Oxide thermoelectrics via a glass-ceramic route

Thermoelektrizität beschreibt die reversible Beeinflussung und Wechselwirkung von Elektrizität und Temperatur T in Systemen abseits des thermischen Gleichgewichtes. In diesen führt ein Temperaturgradient entlang eines thermoelektrischen Materials zu einem kontinuierlichen Ungleichgewicht in der Energieverteilung der Ladungsträger. Dies hat einen Diffusionsstrom der energiereichen Ladungsträger zum kalten Ende und der energiearmen Ladungsträger zum heißen Ende zur Folge. Da in offenen Stromkreisen kein Strom fließt, wird ein Ungleichgewicht der Ströme über das Ausbilden eines elektrischen Feldes kompensiert. Die dadurch entstehende Spannung wird als Seebeck Spannung bezeichnet. Über einen geeigneten Verbraucher, folgend aus dem Ohm'schen Gesetz, kann nun ein Strom fließen und elektrische Energie gewonnen werden. Den umgekehrten Fall beschreibt der sogenannte Peltier Effekt, bei dem ein Stromfluss durch zwei unterschiedliche miteinander verbundene Materialien ein Erwärmen oder Abkühlen der Kontaktstelle zur Folge hat. Die Effizienz eines thermoelektrischen Materials kann über die dimensionslose Größe ZT=S^2*sigma/kappa*T charakterisiert werden. Diese setzt sich zusammen aus den materialspezifischen Größen der elektrischen Leitfähigkeit sigma, der thermischen Leitfähigkeit kappa und dem Seebeck Koeffizienten S als Maß der erzeugten Spannung bei gegebener Temperaturdifferenz. Diese Arbeit verfolgt den Ansatz glaskeramische Materialien mit thermoelektrischen Kristallphasen zu synthetisieren, sie strukturell zu charakterisieren und ihre thermoelektrischen Eigenschaften zu messen, um eine Struktur-Eigenschaft Korrelation zu erarbeiten. Hierbei werden im Detail eine elektronenleitende (Hauptphase SrTi_xNb_{1-x}O_3) sowie eine löcherleitende Glaskeramik (Hauptphase Bi_2Sr_2Co_2O_y) untersucht. Unter dem Begriff Glaskeramiken sind teilkristalline Materialien zu verstehen, die aus Glasschmelzen durch gesteuerte Kristallisation hergestellt werden können. Über den Grad der Kristallisation und die Art der ausgeschiedenen Spezies an Kristallen lassen sich die physikalischen Eigenschaften dieser Systeme gezielt beeinflussen. Glaskeramiken bieten, verursacht durch ihre Restglasphase, eine niedrige thermische Leitfähigkeit und die Fermi Energie lässt sich durch Dotierungen in Richtung des Leitungs- oder Valenzbands verschieben. Ebenso besitzen glaskeramische Materialien durch ihre Porenfreiheit verbesserte mechanische Eigenschaften gegenüber Keramiken und sind weniger anfällig für den Einfluss des Sauerstoffpartialdruckes p_{O_2} auf die Parameter. Ein glaskeramisches und ein gemischt keramisch/glaskeramisches thermoelektrisches Modul aus den entwickelten Materialien werden konzipiert, präpariert, kontaktiert und bezüglich ihrer Leistung vermessen.

Titanate-based paraelectric glass-ceramics for applications in GHz electronics

Das Gebiet der drahtlosen Kommunikationsanwendungen befindet sich in einem permanenten Entwicklungsprozess (Mobilfunkstandards: GSM/UMTS/LTE/5G, glo-bale Navigationssatellitensysteme (GNSS): GPS, GLONASS, Galileo, Beidou) zu immer höheren Datenraten und zunehmender Miniaturisierung, woraus ein hoher Bedarf für neue, optimierte Hochfrequenzmaterialien resultiert. Diese Entwicklung zeigt sich besonders in den letzten Jahren in der zunehmenden Entwicklung und Anzahl von Smartphones, welche verschiedene Technologien mit unterschiedlichen Arbeitsfrequenzen innerhalb eines Geräts kombinieren (data: 1G-4G, GPS, WLAN, Bluetooth). Die für zukünftige Technologien (z.B. 5G) benötigte Performance-steigerung kann durch die Verwendung von auf MIMO basierenden Antennensystemen realisiert werden (multiple-input & multiple-output, gesteuerte Kombination von mehreren Antennen) für welche auf dielectric Loading basierende Technologien als eine der vielversprechendsten Implementierungslösungen angesehen werden. rnDas Ziel dieser Arbeit war die Entwicklung einer geeigneten paraelektrischen Glaskeramik ($varepsilon_{r}$ > 20, $Qf$ > 5000 GHz, |$tau_f$| < 20 ppm/K; im GHz Frequenzbe-reich) im $mathrm{La_{2}O_{3}}$-$mathrm{TiO_{2}}$-$mathrm{SiO_{2}}$-$mathrm{B_{2}O_{3}}$-System für auf dielectric Loading basierende Mobilfunkkommunikationstechnologien als Alternative zu existierenden kommerziell genutzten Sinterkeramiken. Der Fokus lag hierbei auf der Frage, wie die makroskopi-schen dielektrischen Eigenschaften der Glaskeramik mit ihrer Mikrostruktur korreliert bzw. modifiziert werden können. Es konnte gezeigt werden, dass die dielektrischen Materialanforderungen durch das untersuchte System erfüllt werden und dass auf Glaskeramik basierende Dielektrika weitere vorteilhafte nichtelektro-nische Eigenschaften gegenüber gesinterten Keramiken besitzen, womit dielektrische Glaskeramiken durchaus als geeignete Alternative angesehen werden können. rnEin stabiles Grünglas mit minimalen Glasbildneranteil wurde entwickelt und die chemische Zusammensetzung bezüglich Entglasung und Redoxinstabilitäten optimiert. Geeignete Dotierungen für dielektrisch verlustarme $mathrm{TiO_{2}}$-haltige Glaskeramiken wurden identifiziert.rnDer Einfluss der Schmelzbedingungen auf die Keimbildung wurde untersucht und der Keramisierungsprozess auf einen maximalen Anteil der gewünschten Kristallphasen optimiert um optimale dielektrische Eigenschaften zu erhalten. Die mikroskopische Struktur der Glaskeramiken wurde analysiert und ihr Einfluss auf die makroskopischen dielektrischen Eigenschaften bestimmt. Die Hochfrequenzverlustmechanismen wurden untersucht und Antennen-Prototypenserien wurden analysiert um die Eignung von auf Glaskeramik basierenden Dielektrika für die Verwendung in dielectric Loading Anwendungen zu zeigen.

Sistemi hands-free basati su smart-glass a supporto di attivita di customer care di un'impresa

Da alcuni anni in ambito business ed enterprise si sta diffondendo l'utilizzo di dispositivi wearable al fine di rendere più efficiente ed efficace la gestione di molteplici attività e processi aziendali. I sistemi hand-held comunemente utilizzati in ambito lavorativo, tra cui smartphone e tablet, spesso non risultano idonei in contesti in cui un operatore debba interagire con il dispositivo mentre ha le proprie mani impegnate con attrezzature e strumenti di lavoro. I sistemi hands-free rimediano a tali problematiche supportando tecniche di interazione non convenzionali che consentono all'operatore di mantenere libere le proprie mani durante la consultazione del dispositivo e di rimanere concentrato sull'attività che sta svolgendo. I sistemi basati su smart-glass, oltre ad offrire funzionalità hands-free, presentano l'ulteriore vantaggio di poter presentare all'interno del campo visivo dell'utente importanti informazioni di supporto inerenti all'attività che sta svolgendo, avvalendosi anche dell'utilizzo di tecnologie di realtà aumentata. La sinergia tra dispositivi basati su smart-glass e tecniche di realtà aumentata sta destando un crescente interesse sia in ambito accademico che industriale; esiste la possibilità che in un prossimo futuro questa tipologia di sistemi divenga la nuova piattaforma computazionale enterprise di riferimento. L'obiettivo di questo lavoro di tesi è stato lo studio e la progettazione di una soluzione hands-free basata su smart-glass in grado di supportare alcune attività di customer care del Gruppo Loccioni, una società che si occupa dello sviluppo di sistemi automatici di misura e controllo per migliorare la qualità, l'efficienza e la sostenibilità di prodotti, processi ed edifici. In particolare, il sistema sviluppato ha consentito di migliorare la gestione dei processi di manutenzione e riparazione degli impianti energetici sostenibili che il Gruppo Loccioni installa presso le sedi di imprese clienti.

Studio e sviluppo di un Framework in ambiente Android per la realizzazione di Interfacce Utente Innovative basate su Smart Glass

La tesi tratta dell'esplorazione di una possibile interfaccia utente per Smart Glass in un contesto di utilizzo hands-free con elementi virtuali appartenenti ad un sistema di riferimento solidale all'utente e non al dispositivo, e la conseguente realizzazione di un Framework per lo sviluppo di applicazioni Andoid rispondenti a tale interfaccia e relativo test.

Computer-assisted design and manufacture of implants in the late reconstruction of extensive orbital fractures

To evaluate the use of computer-assisted designed and manufactured (CAD/CAM) orbital wall and floor implants for late reconstruction of extensive orbital fractures.

Stab or throw? Biomechanical studies on the injuring potential of glass fragments

During a Christmas party, two male guests started fighting. The perpetrator was allegedly pushed onto a glass table by the victim or fell into the table together with that man so that the glass top broke and caused a cut wound on the perpetrator's back. According to his statement he then threw a fragment of the broken glass table in the direction of the other man hitting him accidentally in a way so that the subclavian artery was severed and he died from exsanguination. Tests on the breaking characteristics of the glass table, the flying behaviour and the kinetics of thrown glass fragments conducted on various models supported the conclusion that the fatal injury on the victim's neck could not have been caused by a thrown glass fragment. It was much more likely that a stab with a blade-shaped glass fragment was the cause of the fatal injuries.

Halogen lamp and led activation of resin-modified glass ionomer restorative material. In vitro microhardness after long term storage

AIM: The purpose of this study was to evaluate the activation of resin-modified glass ionomer restorative material (RMGI, Vitremer-3M-ESPE, A3) by halogen lamp (QTH) or light-emitting diode (LED) by Knoop microhardness (KHN) in two storage conditions: 24hrs and 6 months and in two depths (0 and 2 mm). MATERIALS AND METHODS: The specimens were randomly divided into 3 experimental groups (n=10) according to activation form and evaluated in depth after 24h and after 6 months of storage. Activation was performed with QTH for 40s (700 mW/cm2) and for 40 or 20 s with LED (1,200 mW/scm2). After 24 hrs and 6 months of storage at 37°C in relative humidity in lightproof container, the Knoop microhardness test was performed. Statistics Data were analysed by three-way ANOVA and Tukey post-tests (p<0.05). RESULTS: All evaluated factors showed significant differences (p<0.05). After 24 hrs there were no differences within the experimental groups. KHN at 0 mm was significantly higher than 2 mm. After 6 months, there was an increase of microhardness values for all groups, being the ones activated by LED higher than the ones activated by QTH. CONCLUSION: Light-activation with LED positively influenced the KHN for RMGI evaluated after 6 months.

Proliferation, differentiation and gene expression of osteoblasts in boron-containing associated with dexamethasone deliver from mesoporous bioactive glass scaffolds

Boron is one of the trace elements in the human body which plays an important role in bone growth. Porous mesopore bioactive glass (MBG) scaffolds are proposed as potential bone regeneration materials due to their excellent bioactivity and drug-delivery ability. The aims of the present study were to develop boron-containing MBG (B-MBG) scaffolds by sol-gel method and to evaluate the effect of boron on the physiochemistry of B-MBG scaffolds and the response of osteoblasts to these scaffolds. Furthermore, the effect of dexamethasone (DEX) delivery in B-MBG scaffold system was investigated on the proliferation, differentiation and bone-related gene expression of osteoblasts. The composition, microstructure and mesopore properties (specific surface area, nano-pore volume and nano-pore distribution) of B-MBG scaffolds have been characterized. The effect of boron contents and large-pore porosity on the loading and release of DEX in B-MBG scaffolds were also investigated. The results have shown that the incorporation of boron into MBG scaffolds slightly decreases the specific surface area and pore volume, but maintains well-ordered mesopore structure and high surface area and nano-pore volume compared to non-mesopore bioactive glass. Boron contents in MBG scaffolds did not influence the nano-pore size distribution or the loading and release of DEX. B-MBG scaffolds have the ability to maintain a sustained release of DEX in a long-term span. Incorporating boron into MBG glass scaffolds led to a controllable release of boron ions and significantly improved the proliferation and bone-related gene expression (Col I and Runx2) of osteoblasts. Furthermore, the sustained release of DEX from B-MBG scaffolds significantly enhanced alkaline phosphatase (ALP) activity and gene expressions (Col I, Runx2, ALP and BSP) of osteoblasts. These results suggest that boron plays an important role in enhancing osteoblast proliferation in B-MBG scaffold system and DEX-loaded B-MBG scaffolds show great potential as a release system to enhance osteogenic property for bone tissue engineering application.

High-speed Imaging of a Bulk Metallic Glass During Uniaxial Compression

High-speed imaging directly correlates the propagation of a particular shear band with mechanical measurements during uniaxial compression of a bulk metallic glass. Imaging shows shear occurs simultaneously over the entire shear plane, and load data, synced and time-stamped to the same clock as the camera, reveal that shear sliding is coincident with the load drop of each serration. Digital image correlation agrees with these results. These data demonstrate that shear band sliding occurs with velocities on the order of millimeters per second. Fracture occurs much more rapidly than the shear banding events, thereby readily leading to melting on fracture surfaces.

Temperature-Dependent Defect Dynamics in the Network Glass SiO2

We investigate the long time dynamics of a strong glass former, SiO2, below the glass transition temperature by averaging single-particle trajectories over time windows which comprise roughly 100 particle oscillations. The structure on this coarse-grained time scale is very well defined in terms of coordination numbers, allowing us to identify ill-coordinated atoms, which are called defects in the following. The most numerous defects are O-O neighbors, whose lifetimes are comparable to the equilibration time at low temperature. On the other hand, SiO and OSi defects are very rare and short lived. The lifetime of defects is found to be strongly temperature dependent, consistent with activated processes. Single-particle jumps give rise to local structural rearrangements. We show that in SiO2 these structural rearrangements are coupled to the creation or annihilation of defects, giving rise to very strong correlations of jumping atoms and defects.

The new insight into dynamic crossover in glass forming liquids from the apparent enthalpy analysis

One of the most intriguing phenomena in glass forming systems is the dynamic crossover (T(B)), occurring well above the glass temperature (T(g)). So far, it was estimated mainly from the linearized derivative analysis of the primary relaxation time τ(T) or viscosity η(T) experimental data, originally proposed by Stickel et al. [J. Chem. Phys. 104, 2043 (1996); J. Chem. Phys. 107, 1086 (1997)]. However, this formal procedure is based on the general validity of the Vogel-Fulcher-Tammann equation, which has been strongly questioned recently [T. Hecksher et al. Nature Phys. 4, 737 (2008); P. Lunkenheimer et al. Phys. Rev. E 81, 051504 (2010); J. C. Martinez-Garcia et al. J. Chem. Phys. 134, 024512 (2011)]. We present a qualitatively new way to identify the dynamic crossover based on the apparent enthalpy space (H(a)(') = dlnτ/d(1/T)) analysis via a new plot lnH(a)(') vs. 1∕T supported by the Savitzky-Golay filtering procedure for getting an insight into the noise-distorted high order derivatives. It is shown that depending on the ratio between the "virtual" fragility in the high temperature dynamic domain (m(high)) and the "real" fragility at T(g) (the low temperature dynamic domain, m = m(low)) glass formers can be splitted into two groups related to f < 1 and f > 1, (f = m(high)∕m(low)). The link of this phenomenon to the ratio between the apparent enthalpy and activation energy as well as the behavior of the configurational entropy is indicated.