<p>Strukturiranje elastomernih kompozita dodavanjem različitih vrsta nanopunila je dovelo do značajnog pobolj&scaron;anja njihovih primenskih svojstava, a samim tim i do povećanja njihove potencijalne primene kao pogodnih materijala za specijalne namene. U ovom radu, dobijene su dve grupe elastomernih hibridnih materijala za specijalne namene (na osnovu stirenbutadienskog elastomera i na osnovu termoplastičnih poliuretana).<br />U prvom delu istraživanja, veliki doprinos u razvoju industrije gume je postignut strukturiranju stirenbutadienskih nanokompozita primenom nanočestica punila silicijum(IV)oksida različitih morfolo&scaron;kih svojstava, dobijenih hidrotermičkom i termičkom obradom, primenom tri eksperimentalno modelovana punila silicijum(IV)oksida (dobijena taloženjem iz Na-vodenog stakla sa sumpornom kiselinom), kao i hibridnog punila (kombinacije čestica aktivne čađi i SiO₂ optimalnih svojstava). Izvr&scaron;ena je analiza uticaja strukture, povr&scaron;ine i povr&scaron;inske aktivnosti nanopunila na ojačanje elastomera, kao i provera koncepata, modela i teorija ojačanja na neumreženim i umreženim sistemima stirenbutadienskih elastomera ojačanih modifikovanim punilima SiO₂. Primenom mnogobrojnih metoda karakterizacije, sveobuhvatno je ispitan uticaj nanopunila na karakteristike me&scaron;anja, reolo&scaron;ka svojstva pripremljenih hibridnih nanokompozita, sposobnost umrežavanja u neumreženom materijalu, kao i na toplotna, dinamičko-mehanička i mehanička svojstva umreženih nanokompozita, radi projektovanja i optimizovanja sastava SBR hibridnih materijala za razvoj modelnog protektora sa optimalnim svojstvima za ekolo&scaron;ke ili &quot;zelene pneumatike&quot;. Drugi deo istraživanja je bio posvećen dobijanju segmentiranih poliuretanskih elastomernih nanokompozita primenom alifatičnih polikarbonatnih diola i nanočestica bentonita, koji nalaze primenu u medicini, građevinarstvu, u industriji name&scaron;taja i sportske opreme. Primenom mnogobrojnih metoda za karakterizaciju, ispitan je složen mehanizam uticaja tvrdih segmenata, termodinamičke nekompatibilnosti i prisustva nanočestica punila bentonita na strukturu i morfologiju, kao i na toplotna i dinamičko-mehanička svojstva pripremljenih poliuretanskih termoplastičnih elastomera. Dobijeni podaci o obrazovanju vodoničnih veza, termičkoj stabilnosti i termičkoj dekompoziciji, kao i o temperaturama prelaska u staklasto stanje i oblasti raskidanja čvorova fizičkih veza, predstavljaju značajan doprinos napretku strukturiranja poliuretanskih elastomera i nanokompozita na osnovu alifatičnih polikarbonatnih diola, i omogućavaju primenu ovih materijala za specijalne namene.</p> / <p>The structuring of elastomeric composites by addition of different nanofillers has led to a significant improvement of their end-use properties, and therefore, to their potential application as suitable materials for special applications. In this work, two types of elastomeric hybrid materials for special purposes were obtained (based on styrene-bustadiene elastomer or on segmented thermoplastic polyurethanes).<br />In the first part of the study, a major contribution to the development of the rubber industry was achieved by structuring styrene-butadiene nanocomposites, applying silica nanoparticles of various morphological properties: prepared by hydrothermal or thermal treatment, three experimentally prepared SiO2 fillers (obtained by precipitation from sodium silicate with sulfuric acid), as well as a hybrid filler (combination of carbon black and SiO2 fillers with optimal properties). The analysis of the influence of the nanoparticles structure, surface and surface activity on the reinforcment of SBR elastomers, as well as the verification of concepts, models and reinforcement theories on non-cross-linked and cross-linked systems of styrene-butadiene nanocomposites was performed. Using the numerous characterization methods, the influence of nanofillers on the mixing characteristics, the rheological properties of the prepared hybrid nanocomposites, as well as the thermal, dynamic-mechanical and mechanical properties of cross-linked SBR nanocomposites was studied, in order to design and optimize the composition of SBR hybrid materials for development of environmental friendly or &quot;green&quot; tyre protector model.<br />The second part of the research was devoted to the preparation of segmented polyurethane elastomeric nanocomposites using aliphatic polycarbonate diols and bentonite nanoparticles, that have found the significant application in the medicine, construction, the furniture and sports equipment industry. Applying numerous characterization methods, a complex mechanism of the influence of the hard segments, thermodynamic incompatibility and the presence of bentonite filler on the structure and morphology, as well as on the thermal and dynamic-mechanical properties of the synthesized thermoplastic elastomers was studied. The obtained data on the hydrogen bonds formation, thermal stability and thermal decomposition, as well as the glass transition temperature and physical crosslink disruption temparature range, makes a significant contribution to the progress in structuring of polycarbonate-based polyurethane elastomers and their hybrid materials, and improves their potential applications for the special purposes.</p>

<p>U ovom radu, sintetisani su poli(uretan-izocijanuratni) elastomeri sa kovalentnim<br />čvorovima, katalitičkom ciklotrimerizacijom teleheličnih diizocijanata kao prekursora mreže<br />na osnovu 2,4-toluen-diizocijanata, &alpha;,&omega;-dihidroksipoli(oksipropilen)diola i monoola<br />dietilenglikolmonometiletra. Dobijeni su i termoplastični segmentirani poliuretani, sa<br />čvorovima fizičkog umreženja, jednostepenim postupkom i metodom prepolimerizacije,<br />reakcijom dve vrste alifatskog polikarbonatnog diola, koji se razlikuju u strukturi lanca,<br />heksametilen-diizocijanata i produživača lanca (1,4-butandiola). Sintetisana je i serija<br />poliuretanskih hibridnih materijala, dodatkom 1% <em>m/m</em> nanočestica organski modifikovanih<br />glina (montmorilonita i bentonita). Prioritet rada je bio da se utvrdi uticaj udela elastično<br />aktivnih i visećih lanaca na dinamičko-mehanička svojstva, toplotnu stabilnost i svojstva<br />prigu&scaron;enja poliuretanskih mreža sa izocijanurat (heksahidro-1,3,5-triazin-2,4,6-trion)<br />prstenovima, kao čvorovima. Takođe, cilj istraživanja je bio da se ispita uticaj odnosa<br />reaktivnih grupa diizocijanata, polikarbonatne komponente i produživača lanca, kao i dodatka nanočestica na svojstva povr&scaron;ine, morfologiju, dinamičko-mehanička i toplotna svojstva segmentiranih neojačanih i ojačanih elastomera. Toplotna degradacija poli(uretanizocijanuratnih) mreža i segmentiranih termoplastičnih poliuretana praćena je neizotermskim ispitivanjima, koristeći istovremenu termogravimetrijsku i masenu analizu (TG-MS), kao i istovremenu termogravimetriju i diferencijalno skenirajuću kalorimetriju (TG-DSC). Viskoelastična svojstva i svojstva prigu&scaron;enja dobijenih poliuretanskih elastomera su ispitivana pomoću dinamičko-mehaničke analize (DMA). Toplotno pona&scaron;anje segmentiranih poliuretana i nanokompozita, dobijenih jednostepenim postupkom sinteze, je proučavano modulovanom diferencijalno skenirajućom kalorimetrijom (MDSC). Temperatura prelaska u staklasto stanje i termoplastična svojstva neojačanih i ojačanih poliuretanskih materijala, dobijenih postupkom prepolimerizacije, određeni su primenom diferencijalno skenirajuće kalorimetrije (DSC). Hemijska struktura i formiranje vodoničnih veza dobijenih elastomera proučavane su koristeći Furijeovu transmisionu infracrvenu spektroskopiju (FTIR). Uticaj udela tvrdih segmenata na morfologiju i svojstva povr&scaron;ine segmentiranih poliuretana, ispitivan je pomoću mikroskopije atomskih sila (AFM). Stepen kristalnosti uzoraka i dispergovanje nanočestica u dobijenim hibridnim materijalima su odre&ntilde;eni primenom metode rasipanja X-zraka pod &scaron;irokim uglom (WAXS).</p> / <p> In this work, poly(urethane-isocyanurate) elastomers, with covalent junction points,<br /> were synthesized by catalytic cyclotrimerization of telechelic diisocyanates as network<br /> presursors based on 2.4-tolylenediisocyanate, a,w,dihydroxypoly(oxypropylene) and monool<br /> component 2-(2-metoxyetoxy)ethanol. Thermoplastic polyurethanes, with physical<br /> crosslinking, were obtained by one-step technique and pre-polimerization method, using two<br /> aliphatic polycarbonate diols (differening in chain constitution), hexamethylene-diisocyanate<br /> and chain extender (1,4-butane diol) as reactive components. One serie of polyurethane<br /> hybrid materials was prepared by addition of 1 wt. % of organically modified clay<br /> nanoparticles (bentonite and montmorillonite). The goal of this work was to investigate the<br /> influence of elastically active and dangling chains content on thermal stability, dynamic<br /> mechanical and damping properties of polyurethane networks with heat-resistant<br /> isocyanurate-(hexahydro-1,3,5-triazin-2,4,6-trion) rings, as crosslinks. The aim was also to<br /> determine the influence of diisocyanate, macrodiol and chain extender reactive groups&rsquo; ratio<br /> and nanoparticles addition on surface properties, morphology, dynamic mechanical and<br /> thermal properties of obtained segmented unfilled and filled elastomers. Thermal degradation<br /> of poly(urethane-isocyanurate) networks and segmented thermoplastic polycarbonate-based<br /> polyurethanes was investigated by nonisothermal analysis, using thermogravimetry coupled<br /> with mass spectroscopy analysis (TG-MS) and thermogravimetry coupled with differential<br /> scanning calorimetry (TG-DSC). Viscoelastic and damping properties of obtained<br /> polyurethane elastomers were estimated by dynamic mechanical measurements (DMA).<br /> Modulated differential calorimetry (MDSC) was used to investigate thermal behavior of<br /> segmented polyurethanes and nanocomposites, synthesized using one-step technique. The<br /> glass transition temperature and thermoplastic properties of unfilled and filled polyurethane<br /> materials, prepared by pre-polimerization procedure were assessed by differential scanning<br /> calorimetry (DSC). Fourier transform infrared spectroscopy (FTIR) was used to investigate<br /> the hydrogen bond formation and chemical structure of prepared segmented elastomers. The<br /> investigation of the influence of hard segment content on morphology and surface topography<br /> of prepared segmented elastomers sheets was done by atomic force microscope (AFM). In<br /> order to determine the degree of cristallinity and to evaluate the dispersion of<br /> montmorillonite and bentonite in the polyurethane matrices, the prepared hybrid materials<br /> were characterized by wide angle X-ray scattering (WAXS).</p>

Les silicones auto-cicatrisants de façon autonome (sans stimulus externe) présentent de faibles propriétés mécaniques, limitant leur utilisation industrielle. L’objectif de cette étude était de dépasser cette limitation. Nos travaux se sont intéressés aux copolymères segmentés PDMS-urée constitués de blocs souples (SS) et rigides (HS). Tout d’abord, nous avons étudié la relation entre la structure des bis-urées et les propriétés macroscopiques. Nous avons ainsi montré que la symétrie des HS gouverne la rigidité de ces matériaux. Toutefois, la présence de HS symétriques inhibe la cicatrisation du matériau. Puis, nous avons développé un nouveau concept permettant d’accélérer leur cinétique de cicatrisation. Un stoppeur de chaine macromoléculaire a été ajouté à la formulation de ces silicones thermoplastiques, créant un défaut dans l’assemblage supramoléculaire, conduisant à des clusters organiques plus petits et plus dynamiques. Néanmoins, contrairement aux plastifiants, la chute du module de Young observée par rapport à la matrice est limitée. D’ailleurs, nous reportons la synthèse d’un copolymère PDMS-urée avec un module de traction de 1MPa dont 90% de la contrainte à rupture peut être récupérée après cicatrisation pendant 24h à 25°C. Ce concept a aussi été adapté à un thermoplastique commercial (GENIOMER80). Enfin, notre défi a été d’optimiser la balance entre rigidité et autocicatrisation. Dans ce contexte, nous avons synthétisé de nouvelles matrices plus rigides, ainsi que des additifs avec des groupements associatifs de plus grande énergie cohésive. Nous avons alors pu repousser la limite de rigidité accessible aux silicones auto-cicatrisants de façon autonome (3MPa). / Autonomous self-healable (without external stimulus) silicones exhibit too low mechanical properties restricting their use in industry. The aim of this study was to overcome this limitation. We focused our work on segmented PDMS-urea copolymers made of soft (SS) and hard segments (HS). First the investigation of the relationship between the bis-urea chemical structure and the macroscopic properties was made. Results shown that, the symmetry of HS governs materials rigidity. Moreover, with a too symmetrical HS, the material does not exhibit self-healing abilities. We have developed a new concept improving the healing efficiency of these materials. The idea was to add to the formulation of these silicone thermoplastics a macromolecular chain stopper. The new additive creates a defect in the supramolecular assembly which leads to smaller and more dynamic H-bonding clusters and hence a faster healing kinetic. Unlike plasticizers, this additive deteriorates the tensile modulus only marginally. We therefore report a stress at break recovery of 90% after 24 hours at room temperature for a PDMS-urea copolymer with a tensile modulus of 1MPa. The concept was also extented to a commercial thermoplastic (GENIOMER80). Finally, our last challenge was to manage the balance between rigidity and chains dynamics allowing self-healable materials with good mechanical properties. In this context we have synthesized new matrixes with higher HS percentage and additives with stickers with higher cohesive energy. These new syntheses have led to an improvement of the rigidity limit reachable by the autonomous self-healable silicones (3MPa).

Recently, smart dust or wireless sensor networks are gaining more attention.These autonomous, ultra-low power sensor-based electronic devices sense and process burst-type environmental variations and pass the data from one node (mote) to another in an ad-hoc network. Subsystems for smart dust are typically the analog interface (AI), analog-to-digital converter (ADC), digital signal processor (DSP), digital-to-analog converter (DAC), power management, and transceiver for communication. This thesis project describes an event-driven (ED) digital signal processing system (ADC, DSP and DAC) operating in continuous-time (CT) with smart dust as the target application. The benefits of the CT system compared to its conventional counterpart are lower in-band quantization noise and no requirement of a clock generator and anti-aliasing filter, which makes it suitable for processing burst-type data signals. A clockless EDADC system based on a CT delta modulation (DM) technique is presented. The ADC output is digital data, continuous in time, known as “data token”. The ADC employs an unbuffered, area efficient, segmented resistor-string (R-string) feedback DAC. A study of different segmented R-string DAC architectures is presented. A comparison in component reduction with prior art shows nearly 87.5% reduction of resistors and switches in the DAC and the D flip-flops in the bidirectional shift registers for an 8-bit ADC, utilizing the proposed segmented DAC architecture. The obtained SNDR for the 3-bit, 4-bit and 8-bit ADC system is 22.696 dB, 30.435 dB and 55.73 dB, respectively, with the band of interest as 220.5 kHz. The CTDSP operates asynchronously and process the data token obtained from the EDADC. A clockless transversal direct-form finite impulse response (FIR) low-pass filter (LPF) is designed. Systematic top-down test-driven methodology is employed through out the project. Initially, MATLAB models are used to compare the CT systems with the sampled systems. The complete CTDSP system is implemented in Cadence design environment. The thesis has resulted in two conference contributions. One for the 20th European Conference on Circuit Theory and Design, ECCTD’11 and the other for the 19th IFIP/IEEE International Conference on Very Large Scale Integration, VLSI-SoC’11. We obtained the second-best student paper award at the ECCTD.

An intracranial aneurysm can be a serious, life-threatening condition which may go undetected until the aneurysm ruptures causing hemorrhaging within the brain. The typical treatment method for large aneurysms is by embolization using platinum coils. However, in about 15% of the cases treated by platinum coils, the aneurysm eventually re-opens. The solution to the problem of aneurysm recurrence may be to develop more bio-active materials, including certain polymers, to use as coil implants. In this research, a shape memory polymer (SMP) was investigated as a potential candidate for aneurysm coils. The benefit of a shape memory polymer is that a small diameter fiber can be fed through a micro-catheter and then change its shape into a three-dimensional configuration when heated to body temperature. The SMP was tested to determine its thermo-mechanical properties and the strength of the shape recovery force. In addition, composite specimens containing tantalum filler were produced and tested to determine the mechanical effect of adding this radio-opaque metal. Thermo-mechanical testing showed that the material exhibited a shape recovery force a few degrees above Tg. The effects of the metal filler were small and included depression of Tg and recovery force. SMP coils deployed inside a simulated aneurysm model demonstrated that typical hemodynamic forces would not hinder the shape recovery process. The x-ray absorption capability the tantalum-filled material was characterized using x-ray diffractometry and clinical fluoroscopy. Diffractometry revealed that x-ray absorption increased with tantalum concentration, however, not as the rule of mixtures would predict. Fluoroscopic imaging of the composite coils in a clinical setting verified the radio-opacity of the material.

The performance gap between processor and memory continues to remain a major performance bottleneck in both application specific and general purpose processors. This thesis strives to ease the above bottleneck by exploiting the characteristics of the application domain to improve the cache organization for two distinct processor architectures: (1) application specific processors for packet forwarding, (2) general purpose processors. Packet forwarding algorithms make use of a trie data structure to determine the forwarding route. We observe that the locality characteristics of the nodes at various levels of such a trie are different. Nodes that are closer to the root node, especially those that are immediate children of the root node (level-one nodes), exhibit higher temporal locality than nodes lower down the trie. Based on this observation we propose a novel Heterogeneously Segmented Cache Architecture (HSCA) that uses separate caches for level-one and lower-level nodes, each with carefully chosen sizes. We also propose a new replacement policy to enhance the performance of HSCA. Performance evaluation indicates that HSCA results in up to 32% reduction in average memory access time over a unified cache that shares the same cache space among all levels of the trie. HSCA also outperforms a previously proposed results cache. The use of a large root branching factor in a forwarding trie forcefully introduces a large number of nodes at level-one. Among these, only nodes that cover prefixes from the routing table are useful while the rest, are superfluous. We find that as many as 75% of the level-one nodes are superfluous. This leads to a skewed distribution of useful nodes among the cache sets of the level-one nodes cache. We propose a novel two-level mapping framework that achieves a better nodes to cache set mapping and hence incurs fewer conflict misses. Two-level mapping first aggregates nodes into Initial Partitions (IPs) using lower order bits and then remaps them from IPs into Refined Partitions (RPs), that form sets, based on some higher order bits. It provides flexibility in placement by allowing each IP to choose a different remap function. We propose three schemes conforming to the framework. A speedup in average memory access time of as much as 16% is gained over HSCA. In general purpose processor architectures, the design objectives of caches at various levels of the hierarchy are different. To ensure low access latencies, L1 caches are small and have low associativities, making them more susceptible to conflict misses. The extent of conflict misses incurred is governed by the placement function and the memory access patterns exhibited by the program. We propose a mechanism to learn the access characteristics of the program at runtime by analyzing the repetitive phases of program. We then make use of the two-level mapping framework to dynamically adapt the placement function. Further, we elegantly incorporate two-level mapping into the cache organization without increasing the cache access latency. Performance evaluation reveals that the proposed adaptive placement mechanism eliminates 32—36% of misses on average over a range of cache sizes. To prevent expensive off-chip accesses, L2 caches are larger and have higher associativities. Hence, the replacement policy plays a significant role in determining L2 cache performance. Further, as the inherent temporal locality in memory accesses is filtered out by the L1 cache, an L2 cache using the widely prevalent LRU replacement policy incurs significantly higher misses than the optimal replacement policy (OPT). We propose to bridge this gap through a novel replacement strategy that mimics the replacement decisions of OPT. The L2 cache is logically divided into two components, a Shepherd Cache (SC) with a simple FIFO replacement and a Main Cache (MC) with an emulation of optimal replacement. The SC plays the dual role of caching lines and shepherding the replacement decisions close to optimal for MC. Our proposed organization can cover 40% of the gap between LRU and OPT, resulting in 7% overall speedup.

No description available.

La RFID est une technologie majeure qui connaît depuis plus d'une dizaine d'années un essor considérable en termes d'applications. Cependant son déploiement à grande échelle reste limité par des plusieurs verrous technique et technologique par lesquels la portée de lecture des tags et leur forte sensibilité à l'environnement de l'application. Le travail engagé dans cette thèse vise le développement des nouvelles antennes lecteurs pour systèmes RFID UHF champ proche. Ce type de système exploite la bande UHF de la RFID en zone de champ proche pour la traçabilité des cibles de taille miniature sur une zone proche du lecteur avec une portée limitée. Les tags se trouvant au delà de cette portée ne doivent pas être détectés par le lecteur. L'objectif dans ce travail est d'apporter des solutions au niveau des antennes lecteurs également celles du tag pour assurer une détection des tags sur une zone confinée de l'espace. Actuellement, moyennant l'utilisation d'un tag sous forme de boucle (1*1 cm²), il est possible de lire ce dernier en contact, c'est à dire dans la zone 0 – 10 cm. Il fallait donc pouvoir assurer une lecture fiable (de type couplage EM) pour une portée s'étendant d'une dizaine de centimètres. Les antennes lecteurs champ proche développés dans ce travail sont en mesure d'assurer une zone de lecture limitée (20 à 35 cm) qui s'étend sur une dizaine de centimètres de côté. / RFID is one of the most popular technologies in this decade. However, its deployment at a high scale is limited by several technical and technological limitations as the read range of tags and their sensitivity to the application's environment. In this thesis we focus on the development of new reader antennas for Near Field UHF RFID systems. This type of system uses the UHF RFID band in near field zone for the traceability of miniature size targets on an area near the reader with a limited zone. Tags being outside this zone should not be detected by the reader .One of the objective of this thesis is to provide solutions in terms of readers and tag antennas to ensure detection tags on a confined area of space. Actually, we can read loop RFID tag (1*1 cm²) in contact (read range 0-10 cm). So we have to be able to ensure a good reading of tag (EM coupling) in a range from few centimeters to meters. Near field reader antenna developed in this thesis work, has a limited range between 20 and 30 cm with a large reading zone.

No description available.

La RFID est une technologie majeure qui connaît depuis plus d'une dizaine d'années un essor considérable en termes d'applications. Cependant son déploiement à grande échelle reste limité par des plusieurs verrous technique et technologique par lesquels la portée de lecture des tags et leur forte sensibilité à l'environnement de l'application. Le travail engagé dans cette thèse vise le développement des nouvelles antennes lecteurs pour systèmes RFID UHF champ proche. Ce type de système exploite la bande UHF de la RFID en zone de champ proche pour la traçabilité des cibles de taille miniature sur une zone proche du lecteur avec une portée limitée. Les tags se trouvant au delà de cette portée ne doivent pas être détectés par le lecteur. L'objectif dans ce travail est d'apporter des solutions au niveau des antennes lecteurs également celles du tag pour assurer une détection des tags sur une zone confinée de l'espace. Actuellement, moyennant l'utilisation d'un tag sous forme de boucle (1*1 cm²), il est possible de lire ce dernier en contact, c'est à dire dans la zone 0 – 10 cm. Il fallait donc pouvoir assurer une lecture fiable (de type couplage EM) pour une portée s'étendant d'une dizaine de centimètres. Les antennes lecteurs champ proche développés dans ce travail sont en mesure d'assurer une zone de lecture limitée (20 à 35 cm) qui s'étend sur une dizaine de centimètres de côté. / RFID is one of the most popular technologies in this decade. However, its deployment at a high scale is limited by several technical and technological limitations as the read range of tags and their sensitivity to the application's environment. In this thesis we focus on the development of new reader antennas for Near Field UHF RFID systems. This type of system uses the UHF RFID band in near field zone for the traceability of miniature size targets on an area near the reader with a limited zone. Tags being outside this zone should not be detected by the reader .One of the objective of this thesis is to provide solutions in terms of readers and tag antennas to ensure detection tags on a confined area of space. Actually, we can read loop RFID tag (1*1 cm²) in contact (read range 0-10 cm). So we have to be able to ensure a good reading of tag (EM coupling) in a range from few centimeters to meters. Near field reader antenna developed in this thesis work, has a limited range between 20 and 30 cm with a large reading zone.