Instalações para irradiação com nêutrons foram projetadas e construídas, visando o estabelecimento de procedimentos de calibração de monitores e dosímetros de nêutrons. Uma fonte calibrada de ANTPOT.241 AmBe com atividade de ANTPOT.185 GBq, garantiu rastreabilidade às medidas realizadas, e possibilitou irradiações com taxas de dose que variaram entre 9 nSv s POT.-1 e 0,5 muuSv s POT.-1. No arranjo elaborado para irradiações com nêutrons térmicos, com fluxo calibrado, a taxa de dose utilizada foi 50 nSv s POT.-1. A calibração de um espectrômetro de esferas de Bonner permitiu o estabelecimento dos procedimentos de calibração com base em três métodos propostos por normas internacionais, mostrando serem apropriadas às dimensões da sala de irradiação projetada para essa finalidade. A decoração do espectro de nêutrons, a partir da determinação dos parâmetros de calibração para o detector de esferas de Bonner, permitiu determinar o espectro da fonte de ANTPOT.241 AmBe calibrada, com valores de taxa de fluência, taxa de dose equivalente e energia media, que corresponderam satisfatoriamente aos valores calculados esperados, possibilitando o uso de tal detector na dosimetria de área. Para a dosimetria pessoal, foi elaborado um sistema dosimétrico baseado no uso do polímero CR-39 e no ataque eletroquímico do mesmo. Para isso, foram projetadas e construídas uma câmara para o processamento do detector e uma fonte de alta tensão e alta frequência que mostraram-se adequadas às finalidades propostas. O dosímetro pessoal elaborado utiliza também material conversor (n, alfa) e seu principio de detecção possibilitou determinar um fator de calibração relacionando a resposta do detector com a dose recebida para nêutrons térmicos, epitérmicos e rápidos. Os parâmetros utilizados para o ataque eletroquímico foram: solução de KOH 6N, temperatura de 59°C, campo elétrico alternado de 20 kv IND.ppcm POT.-1, frequência de 2,0 kHz; para a detecção de nêutrons térmicos e epitérmicos o tempo de revelação empregado foi de 3 horas e para nêutrons rápidos de 6 horas. O sistema dosimétrico desenvolvido apresentou sensibilidades a nêutrons térmicos, epitérmicos e rápidos dadas pelos valores (1,46 +/- 0,09) 10 POT.4 traços cm POT.-2 mSv POT.-1, (9 +/- 3) 10² traços cm POT.-2 mSv POT.-1 e (26 +/- 4) traços cm POT.-2 mSv POT.-1 respectivamente. As doses mínimas e máximas detectáveis foram respectivamente 0,002 mSv e 0,6 mSv para nêutrons térmicos, 0,04 mSv e 8 mSv para nêutrons epitérmicos e 1 mSv e 12 mSv para nêutrons rápidos. Tendo em vista as implicações das recomendações do ICRP-60, pode-se concluir que o dosímetro pessoal elaborado neste trabalho apresenta a sensibilidade necessária no caso da monitoração de nêutrons térmicos e epitérmicos, mas que exigiria tempos de integração de doses superiores à mensal no caso da monitoração de nêutrons rápidos.O procedimento proposto para ser realizar a dosimetria de nêutrons é baseado no uso conjugado do dosímetro pessoal elaborado e do espectrômetro de esferas de Bonner enquanto dosímetro de área. / A neutron irradiation facility was designed and built in order to establish a procedure for calibrating neutron monitors and dosimeters. A 185 GBq ANTPOT.241 AmBe source in the air provides neutron doses rates between 9 nSv s POT.-1 and 0,5 muuSv s POT.-1. A calibrated 50 nSv s POT.-1 thermal neutron field is obtained by using a specially designed paraffin block in conjunction with the ANTPOT.241 AmBe source. A Bonner multisphere spectrometer was calibrated, using a procedure based on three methods proposed by international standards. The unfolded ANTPOT.241 AmBe neutron spectrum was determined from Bonner spheres data and resulted in a good agreement with expected values for fluence rate, dose rate and mean energy. A dosimetric system based on the electrochemical etching of CR-39 was developed for personal dosimetry. The dosimeter badge using a (n, alfa) converter, the etching chamber and high frequency power supply were designed and built specially for this project. The electrochemical etching (ECE) parameters used were: a 6N KOH solution, 59°C, 20 kV IND.ppcm POT.-1, 2,0 kHz, 3 hours of ECE for thermal and intermediate neutrons and 6 hours for fast neutrons. The calibration factors for thermal, intermediate and fast neutrons were determined for this personal dosimeter. The sensitivies determined for the developed dosimetric system were (1,46 +/- 0,09)10 POT.4 tracks cm POT.-2 mSv POT.-1 for thermal neutrons, (9 +/- 3)10² tracks cm POT.-2 mSv POT.-1 for intermediate neutrons and (26 +/- 4) tracks cm POT.-2 mSv POT.-1 for fast neutrons. The lower and upper limits of detection were respectively 0,002 mSv and 0,6 mSv for thermal neutrons, 0,04 mSv and 8 mSv for intermediate neutrons and 1 mSv and 12 mSv for fast neutrons. In view of the 1990s ICRP recommendations, it is possible to conclude that the personal dosimeter described in this work is sufficiently sensitive to thermal and intermediate neutrons but fast neutron monitoring at radiological protection level would require an integration period of over a month. The proposed dosimetric procedure is based on the conjugated use of the developed personal dosimeter and the Bonner multisphere spectrometer.

Este trabalho de mestrado trata da implementação de um espectrômetro de correlações angulares perturbadas no Laboratório do Acelerador Pelletron do Instituto de Física da Universidade de São Paulo. O espectrômetro é formado por seis detectores cintiladores com cristais de \'BaF IND.2\', de 3 polegadas de diâmetro por 6 de comprimento, com um sistema eletrônico e de aquisição de dados multiparamétrico padrão CAMAC. Diferentemente do usual, os espectros de energia dos raios gama dos núcleos de prova são adquiridos para cada detector, o que permite manter um controle maior sobre todo o experimento. Além disso, um mesmo experimento pode ser revisto com diferentes abordagens por diversas vezes, pois todas as informações sobre ele são armazenadas. Com a configuração eletrônica adotada, os espectros de energia são obtidos por meio de um QDC (charge to digital converter), dispensando o uso de pré-amplificadores. Os espectros de tempo são adquiridos com um TDC (time do digital converter). A seleção dos eventos de coincidência é realizada computacionalmente, procedimento que pode ser realizado durante a aquisição dos dados. Como a motivação para a implementação desse espectrômetro é o estudo de estruturas e interações de biomoléculas por meio da técnica de correlações angulares (PAC), foram realizadas medidas exploratórias, com o uso do espectrômetro do Laboratório de interações Hiperfinas (LIH) do Centro do Reator de Pesquisas (CRPq) no IPEN, paralelamente à implementação do espectrômetro. As primeiras medições foram realizadas com amostras de vesículas lipídicas. Com essas medidas foi possível notar a influência da variação de tamanho das moléculas (diminuição de tamanho em uma ordem de grandeza) no tempo de correlação rotacional à temperatura ambiente, quando adicionado SDS (sodium dodecyl sulfate) na suspensão para formação de um agregado micelar. As duas séries de medidas seguintes foram realizadas com amostras de SDS nas quais variaram-se as concentrações para se tentar verificar alterações na geometria ou na mobilidade das moléculas em função desse parâmetro. Foi possível notar que o comportamento das funções perturbação experimentais variaram com as amostras, porém não foi possível notar sistemática no comportamtento. Outro fator notado foi a influência do meio. O comportamento das moléculas quando na presença de metanol nas amostras era bem diferente das soluções aquosas. Também não foi possível obter uma conclusão clara quanto à concentração micelar crítica para soluções aquosas. Por fim foram realizadas medidas com amostras de proteína calmodulina. Foram feitas medidas à temperatura ambiente e a 77K. Notou-se que essa proteína é passível de ser estudada por meio da técnica PAC. Para confirmar a presença da proteína nas amostras e também tentar verificar um deslocamento na massa devido à presença do íon \'ANTPOT.111 Cd\' \'ANTPOT.2+\' foram realizadas medidas de espectrometria de massas no Laboratório de Espectrometria de Massas na Embrapa em Brasília. Foi possível confirmar a presença da proteína nas amostras, porém não foi possível notar a presença de \'ANTPOT.111 Cd\' devido à baixa concentração de íons utilizados com a técnica PAC. / This work is related to the implementation of a perturbed angular correlation (PAC) spectrometer at the University of São Paulo Pelletron Laboratory. The spectrometer consists of 6 cylindrical BaF$_2$ scintillator detectors, with 3 inches diameter and 6 inches length and a multiparameter CAMAC data acquisition system. Different from usual, the gamma ray energy spectra of the cascade nuclei are acquired for each detector, which allows us to have more control of the experiment. Besides, the same experiment can be revised with different approaches at any time. With the adopted electronics configuration, the energy spectra are obtained through a QDC (charge to digital converter) module, which dispenses the use of pre-amplifiers. The time spectra are acquired with a TDC (time to digital converter) module. The selection of coincidence events is performed computationally, and this procedure can be evaluated during the data acquisition. The main motivation for implementing this spectrometer is the study of the structure and interactions of biomolecules through the perturbed angular correlation technique. Test measurements were performed, parallel to the spectrometer construction, with the use of the Hyperfine Interactions Laboratory spectrometer at the Centro do Reator de Pesquisas do Instituto de Pesquisas Energéticas e Nucleares (CRPq-IPEN). The first measurements were performed with lipidic vesicles samples. In this case it was possible to observe the influence of the molecule dimension change (decrease in one order) on the rotational correlation time at room temperature, when SDS (sodium dodecyl sulfate) was added in the suspension to form micellar aggregation. The two following series of measurements were performed with SDS samples in which the concentration was varied in order to verify modifications in the geometry or mobility of the molecules as a function of that parameter. The behavior of the experimental perturbation functions varied with the samples. However, it was not possible to point out any systematics in their behavior. The molecules behavior when in presence of methanol in the samples was very different from the aqueous solutions. Also, it was not possible to obtain a clear conclusion about the critical micellar concentration for the aqueous solutions. Finally, the last measurements were performed with calmodulin protein samples, at room temperature and at 77K. In this case we concluded that this protein can be studied through the PAC technique. In order to confirm the presence of the protein in the samples and at same time to verify if any mass displacement occurred due to the presence of the $^{111}$Cd$^{2+}$, mass spectrometry measurements were performed at the Laboratório de Espectrometria de Massas -- Embrapa in Brasília. It was possible to confirm the presence of the protein in the samples, but it was not possible to observe the mass displacement due to the presence of the $^{111}$Cd, since the ions concentration used with the PAC technique is very low.

My research broadly covers various important aspects of microfluidic devices and biosensors. Specifically, this dissertation reports: (1) a new and effective room temperature method of bonding polydimethylsiloxane (PDMS) microfluidics to substrates such as silicon and glass, (2) a new microfluidic pump concept and implementation specifically designed to repeatedly drive a small sample volume (<1 µL) very rapidly (~500 µL/min) through a sensor-containing flow channel to significantly decrease sensor response time through advection-driven rather than diffusion-driven mass transport, (3) use of a new microfluidic material based on polyethylene glycol diacrylate (PEGDA) to implement impedance-based dynamic nanochannel sensors for protein sensing, and (4) an investigation of galvanoluminescence and how to avoid it for conditions important to fluorescence-based dielectrophoresis (DEP) microfluidic biosensors. Over the last decade, the Nordin research group has developed a lab-on-a-chip (LOC) biosensor based on silicon photonic microcantilever arrays integrated with polydimethylsiloxane (PDMS) microfluidics for protein biomarker detection. Integration requires reliable bonding at room temperature with adequate bond strength between the PDMS element and microcantilever sensor substrate. The requirement for a room temperature process is particularly critical because microcantilevers must be individually functionalized with antibody-based receptor molecules prior to bonding and cannot withstand significant heating after functionalization. I developed a new room temperature bonding method using PDMS curing agent as an intermediate adhesive layer. Two curing agents (Sylgard 184 and 182) were compared, as well as an alternate UV curable adhesive (NOA 75). The bond strength of Sylgard 184 was found to be stronger than Sylgard 182 under the same curing conditions. Overnight room temperature curing with Sylgard 184 yields an average burst pressure of 433 kPa, which is more than adequate for many PDMS sensor devices. In contrast, UV curable epoxy required a 12 hour bake at 50 °C to achieve maximum bond strength, which resulted in a burst pressure of only 124 kPa. In many biosensing scenarios it is desirable to use a small sample volume (<1 µL) to detect small analyte concentrations in as short a time as possible. I report a new microfluidic pump to address this need, which we call a reflow pump. It is designed to rapidly pump a small sample volume back and forth in a flow channel. Ultimately, the flow channel would contain functionalized sensor surfaces. The rapid flow permits use of advection-driven mass transport to the sensor surfaces to dramatically reduce sensor response times compared to diffusion-based mass transport. Normally such rapid flow would have the effect of decreasing the fraction of analyte molecules in the volume that would see the sensor surfaces. By configuring the pump to reflow fluid back and forth in the flow channel, the analyte molecules in the small sample volume are used efficiently in that they have many opportunities to make it to the sensor surfaces. I describe a 3-layer PDMS reflow pump that pumps 300 nL of fluid at 500 µL/min for 15 psi actuation pressure, and demonstrate a new two-layer configuration that significantly simplifies pump fabrication. Impedance-based nanochannel sensors operate on the basis of capturing target molecules in nanochannels such that impedance through the nanochannels is increased. While simple in concept, the response time can be quite long (8~12 hours) because the achievable flow rate through a nanochannel is very limited. An approach to dramatically increase the flow rate is to form nanochannels only during impedance measurements, and otherwise have an array of nanotrenches on the surface of a conventional microfluidic flow channel where they are exposed to normal microfluidic flow rates. I have implemented such a dynamic nanochannel approach with a recently-developed microfluidic material based polyethylene glycol diacrylate (PEGDA). I present the design, fabrication, and testing of PEGDA dynamic nanochannel array sensors, and demonstrate an 11.2 % increase in nanochannel impedance when exposed to 7.2 µM bovine serum albumin (BSA) in phosphate buffered saline (PBS). Recently, LOC biosensors for cancer cell detection have been demonstrated based on a combination of dielectrophoresis (DEP) and fluorescence detection. For fluorescence detection it is critical to minimize other sources of light in the system. However, reported devices use a non-noble metal electrode, indium tin oxide (ITO), to take advantage of its optical transparency. Unfortunately, use of non-noble metal electrodes can result in galvanoluminescence (GL) in which the AC voltage applied to the electrodes to achieve DEP causes light emission, which can potentially confound the fluorescence measurement. I designed and fabricated two types of devices to examine and identify conditions that lead to GL. Based on my observations, I have developed a method to avoid GL that involves measuring the impedance spectrum of a DEP device and choosing an operating frequency in the resistive portion of the spectrum. I also measure the emission spectrum of twelve salt solutions, all of which exhibited broadband GL. Finally, I show that in addition to Au, Cr and Ni do not exhibit GL, are therefore potentially attractive as low cost DEP electrode materials.

<p>The superior sensitivity and selectivity obtained with mass spectrometry (MS) is hardly matched by other analytical technologies, therefore it is an indispensable tool for modern society. Traditionally, MS is coupled with chromatography separation and performed in centralized analytical laboratories, which often requires extensive sample preparation and expensive instrumentation. With the advancements in the field of ambient MS and miniature MS, MS analysis at point-of-care (POC) has become a reality. Ambient MS includes a variety of methods for sampling and ionization, but they all share a common feature: they require little to no sample preparation. This has made rapid analysis of untreated sample possible and speed of MS analysis is significantly improved. Miniature MS, on the other hand, shrinks down the sizes of conventional benchtop instruments so they become portable or fieldable. In this dissertation, I documented the developments of ambient MS methods and applications of miniature MS for a variety of health-related topics, which include preclinical pharmacokinetics, intraoperative diagnosis, drug adherence monitoring and food safety. </p>

The electron-electron coincidence (e,2e) technique yields complete kinematical information about the electron impact ionization process. The (e,2e) technique has been widely used to study dynamical effects in ionizing collisions with atomic targets, however studies of molecular ionization using this technique have been very limited. Recently further experimental studies of small molecules have been proposed, as the cross sections of small molecules are now computable using sophisticated theoretical approaches [77, 24]. This thesis presents dynamical investigations for the electron impact ionization of the molecular targets H2O and H2, employing the (e,2e) technique to experimentally measure the triple differential cross section (TDCS). The TDCS is defined as the probability that a bound electron will be ejected from the target atom or molecule (into a particular direction with a defined energy) and the initial electron will be scattered into a particular direction with a particular energy. All TDCSs presented within this thesis were performed using an electron coincidence spectrometer in the coplanar asymmetric geometry at intermediate incident electron energies. This thesis presents the electron impact ionization TDCSs of H2O. A series of measurements were performed using H2O in the vapour form. Measurements of the TDCS are presented for the 2a1 atomic-like orbital and the 1b2, 3a1 and 1b1 molecular orbitals at a common incident electron energy of 250eV, ejected electron energy of 10eV and scattering angle of -15o. The experimental TDCSs are compared with theoretical cross sections that were calculated by Champion et al [25, 26] using a distorted wave Born approach (DWBA). TDCS measurements for the single ionization of the hydrogen molecule, H2 were performed as in recent years there has been evidence that indicates the ejected electron angular distribution is perturbed due to Young-type interference effects. The oscillatory structure which is predicted in the cross section is due to the two-centred nature of the molecule [27, 29]. This thesis presents experimental TDCSs for the ionization of H2 which are compared to TDCSs of helium. A series of measurements for the TDCSs of H2 and He are presented at a common incident electron energy of 250eV and scattering angle of -15o, for a range of ejected electron energies between 10eV and 100eV. The experimental TDCSs are compared with two types of theoretical calculations.

The objective of this thesis was to develop novel technologies for measuring the physical characteristics of high-speed pulse trains, for use in performance monitoring applications. This thesis describes the development of three separate techniques that perform measurements in either the time domain, frequency domain or the phase space of the optical signal. The first section investigates phase-sensitive pulse measurement techniques. A high- resolution SHG-FROG apparatus was custom-designed to measure 40GHz RZ pulse trains, from which an operational characterisation of a Mach-Zehnder modulator (MZM) was realised. A numerical model of a nonlinear pulse compressor was developed to compress 40GHz RZ pulses from 8.5ps down to 3.4ps. These pulses were time-division multiplexed to 80GHz, and phase-retrievals of the 80GHz pulse trains were measured. A comparison between the techniques of SHG-FROG and linear spectrogram has been undertaken for 10GHz pulse sources, exposing SHG-FROG's weaknesses at this particular repetition rate. The second section investigates a simple, time-averaged, nonlinear detection technique. Two-photon absorption in a GaAs/InGaAs quantum-well laser diode was used to measure the duty cycle (and by extension, the pulse duration) of a range of pulse sources. This technique was further developed to measure the extinction ratio of NRZ pulse trains. Additionally, the pulse duration of a mode-locked laser source was measured using the nonlinear absorption in a 1-m length of As2Se3 Chalcogenide glass fiber. This demonstrates that the nonlinear properties of this glass may well find application in future instrumentation. The third section investigates the development of an ultra-high resolution swept heterodyne spectrometer. This spectrometer was used to spectrally-distinguish repetitive 8-bit NRZ patterns at 2.5Gbit/s. It was also used to measure the chirp parameter of an X-cut LiNbO3 MZM, revealing a chirp parameter of απ/2 < 0.1 across a modulation band- width of 250-2500MHz. Additionally, the distinctive CW spectrum of a DFB laser diode was measured. Analysis of the measured CW spectrum yielded a linewidth enhancement factor of α≃ 1.8 and also the relative intensity noise of the DFB laser diode.

<p>The aim of this master's thesis is to develop a method that fully automates a trimming step in the production of a fiber-optical power spectrometer, based on a unique Acusto-Optical Scanning Filter.</p><p>The filter is created by letting an ultrasonic mechanical pulse pass through a chirped Fiber Bragg Grating. The pulse introduces a disturbance in the grating, creating a thin optical transmission window in the otherwise reflective bandwidth. The high demands on the window requires a precise, unit dependent pulse form with unknown properties. Thus each unit needs to be trimmed to reach required performance.</p><p>The manual trimming is largely a trial and error process, that contains two performance tests. We redefine one, eliminating the need to reroute the optical path and reducing the number of fiber weldings. The tests are then quantified, allowing a figure of merit to be based on weighted performance values.</p><p>A brute force method, testing a large set of pulses, is implemented. The set is defined by the parameter space spanned by previously produced units. Due to the large space, the method is too time consuming. Instead it is used to measure the performance spaces of three units. An attempt to largely reduce the parameter space using PCA failed.</p><p>An alternating variables method that finds local performance optima in the parameter space is developed. By using a set of several starting points, the method tends to find several qualified pulses. The method is implemented and successfully verified by trimming new units.</p><p>Finally we propose where to focus improvements of the method in a production ramp up.</p>

Graduation date: 2002

This thesis compiles results of research in two mutuallydependent parts: 1) development of ferromagnetic resonance(FMR) spectrometer to study microwave properties offerromagnetic materials, and 2) characterization of new irongarnets: pulsed laser deposited Y3Fe5O12and Bi3Fe5O12films and Ce:Y3Fe5O12single crystal. First part describes a novelBroadbandFMRSpectrometerdesigned to characterize thin ferromagneticfilms. The spectrometer uses two probeheads: one is the X-bandmicrowave reflection cavity for room temperature measurementsand the in-cryostat microstrip line probe to perform FMRexperiments in the frequency range from 50 MHz to 40 GHz. Veryuniform and stable magnetic field up to 2.4 T, temperatures 4 Kto 420 K, and continuous frequency scan performed byHP8722Dvector network analyzer provide various modes ofoperation. Both probeheads are equipped with two-circlegoniometers to ensure accurate study of magneticanisotropy. The spectrometer was used to make express-analysis ofquality thus to optimize processing parameters of epitaxialiron garnet films grown by pulsed laser deposition (PLD).Comprehensive study of uniaxial and cubic magnetocrystallineanisotropy has been performed for Ce:Y3Fe5O12bulk crystal as well as for Y3Fe5O12and Bi3Fe5O12films grown on different substrates by PLD andreactive ion beam sputtering techniques. BroadbandFMR-spectroscopy revealed difference in spectra of domain wallresonances: instead of“soft”spin modes in filmsgrown by liquid phase epitaxy, PLD-made films show“diffuse”transformation of domains near thesaturation field. This effect indicates non-uniformity ofsaturation magnetization and field of uniaxial anisotropy inPLD-iron garnets. Spin wave resonances in comparison withuniform FMR have been studied to evaluate“localquality”of ferromagnetic films. The resonance field andFMR linewidth behavior were studied at various crystallographicdirections determined by X-ray diffraction. FMR was used to choose PLD-made YIG films with low losses atmicrowave frequencies and to build magnetostatic surface wavesmicrowave bandpass filter. The filter was designed as a planarfilm structure with a microstrip line for transducers. It is afirst demonstration of feasibility to introduce PLD processingtechnique to magnetostatic wave technology. Magneto-optical study of Ce:Y3Fe5O12single crystal complements results ofFMR-spectroscopy of new garnets. <b>Keywords:</b>ferrites, thin films, ferromagnetic resonance,microwaves, FMR spectrometer, magnetic anisotropy,magnetostatic waves.

The optical design of a soft X-ray (90-1100~eV) emission spectrometer for the Resonant Elastic and Inelastic X-ray Scattering (REIXS) beamline to be implemented at the CLS is presented. An overview of soft X-ray optical theory as it relates to diffraction gratings is given. The initial constraints and the process that led to this design are outlined. Techniques and software tools that were developed, using ray-tracing and diffraction grating efficiency calculations, are discussed. The analysis completed with these tools to compare existing soft X-ray emission spectrometer designs is presented. Based on this analysis, a new design with superior performance for this application is proposed and reviewed. This design employs Rowland circle geometry to achieve a resolving power in excess of 2,500 in the range of interest. In addition, a novel design is proposed for a larger extremely high resolution spectrometer which will provide resolving powers exceeding 10,000 throughout the higher end of this range. A review is given of research into the components, manufacturing techniques and tolerances that will be required to produce this spectrometer.