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.

Microwave dielectric properties of MO -La2O3-TiO2 (M = Ca, Sr, Ba) ceramics

Single-phase polycrystalline ceramics in the MO-La2O3-Ti02 (M = Ca, Sr, Ba) system, such as cation-deficient hexagonal perovskites CaLa4Ti4O15, SrLa4Ti4O15, BaLa4Ti4O15, and Ca2La4Ti5O18 and the orthorhombic phases CaLa4Ti5O17 and CaLa8Ti9O31, were prepared through the solid-state ceramic route. The phases and structure of the ceramics were analyzed through x-ray diffraction and scanning electron microscopy. The microwave dielectric properties of the ceramics were studied using a network analyzer. The investigated ceramics show high Er in the range 42 to 54, high quality factors with Q x f in the range 16,222 to 50,215 GHz, and low Tf in the range -25 to +6 ppm3/°C. These high dielectric constant materials with high Q x f up to 50,215 GHz are suitable for applications where narrow bandwidth and extremely low insertion loss is necessary, especially at frequencies around 1.9 GHz

Remediation Of 17-α-ethinylestradiol Aqueous Solution By Photocatalysis And Electrochemically-assisted Photocatalysis Using Tio2 And Tio2/wo3 Electrodes Irradiated By A Solar Simulator.

TiO2 and TiO2/WO3 electrodes, irradiated by a solar simulator in configurations for heterogeneous photocatalysis (HP) and electrochemically-assisted HP (EHP), were used to remediate aqueous solutions containing 10 mg L(-1) (34 μmol L(-1)) of 17-α-ethinylestradiol (EE2), active component of most oral contraceptives. The photocatalysts consisted of 4.5 μm thick porous films of TiO2 and TiO2/WO3 (molar ratio W/Ti of 12%) deposited on transparent electrodes from aqueous suspensions of TiO2 particles and WO3 precursors, followed by thermal treatment at 450 (°)C. First, an energy diagram was organized with photoelectrochemical and UV-Vis absorption spectroscopy data and revealed that EE2 could be directly oxidized by the photogenerated holes at the semiconductor surfaces, considering the relative HOMO level for EE2 and the semiconductor valence band edges. Also, for the irradiated hybrid photocatalyst, electrons in TiO2 should be transferred to WO3 conduction band, while holes move toward TiO2 valence band, improving charge separation. The remediated EE2 solutions were analyzed by fluorescence, HPLC and total organic carbon measurements. As expected from the energy diagram, both photocatalysts promoted the EE2 oxidation in HP configuration; after 4 h, the EE2 concentration decayed to 6.2 mg L(-1) (35% of EE2 removal) with irradiated TiO2 while TiO2/WO3 electrode resulted in 45% EE2 removal. A higher performance was achieved in EHP systems, when a Pt wire was introduced as a counter-electrode and the photoelectrodes were biased at +0.7 V; then, the EE2 removal corresponded to 48 and 54% for the TiO2 and TiO2/WO3, respectively. The hybrid TiO2/WO3, when compared to TiO2 electrode, exhibited enhanced sunlight harvesting and improved separation of photogenerated charge carriers, resulting in higher performance for removing this contaminant of emerging concern from aqueous solution.

Azul de metileno imobilizado na celulose/TiO2 e SiO2/TiO2: propriedades eletroquímicas e planejamento fatorial

The electrochemical properties of methylene blue immobilized on cellulose/TiO2 and mixed oxide SiO2/TiO2 matrices were investigated by means of cyclic voltammetry. The electron mediator property of the methylene blue was optimized using a factorial design, consisting of four factors in two levels. The experimental observations and data analyses on the system indicate that the lowest peak separation occurs for Sil/TiOAM, 1.0 mol L-1 KCl solution and 20 mV s-1 scan rate, while values of current ratio closest to unity were found for Cel/TiOAM independent of electrolyte concentration, 0.2 or 1.0 mol L-1, and scan rate, 20 mV s-1 or 60 mV s-1.

TiO2-Photocatalyzed degradation of phenol in saline media in an annular reactor: hydrodynamics, lumped kinetics, intermediates, and acute toxicity

The photocatalytic degradation of phenol in aqueous suspensions of TiO2 under different salt concentrations in an annular reactor has been investigated. In all cases, complete removal of phenol and mineralization degrees above 90% were achieved. The reactor operational parameters were optimized and its hydrodynamics characterized in order to couple mass balance equations with kinetic ones. The photodegradation of the organics followed a Langmuir-Hinshelwood-Hougen-Watson lumped kinetics. From GC/MS analyses, several intermediates formed during oxidation have been identified. The main ones were catechol, hydroquinone, and 3-phenyl-2-propenal, in this order. The formation of negligible concentrations of 4-chlorophenol was observed only in high salinity medium. Acute toxicity was determined by using Artemia sp. as the test organism, which indicated that intermediate products were all less toxic than phenol and a significant abatement of the overall toxicity was accomplished, regardless of the salt concentration.

Role of the crystallite phase of TiO2 in heterogeneous photocatalysis for phenol oxidation in water

A series of TiO2 samples with different anatase-to-rutile ratios was prepared by calcination, and the roles of the two crystallite phases of titanium(IV) oxide (TiO2) on the photocatalytic activity in oxidation of phenol in aqueous solution were studied. High dispersion of nanometer-sized anatase in the silica matrix and the possible bonding of Si-O-Ti in SiO2/TiO2 interface were found to stabilize the crystallite transformation from anatase to rutile. The temperature for this transformation was 1200 degrees C for the silica-titania (ST) sample, much higher than 700 degrees C for Degussa P25, a benchmarking photocatalyst. It is shown that samples with higher anatase-to-rutile ratios have higher activities for phenol degradation. However, the activity did not totally disappear after a complete crystallite transformation for P25 samples, indicating some activity of the rutile phase. Furthermore, the activity for the ST samples after calcination decreased significantly, even though the amount of anatase did not change much. The activity of the same samples with different anatase-to-rutile ratios is more related to the amount of the surface-adsorbed water and hydroxyl groups and surface area. The formation of rutile by calcination would reduce the surface-adsorbed water and hydroxyl groups and surface area, leading to the decrease in activity.

Novel silica gel supported TiO2 photocatalyst synthesized by CVD method

TiO2 in anatase crystal phase is a very effective catalyst in the photocatalytic oxidation of organic compounds in water. To improve the recovery rate of TiO2 photocatalysts, which in most cases are in fine powder form, the chemical vapor deposition (CVD) method was used to load TiO2 onto a bigger particle support, silica gel. The amount of titania coating was found to depend strongly on the synthesis parameters of carrier gas flow rate and coating time. XPS and nitrogen ads/desorption results showed that most of the TiO2 particles generated from CVD were distributed on the external surface of the support and the coating was stable. The photocatalytic activities of TiO2/silica gel with different amounts of titania were evaluated for the oxidation of phenol aqueous solution and compared with that of Degussa P25. The optimum titania loading rate was found around 6 wt % of the TiO2 bulk concentration. Although the activity of the best TiO2/silica gel sample was still lower than that of P25, the synthesized TiO2/silica gel catalyst can be easily separated from the treated water and was found to maintain its TiO2 content and catalytic activity.

Synthesis of anatase TiO2 supported on porous solids by chemical vapor deposition

Coating anatase TiO2 onto three different particle supports, activated carbon (AC), gamma -alumina (Al2O3) and silica gel (SiO2), by chemical vapor deposition (CVD) was studied. The effect of the CVD synthesis conditions on the loading rate of anatase TiO2 was investigated. It was found that introducing water vapor during CVD or adsorbing water before CVD was crucial to obtain anatase TiO2 on the surface of the particle supports. The evaporation temperature of precursor, deposition temperature in the reactor, flow rate of carrier gas, and the length of coating time were also important parameters to obtain more uniform and repeatable TiO2 coating. High inflow precursor concentration, high CVD reactor temperature and long coating time tended to cause block problem. Coating TiO2 onto small particles by CVD involved both chemical vapor deposition and particle deposition. It was believed that the latter was the reason for the block problem. In addition, the mechanism of CVD process in this study included two parts, pyrolysis and hydrolysis, and one of them was dominant in the CVD process under different synthesis route. Among the three types of materials, silica gel, with higher surface hydroxyl groups and macropore surface area, was found to be the most efficient support in terms of both anatase TiO2 coating and photocatalytic reaction. (C) 2001 Elsevier Science B.V. All rights reserved.

Characterization of pore structure and coordination of titanium in TiO2 and SiO2-TiO2 sol-pillared clays

Titania sol-pillared clay (TiO2 PILC) and silica-titania sol-pillared clay (SiO2-TiO2 PILC) were synthesized by the sol-gel method. Supercritical drying (SCD) and treatment with quaternary ammonium surfactants were used to tailor the pore structure of the resulting clay. It was found that SCD approach increased the external surface area of the PILCs dramatically and that treatment with surfactants could be used to tailor pore size because the mesopore formation in the galleries between the clay layers follows the templating mechanism as observed in the synthesis of MCM-41 materials. Highly mesoporous solids were thus obtained. In calcined TiO2 PILC, ultrafine crystallites in anatase phase, which are active for photocatalytic oxidation of organics, were observed. In SiO2-TiO2 PILCs and their derivatives, titanium was highly dispersed in the matrix of silica and no crystal phase was observed. The highly dispersed titanium sites are good catalytic centers for selective oxidation of organic compounds. (C) 2001 Academic Press.

Novel composites of TiO2 (anatase) and silicate nanoparticles

Thermally stable composite nanostructures of titanium dioxide (anatase) and silicate nanoparticles were prepared from Laponite clay and a sol of titanium hydrate in the presence of poly(ethylene oxide) (PEO) surfactants. Laponite is a synthetic clay that readily disperses in water and exists as exfoliated silicate layers of about 1-nm thick in transparent dispersions of high pH. The acidic sol solution reacts with the clay platelets and leaches out most of the magnesium in the clay, while the sol particles hydrolyze further due to the high pH of the clay dispersion. As a result, larger precursors of TiO2 nanoparticles form and condense on the fragmentized pieces of the leached silicate. Introducing PEO surfactants into the synthesis can significantly increase the porosity and surface area of the composite solids. The TiO2 exists as anatase nanoparticles that are separated by silicate fragments and voids such that they are accessible to organic molecules. The size of the anatase particle can be tailored by manipulating the experimental parameters at various synthesis stages. Therefore, we can design and engineer composite nanostructures to achieve better performance. The composite solids exhibit superior properties as photocatalysts for the degradation of Rhodamine 6G in aqueous solution.

RF Receiver Front End for 28.5 GHz Applications on a 70 GHz F-T SiGe BiCMOS Process

This article presents the design and test of a receiver front end aimed at LMDS applications at 28.5 GHz. It presents a system-level design after which the receiver was designed. The receiver comprises an LNA, quadrature mixer and quadrature local oscillator. Experimental results at 24 GHz center frequency show a conversion voltage gain of 15 dB and conversion noise figure of 14 5 dB. The receiver operates from a 2 5 V power supply with a total current consumption of 31 mA.

Ferromagnetic order in aged Co-doped TiO2 anatase nanopowders

Oxide based diluted magnetic semiconductor (DMS) materials have been a subject of increasing interest due to reports of room temperature ferromagnetism in several systems and their potential use in the development of spintronic devices. However, concerns on the stability of the magnetic properties of different DMS systems have been raised. Their magnetic moment is often unstable, vanishing with a characteristic decay time of weeks or months, which precludes the development of real applications. This paper reports on the ferromagnetic properties of two-year-aged Ti1-xCoxO2-δ reduced anatase nanopowders with different Co contents (0.03≤x≤0.10). Aged samples retain rather high values of magnetization, remanence and coercivity which provide strong evidence for a quite preserved long-range ferromagnetic order. In what concern Co segregation, some degree of metastability of the diluted Co doped anatase structure could be inferred in the case of the sample with the higher Co content.

A new chemical route to synthesise TM-doped (TM = Co, Fe) TiO2 nanoparticles

Since the discovery of ferromagnetism well above room temperature in the Co-doped TiO2 system, diluted magnetic semiconductors based on TiO2 doped with transition metals have generated great interest because of their potential use in the development of spintronic devices. The purpose of this paper is to report on a new and swift chemical route to synthesise highly stable anatase single-phase Co- and Fe-doped TiO2 nanoparticles, with dopant concentrations of up to 10 at.-% and grain sizes that range between 20 and 30 nm. Complementary structural, microstructural and chemical analyses of the different nanopowders synthesised strongly support the hypothesis that a homogeneous distribution of the dopant element in the substitutional sites of the anatase structure has been achieved. Moreover, UV/Vis diffuse reflectance spectra of powder samples show redshifts to lower energies and decreasing bandgap energies with increasing Co or Fe concentration, which is consistent with n-type doping of the TiO2 anatase matrix. Films of Co-doped TiO2 were successfully deposited onto Si (100) substrates by the dip-coating method, with suspensions of Ti1-xCOxO2 nanoparticles in ethylene glycol. ((C)Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008).

Analisador de espectro de baixo custo com frequência de operação entre 2 e 3 GHz

Com o surgimento de novos sistemas de telecomunicações sem fios, que necessitam de maiores potências de emissão e largura de banda disponível, surgem os regulamentos que controlam as emissões rádio. Só assim estas tecnologias podem coexistir em bandas próximas, com o máximo desempenho e com a garantia que os níveis de poluição electromagnética não são ultrapassados. Cada vez mais, regulamentos que limitam a potência da transmissão têm em vista questões de saúde pública e por isso devem ser estritamente respeitados. Para se poder controlar as emissões rádio é necessário um dispositivo que consiga analisar o espectro rádio. Um dos instrumentos fundamentais na metrologia de radiofrequência é o analisador de espectros, que tem como principal função apresentar a potência de porções do espectro em função da frequência. Existem vários tipos de analisadores espectrais, que se baseiam em arquitecturas de recepção distintas. O tipo de analisador define a sua complexidade e o tipo de análises que consegue fazer. Com esta dissertação pretende-se mostrar a implementação de um analisador de espectro portátil, de baixo custo, baseado num receptor heteródino e com uma frequência de operação compreendida entre os 2 e os 3 GHz. Este projecto abrange diversas áreas, desde o hardware de recepção rádio, passando pelo microcontrolador que faz a aquisição de dados e comunicação com o computador, acabando na aplicação que foi desenvolvida em Java para permitir ao utilizador uma interface de utilização simples e funcional. Foi também desenvolvida com sucesso uma antena impressa adequada à banda de frequência referida. Embora tenham existidos problemas simples, um na localização do filtro passa-banda e o outro na resposta do filtro intermédio, os objectivos foram alcançados obtendo-se um analisador de espectro portátil, funcional e de baixo custo, conforme pretendido. O analisador tem um erro máximo na detecção de potência de 2,5 dB e o tempo de varrimento máximo é cerca de 16 segundos com 500 pontos de resolução. Foram realizadas várias medições e uma comparação com um analisador de espectros comercial, para demonstrar o funcionamento e desempenho do analisador desenvolvido, tendo os resultados sido bastante promissores. A funcionalidade deste analisador medir a potência do sinal ao longo do tempo é uma mais-valia face ao analisador comercial utilizado para a comparação.