Smart magnetic dispersions - from switchable release to well-defined hybrid nanofibers

The synthesis, characterization and application of aqueous dispersions of superparamagnetic/polymer hybrid nanoparticles and capsules is described. Implementation of the superparamagnetic moiety into the polymer matrix enables a response of the nanomaterials towards an external magnetic field. Application of the external field is used for two main purposes: i) As heat generator, when an alternating magnetic field is applied. ii) As structuring agent to self-assemble superparamagnetic nanoparticles in the external field.rnIn the first part, superparamagnetic nanoparticles were used as heat generators in order to achieve a magnetic field induced release of an active compound from nanocontainers. To achieve such a release in remote-controlled fashion, the encapsulation of superparamagnetic nanoparticles into polymer nanocapsules was combined with the integration of a thermolabile compound into the shell of the nanocontainers. The magnetic nanoparticles acted as generators for heat, which decomposed the thermolabile compound. Pores were created in the degrading shell and an active substance was released.rn Additionally, the self-assembly of polymer nanoparticles, which were labeled with a superparamagnetic moiety as structuring agent, could be demonstrated. A combination of a magnetic field induced self-assembly and a sintering of neighboring particles upon an increase in temperature above the glass transition temperature of the polymer was used to form stable architectures. Various structures with tunable periodicity could be obtained ranging from smooth linear nanofibers to zigzag fibers. Besides solely creating linear architectures, the frugal process additionally allowed the creation of arrangements in analogy to more complex polymer architectures: By the introduction of defined junction points, the generation of branched structures and networks was demonstrated. Additionally, by tailoring the interaction of differently sized particles, the preparation of nanoparticle arrangements in statistical or block copolymer fashion was shown. Moreover, a reversible linear assembly and linkage of the nanoparticles was demonstrated following a lock/unlock mechanism. Therefore, the particles were locked in their linear assembly by a stable iron(III) hydroxamato-complex and unlocked by addition of a reducing agent and formation of a less stable iron(II)-complex.Further, in various projects with collaboration partners, nanoparticles and nanocapsules were labeled with a superparamagnetic moiety for their use as contrast agents in magnetic resonance imaging or as magnetically separable dispersions.

Heusler compounds for thermoelectric applications

The demands for energy is leading to social and political conflicts in the world. For example, the limited resources of fossil fuels causing a dependence on the oil conveying countries in the world, leading to political discords. One way to save energy is to increase the efficiency of a process. In the field of thermoelectricity waste heat is used to produce electricity, this leads to an improvement of the efficiency. Heusler compounds with C1b structure with the general formula XY Z (X, Y = transition metal, Z = main group element) are in focus of the present thermoelectric research. Their mechanical and thermal stability is exceptional in comparison to the commonly used thermoelectric materials. The possibility to substitute small amounts of elements from the parent compound without destructing the lattice structure allows tuning the electronic properties. This tunability also allows to avoid the use of toxic and expensive elements. The reported thermoelectric Heusler compounds exhibit high electrical conductivity and moderate values of the Seebeck coefficients, which lead to a high powerfactor. The disadvantage of Heusler compounds is their high thermal conductivity. Introducing mass disorder on the X-site lattice is one effective way to produce additional phonon scattering and with it to decrease the thermal conductivity. Another approach is to implement a nano or micro structure in the thermoelectric material. This can be achieved by phase separation, composite materials, pulverization with additional spark plasma sintering or by a complex lattice structure. In the first part of this work, the influence of element substitutions on the Zr0.5Hf0.5NiSn system was investigated, to obtain the knowledge on how to optimize the electronic properties of the Heusler compounds with C1b structure. In line with this, the change of the electronic structure was investigated and a possible mechanism is predicted. In the second part of this work, the phenomenon of phase separation was investigated. First, by applying a phase separation in the well-known system Co2MnSn and subsequently by systematic investiga- tions on the TixZryHfzNiSn. In the third part, the results from the previous parts before were used to produce and explain the best reported Heusler compound with C1b structure exhibiting a Figure of Merit of ZT= 1.2 at 830 K.

Thermoelektrische und strukturelle Eigenschaften gefüllter Skutterudite, sowie Verbesserung ihres Gütefaktors durch Nanostrukturierung

Gefüllte Skutterudite mit der Summenformel MxCo4Sb12 sind vielversprechende thermoelektrische Materialien. Die Standardsynthese führt jedoch oft zur Bildung von MSbx, Sb, CoSb oder CoSb2 als Nebenphasen. In dieser Arbeit wird eine neue zweistufige Synthese vorgestellt, bei der die Bildung des Kieftits (CoSb3) getrennt von dem topotaktischen Füllen mit dem Metallatom M erfolgt. Dieser Ansatz erlaubt eine Durchführung der Reaktion bei niedrigeren Temperaturen mit kürzeren Reaktionszeiten. Ein geringer Antimon-Unterschuss im so erhaltenen Kieftit erhöht die Anzahl der Ladungsträger und unterdrückt die Bildung von Verunreinigungsphasen. Zunächst wurden Skutteruditproben mit der nominellen Zusammensetzung InxCo4Sb12 mit x = 0,12; 0,15; 0,18 und 0,20 in hoher Reinheit hergestellt und mit Spark Plasma Sintering (SPS) kompaktiert. Messaufnahmen mit Potential- und Seebeck-Mikrosonde und Rasterelektronenmikroskop zeigten eine hohe Probenhomogenität. Produkte waren nahezu phasenrein, was eine Untersuchung der Transporteigenschaften ohne Verfälschung durch Nebenphasen ermöglichte. Die quantitative Phasenanalyse mittels Synchrotron-Beugungsdaten zeigte < 0,1 % InSb bei In0,18Co4Sb12 und In0,20Co4Sb12, sowie eine lineare Korrelation zwischen dem wahren Füllgrad und der Gitterkonstante. Die Bindung von < 0,1 % InSb verringerte den Füllgrad der nominellen In0,20Co4Sb12-Probe auf x = 0,144. Die nominelle In0,18Co4Sb12-Probe mit dem wahren Gehalt x = 0,160 hatte den höchsten zT-Wert nahe eins bei 420 °C. Es konnte anschließend die Anwendbarkeit der Synthesemethode für Barium- und mehrfach gefüllte (Na+In) Skutterudite gezeigt werden. Die Na-gefüllte Probe war gegenüber der thermischen Behandlung in der SPS oder der Charakterisierung instabil. Alle Verbindungen wurden gesintert und ihre Transporteigenschaften wurden charakterisiert. Des weiterem wurde der Einfluss der Konzentration der Korngrenzen bei den Mischungen von zu Nanomaßstab vermahlenem In0,18Co4Sb12 (Partikelgrößen zwischen 20 und 100 nm) mit dem ursprünglichen Bulk untersucht. Proben mit verschiedenen Anteilen von Nanopulver wurden gesintert, ihre thermoelektrischen und strukturellen Eigenschaften wurden untersucht. Die Gütezahl zT von 1,39 bei 375 °C wurde bei der Probe mit gleichen Anteilen des Nano- und des unbehandelten Pulvers erreicht. Die Komposite mit Anteilen <10 % oder >75 % des Nanopulvers zeigten keine Verbesserung gegenüber der unbehandelten Verbindung.rn

Prove a fatica su provini differentemente accresciuti a partire da polvere d'acciaio

Lo scopo della prototipazione rapida è la realizzazione di prototipi destinati alle osservazioni al fine di migliorare il progetto in via di sviluppo. Tuttavia, negli ultimi anni si sta cercando di ottenere prototipi che siano già di per sé funzionali e quindi oggetti pronti all'uso. Soprattutto per i materiali metallici, si stanno sviluppando tecniche di prototipazione che tendono a diventare veri e propri processi tecnologici di produzione: una di queste è il processo DMLS (Direct Metal Laser Sintering). La tecnologia di Sinterizzazione Laser Selettiva dei Metalli (DMLS) si realizza attraverso un processo per addizione stratificata, in cui l’utilizzo di un laser ad alta densità di energia permette di fondere metalli in polvere, creando il modello o il prototipo tridimensionale. La tecnologia DMLS risulta estremamente innovativa ed offre la possibilità di sviluppare componenti con un grado di precisione elevato e un livello di dettaglio accurato. I vantaggi di questa tecnologia sono diversi, ma il più importante è l'estrema flessibilità di progetto in quanto si eliminano i vincoli di fabbricazione dettati dalle tecniche di produzione convenzionali basate sull'asportazione di truciolo, dando così piena libertà di design al progettista. Un esempio di applicazione di questa tecnologia è la costruzione di stampi per lo stampaggio ad iniezione: per poter migliorare il ciclo di produzione (in termini di tempo e quindi di denaro) è possibile creare canali di raffreddamento interni ottimizzati con forme e traiettorie diverse dalle tradizionali rettilinee ottenute per foratura. Dunque, associando questa tecnologia con i diversi materiali disponibili in commercio, è possibile costruire manufatti altamente customizzati e performanti a seconda delle varie esigenze. L’obiettivo di questo lavoro è stato quello di stimare e confrontare il limite di fatica per vita infinita di tre serie di provini, ottenuti mediante il processo innovativo DMLS, accresciuti secondo la direzione verticale, orizzontale ed inclinata a 45°; in particolare si è voluto osservare il comportamento dei provini in quest’ultimo caso, non essendoci informazioni precise in letteratura. La polvere di metallo utilizzata per la fabbricazione dei provini è il Maraging Steel, un acciaio dalle caratteristiche meccaniche eccezionali utilizzato soprattutto nel campo aereonautico.

Caratterizzazione sperimentale dell'ossido di stronzio per l'assorbimento del diossido di carbonio da correnti gassose ad alta temperatura e considerazioni sulla sua applicazione industriale in processi CCS

Del granulato di ossido di stronzio (anche nella formula carbonato) è stato testato come nuovo possibile materiale di utilizzo per la cattura ad alta temperatura di diossido di carbonio da effluenti gassosi di scarto. Sono stati condotti diversi esperimenti con strumentazioni già preposte, quali test termogravimetrici, microscopia elettronica (SEM) e Xray (XRD). Mentre per la sperimentazione in quantità più rilevanti di materiale è stato costruito un impianto a letto fisso ex novo. Le prove TG hanno evidenziato una capacità media di sorbente parti a circa il 5% in massa di ossido, a temperature tra i 1100°C e i 1200°C, in situazione di regime (dopo numerosi cicli di carb/calc), con una buona conservazione nel tempo delle proprietà adsorbitive, mentre per le prove a letto fisso, si è registrato un calo di valori variabile tra il 3 e il 4%, con un netto miglioramento nel caso di calcinazione in vapore surriscaldato fino al 5%. Il trattamento in vapore ha sortito l’importante effetto di calcinazione del diossido di carbonio dal sorbente, quindi facilmente separabile dal flusso in uscita, misurato tramite cattura in una soluzione di idrossido di bario. Importanti fenomeni di sintering e densificazione hanno portato ad occludere completamente la camera di reazione sviluppando notevoli sovrappressioni interne. Tali fenomeni sono stati approfonditi tramite analisi SEM e XRD. Si è constatato un aumento notevole della grandezza dei granuli in caso di trattamento in vapore con la formazione di legami stabili e con conservazione della porosità. Nel caso di trattamento senza vapore surriscaldato i granuli hanno sinterizzato tramite formazione di legami, ma sempre con conservazione della macroporosità. Il lavoro di tesi è stato inquadrato nel contesto tecnologico al riguardo le tecniche CCS esistenti ed in progetto, con un attento studio bibliografico riguardo lo stato dell’arte, impianti esistenti, costi, metodi di cattura usati, metodologie di trasporto dei gas, metodologie di stoccaggio esistenti e in progetto. Si sono considerati alcuni aspetti economici per sviluppare un modello previsionale di spesa per una possibile applicazione di cattura per un impianto di produzione energetica. Con la progettazione e dimensionamento di un sistema integrato di adsorbimento tramite l’accoppiamento di 2 reattori dedicati ai cicli di carbonatazione e calcinazione del materiale sorbente. Infine si sono considerati gli aspetti salienti dello stoccaggio del diossido di carbonio in reservoir tramite le tecniche di EOR e EGR (Enhanced Oil/Gas Recovery) utilizzando la stessa CO2 come fluido spiazzante degli idrocarburi in posto. Concludendo il lavoro di tesi e di sperimentazione ha contribuito in modo tangibile allo scopo prefissato, andando a caratterizzare un nuovo materiale per la cattura di diossido di carbonio da effluenti gassosi ad alta temperatura, ed andando a verificare un’importante fenomeno rigenerativo non previsto delle capacità sorbitive dei materiali sottoposti a test.

Modeling And Predicting The Performance Of Infiltrated Solid Oxide Fuel Cell Anodes

Fuel cells are a topic of high interest in the scientific community right now because of their ability to efficiently convert chemical energy into electrical energy. This thesis is focused on solid oxide fuel cells (SOFCs) because of their fuel flexibility, and is specifically concerned with the anode properties of SOFCs. The anodes are composed of a ceramic material (yttrium stabilized zirconia, or YSZ), and conducting material. Recent research has shown that an infiltrated anode may offer better performance at a lower cost. This thesis focuses on the creation of a model of an infiltrated anode that mimics the underlying physics of the production process. Using the model, several key parameters for anode performance are considered. These are the initial volume fraction of YSZ in the slurry before sintering, the final porosity of the composite anode after sintering, and the size of the YSZ and conducting particles in the composite. The performance measures of the anode, namely percolation threshold and effective conductivity, are analyzed as a function of these important input parameters. Simple two and three-dimensional percolation models are used to determine the conditions at which the full infiltrated anode would be investigated. These more simple models showed that the aspect ratio of the anode has no effect on the threshold or effective conductivity, and that cell sizes of 303 are needed to obtain accurate conductivity values. The full model of the infiltrated anode is able to predict the performance of the SOFC anodes and it can be seen that increasing the size of the YSZ decreases the percolation threshold and increases the effective conductivity at low conductor loadings. Similar trends are seen for a decrease in final porosity and a decrease in the initial volume fraction of YSZ.

Magnesium - Tellurium by Powder Methods

Today considerable work is being done in the compressed metal powder field which is gradually ob­taining prominence as a valuable branch of metallurgy. The mass of data, however, has led to many different ideas on the results of sintering.

Powder Metallurgy

The metal powders may be produced in a number of different ways. In metals where the intercrystalline material is brittle enough, they may be ground in a ball mill or eddy mill. The fineness of such a powder is more or less controlled by the grain size of the original metal.

Measurements of the Magnetic Permeabilities of the Iron-Manganese Alloy System Prepared by the Methods of Powder Metallurgy

Powder metallurgy is a branch of metallurgy which produces metallic compacts in their final forms by means of pressure and heat-treatment from the pow­ders. The products of powder metallurgy are being used in our daily lives quite often. For example, the tungsten wires in the electric bulbs to the silver-tin fillings of our teeth.

Electrical Resistivity Measurements of Powder Metal Compacts

This work, as it was originally planned, was the arranging of an apparatus whereby electrical resistivity measurements could be made on powder compacts. It was also to include measurements on a series of copper-nickel compacts both before and after sintering.

Porosity and Oil Absorption Properties of Metal Compacts of Copper - Tin - Graphite

Powder metallurgy, the most recent innovation in met­allurgical process, is not a new art; although not until recently did it become a matter of general interest, this being due not only to the products formed but also to the possibilities of future developments. The manufacture and application of metal powders is now beginning to take a position as a recognized part of the science of metallurgy.

Production of Iron-Tin Compacts by Powder Metallurgy and a Synopsis of their Principle Properties

This thesis is concerned primarily with the production of metal powder compacts of iron and tin. In producing these compacts, the effects of process­ing variables on some of the essential properties of the pellets made were investigated.

Aluminum - Bronze Compacts and their Possible Use as a Bearing Material

In the modern aspect of powder metallurgy, the first use of a sintering process was in making filaments for incandescent electric lamps.In the short while from the day of Edison to the pres­ent, the science of working with metal powders has advanced by leaps and bounds.

Vom Metallpulver zum Gesenk Bauteil

Zur schnellen Herstellung von Metallteilen eignen sich die schichtweise Rapid Prototyping Verfahren. Zum einen ist die direkte Herstellung aus Zweikomponenten-Metallpulver möglich, zum anderen lassen sich aus Kunststoffüberzogenen Metallpulvern durch Infiltration komplexe Metallteile fertigen. Der Vortrag beschreibt die Prozessketten der beiden Verfahren und stellt ihre besonderen Eigenschaften gegenüber. Anhand von Praxisbeispielen wird die tatsächliche Leistungsfähigkeit beider Verfahren aufgeführt. Es werden die beiden Verfahren “Direct Metal Laser Sintering“ (DMLS) und “Indirect Metal Laser Sintering“ (IMLS) zur Herstellung von Gesenken und Bauteilen vorgestellt. Das “Direct Metal Laser Sintering“ wird in Zusammenarbeit mit der Fa. Daimler-Chrysler vorgestellt, die mit ihrer EOS Sinteranlage ein Benchmarkwerkzeug mit konturnaher Kühlung gefertigt haben. Das “Indirect Metal Laser Sintering“ wird an der Universität Duisburg-Essen angewandt. Hier wurden diverse Bauteile bzw. Gesenke in Zusammenarbeit mit der Fa. Powercut oder dem ZBT hergestellt.

Rapid Manufacturing - auch mit SLM

Rapid Manufacturing (RM) wurde als Schlagwort in der letzten Zeit insbesondere aus dem Bereich des Selective Laser Sintering (SLS) bekannt. In dieser inzwischen über 15-jährigen Technologieentwicklung wurden in den vergangenen Jahren bedeutende Fortschritte erzielt, die die Bauteileigenschaften nahe an die Anforderungen für End-Teile heran brachten. So ist das RM denn auch weniger aus der Sicht grösserer Losgrösse zu verstehen. Viel mehr bedeutet Rapid Manufacturing, dass die Bauteile nach einer generativen Fertigung direkt im Endprodukt resp. der Endanwendung zum Einsatz kommt. Das Selective Laser Melting, mit welchem aus metallischen Pulvermaterialien direkt Metallteile in Standardmaterialien hergestellt werden können, ist aufgrund der guten Materialeigenschaften für RM prädestiniert. In den ersten Anwendungsfeldern des SLM–Verfahrens standen die Herstellung von Werkzeugeinsätzen mit konturnaher Kühlung (Conformal Cooling) im Vordergrund, wobei diese Werkzeuge unter dem Begriff RM verstanden werden müssen, da die Werkzeuge direkt für die Endanwendung - den Spritzgussprozess - verwendet werden. Aktuelle Trends gehen jedoch in Richtung der Fertigung von Funktionsteilen z.B. für den Maschinenbau. Obwohl sich in der Fertigung komplexer Funktionsteile noch Probleme, z.B. mit in Bezug auf die generative Baurichtung überhängender Bauteilstrukturen ergeben, zeigen sich trotzdem erhebliche Vorteile eines RM mittels SLM. Neben klaren Vorteilen durch das mögliche Customizing von Bauteilen können bei kleineren Bauteilgrössen auch erhebliche Kostenvorteile erzielt werden. Allerdings zeigen die Grenzen der aktuellen Möglichkeiten, in welchen Bereichen das SLM-Verfahren weiterer Entwicklung bedarf. Themen wie Produktivität, die Problematik der nach wie vor notwendigen Supportstrukturen wie auch Qualitätssicherung müssen in den nächsten Jahren angegangen werden, wenn dieses Verfahren den Schritt hin zu einem etablierten Produktionsverfahren und damit zu breiterer Akzeptanz und Anwendung finden soll