Fluoranthene derivatives as blue fluorescent materials for non-doped organic light-emitting diodes

In this study, we report synthesis of symmetrically and non-symmetrically functionalized fluoranthene-based blue fluorescent molecular materials for non-doped electroluminescent devices. The solid state structure of these fluorophores has been established by single crystal X-ray diffraction analysis. Furthermore, a detailed experimental and theoretical study has been performed to understand the effect of substitution of symmetric and non-symmetric functional groups on optical, thermal and electrochemical properties of fluoranthene. These materials exhibit a deep blue emission and high PLQY in solution and solid state. The vacuum deposited, non-doped electroluminescent devices with the device structure ITO/NPD (15 nm)/CBP (15 nm)/EML (40 nm)/TPBI (30 nm)/LiF (1 nm)/Al were fabricated and characterized. A systematic shift in the peak position of EL emission was observed from sky blue to bluish-green with EL maxima from 477 nm to 490 nm due to different functional groups on the periphery of fluoranthene. In addition, a high luminance of >= 2000 cd m(-2) and encouraging external quantum efficiency (EQE) of 1.1-1.4% were achieved. A correlation of the molecular structure with device performance has been established.

New fluorescent dipolar pyrazine derivatives for non-doped red organic light-emitting diodes

Dipolar fluorescent compounds containing electron-accepting pyrazine-2,3-dicarbonitrile and electron-donating arylamine moiety have been designed and synthesized. The optical and electrochemical properties of these compounds can be adjusted by changing pi-bridge length and the donor (D) strength. Organic light-emitting devices based on these compounds are fabricated. Saturated red emission of (0.67, 0.33) and the external quantum efficiency as high as 1.41% have been demonstrated for one of these compounds.

Biological Response to Wollastonite Doped alpha-Tricalcium Phosphate Implants in Hard and Soft Tissues in Rats

The biological response following subcutaneous and bone implantation of beta-wollastonite(beta-W)-doped alpha-tricalcium phosphate bioceramics in rats was evaluated. Tested materials were: tricalciurn phosphate (TCP), consisting of a mixture of alpha- and beta-polymorphs; TCP doped with 5 wt. % of beta-W (TCP5W), composed of alpha-TCP as only crystalline phase; and TCP doped with 15 wt. % of beta-W (TCP15), containing crystalline alpha-TCP and beta-W. Cylinders of 2x1 mm were implanted in tibiae and backs of adult male Rattus norvegicus, Holtzman rats. After 7, 30 and 120 days, animals were sacrificed and the tissue blocks containing the implants were excised, fixed and processed for histological examination. TCP, TCP5W and TCP15W implants were biocompatible but neither bioactive nor biodegradable in rat subcutaneous tissue. They were not osteoinductive in connective tissue either. However, in rat bone tissue beta-W-doped alpha-TCP implants (TCP5W and TCP15W) were bioactive, biodegradable and osteoconductive. The rates of biodegradation and new bone formation observed for TCP5W and TCP15W implants in rat bone tissue were greater than for non-doped TCP.

1.5 mu m and visible up-conversion emissions in Er3+/Yb3+ co-doped tellurite glasses and optical fibers for photonic applications

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Crystal structure refinement of Co-doped lanthanum chromites

Results of crystal structure refinements and phase quantification for samples of Co-doped lanthanum chromites with nominal composition LaCr(1-x)Co(x)O(3), for x=0.00, 0.10, 0.20, and 0.30, prepared by combustion synthesis are presented. The resulting powders were characterized by scanning electron microscopy and X-ray diffraction (XRD). The XRD patterns were obtained with Cu K alpha radiation for non-doped lanthanum chromite sample and additionally with Cr K alpha radiation for Co-doped lanthanum chromites samples, in order to enhance the signal from scattering. Rietveld analysis of XRD data showed that the studied samples presented the lanthanum chromite with an orthorhombic structure (Pnma), except for the composition with x=0.30, in which the space group was found to be R (3) over barc. (C) 2008 International Centre for Diffraction Data.

Biological response to wollastonite doped α-tricalcium phosphate implants in hard and soft tissues in rats

The biological response following subcutaneous and bone implantation of β-wollastonite(β-W)-doped α-tricalcium phosphate bioceramics in rats was evaluated. Tested materials were: tricalcium phosphate (TCP), consisting of a mixture of α- and β-polymorphs; TCP doped with 5 wt. % of β-W (TCP5W), composed of α-TCP as only crystalline phase; and TCP doped with 15 wt. % of β-W (TCP 15), containing crystalline α-TCP and β-W. Cylinders of 2×1 mm were implanted in tibiae and backs of adult male Rattus norvegicus, Holtzman rats. After 7, 30 and 120 days, animals were sacrificed and the tissue blocks containing the implants were excised, fixed and processed for histological examination. TCP, TCP5W and TCP15W implants were biocompatible but neither bioactive nor biodegradable in rat subcutaneous tissue. They were not osteoinductive in connective tissue either. However, in rat bone tissue β-W-doped α-TCP implants (TCP5W and TCP 15W) were bioactive, biodegradable and osteoconductive. The rates of biodegradation and new bone formation observed for TCP5W and TCP15W implants in rat bone tissue were greater than for non-doped TCP.

Advanced Reaction Systems for Hydrogen Production

[EN] This PhD work started in March 2010 with the support of the University of the Basque Country (UPV/EHU) under the program named “Formación de Personal Investigador” at the Chemical and Environmental Engineering Department in the Faculty of Engineering of Bilbao. The major part of the Thesis work was carried out in the mentioned department, as a member of the Sustainable Process Engineering (SuPrEn) research group. In addition, this PhD Thesis includes the research work developed during a period of 6 months at the Institut für Mikrotechnik Mainz GmbH, IMM, in Germany. During the four years of the Thesis, conventional and microreactor systems were tested for several feedstocks renewable and non-renewable, gases and liquids through several reforming processes in order to produce hydrogen. For this purpose, new catalytic formulations which showed high activity, selectivity and stability were design. As a consequence, the PhD work performed allowed the publication of seven scientific articles in peer-reviewed journals. This PhD Thesis is divided into the following six chapters described below. The opportunity of this work is established on the basis of the transition period needed for moving from a petroleum based energy system to a renewable based new one. Consequently, the present global energy scenario was detailed in Chapter 1, and the role of hydrogen as a real alternative in the future energy system was justified based on several outlooks. Therefore, renewable and non-renewable hydrogen production routes were presented, explaining the corresponding benefits and drawbacks. Then, the raw materials used in this Thesis work were described and the most important issues regarding the processes and the characteristics of the catalytic formulations were explained. The introduction chapter finishes by introducing the concepts of decentralized production and process intensification with the use of microreactors. In addition, a small description of these innovative reaction systems and the benefits that entailed their use were also mentioned. In Chapter 2 the main objectives of this Thesis work are summarized. The development of advanced reaction systems for hydrogen rich mixtures production is the main objective. In addition, the use and comparison between two different reaction systems, (fixed bed reactor (FBR) and microreactor), the processing of renewable raw materials, the development of new, active, selective and stable catalytic formulations, and the optimization of the operating conditions were also established as additional partial objectives. Methane and natural gas (NG) steam reforming experimental results obtained when operated with microreactor and FBR systems are presented in Chapter 3. For these experiments nickel-based (Ni/Al2O3 and Ni/MgO) and noble metal-based (Pd/Al2O3 and Pt/Al2O3) catalysts were prepared by wet impregnation and their catalytic activity was measured at several temperatures, from 973 to 1073 K, different S/C ratios, from 1.0 to 2.0, and atmospheric pressure. The Weight Hourly Space Velocity (WHSV) was maintained constant in order to compare the catalytic activity in both reaction systems. The results obtained showed a better performance of the catalysts operating in microreactors. The Ni/MgO catalyst reached the highest hydrogen production yield at 1073 K and steam-to-carbon ratio (S/C) of 1.5 under Steam methane Reforming (SMR) conditions. In addition, this catalyst also showed good activity and stability under NG reforming at S/C=1.0 and 2.0. The Ni/Al2O3 catalyst also showed high activity and good stability and it was the catalyst reaching the highest methane conversion (72.9 %) and H2out/CH4in ratio (2.4) under SMR conditions at 1073 K and S/C=1.0. However, this catalyst suffered from deactivation when it was tested under NG reforming conditions. Regarding the activity measurements carried out with the noble metal-based catalysts in the microreactor systems, they suffered a very quick deactivation, probably because of the effects attributed to carbon deposition, which was detected by Scanning Electron Microscope (SEM). When the FBR was used no catalytic activity was measured with the catalysts under investigation, probably because they were operated at the same WHSV than the microreactors and these WHSVs were too high for FBR system. In Chapter 4 biogas reforming processes were studied. This chapter starts with an introduction explaining the properties of the biogas and the main production routes. Then, the experimental procedure carried out is detailed giving concrete information about the experimental set-up, defining the parameters measured, specifying the characteristics of the reactors used and describing the characterization techniques utilized. Each following section describes the results obtained from activity testing with the different catalysts prepared, which is subsequently summarized: Section 4.3: Biogas reforming processes using γ-Al2O3 based catalysts The activity results obtained by several Ni-based catalysts and a bimetallic Rh-Ni catalyst supported on magnesia or alumina modified with oxides like CeO2 and ZrO2 are presented in this section. In addition, an alumina-based commercial catalyst was tested in order to compare the activity results measured. Four different biogas reforming processes were studied using a FBR: dry reforming (DR), biogas steam reforming (BSR), biogas oxidative reforming (BOR) and tri-reforming (TR). For the BSR process different steam to carbon ratios (S/C) from 1.0 to 3.0, were tested. In the case of BOR process the oxygen-to-methane (O2/CH4) ratio was varied from 0.125 to 0.50. Finally, for TR processes different S/C ratios from 1.0 to 3.0, and O2/CH4 ratios of 0.25 and 0.50 were studied. Then, the catalysts which achieved high activity and stability were impregnated in a microreactor to explore the viability of process intensification. The operation with microreactors was carried out under the best experimental conditions measured in the FBR. In addition, the physicochemical characterization of the fresh and spent catalysts was carried out by Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES), N2 physisorption, H2 chemisorption, Temperature Programmed Reduction (TPR), SEM, X-ray Photoelectron Spectroscopy (XPS) and X-ray powder Diffraction (XRD). Operating with the FBR, conversions close to the ones predicted by thermodynamic calculations were obtained by most of the catalysts tested. The Rh-Ni/Ce-Al2O3 catalyst obtained the highest hydrogen production yield in DR. In BSR process, the Ni/Ce-Al2O3 catalyst achieved the best activity results operating at S/C=1.0. In the case of BOR process, the Ni/Ce-Zr-Al2O3 catalyst showed the highest reactants conversion values operating at O2/CH4=0.25. Finally, in the TR process the Rh-Ni/Ce-Al2O3 catalyst obtained the best results operating at S/C=1.0 and O2/CH4=0.25. Therefore, these three catalysts were selected to be coated onto microchannels in order to test its performance under BOR and TR processes conditions. Although the operation using microreactors was carried out under considerably higher WHSV, similar conversions and yields as the ones measured in FBR were measured. Furthermore, attending to other measurements like Turnover Frequency (TOF) and Hydrogen Productivity (PROD), the values calculated for the catalysts tested in microreactors were one order of magnitude higher. Thus, due to the low dispersion degree measured by H2-chemisorption, the Ni/Ce-Al2O3 catalyst reached the highest TOF and PROD values. Section 4.4: Biogas reforming processes using Zeolites L based catalysts In this section three type of L zeolites, with different morphology and size, were synthesized and used as catalyst support. Then, for each type of L zeolite three nickel monometallic and their homologous Rh-Ni bimetallic catalysts were prepared by the wetness impregnation method. These catalysts were tested using the FBR under DR process and different conditions of BSR (S/C ratio of 1.0 and 2.0), BOR (O2/CH4 ratio of 0.25 and 0.50) and TR processes (at S/C=1.0 and O2/CH4=0.25). The characterization of these catalysts was also carried out by using the same techniques mentioned in the previous section. Very high methane and carbon dioxide conversion values were measured for almost all the catalysts under investigation. The experimental results evidenced the better catalytic behavior of the bimetallic catalysts as compared to the monometallic ones. Comparing the catalysts behavior with regards to their morphology, for the BSR process the Disc catalysts were the most active ones at the lowest S/C ratio tested. On the contrary, the Cylindrical (30–60 nm) catalysts were more active under BOR conditions at O2/CH4=0.25 and TR processes. By the contrary, the Cylindrical (1–3 µm) catalysts showed the worst activity results for both processes. Section 4.5: Biogas reforming processes using Na+ and Cs+ doped Zeolites LTL based catalysts A method for the synthesis of Linde Type L (LTL) zeolite under microwave-assisted hydrothermal conditions and its behavior as a support for heterogeneously catalyzed hydrogen production is described in this section. Then, rhodium and nickel-based bimetallic catalysts were prepared in order to be tested by DR process and BOR process at O2/CH4=0.25. Moreover, the characterization of the catalysts under investigation was also carried out. Higher activities were achieved by the catalysts prepared from the non-doped zeolites, Rh-Ni/D and Rh-Ni/N, as compared to the ones supported on Na+ and Cs+ exchanged supports. However, the differences between them were not very significant. In addition, the Na+ and Cs+ incorporation affected mainly to the Disc catalysts. Comparing the results obtained by these catalysts with the ones studied in the section 4.4, in general worst results were achieved under DR conditions and almost the same results when operated under BOR conditions. In Chapter 5 the ethylene glycol (EG) as feed for syngas production by steam reforming (SR) and oxidative steam reforming (OSR) was studied by using microchannel reactors. The product composition was determined at a S/C of 4.0, reaction temperatures between 625°C and 725°C, atmospheric pressure and Volume Hourly Space Velocities (VHSV) between 100 and 300 NL/(gcath). This work was divided in two sections. The first one corresponds to the introduction of the main and most promising EG production routes. Then, the new experimental procedure is detailed and the information about the experimental set-up and the measured parameters is described. The characterization was carried out using the same techniques as for the previous chapter. Then, the next sections correspond to the catalytic activity and catalysts characterization results. Section 5.3: xRh-cm and xRh-np catalysts for ethylene glycol reforming Initially, catalysts with different rhodium loading, from 1.0 to 5.0 wt. %, and supported on α-Al2O3 were prepared by two different preparation methods (conventional impregnation and separate nanoparticle synthesis). Then, the catalysts were compared regarding their measured activity and selectivity, as well as the characterization results obtained before and after the activity tests carried out. The samples prepared by a conventional impregnation method showed generally higher activity compared to catalysts prepared from Rh nanoparticles. By-product formation of species such as acetaldehyde, ethane and ethylene was detected, regardless if oxygen was added to the feed or not. Among the catalysts tested, the 2.5Rh-cm catalyst was considered the best one. Section 5.4: 2.5Rh-cm catalyst support modification with CeO2 and La2O3 In this part of the Chapter 5, the catalyst showing the best performance in the previous section, the 2.5Rh-Al2O3 catalyst, was selected in order to be improved. Therefore, new Rh based catalysts were designed using α-Al2O3 and being modified this support with different contents of CeO2 or La2O3 oxides. All the catalysts containing additives showed complete conversion and selectivities close to the equilibrium in both SR and OSR processes. In addition, for these catalysts the concentrations measured for the C2H4, CH4, CH3CHO and C2H6 by-products were very low. Finally, the 2.5Rh-20Ce catalyst was selected according to its catalytic activity and characterization results in order to run a stability test, which lasted more than 115 hours under stable operation. The last chapter, Chapter 6, summarizes the main conclusions achieved throughout this Thesis work. Although very high reactant conversions and rich hydrogen mixtures were obtained using a fixed bed reaction system, the use of microreactors improves the key issues, heat and mass transfer limitations, through which the reforming reactions are intensified. Therefore, they seem to be a very interesting and promising alternative for process intensification and decentralized production for remote application.

Effect of ancillary ligands on the properties of heteroleptic green iridium dendrimers functionalized with carbazole dendrons

A series of heteroleptic green iridium dendrimers functionalized with carbazole dendrons, such as G2(pic) and G2(acac), have been synthesized, in which picolinic acid and acetylacetone are used as the ancillary ligands, respectively. Compared with the corresponding homoleptic iridium dendrimer G2 (8%), these heteroleptic ones can be prepared under mild conditions with total yields as high as 55-67%. Both the dendrimer G2(pic) and G2(acac) display bright green emissions with photoluminescence quantum yields higher than 0.80 in toluene solution. As a result, a maximum external quantum efficiency of 7.1% (21.0 cd/A) for G2(pic) and 7.7% (25.8 cd/A) for G2(acac) has been realized based on non-doped device configuration. The state-of-art performance indicates that the heteroleptic dendrimers can be promising candidates used for non-doped electrophosphorescent devices, especially when the ease of synthesis in a large scale is considered.

Multifunctional bipolar triphenylamine/oxadiazole derivatives: highly efficient blue fluorescence, red phosphorescence host and two-color based white OLEDs

Two simple triphenylamine/oxadiazole derivatives were synthesized and fully characterized; their multifunctionality as highly efficient non-doped blue fluorescence, excellent red phosphorescent host and single-doped two-color based white OLEDs has been demonstrated.

Highly efficient green-emitting phosphorescent iridium dendrimers based on carbazole dendrons

Green-emitting iridium dendrimers with rigid hole-transporting carbazole dendrons are designed, synthesized, and investigated. With second-generation dendrons, the photoluminescence quantum yield of the dendrimers is up to 87% in solution and 45% in a film. High-quality films of the dendrimers are fabricated by spin-coating, producing highly efficient. non-doped electrophosphorescent organic light-ernitting diodes (OLEDs). With a device structure of indium tin oxide/poly(3,4-ethylenedioxythiopheiie):poly(styrene sulfonic acid)/neat dendrimer/1,3,5-tris(2-N-phenylbenzimidazolyl)benzene/LiF/Al, a maximum external quantum efficiency (EQE) of 10.3% and a maximum luminous efficiency of 34.7 cd A(-1) are realized. By doping the dendrimers into a carbazole-based host, the maximum EQE can be further increased to 16.6%. The integration of rigid hole-transporting dendrons and phosphorescent complexes provides a new route to design highly efficient solution-processable dendrimers for OLED applications.

Effect of In concentration in the starting solution on the structural and electrical properties of ZnO films prepared by the pyrosol process at 450 degrees C

Undoped and indium-doped Zinc oxide (ZnO) solid films were deposited by the pyrosol process at 450 degrees C on glass substrates From solutions where In/Zn ratio was 2, 5, and 10 at.%. Electrical measurements performed at room temperature show that the addition of indium changes the resistance of the films. The resistivities of doped films are less than non-doped ZnO films by one to two orders of magnitude depending on the dopant concentration in the solution. Preferential orientation of the films with the c-axis perpendicular to the substrate was detected by X-ray diffraction and polarized extended X-ray absorption fine structures measurements at the Zn K edge. This orientation depends on the indium concentration in the starting solution. The most textured films were obtained for solutions where In/Zn ratio was 2 and 5 at.%. When In/Zn = 10 at.%, the films had a nearly random orientation of crystallites. Evidence of the incorporation of indium in the ZnO lattice was obtained from extended X-ray absorption fine structures at the In and Zn K edges. The structural analysis of the least resistive film (Zn/In = 5 at.%) shows that In substitutes Zn in the wurtzite structure. (C) 2000 Elsevier B.V. B.V. All rights reserved.

New X-ray powder diffraction data and Rietveld refinement for Gd2O3 monodispersed fine spherical particles

Nominally pure Gd2O3 C-form structure from basic carbonate fine spherical particles and its differences concerning the XRD data among literature patterns using Rietveld method is reported. Gd2O3: Eu3+ from basic carbonate and Gd2O3 from oxalate were also investigated. All samples, except the one from oxalate precursor, are narrow sized, 100-200 nm. Only non-doped Gd2O3 from basic carbonate presents XRD data with smaller d(hkl) values than the literature ones. From Rietveld refinement, non-doped Gd2O3 from basic carbonate has the smallest crystallite size and from oxalate shows the greatest one. Also, the unit cell parameters indicate a plan contraction of the Gd2O3 from basic carbonate. The presence of Eu3+ increases crystallite size when basic carbonate precursor is used to prepare Gd2O3 and avoids plan contraction. The structural differences observed among Gd2O3 samples obtained are related to the type of precursor and to the presence or not of doping ion. (C) 2003 Elsevier B.V. (USA). All rights reserved.

Effect of in concentration in the starting solution on the structural and electrical properties of ZnO films prepared by the pyrosol process at 450°C

Undoped and indium-doped Zinc oxide (ZnO) solid films were deposited by the pyrosol process at 450°C on glass substrates from solutions where In/Zn ratio was 2, 5, and 10 at.%. Electrical measurements performed at room temperature show that the addition of indium changes the resistance of the films. The resistivities of doped films are less than non-doped ZnO films by one to two orders of magnitude depending on the dopant concentration in the solution. Preferential orientation of the films with the c-axis perpendicular to the substrate was detected by X-ray diffraction and polarized extended X-ray absorption fine structures measurements at the Zn K edge. This orientation depends on the indium concentration in the starting solution. The most textured films were obtained for solutions where In/Zn ratio was 2 and 5 at.%. When In/Zn = 10 at.%, the films had a nearly random orientation of crystallites. Evidence of the incorporation of indium in the ZnO lattice was obtained from extended X-ray absorption fine structures at the In and Zn K edges. The structural analysis of the least resistive film (Zn/In = 5 at.%) shows that In substitutes Zn in the wurtzite structure. © 2000 Elsevier Science B.V. All rights reserved.

Intrinsic magnetic properties of BixCo2-xMnO 4 spinels obtained by short-time etching

We report the structural and magnetic properties of Co2MnO 4, partially substituted by Bi at the octahedral site. Bismuth enhances ferromagnetism due to a decrease of the Co2+-Co2+ antiferromagnetic interactions and an increase of the Mn3+-Mn 4+ exchanges. Spurious phases (magnetic and/or nonmagnetic oxides) can easily form because of the large differences between the ionic radii of Bi3+ and Co3+, hiding or altering the intrinsic physical properties of the main BixCo2-xMnO4 phase. An easy way to eliminate the secondary phases is using acid reagents. Short-time etching of Bi0.1Co1.9MnO4 using nitric acid was successfully used, keeping most of the properties of the initial compound, with no alteration of the crystallographic structure. Final stoichiometry was respected (∼Bi0.08Co1.82MnO4), meaning that the material after etching definitely contains bismuth elements in its structure and the observed properties are intrinsic to the oxide spinel. Additional experiments were performed as a function of the synthesis conditions, showing that an optimal pH value of 7 allowed the best magnetic response of the non-doped material. © 2013 Elsevier B.V. All rights reserved.

Síntese, dopagem e caracterização das resinas furfurílica e fenol-furfurílica visando a otimização do processamento de carbono vítreo

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)