Studies of catalyzed reaction mechanism between co-polyether (THF/EO) and N-100 by NMR - Interaction and complex formation between reactants and catalysts

To elucidate the mechanism of the catalyzed reaction of co-polyether (EO/THF) with N-100, the interaction and complex formation between reactants and catalysts were investigated by means of NMR spectroscopy. It is shown that the resonance peak of isocyanate carbon splits into two parts when the solutions of N-100 and co-polyether were mixed. The disappearing of proton resonance peak of hydroxyl group in NMR spectra when dibutyltin dilaurate(DBTDL) were added to the copolyether(THF/EO) solution indicates the complex formation, This interaction appears to be a bonding of tin to the oxygen of hydroxyl and make the hydrogen of the hydroxyl group very mobile and active, then exchange with other protons, In the case of triphenyl bismuth(TPB), the high field shift and intensity enhancement of proton peak were observed, which suggest a nucleophilic attack of the bismuth to the hydroxyl hydrogen.

STRUCTURE AND CATALYTIC ACTIVITY FOR PROPYLENE OXIDATION OF BI-MO-NB COMPLEX OXIDE CATALYSTS

The structure and catalytic,activity for propylene oxidation of series oxides B2Mo3-3X-Nb2XO12-4X (X=0.00, 0.02, 0.05, 0.10, 0.15, 0.20, 0.25) have been studied by means of XRD, IR, Raman, SEM, ESR and so on. The results showed that in the range of X < 0.

ELECTRODEPOSITION OF POLYCRYSTALLINE CD-RICH HG1-XCDXTE AND PHOTOELECTRO-CHEMICAL BEHAVIOR OF HG0.09CD0.91TE THIN-FILM

Electrodeposition process of polycrystalline Cd-rich Hg_(1-z)Cd_xTe (x>0.5) in acidic bath of CdSO_4+HTeO_2~+HgCl_2 was investigated. The simultaneous electrodeposition technique of three kinds of ions at the same potential has been achieved. The XRD, SEM and EDAX analysis of the thin film electrodeposited on titanium substrate showed a typical cubic zinc blende polycrystalline structure and homogeneous dispersion. The photoelectrochemical behavior of (1-x)=0.09 polycrystalline thin film in a polysulfide re...

Perovskite-type B-site Bi-doped ceramic membranes for oxygen separation

Novel mixed conducting oxides, B-site Bi-doped perovskites were exploited and synthesized. Cubic perovskite structures were formed for BaBi0.2COyFe0.8-yO3-delta (y less than or equal to 0.4) and BaBixCo0.2Fe0.8-xP3-delta (x=0.1-0.5) The materials exhibited considerable high oxygen permeability at high temperature. The oxygen permeation flux of BaBi0.2Co0.35Fe0.45O3-delta membrane reached about 0.77 x 10(-6) mol/cm(2) s under an air/helium oxygen partial pressure gradient at 900 degrees C, which was much higher than that of other bismuth-contained mixed conducting membranes. The permeation fluxes of the materials increased with the increase of cobalt content, but no apparent simple relationship was found with the bismuth content. The materials also demonstrated excellent reversibility of oxygen adsorption and desorption. Stable time-related oxygen permeation fluxes were found for BaBi0.2CO0.35Fe0.45O3-delta and BaBi0.3Co0.2Fe0.5O3-delta a membranes at 875 degrees C.

Determinação de cádmio e chumbo em brinquedos para crianças com idade inferior a 3 anos

Projeto de Pós-Graduação/Dissertação apresentado à Universidade Fernando Pessoa como parte dos requisitos para obtenção do grau de Mestre em Ciências Farmacêuticas

Chemical vapour deposition of complex ferroic oxide thin films

Herein is presented a novel chemical vapour deposition (CVD) route for the fabrication of oxide ferroelectrics. A versatile layer-by-layer growth mode was developed to prepare naturally super-latticed bismuth based materials belonging to the Aurivillius phase family, with which good control over composition and crystal structure was achieved. In chapter 3, the effect of epitaxial strain on one of the very simple oxide materials TiO2 was studied. It has been found that the ultra-thin TiO2 films demonstrate ferroelectric behaviour when grown on NdGaO3 substrates. TiO2 exists in various crystal phases, but none of them show ferroelectric behaviour. The epitaxial strain due to the substrate, changes the crystal structure from tetragonal to orthorhombic which in turn leads to ferroelectric behaviour. In chapter 4, a unique growth method for multiferroic BiFeO3 (BFO) thin films is shown, where a phase pure BFO thin films can be prepared even in the presence of excess bismuth precursor during the growth process. This type of growth is usually called adsorption controlled growth and can be used for growing various bismuth containing compounds, where the volatility of bismuth can create various types of defects. Chapter 5 describes the growth of Bi4Ti3O12 thin films in a layer-by-layer growth mode. In this section, the effect of Bi and Ti precursor flows on the growth of thin films is discussed and it is shown that how change in precursor flows leads to out-ofphase boundary defects during the layer-by-layer growth mode. In chapter 6, the growth of a compound Bi5Ti3FeO15, which is a 1:1 mixture of BiFeO3 and Bi4Ti3O12, is presented. The growth mechanism of Bi5Ti3FeO15 thin films is presented, where the Fe precursor flow was controlled from zero to the insertion of one full BiFeO3 perovskite unit cell into the Bi4Ti3O12 structure in addition, the effect of iron precursor flow on crystalline properties is demonstrated. The methods presented in this thesis can be adopted to grow ferroelectric and multiferroic films for industrial applications.

Theory of the electronic and optical properties of dilute bismide alloys

Dilute bismide alloys, containing small fractions of bismuth (Bi), have recently attracted interest due to their potential for applications in a range of semiconductor devices. Experiments have revealed that dilute bismide alloys such as GaBixAs1−x, in which a small fraction x of the atoms in the III-V semiconductor GaAs are replaced by Bi, exhibit a number of unusual and unique properties. For example, the band gap energy (E g) decreases rapidly with increasing Bi composition x, by up to 90 meV per % Bi replacing As in the alloy. This band gap reduction is accompanied by a strong increase in the spin-orbit-splitting energy (ΔSO) with increasing x, and both E g and ΔSO are characterised by strong, composition-dependent bowing. The existence of a ΔSO > E g regime in the GaBixAs1−x alloy has been demonstrated for x ≳10%, a band structure condition which is promising for the development of highly efficient, temperature stable semiconductor lasers that could lead to large energy savings in future optical communication networks. In addition to their potential for specific applications, dilute bismide alloys have also attracted interest from a fundamental perspective due to their unique properties. In this thesis we develop the theory of the electronic and optical properties of dilute bismide alloys. By adopting a multi-scale approach encompassing atomistic calculations of the electronic structure using the semi-empirical tight-binding method, as well as continuum calculations based on the k•p method, we develop a fundamental understanding of this unusual class of semiconductor alloys and identify general material properties which are promising for applications in semiconductor optoelectronic and photovoltaic devices. By performing detailed supercell calculations on both ordered and disordered alloys we explicitly demonstrate that Bi atoms act as isovalent impurities when incorporated in dilute quantities in III-V (In)GaAs(P) materials, strongly perturbing the electronic structure of the valence band. We identify and quantify the causes and consequences of the unusual electronic properties of GaBixAs1−x and related alloys, and our analysis is reinforced throughout by a series of detailed comparisons to the results of experimental measurements. Our k•p models of the band structure of GaBixAs1−x and related alloys, which we derive directly from detailed atomistic calculations, are ideally suited to the study of dilute bismide-based devices. We focus in the latter part of the thesis on calculations of the electronic and optical properties of dilute bismide quantum well lasers. In addition to developing an understanding of the effects of Bi incorporation on the operational characteristics of semiconductor lasers, we also present calculations which have been used explicitly in designing and optimising the first generation of GaBixAs1−x-based devices.

Application of CFD in vacuum dezincing process

Most lead bullion is refined by pyrometallurgical methods - this involves a serics of processes that remove the antimony (softening) silver (Parkes process), zinc (vacuum dezincing) and if need be, bismuth (Betterton-Kroll process). The first step, softening, removes the antimony, arsenic and tin by air oxidation in a furnace or by the Harris process. Next, in the Parkes process, zinc is added to the melt to remove the silver and gold. Insoluble zinc, silver and gold compounds are skimmed off from the melt surface. Excess zinc added during desilvering is removed from lead bullion using one of ghree methods: * Vacuum dezincing; * Chlorine dezincing; or * Harris dezincing. The present study concentrates on the Vacuum dezincing process for lead refining. The main aims of the research are to develop mathematical model(s), using Computational Fluid Dyanmics (CFD) a Surface Averaged Model (SAM), to predict the process behaviour under various operating conditions, thus providing detailed information of the process - insight into its reaction to changes of key operating parameters. Finally, the model will be used to optimise the process in terms of initial feed concentration, temperature, vacuum height cooling rate, etc.

The use of mineral trioxide aggregate in endodontics - status report

Mineral trioxide aggregate (MTA) is a clinical product comprising a mixture of Portland cement and bismuth oxide which is currently used as a root−filling material in dentistry. It has good biological compatibility, is capable of promoting both osteogenesis and cementogensis, and is finding increasing use in endodontic therapy. It is dimensionally stable, and provides an acceptable and durable seal for endodontically treated teeth. This article reviews the chemistry and applications of MTA, and highlights the fact that very little is currently known about the hydration chemistry, phase evolution and stability of this cement in physiological environments. However, biological effects of MTA have been well documented and are considered in detail. The article concludes that this material is a useful addition to the range of materials available for clinical application in endodontics.

Studies of switching kinetics in ferroelectric thin films

Experimental studies are reported concerning the importance of interfacial capacitance (including electrode screening, space-charge layers, and/or chemically discrete dead layers). on domain switching behaviour in thin films of ferroelectric lead zirconate-titanate (PZT), strontium bismuth tantalate (SBT), and barium strontium titanate (BST). Emphasis is placed upon studies at applied field values very near the coercive field E, asymmetry in fatigue for positive and negative polarity coercive fields, and in the case of BST, of the coexistence of ferroelectric and paraelectric phases Studies of dielectric loss show important correlations between tan 6 and fatigue (polarization decrease) as a function of bipolar switching cycles N. This is a priori not obvious, since the former is a linear response and the latter, a nonlinear response. Modelling of enlarged interfacial,space-charge layers in PZT films and chemically distinct dead (paraelectric) layers in BST films shows contradictory tendencies of coercive-voltage changes with the growth of passive layers.

Evidence for Strong Breit Interaction in Dielectronic Recombination of Highly Charged Heavy Ions

Resonant strengths have been measured for dielectronic recombination of Li-like iodine, holmium, and bismuth using an electron beam ion trap. By observing the atomic number dependence of the state-resolved resonant strength, clear experimental evidence has been obtained that the importance of the generalized Breit interaction (GBI) effect on dielectronic recombination increases as the atomic number increases. In particular, it has been shown that the GBI effect is exceptionally strong for the recombination through the resonant state [1s2s(2)2p(1/2)](1).

Switching dynamics in ferroelectric thin films: An experimental survey

We have conducted a broad survey of switching behavior in thin films of a range of ferroelectric materials, including some materials that are not typically considered for FeRAM applications, and are hence less studied. The materials studied include: strontium bismuth tantalate (SBT), barium strontium titanate (BST), lead zicronate titanate (PZT), and potassium nitrate (KNO3). Switching in ferroelectric thin films is typically considered to occur by domain nucleation and growth. We discuss two models of frequency dependence of coercive field, the Ishisbashi-Orihara theory where the limiting step is domain growth and the model of Du and Chen where the limiting step is nucleation. While both models fit the data fairly well the temperature dependence of our results on PZT and BST suggest that the nucleation model of Du and Chen is more appropriate for the experimental results that we have obtained.

Dielectronic recombination in He-like, Li-like, and Be-like highly charged ions in the KLL and KLM manifolds

This paper reports a systematic study of the dependence on atomic number of the dielectronic recombination resonance strengths for He-like, Li-like and Be-like ions. Recent measurements of dielectronic recombination resonance strengths for the KLL and KLM manifolds for iron, yttrium, iodine, holmium, and bismuth are also described. The resonance strengths were normalized to calculated electron impact ionization cross sections. The measured resonance strengths generally agree well with theoretical calculations using the distorted wave approximation. However, KLM resonance strength measurements on high atomic number open-shell ions gave higher values than those suggested by calculations. Using recently measured data, along with existing results, scaling laws have been generated as a function of atomic number for He-like, Li-like, and Be-like ions in the KLL and KLM manifolds.

Numerical simulation of a patent technology for sealing of deep-sea oil wells using nonlinear finite element method

For over 50 years bridge plugs and cement have been used for well abandonment and work over and are still the material of choice. However the failures of cement abandonments using bridge plugs has been reported on many occasions, some of which have resulted in fatal consequences. A new patented product is designed to address the shortcomings associated with using bridge plugs and cement. The new developed tools use an alloy based on bismuth that is melted in situ using Thermite reaction. The tool uses the expansion properties of bismuth to seal the well. Testing the new technology in real field under more than 2 km deep sea water can be expensive. Virtual simulation of the new device under simulated thermal and mechanical environment can be achieved using nonlinear finite element method to validate the product and reduce cost. Experimental testing in the lab is performed to measure heat generated due to thermite reaction. Then, a sequential thermal mechanical explicit/implicit finite element solver is used to simulate the device under both testing lab and deep water conditions.

Epitaxial strain and electric boundary condition effects on the structural and ferroelectric properties of BiFeO3 films

The influence of both compressive and tensile epitaxial strain along with the electrical boundary conditions on the ferroelastic and ferroelectric domain patterns of bismuth ferrite films was studied. BiFeO3 films were grown on SrTiO3(001), DyScO3(110), GdScO3(110), and SmScO3(110) substrates to investigate the effect of room temperature in-plane strain ranging from -1.4% to +0.75%. Piezoresponse force microscopy, transmission electron microscopy, x-ray diffraction measurements, and ferroelectric polarization measurements were performed to study the properties of the films. We show that BiFeO3 films with and without SrRuO3 bottom electrode have different growth mechanisms and that in both cases reduction of the domain variants is possible. Without SrRuO3, stripe domains with reduced variants are formed on all rare earth scandate substrates because of their monoclinic symmetry. In addition, tensile strained films exhibit a rotation of the unit cell with increasing film thickness. On the other side, the presence of SrRuO3 promotes step flow growth of BiFeO3. In case of vicinal SrTiO3 and DyScO3 substrates with high quality SrRuO3 bottom electrode and a low miscut angle of approximate to 0.15 degrees we observed suppression of the formation of certain domain variants. The quite large in-plane misfit of SrRuO3 with GdScO3 and SmScO3 prevents the growth of high quality SrRuO3 films and subsequent domain variants reduction in BiFeO3 on these substrates, when SrRuO3 is used as a bottom electrode.