Alternative diesel fuels have been the subject of extensive investigation. Fatty acid methyl ester (FAME) based Biodiesel manufactured from vegetable oils or animal fats is an excellent candidate to replace common diesel fuel being renewable, non-toxic and often giving rise to reduced exhaust gas emissions. The transesterification process has been commonly and widely used to produce biodiesel from vegetable oil or animal fat. Vegetable oils or animal fats generally have viscosities higher than standard diesel oil. This means that it is necessary to reduce the viscosity by means of reacting vegetable oil with alcohol in the presence of a suitable catalyst. The target product for this reaction is methyl ester, with glycerol and potentially soap produced as by products with the process of transesterification. Methylester (Biodiesel) is produced by converting triglycerides to alkylesters. A batch transesterification process has two significant mechanisms, and exhibits a mass transfer controlled region that precedes a second order kinetically controlled region. In order to control the conversion process it is useful to employ process monitoring. In particular monitoring of the mass transfer processes that limits the initial reaction rates could prove to be beneficial in allowing for process optimization and control. This thesis proposes the use of a new method of biodiesel process monitoring using low frequency (15kHz) impedance sensing which is able to provide information regarding the progress of mass transfer and chemical reaction during biodiesel production. An interdigitated (ID) sensor has been used to monitoring the biodiesel process The ID sensor is of simple construction and consists of two sets of interleaved electrodes (fingers). The two sets of electrodes are separated by a gap and when an AC excitation voltage is applied across the interleaved electrodes an oscillating electric field is developed. The response of the fluid surrounding the sensor to the applied excitation was then used to determine progress of the chemical reaction by evaluating the real and complex impedance. A significant and unambiguous change in the components of impedance has been shown to occur during mixing (mass transfer) and transesterification. The impedance measurements gained during transesterification were then used for the development of a system model. A systematic approach was used to select mathematical models and system identification techniques were evaluated. The system identification investigation used real process measurement data in conjunction with the Matlab system identification toolbox.

Slush is a two phase flow of solid particles (crystals) and liquid at the triple point temperature, and constitutes an appealing alternative to liquid propellants for space launchers. The crystals give to the mixture higher density and lower specific enthalpy than liquid, enabling reduced tank volume storage and larger fuel holding time. However, the presence of solid crystals significantly modifies the thermo-hydraulics of the fuel transport, and requires novel predictive tools and diagnostic techniques for efficiently exploiting slush propellants. This thesis contributes to both aspects. In particular, this work studied the flow pressure losses and the heat transfer of solid-liquid mixtures in pipelines, combining experimental and numerical methods. Hydraulic and thermal flow features were analyzed separately with substitute mixtures chosen to mimic the behavior of slush flows in engine fuel feed systems. A dedicated facility was designed and built. The pipeline mounted conventional probes for pressure, temperature and mass flow rate measurements. Moreover, a capacitance-based density meter was developed and validated to measure the mixture's solid content. Optical flow visualization and image processing routines were combined to retrieve particulate phase distribution and velocity fields. The experimental work was complemented with 3D Unsteady Reynolds Averaged Navier Stokes simulations in OpenFOAM. The simulations coupled the Euler-Euler approach with the granular kinetic theory for the treatment of the solid dispersed phase. The model was validated with the experimental results on the pressure drop, heat transfer and solid volume fraction.The resulting physical insights and the proposed empirical correlations on the pressure drop and heat transfer in solid-liquid flows contribute to move a step forward towards slush propelled space launchers. / Doctorat en Sciences de l'ingénieur et technologie / info:eu-repo/semantics/nonPublished

Sensor interfaces are needed to communicate the measured real-world analog values to the base¬band digital processor. They are dominated by the presence of high accuracy, high resolution analog to digital converters (ADC) in the backend. On most occasions, sensing is limited to small range measurements and low-modulation sensors where the complete dynamic range of ADC is not utilized. Designing a subsystem that integrates the sensor and the interface circuit and that works with a low resolution ADC requiring a small die-area is a challenge. In this work, we present a CMOS based area efficient, integrated sensor interface for applications like capacitance, temperature and dielectric-constant measurement. In addition, potential applica-tions for this work are in Cognitive Radios, Software Defined Radios, Capacitance Sensors, and location monitoring. The key contributions in the thesis are: 1 High Sensitivity Frequency-domain CMOS Capacitance Interface: A frequency domain capacitance interface system is proposed for a femto-farad capacitance measurement. In this technique, a ring oscillator circuit is used to generate a change in time period, due to a change in the sensor capacitance. The time-period difference of two such oscillators is compared and is read-out using a phase frequency detector and a charge pump. The output voltage of the system, is proportional to the change in the input sensor capacitance. It exhibits a maximum sensitivity of 8.1 mV/fF across a 300 fF capacitance range. 2 Sensitivity Enhancement for capacitance sensor: The sensitivity of an oscillator-based differential capacitance sensor has been improved by proposing a novel frequency domain capacitance-to-voltage (FDC) measurement technique. The capacitance sensor interface system is fabricated in a 130-nm CMOS technology with an active area of 0.17mm2 . It exhibits a maximum sensitivity of 244.8 mV/fF and a measurement resolution of 13 aF in a 10-100 fF measurement range, with a 10 pF nominal sensor capacitance and an 8-bit ADC. 3 Frequency to Digital Converter for Time/Distance measurement: A new architecture for a Vernier-based frequency-to-digital converter (VFDC) for location monitoring is pre¬sented, in which, a time interval measurement is performed with a frequency domain approach. Location monitoring is a common problem for many mobile robotic applica¬tions covering various domains, such as industrial automation, manipulation in difficult areas, rescue operations, environment exploration and monitoring, smart environments and buildings, robotic home appliances, space exploration and probing. The proposed architecture employs a new injection-locked ring oscillator (ILR) as the clock source. The proposed ILR oscillator does not need complex calibration procedures, usually required by Phase Locked Loop (PLL) based oscillators in Vernier-based time-to-digital convert¬ers. It consumes 14.4 µW and 1.15 mW from 0.4 V and 1.2 V supplies, respectively. The proposed VFDC thus achieves a large detectable range, fine time resolution, small die size and low power consumption simultaneously. The measured time-difference error is less than 50 ps at 1.2 V, enabling a resolution of 3 mm/kHz frequency shift. 4 A bio-sensor array for dielectric constant measurement: A CMOS on-chip sensor is presented to measure the dielectric constant of organic chemicals. The dielectric constant of these chemicals is measured using the oscillation frequency shift of a current controlled os¬cillator (CCO) upon the change of the sensor capacitance when exposed to the liquid. The CCO is embedded in an open-loop frequency synthesizer to convert the frequency change into voltage, which can be digitized using an off-chip analog-to-digital converter. The dielectric constant is then estimated using a detection procedure including the calibration of the sensor. 5 Integrated Temperature Sensor for thermal management: An integrated analog temper¬ature sensor which operates with simple, low-cost one-point calibration is proposed. A frequency domain technique to measure the on-chip silicon surface temperature, was used to measure the effects of temperature on the stability of a frequency synthesizer. The temperature to voltage conversion is achieved in two steps i.e. temperature to frequency, followed by frequency to voltage conversion. The output voltage can be used to com¬pensate the temperature dependent errors in the high frequency circuits, thereby reduc¬ing the performance degradation due to thermal gradient. Furthermore, a temperature measurement-based on-chip self test technique to measure the 3 dB bandwidth and the central frequency of common radio frequency circuits, was developed. This technique shows promise in performing online monitoring and temperature compensation of RF circuits.

With recent advancements in material science, industrial operations are being conducted at higher and higher temperatures. This is apparent in the nuclear industry where a division of the field is working to develop the High Temperature Gas Reactor and the Very High Temperature Gas Reactor concurrently. Both of these facilities will have outlet gas temperatures that are at significantly higher temperatures than the typical water cooled reactor. These increased temperatures provide improved efficiency for the production of hydrogen, provide direct heating for oil refineries, or more efficient electricity generation. As high temperature operations are being developed, instruments capable of measuring the operating parameters must be developed concurrently. Within the gas reactor community there is a need to measure the impurities within the primary coolant. Current devices will not survive the temperature and radiation environments of a nuclear reactor. An instrument is needed to measure the impurities within the coolant while living inside the reactor, where this instrument would measure the amount of the impurity within the coolant. There are many industrial applications that need to measure the ratio of two components, whether it be the amount of particulate in air that is typical to pneumatic pumping, or the liquid to gas ratio in natural gas as it flows through a pipeline. All of the measurements in these applications can be met using a capacitance sensor. Current capacitance sensors are built to operate at ambient temperatures with only one company producing a product that will handle a temperature of up to 400 °C. This maximum operating temperature is much too low to measure the gas characteristics in the High Temperature Gas Reactor. If this measurement technique were to be improved to operate at the expected temperatures, the coolant within the primary loop could be monitored for water leaks in the steam generator, carbon dust buildup entrained in the flow, or used to measure the purity of the coolant itself. This work details the efforts conducted to develop such an instrument. While the concept of designing a capacitance sensor to measure a gas mixture is not unique, the application of using a capacitance sensor within a nuclear reactor is a new application. This application requires the development of an instrument that will survive a high temperature nuclear reactor environment and operate at a sensitivity not found in current applications. To prove this technique, instrument prototypes were built and tested in confined environments and at high temperatures. This work discusses the proof of concept testing and outlines an application in the High Temperature Test Facility to increase the operational understanding of the instrument. This work is the first step toward the ultimate outcome of this work, which is to provide a new tool to the gas reactor community allowing real-time measurements of coolant properties within the core. / Graduation date: 2013

Made available in DSpace on 2016-06-02T19:55:31Z (GMT). No. of bitstreams: 1 4085.pdf: 6460777 bytes, checksum: 9367318799fc091b43ee6716e5057271 (MD5) Previous issue date: 2011-12-22 / Financiadora de Estudos e Projetos / High cell density cultivations of recombinant E. coli are a fast and economical way to produce recombinant proteins. Through this bioprocess, products with high added value and pharmaceuticals of great importance such as insulin, human and bovine growth hormone, protein antigens for formulation of vaccines, enzymes, among others, are obtained. However, keeping these cultivations within the desired conditions becomes a major challenge, since some variables such as dissolved oxygen concentration (DOC) and substrate concentration are difficult to control. Therefore, the development and implementation of an automatic monitoring and control tool are key requirements for the performance of high density cultivation. The present work has as main objectives to study feeding strategies for high cell density cultivation of recombinant Escherichia coli and develop a computational tool capable of ensuring the implementation of the chosen strategies, performing the monitoring, control and supervision of the cultivations. Fed batch cultivations were carried out under the supervision of the tool in a 5 L in-house bioreactor, equipped with sensors for temperature, dissolved oxygen, pH, pressure and biomass (sensor that measures the concentration of viable cells based on permittivity measurements), peristaltic pumps and connected to the gas analyzer. The tool was developed with LabView 8.0 and MatLab 6.5, being the acquisition and communication with the different bioreactor accessories via compact Field Point. Twenty two fed-batch cultivations with 5 different clones of E. coli, BL21(D3) expressing the enzyme penicillin G acylase (PGA) as well as antigenic proteins of S. pneumoniae (PspA3, PspA245 and PspA4Pro) and E. rhusiopathiae (SpaA) were performed during the development of the tool and the studies of feeding strategy. Both defined medium (HDF modified) as complex medium (ZYM-5052 modified), usually having glycerol as main carbon source and IPTG or lactose as inducers were used. In all cultivations, samples were collected to quantify the concentration of cells (dry weight method in filter of 0.22 m and optical density at 600 nm), organic acids, glucose, glycerol and lactose (HPLC) as well as protein expression (densitometry and NIPAB method for PGA) and plasmid stability (plating). The tool SUPERSYS_HCDCR (registered as a free software) developed, implemented and validated in the performed cultivations, carries out the basic functions of bioreactor supervision software, such as monitoring and data acquisition of pressure, temperature, pH, DOC, fraction of CO2 and O2 in the outlet gas as well as real-time estimate of the respiratory quotient, the rate of oxygen consumption and CO2 production. However, it also has the following special features, including: i) automatic control of air and oxygen flow according to cellular demand, ii) automatic activation of the feed pump at the end of the batch; iii) automatic control of feeding flow rate as function of the specific growth rate inferred in real time; iv) automatic control of feeding flow rate constrained by the concentration of dissolved oxygen, v) audible alarms indicating failures in the process; vi) failure messages sent via email; vii) automatic control of dissolved oxygen concentration; viii) control of the bioreactor pressure; and ix) control of bath temperature. Regarding the studies of feeding strategies aimed at biomass productivity increase in high cell density cultivations of recombinant E. coli, using the supervision tool developed together with changes in the composition of the synthetic culture medium available in the literature, a cellular concentrations greater than 150 g/L was achieved in less than 24 hours of cultivation, corresponding to a productivity of 9.2 g/Lh. This value, which is higher than the reported in the literature, was obtained without acetate accumulation and allowing high production of recombinant protein. / Cultivos de alta densidade celular de E. coli recombinante constituem uma tecnica rapida e economica para producao de proteinas recombinantes. Por meio deste bioprocesso, sao obtidos produtos de alto valor agregado e de grande importancia na industria farmaceutica, tais como insulina, hormonios de crescimento humano e bovino, antigenos proteicos para formulacao de vacinas, enzimas, dentre outros. Entretanto, manter estes cultivos dentro das condicoes desejadas se torna um grande desafio, em funcao da dificuldade de controlar variaveis como a concentracao de oxigenio dissolvido (COD) e a concentracao de substrato nos niveis desejados. Por isso, o desenvolvimento e a implementacao de sistemas automaticos de supervisao e controle sao requisitos fundamentais para o bom desempenho de um cultivo de alta densidade. O presente trabalho teve como principais objetivos estudar estrategias de alimentacao para cultivos de alta densidade celular de Escherichia coli recombinante e desenvolver uma ferramenta computacional para suporte na execucao das estrategias escolhidas, realizando o monitoramento, controle e supervisao dos cultivos. Os cultivos em batelada alimentada realizados sob supervisao da ferramenta foram conduzidos em biorreator de 5 L, equipado com sensores de temperatura, oxigenio dissolvido, pH, pressao e biomassa (sensor que mede a concentracao de celulas viaveis a partir dos dados de permissividade), bombas peristalticas e conectado a analisador de gases. A ferramenta foi desenvolvida com os programas LabView 8.0 e MatLab 6.5, sendo a aquisicao e a comunicacao com os diferentes acessorios do biorreator realizada via compact Field Point (National Instruments). Vinte e dois cultivos em batelada alimentada com 5 diferentes clones de E. coli, BL21(D3) expressando a enzima penicilina G acilase (PGA) assim como proteinas antigenicas de Streptococcus pneumoniae (PspA3, PspA245 e PspA4Pro) e de Erysipelothrix rhusiopathiae (SpaA) foram realizados durante o desenvolvimento da ferramenta e dos estudos de estrategia de alimentacao, empregando tanto meio definido (HDF modificado) como meio complexo (ZYM-5052 modificado), tendo glicerol ou glicose como principal fonte de carbono e IPTG ou lactose como indutores. Em todos os cultivos, amostras foram coletadas para quantificar a concentracao de celulas (metodo de massa seca em filtro de 0,22m e leitura da densidade otica a 600 nm), de acidos organicos, glicose, glicerol e lactose (HPLC) e a expressao da proteina (densitometria e metodo NIPAB para a PGA) e a estabilidade de plasmideo (plaqueamento). A ferramenta SUPERSYS_HCDCR (registrada como software livre) desenvolvida, implementada e validada nos cultivos realizados, desempenha as funcoes basicas de softwares de supervisao de biorreatores, tais como: monitoramento e aquisicao de dados de pressao, temperatura, pH, COD, fracao de CO2 e de O2 nos gases de saida; estimativa em tempo real do quociente respiratorio, das velocidades de consumo de oxigenio e de producao de CO2. Esta ferramenta apresenta as seguintes funcionalidades especiais: i) controle automatico das vazoes de ar e de oxigenio de acordo com a demanda celular; ii) acionamento automatico da bomba de alimentacao ao final da batelada; iii) controle automatico da vazao de alimentacao em funcao da velocidade especifica de crescimento inferida em tempo real; iv) controle automatico da alimentacao com restricoes pela concentracao de oxigenio dissolvido; v) alarmes sonoros indicando falhas no processo; vi) envio de mensagens de falhas por email; vii) controle automatico da concentracao de oxigenio dissolvido; viii) controle de seguranca da pressao do biorreator, e ix) controle da temperatura do banho. Em relacao aos estudos das estrategias de alimentacao visando ao aumento da produtividade em biomassa em cultivos de alta densidade celular de E. coli recombinante, com o auxilio da ferramenta de supervisao desenvolvida aliada a modificacoes na composicao do meio de cultivo sintetico disponivel na literatura, foram alcancadas concentracoes celulares maiores que 150 g/L em menos de 24 h de tempo total de cultivo, levando a uma produtividade de 9,2 g/Lh, a qual e superior aos valores relatados na literatura, sem acumulo de acetato e possibilitando elevada producao da proteina recombinante.

MEMS Sensors are widely used for sensing inertial displacements. The displacements arising out of acceleration /Coriolis effect are typically in the range of 1 nm-1 m. This work investigates the realization of high resolution MEMS inertial sensors using novel displacement sensing mechanisms. Capacitance sensing ASIC is developed as part of conventional electronics interface with MEMS sensor under the conventional CMOS-MEMS integration strategy. The capacitance sense ASIC based on Continuous Time Voltage scheme with coherent and non-coherent demodulation is prototyped on AMS 0.35 m technology. The ASIC was tested to sense C = 3.125 fF over a base of 2 pF using on-chip built-in test capacitors. Dynamic performance of this ASIC was validated by interfacing with a DaCM MEMS accelerometer. 200milli-g of acceleration (equivalent to a C = 2.8 fF) over an input frequency of 20Hz is measurable using the developed ASIC. The observed sensitivity is 90mV/g. The ASIC has several programmable features such as variation in trim capacitance (3.125 fF-12.5 pF), bandwidth selection (500 Hz-20 kHz) and variable gain options (2-100). Capacitance detection, a dominant sensing principle in MEMs sensors, experiences inherent limitation due to the role of parasitics when the displacements of interest are below 5 nm range. The capacitive equivalence ( C) for the range of displacements of the order of 5 nm and below would vary in the range atto-to-zepto farad. Hence there is a need to explore alternative sensing schemes which preferably yield higher sensitivity (than those offered by the conventional integration schemes) and are based on the principle of built-in transduction to help overcome the influence of parasitics on sensitivity. In this regard, 3 non-conventional architectures are explored which fall under the direct integration classification namely: (a) Sub-threshold based sensing (b) Fringe field based sensing and (c) Tunneling current based sensing. a) In Sub-threshold based sensing, FET with a suspended gate is used for displacement sensing. The FET is biased in the sub-threshold region of operation. The exponential modulation of drain current for a change in displacement of 1 nm is evaluated using TCAD, and the in uence of initial air-gap variation on the sensitivity factor ( ID=ID) is brought out. For 1% change in air gap displacement (i.e., TGap/TGap, the gap variation resulting due to the inertial force / mass loading) nearly 1050% change in drain current( ID=ID) is observed (considering initial air gaps of the order 100 nm). This validates the high sensitivity offered by the device in this regime of operation. A comparison of sensitivity estimate using the capacitive equivalence model and TCAD simulated model for different initial air-gaps in a FD-SOI FET is brought out. The influence of FDSOI FET device parameters on sensitivity, namely the variation of TSi, TBox, NA and TGap are explored. CMOS compatibility and fabrication feasibility of this architecture was looked into by resorting to the post processing approach used for validating the sub-threshold bias concept. The IMD layers of the Bulk FETs fabricated through AMS 0.35 technology were etched using BHF and IPA mixture to result in a free standing metal (Al) layers acting as the suspended gate. The performance estimate is carried out considering specific Equivalent Gap Thickness (EGT) of 573 nm and 235 nm, to help overcome the role of coupled electrostatics in influencing the sensitivity metric. The sensitivity observed by biasing this post processed bulk FET in sub-threshold is 114% ( ID=ID change) for a 59% ( d/d change). The equivalent C in this case is 370 aF. b) In Fringe eld based sensing approach, a JunctionLess FET (JLFET) is used as a depletion mode device and an out-of-plane gate displacement would help modulate the device pinch-o voltage due to fringe field coupling. The resulting change in the gate fringe field due to this displacement modulates the drain current of the JunctionLess FET. The displacement induced fringe field change (relative to the FET channel) brings about a distinct shift in the ID-VG characteristics of the JLFET. For displacement d = 2 nm, the JLFET with a channel doping of ND = 8X1018cm 3 and a bias point of VG = -47.7 V, 98% enhancement in sensitivity is observed in 3D TCAD simulations. The equivalent C in this case is 29 zF. The role of ground-planes in the device operation is explored. c) In the tunneling current based sensing approach, the beams fabricated using the SOI-MUMPS process are FIB milled so as to create very ne air gaps of the order of nearly 85 nm. Under high electric fields of the order > 8 MV/cm, the lateral displacement based tunneling sensor offers enhanced change in sensitivity for an induced external force at a fixed DC bias. When integrated as an array with varying electrode overlap, this technique can track displacements over a wide range. With the initial beam overlap as 1.2 m, for a lateral displacement of 1.2 m, a 100% change in sensitivity ( ID=ID) is observed. The effect of fringe field can be completely neglected here unlike its capacitive beam equivalent.