This thesis is concerned with kinetic characterisation of theinsertion compound LiMn2O4, which is used as positive electrodematerial in rechargeable lithium batteries. Three different typesof electrode configurations have been investigated, namely singleparticles, thin films and composite electrodes. Differentelectrochemical techniques, i.e. linear sweep voltammetry (LSV),electrochemical impedance spectroscopy (EIS), potential step, andgalvanostatic experiments were applied under various experimentalconditions. The majority of the experimental data were analysedby relevant mathematical models used for describing the reactionsteps of insertion compounds. It was concluded that a model based on interfacialcharge-transfer, solid-phase diffusion and an external iR-dropcould be fairly well fitted to LSV data measured on a singleelectrode system over a narrow range of sweep rates. However, itwas also found that the fitted parameter values vary greatly withthe characteristic length and the sweep rate. This indicates thatthe physical description used is too simple for explaining theelectrochemical responses measured over a large range of chargeand discharge rates. EIS was found to be a well-suited technique for separatingtime constants for different physical processes in the insertionand extraction reaction. It was demonstrated that the impedanceresponse is strongly dependent on the current collector used.According to the literature, reasonable values of theexchange-current density and solid-phase diffusion coefficientwere determined for various states-of-discharge, temperatures andelectrolyte compositions. Experiments were carried out in bothliquid and gel electrolytes. A method which improves thedistinction between the time constants related to thematerial’s intrinsic properties and possible porous effectsis presented. The method was applied to composite electrodes.This method utilises, in addition to the impedance responsemeasured in front of the electrode, also the impedance measuredat the backside of the electrode. Finally, the kinetics of a composite electrode was alsoinvestigated by in situ X-ray diffraction (in situ XRD) incombination with galvanostatic and potentiostatic experiments. Noevidence of lithium concentration gradients could be observedfrom XRD data, even at the highest rate applied (i.e. ~6C), thusexcluding solid-phase diffusion and also phase-boundary movement,as described by Fick’s law, as the ratelimiting step. <b>Key words:</b>linear sweep voltammetry, electrochemicalimpedance spectroscopy, potential step, in situ X-raydiffraction, microelectrodes, electrode kinetics, LiMn2O4cathode, rechargeable lithium batteries

It is generally believed that one of the key parameterscontrolling the normal state and superconducting properties ofhigh temperature superconductors is the charge carrierconcentrationpin the CuO2planes.By changing the non-isovalent dopingconcentration on the RE site as well as the oxygen content in(RE)Ba2Cu3O7−δ, an excellent tool is obtained tovary the hole concentration over a wide range from theunderdoped up to the overdoped regime.In the present thesis thefocus is on the doping effects on the structural and normalstate electrical properties in Nd-123 doped with Ca, La, Pr,Ca-Pr, and Ca-Th.T he effects of doping have been investigatedby X-ray and neutron powder diffraction, and by measurements ofthe resistivity, thermoelectric powerS, and Hall coefficient RH.T he thermoelectric power is a powerful tool forstudies of high temperature superconductivity and is highlysensitive to details of the electronic band structure.Sas a function of temperature has been analyzed in twodifferent two band models.The parameters of these models arerelated to charactristic features of the electron bands and asemiempirical physical description of the doping dependence ofSis obtained.So me important results are following: (i)The valence of Pr in the RE-123 family.Results from thestructural investigations, the critical temperature Tc, and thethermoelectric power indicated a valence +4 at low dopingconcentration, which is in agreement with results of chargeneutral doping in the RE-123 family.(ii)Hole localization. The results of bond valence sum (BVS)calculations from neutron diffraction data showed that holelocalization on the Pr+4site was the main reason for the decrease of thehole concentration p.Differ ent types of localization wereinferred by S measurements for Ca-Th and Ca-Pr dopings.(iii)Competition between added charge and disorder. Theresults of RH measurements indicated that Ca doping introduceddisorder in the CuO2planes in addition to added charge.This could bethe main reason for the observed small decrease of thebandwidth of the density of states in the description of aphenomenological narrow band model.(iv) Empirical parabolic relation between γ and p.S data were analyzed and well described by a two-band modelwith an additional linear T term, γT.An empiricalparabolic relation for γ as a function of holeconcentration has been found. <b>Key words:</b>high temperature superconductors, criticaltemperature, resistivity, thermoelectric power, Hallcoefficient, X-ray diffraction, Neutron diffraction, NdBa2Cu3O7−δ, hole concentration,substitution.

Crystallographic and spectroscopic studies have been performed of structures, coordination and chemical bonding for series of trivalent metal ions solvated by two oxygen-coordinating solvents, water and dimethyl sulfoxide (DMSO). The hydrated scandium(III) and lanthanoid(III) ions, La to Lu, are surrounded by tricapped trigonal prisms of aqua ligands in the isomorphous series of trifluoromethanesulfonates, [M(H2O)n](CF3SO3)3. For the smallest ions, M = Er, Tm, Yb, Lu, Sc, the hydration numbers decrease, n = 8.96(5), 8.8(1), 8.7(1), 8.5(1), 8.0(1), respectively, with decreasing size of the ion. The crystal structures at ambient temperature indicate randomly distributed vacancies of the capping oxygen atoms, and 2H solid-state NMR of the diamagnetic [M(H2O)n](CF3SO3)3, M = Sc, Lu, Y and La compounds revealed increasing mobility of the water ligands in the coordination sphere with increasing temperature, also for the fully nonahydrated LaIII and YIII ions. The stretching force constants of the Ln-O bonds, evaluated from vibrational spectroscopy, increased from 0.81 to 1.16 N cm-1 for the Ln-6O trigonal prism in a smooth correlation with the bond distances from La to Lu. For the capping Ln-3O bonds the increase from 0.49 to 0.65 N cm-1 reflects the increased ligand-ligand repulsion with decreasing ion size. This is also the reason for the water deficiency of the Er, Tm, Yb, Lu and Sc salts, and for [Sc(H2O)8.0](CF3SO3)3 the repulsion induced a phase transition at about 185 K that, by low temperature crystallography, was found to distort the coordination of water molecules toward a monocapped trigonal prism around the scandium(III) ion. All crystal structures of the octakis(dimethyl sulfoxide)lanthanoid(III) iodides comprise discrete [Ln(dmso)8]3+ complexes surrounded by iodide ions. The lanthanum(III) and praseodymium(III) compounds crystallize in the orthorhombic space group Pbca with more efficient packing than for the heavier and smaller ions in the lanthanoid series, which crystallize in the monoclinic space group P21/n. The group 13 metal ions, aluminium(III), gallium(III), indium(III), thallium(III), and also scandium(III) of group 3, form crystalline hexakis(dimethyl sulfoxide) solvates in the space group R 3, with octahedral MO6 coordination entities, which are increasingly compressed along one threefold axis for increasing ionic size. EXAFS measurements on the solvated ions display similar M-O bond distances in dimethyl sulfoxide solution as in the solid solvates. For all the solid dimethyl sulfoxide solvates the strength and nature of the metal-oxygen bond has been evaluated by normal coordinate analysis of vibrational spectra, and correlated with the S-O stretching vibrational mode. Distortions from regular octahedral six coordination are discussed for the hydrated isoelectronic soft mercury(II) and thallium(III) ions in the solid bisaquamercury(II) and trisaquatallium(III) trifluoromethanesulfonates, in terms of pseudo Jahn-Teller effects (PJTE). Mercury(II), generally more strongly influenced by PJTE distortions, displays a 2 + 4 Hg-O coordination forming chains that are held together in sheets by hydrogen bonds and in layers by van der Waals interactions, which explain the fragile structure of the crystals.

Demands for zero greenhouse-gas emission vehicles have sharpened with today’s increased focus on global warming. Hydrogen storage is a key technology for the implementation of hydrogen powered vehicles. Metal hydrides can claim higher energy densities than alternative hydrogen storage materials, but a remaining challenge is to find a metal hydride which satisfies all current demands on practical usability. Several metals store large amounts of hydrogen by forming a metal hydride, e.g., Mg, Ti and Al. The main problems are the weight of the material and the reaction energy between the metal and hydrogen. Magnesium has a high storage capacity (7.6 wt.% hydrogen) in forming MgH2; this is a slow reaction, but can be accelerated either by minimizing the diffusion length within the hydride or by changing the diffusion properties. Light-metal hydrides have been studied in this thesis with the goal of finding new hydrogen storage compounds and of gaining a better understanding of the parameters which determine their storage properties. Various magnesium-containing compounds have been investigated. These systems represent different ways to address the problems which arise in exploiting magnesium based materials. The compounds were synthesized in sealed tantalum tubes, and investigated by in situ synchrotron radiation X-ray powder diffraction, neutron powder diffraction, isothermal measurements, thermal desorption spectroscopy and electron microscopy. It is demonstrated that hydrogen storage properties can be improved by alloying magnesium with yttrium or scandium. Mg-Y-compounds decompose in hydrogen to form MgH2 nano-structures. Hydrogen desorption kinetics are improved compared to pure MgH2. The influence of adding a third element, gallium or zinc has also been studied; it is shown that gallium improves hydrogen desorption from YH2. ScAl1-xMgx is presented here for the first time as a hydrogen storage material. It absorbs hydrogen by forming ScH2 and Al(Mg) in a fully reversible reaction. It is shown that the hydrogen desorption temperature of ScH2 is reduced by more than 400 °C by alloying with aluminium and magnesium.

Thermal mismatch between different components of a system could cause of problems like residual stress induced cracking, thermal fatigue or even optical misalignment in certain high technology applications. Use of materials with customized thermal expansion coefficient is a counter-measure to resolve such problems. Zirconium tungstate (ZrW2O8) with negative thermal expansion coefficient is capable of being used in synthesis of composites with tailored coefficient of thermal expansion (CTE). In this work, the sol-gel method which had been already set up in our group was characterized and the sources of the factors imposing impurities in the product were distinguished in all the steps of precursor preparation and heat treatment. In the second part of study, zirconium tungstate particles synthesized by the sol-gel method were utilized as core in synthesis of ZrW2O8&ndash / ZrO2 core&ndash / shell composite particles. Shell layer was composed of ZrO2 nanocrystallites and precipitated from an aqueous solution by urea hydrolysis. Volume of the shell was effectively controlled by concentration of the initial zirconium ion in the solutions. The rate of precipitation was a function of the ratio of initial urea concentration to zirconium ion. It is hypothesized that isolation of the ZrW2O8 within a layer of ZrO2, will be a key element in solving problems associated with reactivity of ZrW2O8 towards other components in sintering of ceramic&ndash / ceramic composites with tuned or zero thermal expansion coefficient.

A 25% niobium substituted sitinakite was exchanged with strontium as time resolved X-ray diffraction data was collected. The structural modeling of this data by Rietveld method1 has lead to the determination of the atomic positions of the ions and unit cell parameters as strontium occupancy increases. The starting material of the exchange experiment is the protonated phase, H2Nb0.67Ti1.33SiO7·1.9 H2O, with space group P42/mcm2,3. Once strontium (Sr2+) enters the unit cell, extra-framework H2O molecules shift to provide the necessary hydration coordination. These new positions of H2O result in a lowering of symmetry to the P-42m space group, and it is thought that the new hydrogen bonding network serves to enhance strontium ion diffusion into the channels of sitinakite. Exchange of strontium into the microporous material reaches a maximum fractional occupancy of 21% when a 10.0 mM strontium ion solution is forced over the powdered material. Sequestration of strontium into this material has contributed valuable information to the study of microporous materials and ion exchange chemistries.

No description available.

No description available.

Acoustic micro-sensors have already been applied in mass sensing including surface acoustic wave (SAW), flexural plate wave (FPW), thickness shear mode (TSM) and shear horizontal acoustic plate mode (SH-APM). The FPW micro-sensor is very suitable for liquid-sensing and bio-sensing applications due to the high mass-sensitivity and low phase-velocity in liquid. However, the conventional FPW micro-sensors presented a high insertion-loss (IL) and a low signal-to-noise ratio so it is difficult to combine with IC into a micro-system. To overcome these drawbacks, this study combine the Microelectromechanical System (MEMS) technology and the high C-axis orientation ZnO piezoelectric thin-film to develop a low insertion loss, low operation frequency, and high electromechanical coupling coefficient FPW device. In this study, a high C-axis orientation ZnO piezoelectric thin-film with a 20944A.U. X-Ray diffraction intensity at 34.200 degree and a 0.573 degree full width at half maximum (FWHM) was deposited by a commercial magnetic radio-frequency (RF) sputter system. The total processes of the FPW micro-sensor included five photolithography and seven thin-film depositions. In this study a low operation frequency (0.1MHz), low insertion loss (11dB to 14dB) and high electromechanical coupling coefficient (11%) FPW sensor was developed and fabricated.

The SUMO protein was named Small Ubiquitin-like MOdifier because its 3-D structure was similar to Ubiquitin. In human, three SUMO proteins were discovered, namely, SUMO-1/2/3. The recombinant ¡µ1-8, 94-95 SUMO-2 protein with 10 histidine residues at its N-terminus was expressed using E. coli. BL-21(DE3), purified at 4 oC and crystallized at room temperature. The surface properties of human SUMO-1/2/3 proteins and 3-D structure of ¡µ1-8, 94-95 SUMO-2 protein were analyzed using computer modeling and X-ray diffraction technology respectively. The two-step purification by immobilized metal ion affinity chromatography(IMAC) was developed to yield ¡µ1-8, 94-95 SUMO-2 protein that reached 60 mg/ml for crystallization. On protein expression, 120 mg protein was obtained from 6 L bacterial growth broth. Crystals of ¡µ1-8, 94-95 SUMO-2 were obtained by the hanging-drop vapor diffusion method and many different crystal forms were observed. One of single crystal with triangular plate polyhedron form diffracted to 1.6 &#x00C5; resolution, the other one with rectangular polyhedron form diffracted to 1.2 &#x00C5;. Analysis of the diffraction pattern suggests the crystals belong to R3 space group, the former one owned unit cell parameters a= b=75.3 &#x00C5;, c=29.2 &#x00C5;, £\=90¢X, £]=90¢X,£^=120¢X, and the later one owned unit cell parameters a= b=74.9 &#x00C5;, c=33.2 &#x00C5; and the same angles respectively. The R factor and Rfree of refinement are 0.133 and 0.190 with highly precise phase on 3-D structure of SUMO-2 protein. Comparison of crystal structure between human SUMO-2 and yeast SMT3 showed that the r.m.s. deviation of C£\ coordinate is 1.054 &#x00C5;. In addition, comparison of SUMO-1 NMR structure and SMT3 crystal structure showed that the r.m.s. deviation of C£\ coordinates is 2.736 &#x00C5;. Hence, the structures of SUMO-2 and SMT3 are more similar each other than those of SUMO-1and SMT3.