Apresenta-se aqui o estudo de interdifusão e reação no estado sólido em bicamadas de filmes finos de Fe-Al quando submetidas a tratamento térmico em alto vácuo. Três tipos de tratamento forma utilizados, isocrônico, isotérmico e sequencial. Utilizou-se quatro técnicas de análise, Retroespalhamento Rutherford de Partículas Alfa, Medidas de Resistência de Folha, Espectroscopia Mössbauer de Elétrons de Conversão e Difração de Raios-X. Este trabalho é composto de quatro partes. A primeira corresponde ao estudo, por Retroespalhamento Rutherford de Partículas Alfa, da interdifusão entre Fe e i Al. A segunda compreende o monitoramneto, por medidas de resistência de folha, das tranformações metalúrgicas que ocorreram na bicamada de Fe-Al. Na terceira parte apresenta-se a caracterização por Espectroscopia Mössbauer de Elétrons de Conversão e Difração de Raios-X das fases que se formaram. A quarta e última parte é dividida em duas. Uma correspondendo a um estudo de difusão do Al no Fe, o qual tem por obejetivo complementar os resultados obtidos na primeira parte deste trabalho, e a outra descreve o estudo detalhado da estabilidade térmica das fases obtidas. / This work presents the study of the interdiffusion and solid phase reaction in thin films Fe-Al bilayered systems when subjected to thermal treatment in a high vacuum furnace. Three different thermal treatments were performed, isochronous, isothermal and step annelings. The present study was accoplished using four analytical technics, Rutherford Backscattering Spectrometry. Sheet Resistence Measurements. Conversion Electron Mössbauer Spectroscopy, and X-Rays Diffraction. The work is divides in four parts. The first one deals with the study of the interdiffusion between the Fe and Al films by means of Rutherford Backscattering Spectrometry. The second part presents the monitoring of the metallurgical transformations occuring in the thin film bilayered system using sheet resistende measurements. The third part is concerned with the chacterization of the phases formed after thermal treatments as identified by Conversion Electron Mössbauer Spectrometry and Ray Diffraction. The last part studies the thermal stability of the phases obtained by thermal treatments.

Chen, Fan. / "October 2010." / Thesis (M.Phil.)--Chinese University of Hong Kong, 2011. / Includes bibliographical references (leaves 85-91). / Abstracts in English and Chinese. / ABSTRACT --- p.III / 摘要 --- p.IV / ACKNOWLEDGENTS --- p.V / TABLE OF CONTENTS --- p.VI / LIST OF FIGURES --- p.VIII / LIST OF TABLES --- p.X / SYMBOLS AND ABBREVIATIONS --- p.XI / Chapter CHAPTER 1 --- INTRODUCTION --- p.1 / Chapter 1.1 --- Mass spectrometry in proteomics --- p.1 / Chapter 1.2 --- Fourier-transform ion cyclotron resonance mass spectrometry --- p.2 / Chapter 1.2.1 --- Introduction --- p.2 / Chapter 1.2.2 --- Ionization --- p.3 / Chapter 1.2.3 --- Ions in ICR --- p.4 / Chapter 1.2.4 --- Ions excitation and detection --- p.7 / Chapter 1.3 --- Tandem mass spectrometry --- p.8 / Chapter 1.4 --- Electron capture dissociation --- p.12 / Chapter 1.4.1 --- Features ofECD --- p.13 / Chapter 1.4.2 --- Two popular mechanisms for ECD --- p.14 / Chapter 1.4.2.1 --- The Cornell mechanism --- p.15 / Chapter 1.4.2.2 --- The Utah-Washington mechanism --- p.17 / Chapter 1.4.3 --- Recombination energy --- p.19 / Chapter 1.5 --- Outline of the present work --- p.21 / Chapter CHAPTER 2 --- INSTRUMENTATION AND EXPERIMENTAL --- p.22 / Chapter 2.1 --- Fourier-transform ion cyclotron resonance mass spectrometer --- p.22 / Chapter 2.1.1 --- Vacuum system --- p.24 / Chapter 2.1.2 --- Nanospray system --- p.26 / Chapter 2.1.3 --- Ion transfer system --- p.29 / Chapter 2.1.4 --- Infinity´ёØ cell --- p.29 / Chapter 2.1.5 --- Electron emission source --- p.31 / Chapter 2.1.6 --- Data acquisition system --- p.32 / Chapter 2.2 --- Experimental --- p.32 / Chapter 2.2.1 --- Simple ESI acquisition pulse program --- p.32 / Chapter 2.2.2 --- ESI-ECD acquisition pulse program --- p.35 / Chapter CHAPTER 3 --- FRAGMENTATION OF MODEL PEPTIDE IONS IN DIFFERENT CHARGE STATES UNDER ECD CONDITIONS --- p.38 / Chapter 3.1 --- Introduction --- p.38 / Chapter 3.2. --- Experimental --- p.41 / Chapter 3.2.1 --- Sequence design and sample preparation --- p.41 / Chapter 3.2.2 --- ECD under fourier-transform ion cyclotron mass spectrometer --- p.43 / Chapter 3.3 --- Results and discussion --- p.43 / Chapter 3.3.1 --- General features of ECD spectra --- p.43 / Chapter 3.3.1.1 --- ECD of RRRR --- p.43 / Chapter 3.3.1.2 --- ECD of KKKK --- p.47 / Chapter 3.3.2 --- Effect of charge state of precursor ions --- p.49 / Chapter 3.3.3 --- Effect of proton carriers --- p.52 / Chapter 3.3.4 --- Effect of proton carrier location --- p.54 / Chapter 3.4 --- Conclusions --- p.60 / Chapter CHAPTER 4 --- EFFECT OF PRECURSOR ION HETEROGENEITY ON ECD FRAGMENTATION --- p.62 / Chapter 4.1 --- Introduction --- p.62 / Chapter 4.2 --- Method --- p.63 / Chapter 4.2.1 --- Preferential dissociation index --- p.64 / Chapter 4.2.2 --- Precursor ion heterogeneity --- p.65 / Chapter 4.3 --- Results and discussion --- p.67 / Chapter 4.3.1 --- PDI in model peptides --- p.67 / Chapter 4.3.2 --- PIH and PDI in RRRR and KKKK --- p.71 / Chapter 4.3.3 --- PDI and PIH in two-lysine containing peptides --- p.73 / Chapter 4.3.4 --- PDI and PIH in other peptides --- p.80 / Chapter 4.4 --- Conclusions --- p.82 / Chapter CHAPTER 5 --- CONCLUSIONS --- p.83 / References --- p.85 / Chapter Appendix I: --- Pulse program for simple MS and MS/MS experiment --- p.92 / Chapter (A) --- Simple ESI FT-ICR MS experiment --- p.92 / Chapter (B) --- ESI ECD FT-ICR MS experiment --- p.95 / Chapter Appendix II: --- ECD spectra of AC-XAAAXAAAXAAAX-NH2 peptide series in different charge states --- p.99 / Chapter Appendix III: --- The PDI of the hypothetic peptide --- p.110 / Chapter Appendix IV: --- The PIH among the investigated system --- p.111

L'objectif de cette thèse a été d'augmenter la densité d'énergie des supercondensateurs. La première partie de cette thèse a été consacrée à l'amélioration des performances d'une électrode de carbone pour supercondensateur en étudiant à la fois un mélange de liquides ioniques ainsi que des carbones offrant différents types de microstructures. Une augmentation importante de la capacité spécifique sur une large gamme de températures (-50°C ;100°C) est obtenue en couplant un mélange eutectique de liquides ioniques, (PIP13-FSI)0.5 (PYR14-FSI)0.5, avec un oxyde de graphite exfolié par micro-onde et activé par KOH (a-MEGO). Cette première partie de la thèse met ainsi l'accent sur l'importance d'optimiser l'interface carbone/électrolyte afin de maximiser la densité. Dans la deuxième partie, les mécanismes de stockage des charges dans les pores des carbones à l'échelle moléculaire ont été étudiés in-situ grâce à une microbalance électrochimique à cristal de quartz (EQCM). Les études EQCM ont été menées dans deux systèmes électrode/électrolyte : (1) des carbones dérives de carbure dans des électrolytes à base de EMI-TFSI et (2) un carbone activé dans l'électrolyte PEt4BF4. Les résultats d'EQCM et de RMN in-situ montrent comment les ions différents et les molécules du solvant sont impliqués pendant la charge. Ces résultats sont très encourageants et montrent que l'EQCM constitue une sonde dont la sensibilité permet d'étudier la dynamique des ions dans la porosité des électrodes de carbone lors de la charge et de la décharge des supercondensateurs. / The aim of this PhD work focuses on different approaches to improve the energy density of supercapacitors. First part of this thesis work is to improve the performance of supercapacitor by using ionic liquid mixtures as electrolytes and carbons with different microstructures. A significant increase of specific capacitance over wide temperature range (-50 to 100°C) was obtained by using an eutectic ionic liquid mixture, (PIP13-FSI)0.5 (PYR14-FSI)0.5, with an activated microwave exfoliated graphite oxide (a-MEGO). These results evidence that optimization of the carbon/electrolyte interface is of great importance for maximizing the capacitive energy. In the second part of the thesis, the charge storage mechanisms in the porous carbons at molecular scale have been studied using Electrochemical Quartz Crystal Microbalance (EQCM). EQCM studies were conducted on two electrode/electrolyte systems: (1) carbide-derived carbons in neat and solvated EMI-TFSI ionic liquid under dynamic charging condition and (2) YP-50F activated carbon in solvated PEt4BF4 electrolyte under steady state charging condition. EQCM and in-situ NMR results showed how different ions and solvent molecules are involved in the charging process. These results provide a direct molecular-level insight into the charge storage process, showing that EQCM is promising electrogravimetric probe to study compositional changes in carbon microspores during charging/discharge of supercapacitors.

L'objectif du projet est la mesure du rapport de la masse de l'électron à celle du proton par spectroscopie vibrationnelle à deux photons sans effet Doppler de H2+. Le refroidissement des ions H2+ est nécessaire et ne peut être fait que par refroidissement sympathique par des ions Be+ refroidis par laser. La première partie présente la conception et la réalisation d'un piège linaire adapté au confinement des ions H2+ et Be+ et permettant les accès optiques nécessaires pour les lasers et l'imagerie. La seconde partie décrit les sources laser à 626 (à base de diodes laser ou de lasers à fibres) ainsi que la cavité de doublage de fréquence utilisés pour obtenir le faisceau à 313 nm pour refroidir les ions Be+. La dernière partie expose les premiers résultats obtenus qui montrent que le montage est opérationnel. Elle présente l'observation et la caractérisation de cristaux de Coulomb de Be+ ainsi que des cristaux de Coulomb mixtes Be+/H2+ où les ions H2+ sont créés par impact électronique à partir du gaz résiduel. Ces résultats montrent que le montage est prêt pour réaliser la spectroscopie de H2+. / The objective of the project is to perform high-resolution Doppler-free two-photon vibrational spectroscopy of the H2+ molecular ion for accurate electron to proton mass ratio determination. Trapping and laser-cooling of the H2+ ions is necessary. Since H2+ molecular ions cannot be directly laser cooled, a solution is the implementation of sympathetic cooling via a laser cooled Be+ ions. In the first part of this thesis the design and implementation of a linear Paul trap is presented. This trap is suitable to confine H2+ and Be+ ions while allowing good optical access for multiple laser sources and the imaging system. The second part describes a low power, diode based laser system to provide narrow linewidth 626nm light, and a high power, fiber laser based laser system. Subsequently, a bow-tie cavity is presented to frequency double the 626nm light to obtain 313nm light for Be+ Doppler-cooling. In the last part the operational readiness of the trap and the fiber laser based 313nm laser source is demonstrated by the observation of Be+ Coulomb crystals. Electron impact ionization of H2 present in the residual gas allows to observe sympathetic cooling and shows that the developed setup can provide the experimental conditions for precision spectroscopy of H2+.

This work represents a first look at the general spatial distribution of trace metals and the inorganic carbon system in the surface waters of Tampa Bay. Tampa Bay's chemical environment bears many influences ranging from hydrological and geological to anthropogenic and meteorological. A large y-shaped estuary on the west-central side of the Florida Peninsula, Tampa Bay extends over 400 square miles and has a 2200 square mile watershed that includes extensive swamps, scrub, agricultural lands and densely urbanized areas. Reaching 37 miles from the northernmost point of Old Tampa Bay to the mouth of the estuary near the Sunshine Skyway Bridge, it is home to the largest port in Florida, and overall places 17th in the nation for tonnage. In addition to its ports, Tampa Bay supports the requirements of a broad range of industries including: ship building and repair, power generation, wastewater processing, development, and recreational and commercial fishing. The region experiences high rainfall during the summer and much reduced rainfall during the remaining portions of the year. The bay has a broad gradient of mixing intensities, with residence times ranging from 100+ days in Old Tampa Bay to less than 20 days at the mouth. Seventy-one percent of Tampa Bay's freshwater input is delivered by four primary rivers: the Hillsborough, Alafia, Manatee and Little Manatee; and the region is strongly influenced by spring outflow from the Floridan Aquifer. The largest river, the Hillsborough, spans 54 miles from the Green Swamp to its mouth in Hillsborough Bay. Samples were collected over a two-week period in January of 2013 along 13 sites on the Hillsborough River and 26 stations in Tampa Bay. Metal concentration analyses were conducted on twelve elements using inductively coupled plasma mass spectrometry (ICP-MS). These twelve elements included sodium, lithium, magnesium, calcium, strontium, barium, vanadium, molybdenum, manganese, nickel, antimony, and uranium. Within Tampa Bay, sodium, lithium, and magnesium exhibited strongly conservative behavior (showing simple two-end-member mixing). Calcium, strontium, molybdenum, and uranium show quasi-conservative behavior, with localized deviations from simple mixing of fresh water and seawater end members. The remaining elements showed variable behavior driven by solubility, redox reactions, and/or unique localized inputs based on local geology. Comparisons of baywater calcium concentrations and the concentrations of lithium, magnesium, strontium and barium revealed simple relationships that are promising for use in interpretations of otolith chemistry of teleosts and some agnatha (Campana, 1999; Carlström, 1963). Samples were collected from both the river and the bay for CO2 system analyses. Spectrophometric pH measurements were obtained using purified m-Cresol Purple (mCP) and the procedures of Liu et al. (2011). Dissolved inorganic carbon (DIC) was processed according to CDIAC's Guide to Best Practices, SOP:2 (Dickson, Sabine, & Christian, 2007). Total alkalinity samples were processed using the spectrophotometric procedures of Yao and Byrne (1998). Dissolved inorganic carbon in the bay ranged between 3500 µMol/L and 2250 µMol/L and, in the Hillsborough River, peaked at 3700 µMol/L just below the Green Swamp. A comparison of measured total alkalinity and calculated alkalinity (obtained using pH and DIC and CO2sys software) demonstrated the presence of substantial organic base concentrations within the bay.

Abstract not available

In this research, the determination of trace concentrations of heavy metal ions was investigated using peptide modified electrochemical biosensors. The biosensor has several advantages over atomic absorption spectroscopy and inductively coupled plasma mass spectrometry by offering greater simplicity in use and the possibility of determining the bioavailability of heavy metals. Oligopeptides were modified on the electrode surface through the spontaneous self-assembly of thiols on gold. Firstly, 3-mercaptopropionic acid (MPA) was self-assembled onto the gold surface followed by activation of the carboxyl groups using a combination of carbodiimide and succinimide chemistry for coupling of the N-terminus of the peptide to occur. Using this generic strategy, Gly-Gly-His was used for the determination of copper ions. Cu2+ was accumulated at the MPA-Gly-Gly-His modified electrode at open circuit potential followed by electrochemical measurements. The reduction of Cu2+ to form underpotential deposited copper in the Osteryoung square wave voltammogram was used for quantification. The influence of various factors on the performance was investigated and after the optimal conditions had been identified, the biosensor was used for Cu2+ calibration and was applied to the analysis of a real sample. For Cd2+ detection, two different peptides covalently attached to MPA were investigated, g-Glu-Cys-Gly (GSH) and His-Ser-Gln-Lys-Val-Phe, with the latter sensor exhibiting a lower Cd2+ detection limit, higher sensitivity and greater selectivity. Although the success of MPA as a peptide linker to the gold surface had been shown for the detection of Cu2+ and Cd2+, a more viable approach was necessary for the stable detection of a wider range of metal ions. A more stable self-assembled monolayer of thioctic acid (TA) was identified in which human angiotensin I was attached. This alternate modification procedure was superior to MPA-angiotensin I for Pb2+ detection in terms of stability and reusability with the drawback being sensitivity. The newly identified strategy was also applied to the determination of Ag+ using TA-methionine enkephalin modified electrodes. A sensor array for Cu2+ was also investigated as well as an extension to the simultaneous determination of multianalytes using four different modified electrodes. Combining a soft-modelling approach, the responses of Cu2+, Cd2+ and Pb2+ could be deconvoluted.

This study investigates the fusion and scattering of nuclei at energies spanning the Coulomb barrier. The coupling of the relative motion of the nuclei to internal degrees of freedom can be thought to give rise to a distribution of potential barriers. ¶ Two new methods to extract representations of these potential barrier distributions are suggested using the eigen-channel model. The new techniques are based on measurements of quasi-elastic and elastic backscattering excitation functions, from which the representations are extracted by differentiation. A third method utilizing transfer excitation functions is introduced using qualitative arguments. The techniques are investigated experimentally for the reactions 16O + 92Zr, 144,154Sm, 186W and 208Pb. The results are compared with barrier distribution representations obtained from fusion data. The methods are further explored using the systems 40Ca + 90,96Zr and 32S + 208Pb, for which scattering and fusion excitation functions have been measured. The new barrier distribution representations are consistent with the one from fusion. They are direct evidence of the effects of the internal degrees of freedom on channels other than the fusion channel. ¶ The new representations are, however, less sensitive to the barrier distribution compared to their fusion counterpart. This observation is investigated using coupled-channels calculations. They suggest that residual weak reaction channels, which are not included in the coupling matrix, are responsible for the reduction in sensitivity. In the case of quasi-elastic scattering a distortion of the barrier structure above the average barrier is observed. This effect appears to be due to the de-phasing of the scattering amplitudes contributing to each eigen-channel. Using the heaviest system, 32S + 208Pb, it is demonstrated that there is no improvement in sensitivity to the barrier distribution for systems with large Sommerfeld parameters. This suggests that diffraction effects are not likely to be the cause of the sensitivity reduction. ¶ The new techniques may be employed successfully in systems with pronounced barrier structure below the average barrier. This is the case for the reactions 40Ca + 90,96Zr. It is shown that for these systems the quasi-elastic scattering and the fusion representations of the barrier distribution contain the same information. The extracted barrier distributions for the two reactions are distinctively different. They are compared to assess the relative importance of collective excitations and neutron transfer in fusion. Exact coupled-channels calculations show that the distribution for 40Ca + 90Zr arises from coupling of the relative motion to double phonon excitations of 90Zr. Further calculations suggest that the reaction 40Ca + 96Zr involves additional coupling to sequential neutron transfer, which is proposed to be a precursor of neutron-neck formation. ¶ Double phonon excitations are also seen to be important in the system 32S + 208Pb, for which the barrier distribution representations show in addition signatures of one and two neutron transfer.

Most metal ions have negative impacts on pulp mill operations. The concentrations of metal ions on pulp fibers and in washwaters rise significantly with increased wastewater recycling. The development of technology to remove these metal ions requires an understanding of how metal ions are bound to pulp components. It is also desirable to predict distribution of metal ions between the pulp fibers and the washwaters. The adsorption isotherms for eight metal ions (Ca, Ba, Mn, Zn, Pb, Cd, Ni, Na) were measured on bleached and unbleached (brownstock) kraft pulps at neutral pH and temperatures ranging from 25 to 75��C. On bleached pulps, the metal ion adsorption increased rapidly with increasing metal ion concentration in solution and then leveled off. At neutral pH, the adsorption on bleached pulp was stoichiometric to the carboxylate sites, whereas the adsorption on unbleached pulp was not, especially at high metal ion concentration in solution and low temperature. The pH isotherms specify the adsorption isotherms of sodium and calcium on wood pulps as pH ranging from 2.5 to 11.0. The pH isotherms on bleached pulp with only COOH functional groups (pK[subscript a] of 3.77) were saturated at pH 4 and above, whereas those on brownstock pulp with both COOH and PhOH (pK[subscript a] of 10) functional groups increased in two steps, at pH 4 and 8. The brownstock pulp is heterogeneous material. Therefore, only the empirical Freundlich model was applied to the data. To predict the metal ion adsorption on bleached pulps, two fundamental equilibrium models were developed: the multi-component ion exchange and the Donnan equilibrium models. The ion-exchange model better predicts the metal adsorption at neutral pH, whereas the Donnan equilibrium model more accurately predicts the pH isotherms. The adsorption kinetics of Ba����� and Ni����� were measured on wood pulps as a function of mixing speed, initial metal ion concentration, and temperature. The adsorption of metal ions reached equilibrium rapidly. The intraparticle diffusion model, based on first principle with a linear relationship assumption between adsorbed and free metal ion concentration, satisfactorily predicted the adsorption kinetics at low metal ion concentration in solution. / Graduation date: 2001

Graduation date: 1999