on the Hough transform which is feature extraction technique for extracting quantitative information has also been developed and used for gas-on-liquid impinging injectors. A comparative study of conventional liquid-on-liquid doublet with gas-on-liquid impinging injectors are first made to establish the importance of studying gas-on-liquid impinging injectors. The study identifies the similarities and differences between the two types and highlights the features that make such injectors attractive as replacements to coaxial configuration. Spray structure, drop-size mass distributions are quantified for the purpose of comparison. This is followed by a parametric study of the gas-on-liquid impinging injectors carried out using identified control variables. Though momentum ratio appeared to be a suitable parameter to describe the spray at any given impingement angle, the variations due to impingement angle had to be factored in. It was found that normal gas momentum to liquid mass is an apt parameter to generalize the spray characteristics. It was also found that using identical nozzles for desired mass ratio could lead to rather large deflection of the spray which may not be acceptable in combustion chamber design. One way of overcoming this is to work with unequal orifice sizes for gas and liquid. It was found that using smaller gas orifice for a given liquid orifice resulted in lower SMD (Sauter Mean Diameter of the spray) for constant gas and liquid mass flow rates. This is attributable to the high dynamic pressure of gas in the case of smaller gas orifices for the same mass flow rate. The impinging liquid jets with unequal momentum in the doublet configuration would result in non-uniform mass and mixture ratio distribution within the combustion chamber which may have to operate under varying conditions of mass flow rates and/or mixture ratio. The symmetrical arrangement of triplet configuration can eliminate this problem at the same time generating finely atomized spray and a homogeneous mixture ratio. In view of the scanty literature available in this field, the atomization characteristics of the spray generated by liquid centered triplet jets are examined in detail. It was found that as in the case of gas-on-liquid impinging doublets, normal gas momentum to liquid mass is an ideal parameter in describing the spray. Variants of this configuration are studied recently for many other applications too. As done in the case of doublets, efforts have also been made to compare gas centered triplet to liquid-liquid triplet. It was found that the trend of SMD of gas centered triplet is different from that of liquid-liquid triplets, thus pointing to a different mechanism in play. The SMD in the case of liquid-liquid triplets decreases monotonically with increasing specific normal momentum. It is to be noted that specific normal momentum is an ideal parameter for describing the spray characteristics of liquid-liquid triplets and doublets. In the case of gas centered triplet the SMD first increases and then decreases with specific normal momentum, the inversion point depends on the gas mass flow rate for a constant specific normal momentum. The thesis concludes with a summary of the major observations of spray structures for all the above injector configurations and quantifies the parametric dependencies that would be of use to engineering design

Atomization of fuel is an important pre-requisite for efficient combustion in devices such as gas turbines, liquid propellant rocket engines, internal combustion engines and incinerators. The overall objective of the present work is to explore air-assisted atomization strategies for high viscosity fuels and liquids. Air-assisted atomization is a twin-fluid atomization method in which energy of the gas is used to assist the atomization of liquids. Broadly, three categories of air-assisted injection, i.e., effervescent, impinging jet and pre-filming air-blast are studied. Laser-based diagnostics are used to characterize the spray structure in terms of cone angle, penetration and drop size distribution. A backlit direct imaging method is used to study the macroscopic spray characteristics such as spray structure and spray cone angle while the microscopic characteristics are measured using the Particle/droplet imaging analysis (PDIA) technique. Effervescent atomization is a technique in which a small amount of gas is injected into the liquid at high pressure in the form of bubbles. Upon injection, the two-phase mixture expands rapidly and shatters the liquid into droplets and ligaments. Effervescent spray characteristics of viscous fuels such as Jatropha and Pongamia pure plant oils and diesel are studied. Measurements are made at various gas-to-liquid ratios (GLRs) and injection pressures. A Sauter Mean Diameter (SMD) of the order of 20 µm is achieved at an injection pressure of 10 bar and GLR of 0.2 with viscous fuels. An image-based method is proposed and applied to evaluate the unsteadiness in the spray. A map indicating steady/unsteady regime of operation has been generated. An optically accessible injector tip is developed which has enabled visualization of the two-phase flow structure inside the exit orifice of the atomizer. An important contribution of the present work is the correlation of the two-phase flow regime in the orifice with the external spray structure. For viscous fuels, the spray is observed to be steady only in the annular two-phase flow regime. Unexpanded gas bubbles observed in the liquid core even at an injection pressure of 10 bar indicate that the bubbly flow regime may not be beneficial for high viscosity oils. A novel method of external mixing twin-fluid atomization is developed. In this method, two identical liquid jets impinging at an angle are atomized using a gas jet. The effect of liquid viscosity (1 cP to 39 cP) and surface tension (22 mN/m to 72 mN/m) on this mode of atomization is studied by using water-glycerol and water-ethanol mixtures, respectively. An SMD of the order of 40 µm is achieved for a viscosity of 39 cP at a GLR of 0.13 at a liquid pressure of 8 bar and gas pressure of 5 bar. It is observed that the effect of liquid properties is minimal at high GLRs where the liquid jets are broken before the impingement as in the prompt atomization mode. Finally, a pre-filming air-blast technique is explored for transient spray applications. An SMD of 22 µm is obtained with diesel at liquid and gas pressures as low as 10 bar and 8.5 bar, respectively. With this technique, an SMD of 44 µm is achieved for Jatropha oil having a viscosity 10 times higher than that of diesel.

The goal of this work is to experimentally assess the influence of limiting walls of Škoda Octavia 3 automobile cabin to the air jet flowing from the right-front situated automotive vent which is part of a car dashboard. The experiment is performed by the smoke visualization method. There is a single construction option measured for an experiment. The setup of the vanes direction and the air flow rate are modified for this option. The experiment is divided into two phases. In the first phase, the visualization of the free air flow is conducted. In the second phase, exit plates are constructed and consequently, the visualization of the wall-jet flow is conducted. The results of both are compared to each other. The results imply that the influence of the surrounding surfaces must be taken into account with the increasing flow rate for the vanes set in the direction of upper-right, middle-right, and middle-middle. There is a direct interaction between the flow and exit plates (the flow impact, the Coanda effect). The free flow does not contain the information about the mutual interaction between the flow and the exit plates, as it is in the case of the wall-jet flow. In the case of the wall-jet flow, the opening of the flow takes place due to the effect of the impact and the subsequential suction caused by the Coanda effect. The exit plates substituting the car dashboard and the front window contribute to the prevention of the air intake from surrounding space and consequently to earlier flow opening from the vent. The present work also contains the measurement methodology and the image evaluation, the comparison with previous free flow measurements (70% match) and the comparison to the measurement of hot-wire anemometry method.

The phenomenon of gas entrainment, as a result of impinging liquid jets, was experimentally investigated. The purpose of these investigations was to create a solid experimental database necessary for the development and validation of computational fluid dynamics (CFD) codes. In this work, various experimental setups were built to allow employing various imaging measurement techniques with high spatial and temporal resolution. High-speed imaging was applied for characterizing the flow structure that develops under the free surface. It was found that gas entrainment takes place as soon as the jet impact velocity overcomes the value of 1.2 m/s. The bubble plume, formed as a result of impingement, consists of two distinct regions: an inner region with high turbulence and fine freely dispersed bubbles and an outer region, where larger bubbles move towards the free surface. Two mechanisms are responsible for the occurrence of gas entrainment. High-speed camera observations were validated by means of ultrafast x-ray computed tomography, an innovative non-intrusive measurement technique. Also, quantitative information regarding the bubble plume was acquired from the high-speed observations, in terms of: penetration depth, width and spreading angle of the bubble plume. Measurements, based on two wire-mesh sensors, were performed to assess the gas entrainment rate. In these measurements, void fraction distributions and gas velocities were quantified. The entrainment rate was calculated as an integral over the entrained volumetric gas fraction. It was found to be a function of the jet velocity and length. Results were validated using dual-plane x-ray computed tomography. Results were in agreement with the ones obtained from the wire-mesh sensors and approximately four to six times smaller than predictions found in related publications. Instantaneous as well as time-averaged velocity fields of the continuous phase were gained by means of particle image velocimetry (PIV). Axial time-averaged velocities followed a power law profile, typical for fully developed flow conditions. Two recirculating vortices were found in the flow: one occurs as a result of the water adhering to the lateral wall of the tank and the flow being confined by the bottom wall, while the second one is generated in the wake of rising bubbles. Bubble entrainment was found to reduce liquid phase mean velocities and to enhance fluctuations in the streamwise direction. This is reflected in the distribution of the turbulence kinetic energy. Last but not least, several examples of comparisons between experimental data and CFD results stand to demonstrate the importance of the experimental observations gathered in the frame of this work. It is shown that the experimental data provides a good basis not only for qualitative comparisons, but also for quantitative correlations.

Die ökologischen und ökonomischen Anforderungen der heutigen Zeit verlangen energieeffiziente Verarbeitungsverfahren. Vor diesem Hintergrund befasst sich diese Arbeit mit dem Kunststoffblasformprozess, der neben dem für die Kunststoffverarbeitung typischen hohen Energiebedarf zusätzlich ein hohes Maß an energieintensiv zu erzeugender Druckluft erfordert. Ausgehend von einer ausführlichen Energiebilanz des Extrusionsblasformprozesses wurde der zur Formgebung (Blasluft) und zur inneren Blasteilkühlung (Spülluft) benötigte Drucklufteinsatz als eine energetische Schwachstelle identifiziert. Zur Reduzierung des erforderlichen Druckluftaufwands bei der Formgebung wird die Prozessrückführung der Blasluft detailliert betrachtet. Weiterhin wird ein Speichersystem vorgestellt, das eine sekundäre Nutzung der bei der inneren Blasteilkühlung kontinuierlich anfallenden druckbehafteten Prozessabluft ermöglicht. Abschließend wird ein Ansatz zum effektiven Drucklufteinsatz bei der inneren Kühlung flaschenförmiger Blasteile aufgezeigt, der durch gezieltes Ausnutzen von für den Wärmeübergang günstiger Strömungsverhältnisse eine Kühlzeitverkürzung sowie eine Reduzierung des Druckluftaufwands verspricht.:1 Einleitung 2 Prozessanalyse des Blasformverfahrens 3 Motivation, Zielstellung und Aufbau der Arbeit 4 Energetische Bilanzierung des Extrusionsblasformverfahrens 5 Reduzierung des Druckluftaufwands bei der Formgebung 6 Sekundärnutzung der zur inneren Blasteilkühlung verwendeten Druckluft 7 Effektive Druckluftnutzung bei der inneren Kühlung flaschenförmiger Blasteile 8 Zusammenfassung und Ausblick / Today's ecological and economic requirements demand energy-efficient processing methods. Against this background, this thesis deals with the plastic blow moulding process, which, in addition to the high energy demand typical for plastics processing, requires a high degree of energy-intensive compressed air. Based on a detailed energy balance of the extrusion blow moulding process, the use of compressed air required for forming (blow air) and for internal cooling of the blowing parts (purge air) was identified as an energetic weak point. In order to reduce the amount of compressed air required for forming, a feedback process used to recycle the blowing air is investigated in detail. Furthermore, a storage system will be presented which allows a secondary use of the pressurized process exhaust air, which is continuously generated during the internal cooling of the blowing part. Finally, an optimization approach for the effective use of compressed air for the internal cooling of bottle-shaped blow-moulded parts is presented, which promises a shortening of the cooling time and a reduction of the compressed air required through the targeted use of favourable flow conditions for heat transfer.:1 Einleitung 2 Prozessanalyse des Blasformverfahrens 3 Motivation, Zielstellung und Aufbau der Arbeit 4 Energetische Bilanzierung des Extrusionsblasformverfahrens 5 Reduzierung des Druckluftaufwands bei der Formgebung 6 Sekundärnutzung der zur inneren Blasteilkühlung verwendeten Druckluft 7 Effektive Druckluftnutzung bei der inneren Kühlung flaschenförmiger Blasteile 8 Zusammenfassung und Ausblick

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Im Rahmen der vorliegenden Arbeit wurden Metallchalkogenid-Nanopartikel bzw. Quantum Dots größenselektiv mittels kontinuierlicher MicroJet-Reaktor-Technologie in wässrigem Medium erzeugt. Aufgrund der sehr kurzen Mischzeiten im µs- bis ms-Bereich können Keimbildung und -wachstum im MicroJet-Reaktor zeitlich voneinander separiert werden. Die Begrenzung des Partikelwachstum durch den Einsatz von Stabilisatoren oder geringer Präkursorkonzentrationen ermöglichten die Synthese von monodispersen, nanokristallinen Produkten mit sehr schmaler Partikelgrößenverteilung. Ausgehend von den wasserlöslichen Präkursoren Cadmiumnitrat und Natriumsulfid wurde sowohl eine Synthesestrategie für elektrostatisch- als auch Liganden-stabilisierte CdS-Nanopartikel entwickelt. Es wurden zahlreiche Reaktionsparameter wie Temperatur, Präkursorverhältnis, Konzentration oder Fällungsmittel variiert und der Einfluss auf die Partikelgröße überprüft. In weiteren Untersuchungen konnte die Übertragbarkeit der MicroJet-Reaktor-Synthese auf die Metallchalkogenide Cadmiumzinksulfid, Silbersulfid und Silberindiumsulfid validiert werden. Auch komplexere Systeme wie Core/Shell Partikel sind mittels postsynthetischer Beschichtung der im MicroJet-Reaktor hergestellten Nanopartikel möglich. Erste Experimente zur Synthese von CdSe bestätigten die Eignung des kontinuierlichen Verfahrens zur Fällung höherer Chalkogenide.:1 Einleitung 1 1.1 Halbleiternanopartikel 3 1.1.1 Bandstruktur des Festkörpers 3 1.1.2 Interbandübergänge in direkten und indirekten Halbleitern 7 1.1.3 Quantum Confinement 15 1.2 Fällung von Nanopartikeln im MicroJet-Reaktor 20 1.2.1 Partikelbildung durch Kristallisation 20 1.2.2 Funktionsprinzip des MicroJet-Reaktors 22 1.2.3 State of the Art 25 1.3 Nanoskalige Metallchalkogenide 29 1.3.1 Cadmiumchalkogenide 29 1.3.2 Near-Infrared Quantum Dots 31 1.3.3 Core/Shell-Partikel 34 1.4 Zielsetzung 37 2 Ergebnisse und Diskussion 39 2.1 Allgemeines 39 2.2 Cadmiumchalkogenide 47 2.2.1 Hydrothermalsynthese von CdS im Laborautoklaven 47 2.2.1.1 Wiederholbarkeit 48 2.2.1.2 Einfluss des Präkursorverhältnis 50 2.2.1.3 Versuchsplanung zur Untersuchung ausgewählter Reaktionsparameter 51 2.2.1.4 Effektberechnung zur Untersuchung ausgewählter Einflussfaktoren 54 2.2.1.5 Beobachtungen und Charakterisierung 56 2.2.2 Kontinuierliche Synthese von CdS im MicroJet-Reaktor 62 2.2.2.1 MJR-Synthese von CdS aus Cd(NO3)2 und Na2S 62 2.2.2.2 MJR-Synthese von CdS aus Cd(NO3)2 und Thioacetamid 71 2.2.3 CdS/ZnS Core/Shell und Cd1-xZnxS Quantum Dots 76 2.2.3.1 CdS/ZnS Core/Shell Quantum Dots 77 2.2.3.2 Cd1-xZnxS Quantum Dots 88 2.2.4 Hydrothermalsynthese von CdSe im Laborautoklaven 99 2.2.4.1 Wiederholbarkeit 99 2.2.4.2 Präkursorverhältnis Cd2+:Se2- 101 2.2.4.3 Versuchsplanung zur Untersuchung ausgewählter Reaktionsparameter 104 2.2.4.4 Effektberechnung zur Untersuchung ausgewählter Einflussfaktoren 108 2.2.4.5 Beobachtungen und Charakterisierung 111 2.2.5 Kontinuierliche Synthese von CdSe im MicroJet-Reaktor 116 2.3 Near-Infrared Quantum Dots 121 2.3.1 Kontinuierliche Synthese von AgS2 im MJR-Reaktor 121 2.3.1.1 Elektrostatisch stabilisierte Ag2S Quantum Dots 121 2.3.1.2 Ag2S/ZnS Core/Shell Quantum Dots 138 2.3.1.3 Ligandenstabilisierte Ag2S Quantum Dots 143 2.3.2 Kontinuierliche Synthese von Indiumsilbersulfid im MJR-Reaktor 152 3 Experimenteller Teil 165 3.1 Synthesen 165 3.1.1 Verwendete Chemikalien 165 3.1.2 Hydrothermalsynthese im Laborautoklaven 166 3.1.2.1 Versuchsaufbau 166 3.1.2.2 Cadmiumsulfid 167 3.1.2.3 Cadmiumselenid 168 3.1.2.4 Silbersulfid 169 3.1.3 Kontinuierliche Synthese im MicroJet-Reaktor 169 3.1.3.1 Versuchsaufbau und Durchführung der MicroJet-Reaktor-Synthese 169 3.1.3.2 Synthese Liganden-stabilisierter Metallsulfide 171 3.1.3.3 Synthese elektrostatisch stabilisierter Metallsulfide 171 3.1.3.4 Synthese von Cadmiumselenid 172 3.1.3.5 Synthese von Core-Shell-Partikeln 172 3.2 Analytische Methoden 173 3.2.1 Dynamische Lichtstreuung (DLS) 173 3.2.2 Statische Lichtstreuung (SLS) 173 3.2.3 UV/Vis-Absorptionsspektroskopie 173 3.2.4 Photolumineszenz (PL)-Spektroskopie 174 3.2.5 Transmissionselektronenmikroskopie (TEM) 174 3.2.6 Rasterelektronenmikroskopie (REM) 175 3.2.7 Optische Emissionsspektroskopie mit induktiv gekoppeltem Plasma (ICP-OES) 175 3.2.8 Röntgenfluoreszenzanalyse (RFA) 176 3.2.9 Pulver-Röntgendiffraktometrie (PXRD) 176 3.2.10 RAMAN-Spektroskopie 177 3.2.11 Abgeschwächte Totalreflexions-Infrarotspektroskopie (ATR-FTIR) 177 4 Zusammenfassung und Ausblick 179 5 Literatur 182 6 Anhang 195 / In the present work, metal chalcogenide nanoparticles or Quantum Dots were obtained size-selectively using continuous MicroJet Reactor technology. Due to the short mixing times in the µs to ms range, crystallite nucleation and crystal growth are well separated and enable concentration-limited particle growth. Alternatively, particle growth can be limited by stabilizers. Starting from the water-soluble precursors Cd(NO3)2 and Na2S, a synthesis strategy for both electrostatic and ligand stabilized CdS nanoparticles in aqueous medium was developed. The nanocrystalline products obtained were characterized by a narrow, monodisperse particle size distribution. Examining the influence of the particle size, numerous reaction parameters e. g. temperature, ratio of precursors, concentration or precipitant were varied. In further investigations, the transferability of the MicroJet Reactor synthesis to the metal chalcogenides (Cd,Zn)S, Ag2S and AgInS2 was validated. By means of post-synthetic coating of the nanoparticles produced in the MicroJet Reactor, more complex systems such as CdS/ZnS or Ag2S/ZnS core/shell particles are accessible. Initial experiments on the synthesis of CdSe confirmed the suitability of the continuous process for precipitation of selenides.:1 Einleitung 1 1.1 Halbleiternanopartikel 3 1.1.1 Bandstruktur des Festkörpers 3 1.1.2 Interbandübergänge in direkten und indirekten Halbleitern 7 1.1.3 Quantum Confinement 15 1.2 Fällung von Nanopartikeln im MicroJet-Reaktor 20 1.2.1 Partikelbildung durch Kristallisation 20 1.2.2 Funktionsprinzip des MicroJet-Reaktors 22 1.2.3 State of the Art 25 1.3 Nanoskalige Metallchalkogenide 29 1.3.1 Cadmiumchalkogenide 29 1.3.2 Near-Infrared Quantum Dots 31 1.3.3 Core/Shell-Partikel 34 1.4 Zielsetzung 37 2 Ergebnisse und Diskussion 39 2.1 Allgemeines 39 2.2 Cadmiumchalkogenide 47 2.2.1 Hydrothermalsynthese von CdS im Laborautoklaven 47 2.2.1.1 Wiederholbarkeit 48 2.2.1.2 Einfluss des Präkursorverhältnis 50 2.2.1.3 Versuchsplanung zur Untersuchung ausgewählter Reaktionsparameter 51 2.2.1.4 Effektberechnung zur Untersuchung ausgewählter Einflussfaktoren 54 2.2.1.5 Beobachtungen und Charakterisierung 56 2.2.2 Kontinuierliche Synthese von CdS im MicroJet-Reaktor 62 2.2.2.1 MJR-Synthese von CdS aus Cd(NO3)2 und Na2S 62 2.2.2.2 MJR-Synthese von CdS aus Cd(NO3)2 und Thioacetamid 71 2.2.3 CdS/ZnS Core/Shell und Cd1-xZnxS Quantum Dots 76 2.2.3.1 CdS/ZnS Core/Shell Quantum Dots 77 2.2.3.2 Cd1-xZnxS Quantum Dots 88 2.2.4 Hydrothermalsynthese von CdSe im Laborautoklaven 99 2.2.4.1 Wiederholbarkeit 99 2.2.4.2 Präkursorverhältnis Cd2+:Se2- 101 2.2.4.3 Versuchsplanung zur Untersuchung ausgewählter Reaktionsparameter 104 2.2.4.4 Effektberechnung zur Untersuchung ausgewählter Einflussfaktoren 108 2.2.4.5 Beobachtungen und Charakterisierung 111 2.2.5 Kontinuierliche Synthese von CdSe im MicroJet-Reaktor 116 2.3 Near-Infrared Quantum Dots 121 2.3.1 Kontinuierliche Synthese von AgS2 im MJR-Reaktor 121 2.3.1.1 Elektrostatisch stabilisierte Ag2S Quantum Dots 121 2.3.1.2 Ag2S/ZnS Core/Shell Quantum Dots 138 2.3.1.3 Ligandenstabilisierte Ag2S Quantum Dots 143 2.3.2 Kontinuierliche Synthese von Indiumsilbersulfid im MJR-Reaktor 152 3 Experimenteller Teil 165 3.1 Synthesen 165 3.1.1 Verwendete Chemikalien 165 3.1.2 Hydrothermalsynthese im Laborautoklaven 166 3.1.2.1 Versuchsaufbau 166 3.1.2.2 Cadmiumsulfid 167 3.1.2.3 Cadmiumselenid 168 3.1.2.4 Silbersulfid 169 3.1.3 Kontinuierliche Synthese im MicroJet-Reaktor 169 3.1.3.1 Versuchsaufbau und Durchführung der MicroJet-Reaktor-Synthese 169 3.1.3.2 Synthese Liganden-stabilisierter Metallsulfide 171 3.1.3.3 Synthese elektrostatisch stabilisierter Metallsulfide 171 3.1.3.4 Synthese von Cadmiumselenid 172 3.1.3.5 Synthese von Core-Shell-Partikeln 172 3.2 Analytische Methoden 173 3.2.1 Dynamische Lichtstreuung (DLS) 173 3.2.2 Statische Lichtstreuung (SLS) 173 3.2.3 UV/Vis-Absorptionsspektroskopie 173 3.2.4 Photolumineszenz (PL)-Spektroskopie 174 3.2.5 Transmissionselektronenmikroskopie (TEM) 174 3.2.6 Rasterelektronenmikroskopie (REM) 175 3.2.7 Optische Emissionsspektroskopie mit induktiv gekoppeltem Plasma (ICP-OES) 175 3.2.8 Röntgenfluoreszenzanalyse (RFA) 176 3.2.9 Pulver-Röntgendiffraktometrie (PXRD) 176 3.2.10 RAMAN-Spektroskopie 177 3.2.11 Abgeschwächte Totalreflexions-Infrarotspektroskopie (ATR-FTIR) 177 4 Zusammenfassung und Ausblick 179 5 Literatur 182 6 Anhang 195