Дисертації з теми "Thick polymers"

In this thesis we develop coarse grained models aiming at understanding physical problems arising from phase transitions which occur at the single molecule level. The thesis will consist of two parts, grossly related to and motivated by the two subjects dealt with above. In the first half, we will focus on critical phenomena in stretching experiments, namely in DNA unzipping and polymer stretching in a bad solvent. In the second part, we will develop a model of thick polymers, with the goal of understanding the origin of the protein folds and the physics underlying the folding ‘transition’, as well as with the hope of shedding some light on some of the fundamental questions highlighted in this Introduction. In the first part of the thesis we will introduce a simple model of self-avoiding walks for DNA unzipping. In this way we can map out the phase diagram in the force vs. temperature plane. This reveals the present of an interesting cold unzipping transition. We then go on to study the dynamics of this coarse grained model. The main result which we will discuss is that the unzipping dynamics below the melting temperature obeys different scaling laws with respect to the opening above thermal denaturation, which is governed by temperature induced fluctuating bubbles. Motivated by this and by recent results from other theoretical groups, we move on to study the relation to DNA unzipping of the stretching of a homopolymer below the theta point. Though also in this case a cold unzipping is present in the phase diagram, this situation is richer from the theoretical point of view because the physics depends crucially on dimension: the underlying phase transition indeed is second order in two dimensions and first order in three. This is shown to be intimately linked to the failure of mean field in this phenomena, unlike for DNA unzipping. In particular, the globule unfolds via a series (hierarchy) of minima. In two dimensions they survive in the thermodynamic limit whereas if the dimension, d, is greater than 2, there is a crossover and for very long polymers the intermediate minima disappear. We deem it intriguing that an intermediate step in this minima hierarchy for polymers of finite length in the three-dimensional case is a regular mathematical helix, followed by a zig-zag structure. This is found to be general and almost independent of the interaction potential details. It suggests that a helix, one of the well-known protein secondary structure, is a natural choice for the ground state of a hydrophobic protein which has to withstand an effective pulling force. In the second part, we will follow the inverse route and ask for a minimal model which is able to account for the basic aspects of folding. By this, we mean a model which contains a suitable potential which has as its ground state a protein-like structure and which can account for the known thermodynamical properties of the folding transition. The existing potential which are able to do that[32] are usually constructed ‘ad hoc’ from knowledge of the native state. We stress that our procedure here is completely different and the model which we propose should be built up starting from minimal assumptions. Our main result is the following. If we throw away the usual view of a polymer as a sequence of hard spheres tethered together by a chain (see also Chapter 1) and substitute it with the notion of a flexible tube with a given thickness, then upon compaction our ’thick polymer’ or ’tube’ will display a rich secondary structure with protein-like helices and sheets, in sharp contrast with the degenerate and messy crumpled collapsed phase which is found with a conventional bead-and-link or bead-and-spring homopolymer model. Sheets and helices show up as the polymer gets thinner and passes from the swollen to the compact phase. In this sense the most interesting regime is a ‘twilight’ zone which consists of tubes which are at the edge of the compact phase, and we thus identify them as ‘marginally compact strucures’. Note the analogy with the result on stretching, in which the helices were in the same way the ‘last compact’ structures or the ‘first extended’ ones when the polymer is being unwinded by a force. After this property of ground states is discussed, we proceed to characterize the thermodynamics of a flexible thick polymer with attraction. The resulting phase diagram is shown to have many of the properties which are usually required from protein effective models, namely for thin polymers there is a second order collapse transition (O collapse) followed, as the temperature is lowered, by a first order transition to a semicrystalline phase where the compact phase orders forming long strands all aligned preferentially along some direction. For thicker polymers the transition to this latter phase occurs directly from the swollen phase, upon lowering T, through a first order transition resembling the folding transition of short proteins.

UV curing is using UV light as the energy source to induce the polymerization of liquid monomers and oligomers to form a solid polymer. Because UV polymerization is fast and energy-saving and a UV curable system has no VOC (volatile organic compound), this new technology has developed rapidly from thin film applications to thick sample applications. In addition, since the UV cure process can be controlled spatially and temporally, it also has an important application to make gradient materials with locally optimized properties. However, most research on UV cure is based on thin film applications, and the cure kinetics of thick samples are more complex and not well understood.;In this study, we focus on the UV cure kinetics of CD540 (ethoxylated (4) Bisphenol-A dimethacrylate) thin and thick samples (2-8 mm). A photo-bleaching initiator, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (Irgacure 819), is used in the system. UV cure kinetics are complex, especially when the sample is thick, since the light intensity is a function of depth and also a function of exposure time. In order to understand the complex cure kinetics of thick samples, we first studied the variation in the transmitted intensity and initiator concentration through the depth in thick samples. Based on the experimental measured transmitted intensity, a Matlab program was written to predict the intensity versus depth and exposure time of a thick sample. Then, the UV cure kinetics of thin samples (0.05 mm) were studied. In this part, we studied the effect of light intensity, initiator concentration, and temperature on the cure kinetics experimentally and theoretically. A model was developed based on a unimolecular termination mechanism in order to predict the cure kinetics at different conditions for thin samples. Combining the Matlab program for calculating the intensity in thick samples and the model for calculating the cure kinetics of thin samples, the cure kinetics through the depth of thick samples were predicted and compared with experimental results measured by frequency dependent dielectric sensing.;The diffusion of free radicals in a UV cure free radical cure system was studied by monitoring the cure in the dark nonirradiated region under a mask. In addition, a free radical thermal cure of an acrylic resin was characterized in order to study oxygen diffusion from the surface layers into deeper layers.

This objective of this project is to develop an understanding of the ink and its interaction with substrate of Penny & Giles controls Ltd's conductive plastic potentiometers, so as to develop alternate ink, substrate and processing methods. Conductive plastic potentiometers comprises, a track containing polymer binder and carbon black, printed on a base plastic substrate. The objectives have to take into account the performance ofthe potentiometers, which are to be improved or maintained. The first stage of the project was concerned with investigating the properties of the carbon black used in the inks, which have a major effect on the performance of the potentiometers. Ten different carbon blacks with different properties were selected. The carbon blacks properties for most of these were characterised by techniques that included transmission electron microscopy, x-ray photoelectron spectroscopy, differential scanning calorimetry, laser induced mass spectrometry and the scanning electron microscope. Inks were made with most of individual carbon blacks, and then tracks were produced on the diallyl phthalate plastic substrate. The electric resistance of these tracks was measured allowing the effect of carbon black properties on performance of the track to be studied. Various carbon black were found to provide similar performance to the Vegetabke MR842N, carbon black used currently. The next stage was the investigation of effect of binder on the performance of resistor using the same techniques as used in the first stage so that comparison could be made with the current binder. A phenolic binder was used and again showed similar properties to the DAIP binder used currently

A busca por membranas com propriedades adequadas a separação de gases em escala industrial tem levado a modificação e sIntese de polImeros de engenharia, com objetivo de obter membranas com propriedades adequadas. Uma das modificaçoes que tem se apresentado promissora é a inserção de grupos sulfônicos em polImeros comerciais. Espera-se que o polImero sulfonado apresente um aumento na permeação de gases polares, em relação a gases apolares, devido a sua estrutura mais polar e flexIvel. Neste contexto, o objetivo do presente trabalho é a sIntese e caracterização de membranas de poli(éter imida) sulfonada para a permeação de gases. Um planejamento experimental foi desenvolvido, em diferentes condiçoes reacionais de temperatura, tempo e excesso de um dos reagentes (ácido acético), para a sIntese de poli(éter imida) sulfonada (SPEI). Através deste planejamento, constatou-se que as variáveis que mais influenciam o grau de sulfonação são a temperatura e o tempo. O polImero com o maior grau de sulfonação, determinado por capacidade de troca iônica (IEC= 92 mEq H+/g), foi utilizado para o preparo da membrana de SPEI, obtida pela técnica de inversão de fase por evaporação do solvente, utilizando-se clorofórmio como solvente. Este filme foi caracterizado a partir das seguintes análises: espectroscopia de infravermelho (FTIR), calorimetria diferencial de varredura (DSC), análise termogravimétrica (TGA) e microscopia eletrônica de varredura (MEV), a fim de avaliar a influência da inserção do grupo sulfônico na matriz polimérica. O espectro de infravermelho de SPEI apresentou bandas relacionadas as vibraçoes assimétricas em 1240 cm-1 (ligação O=S=O), ligação simétrica em 1171 cm-1 (O=S=O) e ligação S-O entre 1010-1024 cm-1. Isto indica a presença de grupos sulfônicos. A análise de DSC foi realizada entre 150-250C. Nesta faixa, não foram observadas alteraçoes na temperatura de transição vItrea (Tg) do polImero modificado (217C). Acredita-se que a decomposição do grupo sulfona aconteça antes da temperatura atingir o Tg do polImero. Esta suposição é confirmada na análise de TGA. As imagens de MEV mostraram que foram obtidos filmes livres de poros e defeitos. A membrana da SPEI foi utilizada no ensaio de permeaçao dos gases 02, N2 e C02, a fim de determinar a permeabilidade e seletividade da membrana. As permeabilidades encontradas para o gas oxigênio foram de 0,76 barrer para a PEI e 0,46 barrer para a SPEI. A seletividade do dióxido de carbono em relaçao ao oxigênio aumentou de 3,5, na membrana de PEI, para 4,83, na membrana de SPEI. Em relaçao ao nitrogênio, as permeabilidades medidas foram 0,064 barrer e 0,043 barrer, para a PEI e para a SPEI, respectivamente, enquanto a seletividade em relaçao ao C02 aumentou de 41,1 para 55,5. Estes resultados indicam que o efeito de sorçao predominou devido ao aumento das interaçöes moleculares, reduzindo assim o volume livre, o que tornou a membrana sulfonada mais compacta, com permeabilidade menor e maior seletividade. Estes resultados corroboram com a premissa de que a sulfonaçao é um processo promissor para o desenvolvimento de membranas mais eficientes.
The search for membranes with suitable properties for gas separation in industrial scale has led to the modification and synthesis of engineering polymers with the purpose of obtaining membranes with superior properties. 0ne of the modifications that have been considered promising is the insertion of sulfonic groups in commercial polymers. Due to its structure more polar and flexible, it is expected that the sulfonated polymer present an increase in polar gas permeation in relation to nonpolar gases. In this context, the objective of this work is the synthesis and characterization of membranes of poly (ether imide) sulfonated for the permeation of gases. An experimental design was developed in different reaction conditions of temperature, time and an excess of one of the reagents (acetic acid), for the synthesis of poly (ether imide) sulfonated, SPEI. Through this planning, it was found that the variables that most influenced the degree of sulfonation are temperature and time. The polymer with the highest degree of sulfonation, by ion exchange capacity (IEC = 92 mEq H+ I g), was used to prepare SPEI membrane obtained by the technique of solvent evaporation, using chloroform. This film was characterized from the following analysis: infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and scanning electron microscopy (SEM) to evaluate the influence of insertion of the sulfonic group in the polymer matrix. The infrared spectrum showed bands of SPEI related to asymmetric vibrations at 1240cm- 1 (S = 0 = 0), in symmetric stretch at 1171 cm-1 (0 = S = 0) and S0 stretch between 1010-1024cm-1. This indicates the presence of sulfonic groups. The DSC analysis was carried out between 150-250C. In this range, there are no significant changes in glass transition temperature of the modified polymer (217C). It is believed that the decomposition of the sulfone group occurs before the temperature reaches the Tg of the polymer. This assumption is confirmed in the TGA analysis. The images of SEM showed that films were obtained free of pores and defects. The membrane SPEI obtained by the technique of solvent evaporation, was used for testing permeation of gases 02, N2 and C02 in order to determine the permeability and selectivity of the membrane. The permeabilities found for oxygen were 0.76 barrer for PEI and 0.46 barrer for SPEI. The selectivity of carbon dioxide relative to oxygen increased from 3.5 to 4.83. Regarding nitrogen, the permeability measurements were 0.064 barrer and 0.043 barrer for the PEI and the SPEI, respectively, while the selectivity relative to C02 increased from 41.1 to 55.5. These results indicate that the predominant effect of sorption due to increased molecular interactions, thus reducing the free volume, made the membrane sulfonated more compact with lower permeability and higher selectivity. These results agree with the premise that the sulfonation is a promising process for the development of more efficient membranes.

Communication systems at microwave and millimetre wave regimes require compact broadband high gain antenna devices for a variety of applications, ranging from simple telemetry antennas to sophisticated radar systems. High performance can usually be achieved by fabricating the antenna device onto a substrate with low dielectric constant or recently through micromachining techniques. This thesis presents the design, fabrication, assembly and characterisation of microstrip and CPW fed micromachined aperture coupled single and stacked patch antenna devices. It was found that the micromachining approach can be employed to achieve a low dielectric constant region under the patch which results in suppression of surface waves and hence increasing radiation efficiency and bandwidth. A micromachining method that employs photolithography and metal deposition techniques was developed to produce high efficiency antenna devices. The method is compatible with integration of CMOS chips and filters onto a common substrate. Micromachined polymer rims (SU8 photoresist) was used to create millimetre thick air gaps between the patch and the substrate. The effect of the substrate materials and the dimensions of the SU8 polymer rims on the performance of the antenna devices were studied by numerical simulation using Ansoft HFSS electromagnetic field simulation package. The antenna structures were fabricated in layers and assembled by bonding the micromachined polymer spacers together. Low cost materials like SU8, polyimide and liquid crystal polymer films were used for fabrication and assembly of the antenna devices. A perfect patch antenna device is introduced by replacing the substrate of a conventional patch antenna device with air in order to compare with the micromachined antenna devices. The best antenna parameters for a perfect patch antenna device with air as a substrate medium are ~20% for bandwidth and 9.75 dBi for antenna gain with a radiation efficiency of 99.8%. In comparison, the best antenna gain for the simple micromachined patch antenna device was determined to be ~8.6 dBi. The bandwidth was ~20 % for a microstrip fed device with a single patch; it was ~40 % for stacked patch devices. The best bandwidth and gain of 6.58 GHz (50.5%) and 11.2 dBi were obtained for a micromachined sub-array antenna device. The simulation results show that the efficiency of the antenna devices is above 95 %. Finally, a novel high gain planar antenna using a frequency selective surface (FSS) was studied for operation at ~60 GHz frequency. The simulation results show that the novel antenna device has a substantial directivity of around 25 dBi that is required for the emerging WLAN communications at the 60 GHz frequency band.

Carbon fibre reinforced polymer, or CFRP composite materials, play an increasingly important role in modern manufacturing. They are widely used in aerospace, and their use is currently spreading to other industries where high strength-to-weight ratios are required. However, machining of composites is still a challenging task and often hampered by poor quality. Despite the extensive research that was conducted on the machining of composite materials over the last few years, mechanical drilling still suffers from delamination, fibre pull-out and poor surface finish, whereas laser cutting produces microstructured defects and a taper problem. This thesis reports on the drilling of CFRP composites by demonstrating the possibility of drilling small diameter holes (i.e. 8mm) into 25.4mm thick carbon fibre reinforced polymer composites (CFRPs) using mechanical drilling and laser drilling as stand-alone processes and as a sequential combination. The research involved four main phases of experimental testing. The first part of Phase 1 involved!preliminary experiments of drilling thick CFRP to identify the most suitable drilling strategy. Three mechanical drilling strategies conducted in the same parameter by using a 2-flute uncoated WC twist drill that was assessed with respect to feasibility of drilling thick CFRP. The results showed that the single-step strategy was the most feasible strategy to drill thick CFRP compared to 2- and 4-peck drilling strategies. The second part of Phase 1 concerned the influence of speed-feed combinations on hole quality by utilising three twist drills with different materials and geometries in both an uncoated and coated condition. The results indicated that a significant increase in peel-up delamination was found with increasing feed rate. In contrast, using a constant feed rate but increasing the spindle speed seemed to reduce peel-up delamination. Furthermore, the hole entry for 2-flute uncoated WC drill bits was an uncommon study finding because most of the previous researchers experienced more damages at the hole exit and their investigation focused on the hole exit only. Currently, implementation of laser technology in cutting and drilling composites is becoming popular as an alternative solution. Various experiments were conducted with the goal of identifying the effects of machining parameters on key output measures (i.e. heat affected zone (HAZ), hole depth and other damages) in drilling of 25.4 mm thick CFRP by using a fibre laser. Phase 2 involved a number of machining parameters selected to identify the potential of a fibre laser in drilling thick CFRP composites (i.e. laser power, scanning speed, focal point plane position (FPP), assisted-gas type and gas pressure). The results proved that a fibre laser could penetrate thick CFRP to a 22mm depth only. Moreover, the spiral trepanning strategy was able to penetrate 80% out of the total thickness of the CFRP in continuous wave (CW) mode, whereas the modulated laser beam (i.e. laser pulse mode) can penetrate 67% only. This result was a major recorded breakthrough because previous research attempts cut up to 5mm only. Laser power proved to be the most influential factor for hole depth in laser drilling of thick CFRP when the spiral trepanning strategy was applied. Machining trials were conducted in Phase 3 by using a 16kW fibre laser in modulated pulsed laser mode. In this phase, laser power of more than 1kW was attempted to cut the whole thickness of CFRP composites in CW mode, but it was unsuccessful. However, a new parameter was discovered (i.e. the cooling time between passes in modulated pulsed mode), which proved a considerable reduction of HAZ when the higher cooling time was imposed. Finally, phase 4 involved the experiments of sequential laser-mechanical drilling. A 1kW fibre laser was selected as a pre-drilling or initial step and followed by mechanical drilling as the final step. The sequential drilling method successfully reduced thrust force and torque for mechanical drilling by an overall average of 61%, resulting in high productivity and decreasing the thermal and mechanical stresses in the cutting tool and, in turn, promoting higher tool life. The highest delamination factor (Fda) ratio was experienced by the sequential laser 8mm – mechanical 8mm for both tools (i.e. 2- and 3-flute uncoated tungsten carbide) and laser pre-drilling strategies (i.e. single- and double-side). Thus, a novel laser-mechanical sequential drilling technique was developed, evaluated and tested in the drilling of thick CFRP composites; this is the first time ever in drilling thick CFRP (i.e. 25.4mm).

This thesis describes a study into the development of an optimum material and fabrication process for the production of thick film pH electrodes. These devices consist of low cost, miniature and rugged pH sensors formed by screen printing a metal oxide bearing paste onto a high temperature (-850 °C) fired metal back contact supported on a standard alumina substrate. The pH sensitive metal oxide layer must be fabricated at relatively low temperatures (<300 °C) in order to maintain the pH sensitivity of the layer and hence requires the use of a suitably stable low temperature curing binder. Bespoke fabricated inks are derived from a Taguchi style factorial experimental plans in which, different binder types, curing temperatures, hydration level and percentage mixtures of different metal oxides and layer thicknesses were investigated. The pH responses of 18 printed electrodes per batch were assessed in buffer solutions with respect to a commercial reference electrode forming a complete potentiometric circuit. The evaluation criteria used in the study included the device-to-device variation in sensitivity of the pH sensors and their sensitivity variation as a function of time. The results indicated the importance of the choice of binder type in particular on the performance characteristics. Reproducible device-to-device variation in sensitivity was determined for the best inks found, whatever the ink fabrication batch. A reduction in the sensitivity variation with time has been determined using the mathematical models derived from an experimental plan. The lack of reproducibility of the sensitivity magnitude, regardless of the ink manufacturing batch, seems to be a recurrent problem with prototype inks. Experimental sub-Nernstian responses are discussed in the light of possible pH mechanisms.

The research described in this doctoral thesis work was mainly focused towards the low pressure inductively excited PECVD of organic precursors for biomaterials. An open air atmospheric pressure DBD plasma jet was also studied for the antifouling applications. Systematic studies were carried out in order to optimize the deposition of plasma polymerized (PP) coatings which were deposited at different process parameters for biomedical applications. The optimized amphiphilic PFDA-DEGVE coatings, presented no adhesion with respect to BSA as well as Lysozyme proteins. The plasma processing parameters were optimized using DoE methodology. By adjusting the process parameters, the chemical compositions of the PCL- PEG coatings were tailored to be cell adherent, convenient for biomedical implants such as artificial skin substrates, or cell repellent which could be used for antibiofouling surfaces for urethral catheters, stents etc. Multilayer biodegradable coatings based on PCL- PEG polymers were successfully used for controlled delivery of anticancer drug and tested in vitro. PP Poly (2-ethyl 2-oxazoline), having a peptidomimetic structure was deposited by LP. Such polymers are considered to be a prime candidate for an alternative of PEG like surfaces for antibiofouling applications. The last chapter was devoted to open air AP argon plasma jet. The deposited PEG coatings had 56. 3% of ether functions and were cell repellent as compared to a positive control (PS). This study has shown the capability of plasma processes for the deposition of (co-) polymer coatings with tailorable surface chemical compositions, with considerable promises for the variety of biomedical applications
Les recherches effectuées dans cette thèse se concentrent essentiellement sur la PECVD par plasma basse pression à partir de précurseurs organiques pour la synthèse de biomatériaux. Un procédé à jet de plasma hors équilibre à couplage DBD a aussi été développé pour élaborer des surfaces anti-bioadhésives. Les conditions opératoires ont été optimisées afin de pouvoir répondre à plusieurs applications biomédicales. Des copolymères amphiphiles à base de PFDA-PEG, élaborés et optimisés par des plans d’expériences, n’ont montré aucune adhésion vis à vis des protéines BSA et Lysozyme. Les polymères PCL-PEG ont aussi été étudiés, et les différentes compositions ont permis d’obtenir soit de bonnes propriétés d’adhésion cellulaire, permettant ainsi d’envisager des applications en ingénierie tissulaire, soit des surfaces anti-bioadhésives, intéressantes pour élaborer des cathéters ou des stents. Les copolymères PCL-PEG déposés en multicouches ont permis de contrôler les cinétiques de relargage de médicaments et de réaliser des tests in vitro. Nous avons aussi travaillé sur le remplacement des PEG en déposant un polymère mimant la structure des peptides ; le polyoxazoline. Les résultats obtenus ont donné de bonnes propriétés anti-fouling. Enfin, des surfaces anti-bioadhésives ont été élaborées par PECVD à pression atmosphérique. Les résultats obtenus ont montré une rétention des fonctions éthers de 56. 3% et les surfaces correspondantes repoussent les cellules. En conclusion, les travaux menés au cours de cette thèse ont montré que les procédés plasma permettent de déposer des (co)polymères permettant de répondre à une large palette d’applications dans le domaine biomédical

Biosensors have a multitude of important applications in basic research, environmental monitoring, biodefense, and medicine. This research aims to show that Ionic Self-Assembled Multilayers (ISAMs) adsorbed on Long Period Gratings (LPGs) can serve as a highly sensitive, robust, inexpensive optical-based biosensor platform. The ISAM technique is a layer-by-layer deposition method that builds nanometer-thick films based on the principle of Coulomb attraction between oppositely charged polyelectrolyte solutions while LPGs cause strong attenuation bands that enable an optical fiber to be extremely sensitive to changes in the surrounding environment. LPGs have been shown to be highly sensitive to the adsorption of nanoscale self-assembled films on the optical fiber cladding surface. In this work, we utilize Turnaround Point (TAP) LPGs, which possess even greater sensitivity than standard LPGs. This thesis focuses on evaluation of approaches to increasing the sensitivity of the sensor platfom, implementation of a biosensor for detection of several biomolecules, and preliminary evaluation of the potential for pH sensing. For a thin-film coated TAP LPG, we have demonstrated that shifts in the transmitted light intensity at the resonant wavelength of the LPG can result from the variation in film thickness and/or refractive index. We have observed decreases in intensity as large a 7 dB for one bilayer of ISAM film (~1 nm), which corresponds to an 80% decrease in the transmitted light intensity at the resonant wavelength. We have also shown that the sensitivity of the TAP LPG sensor can be increased by implementing nm-thick ISAM films that have a refractive index greater than silica. Furthermore, it is shown that incorporation of silica nanoparticles into the ISAM films significantly increases sensitivity through increased surface area and thickness. The biotin-streptavidin system was used as a model for implementaion and optimization of the ISAM-coated TAP LPG biosensor platform. Through evaluation of various biotin derivatives to maximize the amount functionalized onto the ISAM film, optimization of the ISAM film properties, and use of LPGs designed for higher sensitivity, the minimum detectable concentration of streptavidin was decreased from 0.0125 mg/ml to 12.0 ng/ml. The biosensor platform was then tested on prostate specific antigen (PSA), which is used as a clinical marker for early diagnosis of potential prostate cancer. Using a direct crosslinking approach of the monoclonal antibody to PSA into the ISAM film, a sensitivity level of 11.64 ng/ml PSA was obtained through combined optimization of the ISAM film and antibody surface coverage. Finally, the potential of ISAM TAP LPGs as pH sensors was examined based on the pH dependent swelling of ISAM films.
Ph. D.

Cette thèse de doctorat porte sur l'étude et la réalisation d'une plateforme de pesage dynamique pour véhicule roulant basée sur un concept d'intégration de la charge. Ce concept est mis en œuvre en vue de pouvoir minimiser la taille et l'encombrement de ce type de dispositif tout en effectuant des pesées présentant des caractéristiques métrologiques acceptables. Nous démontrons tout d'abord au travers de la réalisation d'un prototype et de plusieurs campagnes d'essais, la faisabilité de la méthode utilisée. Nous évaluons dans un deuxième temps les performances présentées par le prototype lors du pesage de véhicules légers roulant jusqu'à des vitesses de 35km/h. Une étude est ensuite menée sur les jauges de déformation piézorésistives et les jauges piézoélectriques réalisées en couches épaisses grâce à des techniques de sérigraphie. Nous caractérisons ces transducteurs avec pour objectif leur utilisation dans des dispositifs de pesage en remplacement des jauges de déformation classiques à filaments métalliques
This PhD thesis is devoted to the study and implementation of a weigh-in-motion platform for vehicle based on a concept of integration of load. This concept is used to minimize the size of this kind of device while performing weighings with acceptable results. First, we show thanks to a protoype and several test campagns, the feasability of the method used. In a second time, we evaluate the performances of the prototype in terms of precision and repeatability with the dynamic weighing of vehicles at speeds up to 35km/h. A study is finally conducted on thick-film piezoresitive strain gauges and piezoelectric gauges manufacturing by a screen-printing process with cermet and polymer pastes. We characterize these tranducers with the goal of used them as an alternative of conventional foil strain gauges

Avec la demande sans cesse renouvelée de matériaux éco-compatibles pour l’électronique de demain, les polymères conducteurs se sont imposés comme une alternative intéressante aux matériaux déjà existants. Ils doivent leur popularité principalement à leurs propriétés électriques, optoélectroniques, thermo-chromiques, luminescentes et mécaniques, couplées à leur bonne processabilité et leur faible impact environnemental. Parmi eux, le poly(3,4-ethylenedioxythiophene) (PEDOT) est certainement le plus connu est le plus utilisé. De nombreuses études se sont focalisées sur l’optimisation de sa conductivité électrique et des progrès remarquables ont été réalisés. Cependant, la compréhension fine de la relation structure/propriétés de ce matériau reste à élucider. C’est ainsi que dans le cadre de cette thèse nous avons décidé de plusieurs objectifs qui sont (1) la synthèse de PEDOT hautement conducteurs à structure contrôlée et optimisée, (2) l’étude des propriétés électriques, structurales et de transport électroniques dans ces PEDOT, (3) l’étude de leurs propriétés thermoélectriques et (4) l’étude de leur stabilité sous différentes conditions afin de valider leurs potentielles applications. Ainsi, après une revue de la littérature sur le PEDOT, nous étudions l’amélioration de la conductivité électrique du PEDOT:OTf et du PEDOT:Sulf, qui atteint dorénavant des valeurs à hauteur de 5400 S cm-1. Différentes techniques de caractérisation nous ont permis de mener une étude exhaustive de leurs propriétés électriques et structurales ainsi que des mécanismes de transport électronique qui en découlent. Nous nous sommes ensuite intéressés à deux de leurs propriétés thermoélectriques, l’effet Joule et l’effet Seebeck, le premier pour des applications en chauffage et le deuxième pour la récupération d’énergie. L’utilisation pour la première fois du PEDOT comme film chauffant flexible transparent est d’ailleurs présentée. On démontre par exemple que PEDOT:Sulf présente une résistance carrée de 57 Ω sq-1 pour 87.8 % de transparence et qu’une température de 138 °C peut être atteinte lorsqu’on applique 12 V. Cette thèse se conclut sur l’étude de la stabilité de nos matériaux de PEDOT sous différentes atmosphères ainsi que l’étude des mécanismes de dégradation
With the rising demand of flexible, low cost and environmentally friendly materials for future technologies, organic materials are becoming an interesting alternative to already existing inorganic ones. Organic photovoltaics, organic light emitting diodes, organic field effect transistors, organic thermoelectricity, organic transparent electrodes are all evidences of how organic materials are sought for tomorrow. Materials which can fulfill the requirements specifications of future technologies are conducting polymers, which owe their popularity to their outstanding electrical, optoelectronic, thermochromic, lighting and mechanical properties. Moreover, they exhibit good processability even on flexible substrates and low environmental impact. Poly(3,4-ethylenedioxythiophene) (PEDOT) is certainly the most known and most used conducting polymer because it is commercially available and shows great potential for organic electronics. Studies dedicated to PEDOT films have led to high conductivity enhancements. However, an exhaustive understanding of the mechanisms governing such enhancement is still lacking, hindered by the semi-crystalline nature of the material itself. In such a context, this thesis has four objectives which are (1) the synthesis of PEDOT materials with an optimized and controlled structure to enhance the electrical properties, (2) the thorough characterization of the as-synthesized PEDOT in order to understand the charge transport mechanisms, (3) the study of their thermoelectric properties and (4) the study of their stability under different environments and stresses. Thus, after a literature review on PEDOT materials, we present the enhancement of the electrical conductivity of PEDOT:OTf and PEDOT:Sulf up to 5400 S cm-1 via a structure and dopant engineering, and then thoroughly study their electrical and electronic transport properties. Subsequently, two thermoelectric properties of PEDOT are investigated, namely its resistive Joule heating ability and its Seebeck effect, for both heating and energy harvesting applications. A novel application of PEDOT as flexible transparent heater is demonstrated in the first case. PEDOT:Sulf for example exhibited a sheet resistance of 57 Ω sq-1 at 87.8 % transmittance and reached a steady state temperature of 138 °C under 12 V bias. Finally, this thesis is concluded with the ageing and stability of our PEDOT based materials under different environmental stresses. While PEDOT is stable under mild conditions, heavy degradations can occur under harsh conditions. The degradation mechanisms are then investigated in this last part

This thesis describes optimization and modification of standard thick-film electrochemical sensor to be able to be used for detection in microvolumes. In the theoretical part, the thick film technology is described. The work is then focused on the wettability of surfaces followed by introduction to electrochemistry and electro-analytical methods. In the experimental part, screen-printing of various types of thick film pastes on ceramic substrates for determination of their wettability and the following modification of the sensors with thick-film paste and with Parylene vaporization can be found, as well as the basic electrochemical measurements in microvolume using the modified sensor. Finally the results are summarized in conclusion.

L’amélioration des systèmes électroniques pour le déploiement de l'avion tout électrique dépend de la capacité des composants passifs, tels que les condensateurs, à réduire leur volume, leur masse et leur coût, et augmenter leurs performances et leur fiabilité, particulièrement dans l’environnement aéronautique. Dans ce contexte, cette thèse a eu pour objectif l’étude et le développement de nouvelles technologies de condensateurs pour des applications avioniques. Dans la première partie des travaux, nous abordons l’évaluation de condensateurs céramique de puissance. La technologie céramique constitue, en effet, l’une des rares solutions matures capables de répondre aux exigences des équipementiers. La caractérisation, l’analyse des mécanismes de défaillance, de leurs effets et de leur criticité (AMDEC) ainsi que l’étude de fiabilité et de robustesse de composants commerciaux présentant des architectures originales (condensateurs multi-chips) ont été réalisées. Ces résultats ont été complétés par une étude plus amont sur la caractérisation de céramiques frittées par frittage flash (SPS). Les permittivités colossales de ces matériaux permettraient d’accroitre la fiabilité et la miniaturisation des condensateurs tout en conservant de fortes valeurs de capacité et de tension nominale. La seconde partie, plus fondamentale, a été consacrée au développement de nanoparticules céramique/polymère coeur-écorce pour des applications de condensateurs enterrés, opérant aux radiofréquences. La synthèse et les caractérisations physico-chimiques des nanocomposites ainsi que les procédés de fabrication de condensateurs en couches épaisses sont, en premier lieu, décrits. Une méthode de caractérisation électrique large bande a été mise au point pour permettre l’analyse des propriétés diélectriques et des mécanismes de conduction des nanoparticules. Les performances des dispositifs ont été recherchées en fonction de la température et des procédés de mise en forme. En outre, la durabilité en température de ces derniers a été évaluée
The improvement of electronic systems for the deployment of all-electric aircrafts depends on the ability of passive components, such as capacitors, to reduce their volume, weight and cost, and to increase their performance and reliability, particularly in the aeronautical environment. In this context, the objective of this thesis was to study and develop novel capacitor technologies for avionics. In the first part of this work, the evaluation of power ceramic capacitors has been discussed. Indeed, the ceramic technology appeared to be one of the few mature solutions meeting the requirements of OEMs. The characterization, the failure mode, effects and criticality analysis (FMECA) and reliability and robustness assessment of commercial components using original architectures (multi-chip capacitors) have been performed. These results have been completed by a more advanced study on the characterization of new ceramics sintered by spark plasma sintering (SPS). The colossal permittivity of these materials could allow to increase reliability and miniaturization of capacitors while maintaining high values of capacitance and voltage rating. The second part, more fundamental, is devoted to the development of core-shell ceramic/polymer nanoparticles for embedded capacitors operating at radiofrequencies. The synthesis and the physicochemical characterization of the nanocomposites as well as the manufacturing processes of the thick film capacitors are first described. A new broadband electrical characterization methodology has been developed to analyze the dielectric properties and the conduction mechanisms of the nanoparticles. The effects of the temperature and the manufacturing process on the device performance have been investigated. In addition, the durability was evaluated

Dans le domaine moléculaire, les polymères sont observés et étudiés par microscopie. Les formes obtenues sont souvent imprécises en raison de l'effet de convolution et de diffraction de l'acquisition par microscopie. Par conséquent, le polymère apparait comme une courbe épaisse, bruitée et floue. Pour étudier les caractéristiques d'une chaîne de polymère, une des approches possibles consiste à réduire la forme acquise par microscope à une représentation minimale, soit une courbe. Cette dernière doit représenter au mieux l'objet étudié malgré les différentes difficultés rencontrées telles que la qualité des images ou les imprécisions dues à la discrétisation. De plus, un polymère adopte un mouvement "Reptilien" et peut former des géométries complexes telles que des courbes fermées ou avec boucles. L'objet de cette thèse est donc l'extraction de courbes visant à fournir une représentation minimale des polymères à des fins d'analyse. La méthode que nous proposons comprend deux grandes étapes à savoir : L'extraction des géodésiques et leur fusion. La première étape consiste à calculer un ensemble de géodésiques, chacune parcourant une partie distincte de la forme. Ces morceaux de géodésiques sont fusionnés dans la seconde étape afin de générer la courbe complète. Afin de représenter la reptation, les géodésiques doivent être fusionnées dans un ordre précis. Nous modélisons ce problème par graphes et nous cherchons l'ordre de fusion en parcourant le graphe. La fusion est effectuée selon le chemin optimal minimisant différentes contraintes
In the molecular field, polymers are observed and studied by microscopy. The shapes obtained are often inaccurate because of the convolution and diffraction effect of microscopy. Therefore, the polymer appears as a thick, noisy and fuzzy curve. In order to study a polymer chain, one of the possible approaches consists in reducing the acquired shape to a minimal representation, ie a curve. This curve must represent the studied object in the best way, despite the various encountered difficulties, such as the quality of the images or inaccuracies due to discretization. In addition, a polymer performs a "Reptilian" movement and can form complex geometries such as closed and looped curves. The object of this thesis is, therefore, the extraction of curves aimed at providing a minimal representation of the polymers for analysis. The proposed method comprises two major steps: geodesics extraction and their fusion. The first step is to compute a set of geodesics, each one traversing a distinct part of the shape. These pieces of geodesics are fused in the second step to generate the complete curve. In order to represent the reptation, the geodesics have to be merged in a precise order. We model this problem by graphs and consider the fusion as a graph traversal problem. The fusion is performed according to the optimal path minimizing various constraints

碩士
明志科技大學
機電工程研究所
97
In this paper we apply an inclined-exposure technology and a special design inclined-exposure aiming system to make a new optical micro-structure and replace the traditional mechanical extra work or injection molding optical component. The thick-film negative photoresist SU-8 was used in the experiment, because the polymer material have the feature of stronger and not easy to be changed shape in high temperature (~100°C). At the mean time, using inclined-exposure mechanism to help the angle accuracy to ±30’, and lower the surface roughness to in 300μm×300μm range. The structure of micro reflective mirror is using polymer material with a 1.4mm high micro structure, which is made by low spin and surface tension. In order to resolve the diffraction phenomenon bringing from the non flatness of thick-photoresist, we apply the material, which has the same refractove index as photoresist, to fill in between mask and photoresist, and make use of filter to filter out the UV light, which is lower than 365nm to improve the non parallel structure caused by the difference of the penetration depth of different wavelength. In this research we also developed the anti-reflection technology, and used Fresnel equation to solve the problem of second reflection from substrate surface caused by inclined-exposure. In order to deal with the difficulty of coating on micro mirror, we used optical UV tape as the material when coating and making a pair of mirror group, inaccuracy of shift can be reduced to 60μm-80μm. If this technology could be successfully developed, it can help to improve the design and fabricate of optical pick-up device.