Dynamic modelling and optimization of three different processes namely (a) bulk polymerization of styrene, (b) solution polymerization of methyl methacrylate (MMA) and (c) emulsion copolymerization of Styrene and MMA in batch and semi-batch reactors are the focus of this work. In this work, models are presented as sets of differential-algebraic equations describing the process. Different optimization problems such as (a) maximum conversion (Xn), (b) maximum number average molecular weight (Mn) and (c) minimum time to achieve the desired polymer molecular properties (defined as pre-specified values of monomer conversion and number average molecular weight) are formulated. Reactor temperature, jacket temperature, initial initiator concentration, monomer feed rate, initiator feed rate and surfactant feed rate are used as optimization variables in the optimization formulations. The dynamic optimization problems were converted into nonlinear programming problem using the CVP techniques which were solved using efficient SQP (Successive Quadratic Programming) method available within the gPROMS (general PROcess Modelling System) software. The process model used for bulk polystyrene polymerization in batch reactors, using 2, 2 azobisisobutyronitrile catalyst (AIBN) as initiator was improved by including the gel and glass effects. The results obtained from this work when compared with the previous study by other researcher which disregarded the gel and glass effect in their study which show that the batch time operation are significantly reduced while the amount of the initial initiator concentration required increases. Also, the termination rate constant decreases as the concentration of the mixture increases, resulting rapid monomer conversion. The process model used for solution polymerization of methyl methacrylate (MMA) in batch reactors, using AIBN as the initiator and Toluene as the solvent was improved by including the free volume theory to calculate the initiator efficiency, f. The effects of different f was examined and compared with previous work which used a constant value of f 0.53. The results of these studies show that initiator efficiency, f is not constant but decreases with the increase of monomer conversion along the process. The determination of optimal control trajectories for emulsion copolymerization of Styrene and MMA with the objective of maximizing the number average molecular weight (Mn) and overall conversion (Xn) were carried out in batch and semi-batch reactors. The initiator used in this work is Persulfate K2S2O8 and the surfactant is Sodium Dodecyl Sulfate (SDS). Reduction of the pre-batch time increases the Mn but decreases the conversion (Xn). The sooner the addition of monomer into the reactor, the earlier the growth of the polymer chain leading to higher Mn. Besides that, Mn also can be increased by decreasing the initial initiator concentration (Ci0). Less oligomeric radicals will be produced with low Ci0, leading to reduced polymerization loci thus lowering the overall conversion. On the other hand, increases of reaction temperature (Tr) will decrease the Mn since transfer coefficient is increased at higher Tr leading to increase of the monomeric radicals resulting in an increase in termination reaction.

Palladium complexes of bis(di-tert-butylphosphinomethyl)benzene (DTBPMB) show remarkably high activity as alkene methoxycarbonylation catalysts, in addition to numerous other catalytic conversions, and are currently being commercialised by Lucite in ethene methoxycarbonylation to methyl propanoate. Any large-scale exploitation of this catalyst system for heavier products, however, is likely to be hindered by catalyst-product separation problems common to homogeneous catalysts; hence modification of this catalyst system to allow facile product separation was investigated. Tethering of DTBPMB residues onto polystyrene via Suzuki-type coupling of suitable precursors onto bromopolystyrene and boronic acid functionalised polystyrene resins was investigated and the phosphine was successfully immobilised. Phosphination of the resins was not complete however and as such there is concern that other phosphine residues may be present which do not exhibit a bidentate binding motif. The synthesis of a potassium sulfonate derivative of DTBPMB (KBPMBS) was successful and immobilisation of this onto ion exchange resins was also investigated. Some preliminary results from studies into 1-octene methoxycarbonylation using palladium complexes of these resins were obtained. Supporting of this diphosphine onto silica via a sol-gel co-condensation methodology was also investigated; the synthesis of a suitably functionalised precursor containing a sulfonamide linkage was successful via protection of the diphosphine using borane. Although formation of the silica support was successful, attempts to deprotect the phosphine-borane resulted in cleavage of the ligand from the support. An alternative route to this supported ligand was attempted and others discussed. Synthesis of a suitable sol-gel precursor via alkene hydrosilation was also attempted and is discussed. Supporting of the sulfonated phosphine, KBPMBS onto silica functionalised with imidazolium tethered residues was also investigated, although complete leaching of the phosphine from the support by methanol washing was observed. Immobilisation of the synthesised KBPMBS ligand in an ionic liquid (IL) phase was investigated. Complex formation and catalytic activity were demonstrated and a positive effect on conversion was observed upon addition of carbon dioxide to the system; possibly due to the increased CO solubility within the IL phase. Efficient product separation from the IL-immobilised catalyst system was demonstrated, both by organic extraction and using supercritical carbon dioxide flow. However, poor catalyst stability under these conditions appears to present a barrier to recycling this system, with loss of conversion observed on catalyst recycling. Other attempts to immobilise the DTBPMB ligand are discussed and reduction of the sulfide derivative of DTBPMB was demonstrated using hexachlorodisilane, which could be used as a general synthetic strategy for protecting highly electron rich phosphines. It is possible that increasing the bulk of the DTBPMB ligand may increase catalyst stability and result in catalyst systems with higher turnover numbers. Therefore syntheses of bulky ligands based on the DTBPMB backbone were investigated. 1,2,4,5-tetrakis(di(tert-butyl)phosphinomethyl)benzene was successfully synthesised although palladium complexes of this showed no activity in catalytic methoxycarbonylation. Attempts to synthesise a related biphenyl-based tetraphosphine is also discussed, although isolation of this in a pure form was not achieved. Routes toward tetraphenyl and dimethyl-diphenyl functionalised derivatives of DTBPMB have also been explored, although only a monophosphine was isolated due to difficulties in obtaining an intermediate di(chloromethyl) precursor in both synthetic pathways, although this now appears to have been overcome.

L'objectif de ces travaux était de mettre au point des vecteurs de diffusion efficaces du thymol pour lutter contre un acarien parasite des abeilles. Le choix s'est porté sur la formation de nano-objets par émulsification spontanée pouvant libérer efficacement du thymol grâce à leur grande surface spécifique. L'émulsification spontanée par « effet Ouzo » a été choisie en raison de (i) la simplicité du procédé nécessaire pour son application par les apiculteurs et de (ii) la possibilité de former une grande diversité de nano-objets. L'émulsification spontanée par effet Ouzo a tout d'abord été étudiée fondamentalement avec un polymère (nanoprécipitation), le polyméthacrylate de méthyle (PMMA), pour s'affranchir des phénomènes déstabilisants typiques des émulsions tels que le mûrissement d'Ostwald et la coalescence. Cette étude a permis de définir clairement les compositions du système PMMA/solvant/eau pour lesquelles la nanoprécipitation du PMMA induit la formation exclusive de nanoparticules de distribution de taille étroite (zone Ouzo) ou la formation de nanoparticules additionnées de macroparticules (zone non-Ouzo), séparées par la limite Ouzo. Deux mécanismes de formation des nanoparticules ont été déduits suivant la sursaturation du PMMA (nucléation et croissance ou nucléation et agrégation). L'influence des stabilisants a montré l'importance de l'adsorption des ions OH- sur la taille des nanoparticules et sur le déplacement de la limite Ouzo alors que seule la stabilité colloïdale est améliorée avec l'ajout de tensioactifs. Cette étude fondamentale a servi de base pour la formation des nanogouttelettes de thymol et des nanocapsules thymol-PVA réticulé et thymol-PMMA par effet Ouzo. Des nanoparticules thymol-PVP ont également été formées par complexation de la poly(N-vinyl-2-pyrrolidone) en milieu aqueux. Ces nano-objets de thymol ont été testés sur des ruches infestées pour déterminer leur efficacité d'éradication de l'acarien Varroa Destructor. / The objective of this work dealt with setting up efficient thymol diffusion vectors to fight against a bee mite, the Varroa Destructor. The formation of nano-objects by spontaneous emulsification was investigated because they provide large specific area to enhance thymol evaporation. Spontaneous emulsification by so-called Ouzo effect was chosen because of (i) the simplicity of the process necessary for the transfer to beekeepers and (ii) the great diversity of nano-objects morphologies which can be designed. Spontaneous emulsification by Ouzo effect was first studied fundamentally with a polymer (nanoprecipitation), the poly(methyl methacrylate) (PMMA), in order to avoid typical emulsion destabilizing phenomena such as Ostwald ripening and coalescence. This study enabled to clearly define the PMMA/solvent/water system compositions for which PMMA nanoprecipitation induces only formation of nanoparticles with a narrow size distribution (Ouzo domain) or formation of microparticles besides nanoparticles (non-Ouzo domain), separated by the Ouzo boundary. Two nanoparticles formation mechanisms were deduced with respect to the supersaturation of PMMA (nucleation and growth or nucleation and aggregation). Stabilizers influence set off the importance of OH- ions adsorption on nanoparticles size and on Ouzo boundary shifting whereas only colloidal stability is improved through surfactant addition. This fundamental study laid down basis for thymol nanodroplets and for thymol-cross linked PVA and thymol-PMMA nanocapsules formation by Ouzo effect. Thymol-PVP nanoparticles were also prepared by poly(N-vinyl-2-pyrrolidone) complexation in aqueous medium. These thymol nano-objects were tested on infested beehives to determine their efficiency to eradicate the Varroa Destructor mite.

Der Einsatz von organischen Materialien, insbesondere von Polymeren, hat zahlreiche Vorteile gegenüber dem Einsatz klassischer Materialien in der Mikroelektronik. Zu diesen zählen Flexibilität, geringes Gewicht, Verarbeitbarkeit durch Verfahren aus Lösung bei Raumtemperatur ohne Notwendigkeit vakuumbasierter Prozesse zur Abscheidung und vieles mehr. Dies ermöglicht eine energie- und kosteneffiziente Herstellung elektronischer Bauteile wie organische Feldeffekttransistoren (OFETs) oder Leuchtdioden (OLEDs), welche durch Prozesse wie dem Rolle-zu-Rolle-Druckverfahren nicht länger auf kleine Flächen begrenzt sind. Zur Herstellung polymerbasierter OFETs mit optimiertem Eigenschaftsprofil sind neben innovativen Halbleitern vor allem auch neue Dielektrika mit verbesserten elektrischen Eigenschaften erforderlich, zu deren Entwicklung die vorliegende Arbeit beitragen sollte. Das häufig verwendete Polymethylmethacrylat ist für den Einsatz als Gate-Dielektrikum für die organische und gedruckte Elektronik nur bedingt geeignet. Es zeigt einige Nachteile wie eine mangelnde Stabilität gegenüber bestimmten organischen Lösungsmitteln, was zu Quellung oder Anlösen des Dielektrikums während des Aufbringens weiterer Schichten führen kann. Durch Copolymerisation von Methylmethacrylat mit funktionalisierten Comonomeren sollten die Probleme gelöst und optimierte Methacrylat-Copolymere entwickelt werden. Die Copolymere wurden über freie radikalische sowie RAFT-Polymerisation synthetisiert. Allen gemeinsam sind vernetzbare Comonomere, um die Lösungsmittelstabilität zu verbessern und somit die Durchbruchfeldstärke des Dielektrikums zu erhöhen. Als Vernetzer wurden 4-Benzoylphenylmethacrylat (BPMA) oder Propargylmethacrylat (PgMA) gewählt. BPMA ist UV-vernetzbar, Copolymere mit PgMA können in Gegenwart von mehrfunktionalen Aziden wie 1,3,5-Tris(azidomethyl)benzen (TAMB) durch Click-Reaktion thermisch vernetzt werden. Ein weiterer Aspekt ist die Erhöhung der relativen Permittivität des Dielektrikums zur Steigerung der Kapazität der dielektrischen Schicht, wodurch unter anderem die Betriebsspannung des Transistors reduziert werden kann. Dieses Ziel sollte durch Komposite mit BaTiO3-Nanopartikeln erreicht werden. Zusätzlich zur Steigerung der Permittivität kann dies durch Verringerung der Filmdicke realisiert werden, was jedoch vermehrt zu Leckströmen führen könnte. Neben den dielektrischen Materialeigenschaften spielt vor allem auch die Grenzfläche zwischen Dielektrikum und Halbleiter eine wesentliche Rolle. Um die Interaktionen an dieser zu verbessern, wurden Comonomere mit selbstorganisierenden Seitenketten in die Polymerstruktur eingebracht. Die Kombination dieser Dielektrika mit chemisch angepassten Halbleitern mit vergleichbaren Seitenkettenfunktionalitäten soll dazu führen, dass die beiden Komponenten durch die Seitenketten verstärkt miteinander wechselwirken. Monomersynthesen sowie anschließende Copolymerisationen waren in hohen Ausbeuten und ausreichenden Molmassen bezüglich der Copolymere erfolgreich. Die strahleninduzierte Vernetzung konnte durch systematische Untersuchungen optimiert und die thermische Vernetzung bei moderaten Temperaturen nachgewiesen werden. Die Vernetzbarkeit von Copolymeren mit selbstorganisierenden Seitenketten erwies sich als gehindert. Hierfür wurde ein Vorschlag zur Erhöhung der Flexibilität der Vernetzerseitenkette unterbreitet. Für die Copolymere P(MMA/BPMA) und P(MMA/PgMA) konnten die Durchbruchfeldstärken in Folge der Vernetzung von < 0.3 MV/cm für PMMA auf bis zu mehr als 5 MV/cm gesteigert werden. BaTiO3-Nanopartikel konnten durch geeignete Methoden erfolgreich synthetisiert werden. Durch Variation der Reaktionsbedingungen war eine gezielte Steuerung der Primärpartikelgröße möglich. So wurden Partikel der Größe < 10 nm, 26 nm und 55 nm realisiert. Die Dispersion der Partikel in organischen Lösungsmitteln sowie in der Polymermatrix war stark abhängig von der Größe der Primärartikel, der Oberflächenmodifikation sowie der Neigung zur Agglomeration. Modifizierte Partikel mit einem Durchmesser < 10 nm konnten sehr gut in Lösungsmitteln wie auch in der Polymermatrix dispergiert werden (Abbildung 2). Eine Steigerung der relativen Permittivität der Nanokomposite blieb jedoch aufgrund der zu geringen Größe der Primärpartikel aus. Darüber hinaus wurden deutlich schlechtere Durchbruchfeldstärken beobachtet. Copolymere mit der Fähigkeit zur Selbstorganisation sollten durch zwei Konzepte realisiert werden. Im ersten System führte die Polymerisation von x-[4-(4´-Cyanophenyl)phenoxy]alkylmethacrylaten mit Spacerlängen von x = 6 und x = 8 nur in Homopolymeren zu ausgeprägter Selbstorganisation. Copolymere mit 50 mol% waren weitgehend isotrop und wiesen zudem ungenügende dielektrische Eigenschaften auf. Das zweite System basiert auf semifluorierten Methacrylat-Copolymeren mit H10F10-Seitenketten (10 CH2- und 10 CF2-Gruppen). Diese zeigten schon ab einem Gehalt von circa 35 mol% gute Selbstorganisation und bildeten ein geordnetes alternierendes Schichtsystem aus Haupt- und Seitenketten im Bulk und in dünnen Filmen. Die dielektrischen Eigenschaften können mit denen bekannter fluorierter Polymerdielektrika wie CYTOP konkurrieren. Damit stehen die semifluorierten Copolymere zukunftsorientiert zur Kombination mit Halbleitern, welche die gleichen Seitenkettenfunktionalitäten tragen, bereit, um so durch starke Interaktionen zwischen Dielektrikum und Halbleiter die Grenzfläche zu optimieren. Mit thermisch vernetztem P(MMA/PgMA) konnten OFETs mit den Halbleitern Pentacen bzw. C60 erfolgreich hergestellt und vermessen werden. Beide Transistoren liefern gute und mit Literaturwerten vergleichbare Kenngrößen. Die Ladungsträgermobilitäten und Ion/Ioff-Verhältnisse betragen 0.3 cm²/Vs und 6.0x10^5 im Pentacen-basierten Transistor beziehungsweise 1.3 cm²/Vs und 4.4x10^5 im OFET mit dem Halbleiter C60. Damit konnte in dieser Arbeit die Steigerung der Durchbruchfeldstärke durch geeignete Vernetzung der Copolymere realisiert werden. Die thermische Vernetzung fand bei deutlich geringeren Temperaturen als zahlreiche in der Literatur beschriebene Reaktionen statt. Die Synthese und Modifizierung von BaTiO3-Nanopartikeln und auch die Bildung entsprechender PMMA-BaTiO3-Nanokomposite war erfolgreich, führte jedoch nicht wie erwartet zu einer Steigerung der relativen Permittivität der Dielektrika-Schichten. Vernetzbare und selbstorganisierende semifluorierte Methacrylat-Copolymere konnten polymerisiert und charakterisiert werden und stehen als innovative dielektrische Materialien für Untersuchungen in OFETs zur Verfügung. Das Copolymer P(MMA/PgMA) wurde zielführend in organischen Feldeffekttransistoren eingesetzt und führte zu guten elektrischen Eigenschaften der Bauteile.

<p>U uvodnom delu doktorske disertacije opisuje se kompleksnost problematike kori&scaron;ćenja polimera za bazu zubne proteze, sa osvrtom na njihove op&scaron;te osobine, stepen biokompatibilnosti i njihove mehaničke karakteristike. Detaljno je opisana problematika ispitivanja stomatolo&scaron;kih materijala i napravljeno je poređenje i korelacija između in vitro i in vivo načina ispitivanja biokompatibilnosti. Drugi deo obuhvata ispitivanje čvrstoće polimera za bazu zubne proteze i analizu uticaja osobina materijala u odnosu na biolo&scaron;ku sredinu u kojoj obavljaju svoju funkciju, i u odnosu na sile kojima su tokom funkcije materijali izloženi. Cilj doktorske disertacije je utvrđivanje stepena biokompatibilnosti i mehaničkih karakteristika toplopolimerizujućih, hladnopolimerizujućih i termoplastičnih akrilata za bazu zubne proteze. Istraživanje je obuhvatilo 3 komercijalna materijala iz grupe akrilata, koji se razlikuju po hemijskom sastavu i načinu polimerizacije. Ispitivanje biokompatibilnosti rađeno je u in vitro i in vivo uslovima. Ispitivanje na ćelijskim kulturama obuhvatalo je dve ćelisjke linije (MRC 5 i L929) sa dva načina kontakta između ćelija i materijala (direktan, indirektan) i dva načina određivanja biolo&scaron;kog ishoda (MTT test, Agar difuzioni test). Istraživanje urađeno in vivo obuhvatalo je test subkutane implantacije, na animalnom modelu pacova, i test iritacije oralne sluzokože na animalnom modelu hrčka. Oba testa rađena su u skladu sa standardom ISO 10993. Cilj in vivo istraživanja bio je ispitivanje reakcije tkiva na implantirani materijal, računajući i zavr&scaron;nu integraciju ili dezintegraciju implantiranog materijala. Prednost in vivo istraživanja nalazi seu analizi uticaja materijala na sterilno živo tkivo, uz praćenje imunolo&scaron;ke reakcije, kao dopuna prethodnom istraživanju na ćelijskim kulturama. Dopunski deo in vivo ispitivanja biokompatibilnosti određen je prema kliničkoj upotrebi ispitivanih materijala, zbog čega je odabran test oralne iritacije sluzokože. Sluzokoža bukalne kesice sirijskog hrčka sastoji se od pločasto slojvitog epitela sa orožavanjem, &scaron;to je predstavljao dobar model za ispitivanje polimera za bazu zubne proteze, po&scaron;to zubna proteza naleže na sluzokožu nepca i rezidualnog alveolarnog grebena koja takođe orožava. Drugi deo disertacije obuhvatao je ispitivanje mehaničkih karakteristika, pri čemu su urađeni test zatezne čvrstoće, test savojne čvrstoće, test čvrstoće loma i mikrotvrdoće, uz dopunsku analizu pratećih parametara. Rezultati ispitivanja biokompatibilnosti pokazali su da su testovi biokompatibilnosti osetljivi na upražnjeni metodolo&scaron;ki postupak. Ispitivanjem na ćelijskim kulturama nisu utvrđene značajne razlike u citotoksičnosti između toplopolimerizujućih, hladnopolimerizujućih i termoplastičnih akrilata. Takođe, rezultati su se razlikovali u odnosu na tip ćelijske kulture i način provere biolo&scaron;kog ishoda, &scaron;to se slaže sa prethodnim navodima o kompleksnoj problematici njihovog međusobnog poređenja. Ispitivanjem biokompatibilnosti subkutanom implantacijom praćen je inflamatorni odgovor tkiva u vremenskom intervalu od 90 dana. Reakcija organizma na implantirani materijal posmatrana je kroz ćelijske i tkivne parametre, u skladu sa ISO 10993. Dodatno je urađena i analiza hrapavosti implantiranih materijala. Histolo&scaron;kom analizom utvrđena je razlika u inflamatornom odgovoru u odnosu na kori&scaron;ćeni materijal, kao i prema vremenskom intervalu implantacije. Test oralne iritacije sluzokože nije se pokazao kao dovoljno senzitivan za ispitivanje ovih vrsta materijala. Ispitivanjem mehaničkih karakteristika utvrđene su razlike između toplopolimerizujućih, hladnopolimerizujućih i termoplastičnih akrilata. Najveći stepen čvrstoće utvrđen je kod toplopolimerizujućih akrilata dok je najveća konzistentnost rezultata bila u grupi termoplastičnih akrilata. Prezentovano istraživanje predstavlja prvu detaljnu analizu biokompatibilnosti i mehaničkih karaktestistika polimera za bazu zubne proteze.</p> / <p>The introduction describes the complexity of use of denture base materials, with regard to their general characteristics, biocompatibility and mechanical properties. Issues related to the testing of dental materials is described in detail and comparison is made between in vitro and in vivo methods of biocompatibility testing. The second part further covers the determination of strength of previously used materials, in relation to biological environment in which their function is conducted and in relation to the influence of masticatory forces which can contribute to their mechanical failure. The aim of the presented research was to assess the degree of biocompatibility and mechanical properties of cold curing, hot curing and thermoformed denture base materials. The research included three denture base materials, which differed according to their chemical composition and polymerization protocols. The biocompatibility testing was carried out in in vitro and in vivo conditions. The in vitro experiments covered two different cell lines (MRC 5 human lung fibroblasts and L929 mouse fibroblasts) with two types of contact (direct, indirect) and two different types of quantification of biological outcome (MTT assay and Agar overley test). The in vivo assessment of biocompatibility covered the subcutaneous implantation test, on the animal model of Wistar rat, and oral mucosa irritation test, on the animal model of sirian hamster. Both tests were conducted according to the ISO 10993. The aim of the in vivo investigation was to evaluate tissue reactions to the implanted materials, including the final integration or disintegration of the tested materials. The advantage of in vivo investigation included the possibility of monitoring the materials influence on living tissues, with the analysis of imunological response as an addition to the previously conductedresearchon cell cultures. The supplemental part of in vivo investigation was chosen according to the clinical use of the tested materials, which included the oral mucosa irritation test.The mucosa of hamster buccal pouch consists of stratified squamos epithelium, which is considered to be an adequate replacement for the human denture supporting tissues, which also consist of the same type of epithelium. The second part of thesis includes the determination of mechanical properties of denture base materials. It consists of four types of tests: tensile strength test, bending strength test, fracture toughness test and microhardness tests, followed by the analysis of corresponding parameters. The results of the biocompatibility tests showed that the biological outcome of the applied method is highly depended on the methodological procedure. The investigation conducted in vitro, on two different cell lines, did not show significant difference in cytotoxicity between hot curing, cold curing and thermoformed denture base materials. Also, the results were influenced by the type of cell culture and the evaluation method of biological outcome, which agrees with the previous allegations about the complexicity of their mutual comparison. The subcutaneous implantation test covered the inflammatory response in the time period of 90 days. The organism reaction to the implanted material was determined through the cell and tissue parameters of organism response, evaluation of which was conducted according to the ISO 10993. Additionally, the surface roughness of the implanted specimens of materials was also measured. The inflammatory response of the ogranism was influenced by the type of the implanted material and the time interval of implantation. The oral mucosa irritation test has proven not to be sufficiently sensitive for testing of this type of materials. Testing of the mechanical properties od denture base materials, revealed the difference between the cold curing, hot curing and thermofomed denture base materials. The highest strength was observed in hot curing materials, while the highest consistency of the results was observed in thermoformed resins. The presented investigation presents the first detail analysis of the biocompatibility and mechanical properties of the denture base materials, and as such presents a novelty in the field of dental materials characterization.</p>

L’objectif de cette thèse est de proposer une stratégie simplifiée et précise pour caractériser et modéliser le comportement mécanique des polymères amorphes de l'état quasi-fluide à l'état solide.L'étude a été réalisée sur des PMMA de masses molaires et de degré de réticulations différentes.D’abord, le comportement mécanique dans le domaine viscoélastique linéaire est étudié à l'aide de tests DMTA et rhéologiques. Il ressort de l’étude que l'augmentation de la masse molaire et du degré de réticulation augmentait les modules de stockage et de perte en tant que la transition α. En parallèle, l'utilisation du principe de superposition temps-température a permis de déterminer «des vitesses de déformation équivalentes à la température de référence».Ensuite, le comportement mécanique à grande déformation est étudié par essais cycliques en traction uni-axial et de cisaillement à haute température et couplés à la DIC. De plus, les effets de la vitesse de déformation et de la température ont été couplés grâce à "vitesse de déformation équivalent à la température de référence" extrait des observations dans le domaine linéaire. Les résultats ont montré que cibler la même vitesse de déformation équivalente conduira aux mêmes courbes contrainte-déformation, c'est-à-dire la même réponse mécanique. Ceci permet de réduire le nombre de tests expérimentaux nécessaires pour caractériser le comportement mécanique des polymères amorphes.Enfin, un modèle basée dans un cadre thermodynamique a été utilisée pour reproduire la réponse mécanique des PMMAs à grande déformation. Le modèle présentait un bon accord avec les données expérimentales, étant capable de reproduire des comportements visco-élasto-plastiques, viscoélastiques, hyperélastiques et visco-hyperelastiques pour la traction cyclique. / The present PhD thesis proposes a simplified and accurate strategy for characterising and modelling the mechanical behaviour of amorphous polymers from the quasi-fluid state up to the solid state.The study was carried out on PMMAs with different molar masses and crosslinking degree.First, we addressed the mechanical behaviour in the linear viscoelastic domain using DMTA and rheological tests. Results showed that increasing the molar mas and crosslinking degree increased the elastic and loss moduli as the α-transition. In parallel, using the time-temperature superposition principle allowed determining “equivalent strain rates at reference temperature”.Then, we performed uniaxial tensile and shear uploading-unloading tests at high temperature and coupled with DIC, to characterise the mechanical behaviour at large strain. Additionally, strain rate and temperature effects were coupled by means of the “equivalent strain rate at reference temperature” extracted from observations in the linear domain. Results showed that targeting the same equivalent strain rate lead to the same stress-strain curves, i.e. same mechanical response. This allows reducing the number of experimental tests needed to characterise the mechanical behaviour of amorphous polymers.Finally, a constitutive modelling based in a thermodynamics framework, was used to reproduce the mechanical response of the PMMAs at large deformation. The model presented a good agreement with the experimental data, being able to reproduce viscoelastoplastic, viscoelastic, hyperelastic and viscohyperelastic behaviours for cyclic loading tensile.

Este estudo teve o objetivo de avaliar in vitro a influência da alteração dimensional de resinas acrílicas para base de prótese total submetidas a diferentes formas de processamento sobre a posição da cabeça da mandíbula, buscando estabelecer uma possível relação com a etiologia das disfunções crânio-mandibulares nos pacientes usuários desse tipo de prótese. Foram duas etapas: a primeira parte enfocou o papel do tipo de prensa (Getom ou de cozimento) e da força de prensagem para fechamento da mufla (1000 ou 1500 kgf) utilizados no processamento de duas resinas: Lucitone 550 e QC–20 e somente da força de prensagem para a resina Acron MC. Já a segunda parte do estudo teve o intuito de avaliar a influência dos ciclos de polimerização curtos e longos na alteração dimensional de cinco resinas: as mesmas três da primeira parte, além da Clássico e Ondacryl. As próteses superiores acrilizadas foram remontadas em articulador totalmente ajustável, tendo como referência a posição de máxima intercuspidação (MIC). Nessa posição de maior estabilidade oclusal, foi vazado gesso tipo IV no espaço entre as esferas condilares do articulador e as paredes dos estojos condilares. Após a cristalização, esses corpos-de-prova de gesso foram removidos do estojo condilar e suas dimensões medidas e submetidas à análise estatística por meio de um modelo de análise de variância com medidas repetidas que permitiu concluir que houve variações na posição da “cabeça da mandíbula" em 625 das 630 medidas efetuadas; as médias de movimentação condilar variaram de 0,118 (DP = 0,0968) a 1,956 mm (DP = 0,414) e ocorreram principalmente no sentido posterior do lado esquerdo; na maioria dos casos em que a força de prensagem agiu como fator devariação, os deslocamentos obtidos com 1500 kgf foram menores do que aqueles obtidos com 1000 kgf; nos casos em que o tipo de prensa agiu como fator de variação, ora os menores deslocamentos foram obtidos com a prensa de cozimento, ora com a Getom; o ciclo empregado na polimerização não influenciou significativamente na estabilidade dimensional das próteses totais e a única diferença encontrada envolveu a resina Clássico, que levou aos maiores deslocamentos no sentido posterior do lado esquerdo. / The purpose of this study was to evaluate in vitro the influence of dimensional changes in denture base acrylic resins submitted to different processing methods on the position of the mandibular condyle. This was done to establish a relation between these dimensional changes and the etiology of temporomandibular disorders in complete denture wearers. This research was divided into two parts. The first part focused on the type of press (conventional water bath or Getom), on the pressing force for flask closure (1000 or 1500 kgf) when processing Lucitone 550 and QC-20 resins, and on the pressing force when processing Acron MC resin. The purpose of the second part was to evaluate the influence of polymerization time on the dimensional stability of five resins, namely Lucitone 550, QC-20, Acron MC, Clássico and Ondacryl. The polymerized upper prostheses were remounted on a fully adjustable articulator, using the maximal intercuspal position (MIP) as reference. Type IV dental stone was poured into the space between the condylar spheres and the condylar walls. After the dental stone dried, the samples were removed from the articulator and their dimensions were measured and submitted to analysis of variance with repeated measures. The following conclusions were drawn: 625 from 630 measurements done showed changes in the position of the “mandibular condyle" and mean values for condylar movement ranged from 0.118 (SD = 0.0968) to 1.956 mm (SD = 0.414) and occurred mainly in the posterior direction on the left side; in most cases where the pressing force influenced the condylar position, the changes were smaller in 1500 kgf group than in the 1000 kgf group; in the cases where the type of press influenced the changes in condylar position, the smallest values were found in both groups, sometimes with Getom and other times with conventional water bath press; polymerization time did not significantly affect the dimensional stability of the dentures and the greatest changes occurred in the posterior direction on the left side with Clássico resin.

Foram desenvolvidos e manufaturados compósitos porosos com estrutura de gradiente funcional em Poli (metacrilato de metila) (PMMA) e Hidroxiapatita (HAp) aplicáveis como implantes ósseos. O PMMA é largamente utilizável e aceito como material de implante tem boas propriedades mecânicas, baixo custo, fácil manufatura, porém é considerado bioinerte. A HAp é uma cerâmica comprovadamente bioativa, porém de baixas propriedades mecânicas, alto custo e de difícil manufatura. O PMMA com estrutura funcional e HAp apresentou valores próximos a 50 MPa, mas com potencial de melhoria. O objetivo deste desenvolvimento é produzir um implante com a sua superfície porosa e bioativa, para que este possa ser osteointegrado em um tempo menor ao tecido hospedeiro, melhorando a relação: material implantado/leito receptor. O conceito é baseado em uma estrutura de núcleo denso em PMMA e camada superficial porosa com superfície bioativa. A camada de PMMA porosa foi desenvolvida utilizando-se o carboximetilcelulose (CMC) como agente porogênico e HAp como agente bioativador da matriz polimérica. Foram elaboradas análises de bicompatibilidade, resistência mecânica, macro e microestrutura. Para testar a biocompatibilidade foram realizados inicialmente testes in vitro com cultura de células VERO, visando investigar a toxicidade dos materiais constituintes, a influência do novo biomaterial em atividades celulares e o comportamento destes em condições próximas daquelas a serem encontradas no ambiente de implantação. Em seguida, os testes in vivo realizados em coelhos averiguaram a interação tecido-material (bioatividade), a biocompatibilidade do material, e a potencialidade do uso do material em aplicação à superfícies (osteointegração). Foi realizada análise histológica dos tecidos explantados, onde os resultados basearam-se na análise da morfologia geral dos componentes teciduais encontrados junto ao implante. A caracterização da superfície foi realizada por testes de rugosidade, por microscopia ótica e eletrônica de varredura. Foram realizados ensaios mecânicos de compressão para analisar a resistência mecânica do biomaterial. Os resultados in vitro mostraram que os materiais utilizados não apresentaram qualquer indício de toxicidade. Através das imagens realizadas em MEV (Microscopia Eletrônica de Varredura) pode se observar o crescimento de células VERO na superfície do material e em direção aos poros da matriz. A análise macroestrutural dos poros também obtida por MEV demonstrou em uma caracterização inicial do material que este apresentou características biomiméticas como poros em formato oblongo e interconectados. A média obtida do tamanho dos poros foi de aproximadamente 250 \'mü\'m. Os resultados dos ensaios mecânicos de compressão mostraram que o PMMA denso é o que mais se aproximou do tecido ósseo cortical com 101 MPa. Por fim, os resultados histológicos apontam para a biocompatibilidade do compósito, tornando-o assim aplicável como camada superficial de implantes. / Were developed and manufactured porous composite with functional gradient structure in Polymethylmethacrylate (PMMA) and hydroxyapatite (HAp) applicable as bone implants. PMMA is widely used and accepted as implant material, has good mechanical properties, low cost, easy manufacturing and considered a bioinert biomaterial, the Hap is a demonstrably bioactive ceramic with poor mechanical properties, high cost and difficult to manufacture. The PMMA functional structure and HAp had values close to 50 MPa, but with potential for improvement. The objective of this development was produced an implant with a porous surface and bioactive to be osteointegrated in a less time, improving the relationship: implanted material/receiver bed. The concept is based on a dense structure core of PMMA and a porous bioactive surface layer. The porous PMMA was developed using the carboxymethylcellulose (CMC) as a porogenic agent and hap to bioactive the PMMA matrix. Biocompatibility tests, mechanical strength tests and macro and microstructure analisys were carried out. To evaluated the biocompatibility of this material were made primarily in vitro tests, the VERO cells were used in vitro analysis aimed investigate the toxicity of the constituent materials, the influence of the new biomaterial in cellular activities and behavior in these conditions close to those to be found in the environment of deployment. Then, in vivo tests conducted in rabbits evaluated the interaction with tissue-material (bioactivity), the biocompatibility of the material, and the potential use of the material in the application areas (osseointegration). Were performed histological analysis of tissues, where the results were based on the analysis of the general morphology of the tissue components found near the implant. The surface characterization was performed by roughness tests, optical microscopy and SEM. Mechanical tests were conducted to examine the compressive strength of biomaterial. Results in vitro showed that the materials did not present any evidence of toxicity. The samples were analyzed by SEM where the growth of cells can be observed in the surface of the material and towards to the pores. The macrostructural analysis also obtained by SEM showed in an initial characterization of the material that presented bone biomimetics characteristics with oblong pores with interconnected. The average pore size obtained was approximately 250 \'mü\'m. The results of mechanical tests showed that the compression of PMMA is the densest approached the cortical bone tissue near 101 MPa. Finally, the histological results point to the biocompatibility of the composite, thus making it applicable to the surface layers of implants.

Une nouvelle méthode de détection sans marquage des interactions biomoléculaires a été développée. Elle est basée sur la conception d’une couche sensible supportée innovante réalisée par la technique de Langmuir‐Blodgett. Cette couche est composée d'un lipide à tête polaire immobilisant un cation métallique divalent capable (i) de chélater une molécule possédant une affinité pour ce type de cation et (ii) de catalyser la réaction de chimiluminescence du luminol. L'intensité du signal chimiluminescent est modulée par la présence de biomolécules fixées en surface de la couche sensible, qui modifient l'environnement immédiat du cation métallique. La variation du signal chimiluminescent (issu de la catalyse par le cation immobilisé) a pu être quantifiée et corrélée à une gamme de concentration d’histamine et d’anticorps. Les potentialités de cette approche ont finalement été exploitées pour développer une puce de PMMA de type macropuce immobilisant la monocouche de lipides. / A new label‐free detection method for biomolecular interactions was developed. It is based on the development of an original sensitive layer performed with the Langmuir‐ Blodgett technique. This layer is composed of a lipid which immobilized a bivalent metallic cation on his polar head, able (i) to chelate a molecule which has an affinity for this cation and (ii) to catalyze the luminol chemiluminescent reaction. The chemiluminescent signal intensity is modulated by the presence of immobilized biomolecules on the sensitive layer surface, which modifies the immediate environmentof the metallic cation. The chemiluminescent signal variation (from catalysis by the metallic cation) has been quantified and correlated to a histamine and antibody concentration range. The potentialities of this approach have finally been employed to achieve a PMMA chip (macroarray type), immobilizing the lipid monolayer.

<p>In the presented work, immunosensors for detection of Aflatoxin B1 based on different immobilization platforms were studied. Synthesis of an electroactive hydrogel was also carried out. Aflatoxins are a group of mycotoxins that have deleterious effects on humans and are produced during fungal infection of plants or plant products. Electrochemical immunosensor for the determination of Aflatoxin B1 (AFB1) was developed with anti-aflatoxin B1 antibody immobilized on Pt electrodes modified with polyaniline (PANi) and polystyrene sulphonic acid (PSSA). Impedimetric analysis shows that the electron transfer resistances of Pt/PANi-PSSA electrode, Pt/PANi-PSSA/AFB1-Ab immunosensor and Pt/PANi-PSSA/AFB1-Ab incubated in BSA were 0.458, 720 and 1066 k&Omega / , respectively. These results indicate that electrochemical impedance spectroscopy (EIS) is a suitable method for monitoring the change in electron-transfer resistance associated with the immobilization of the antibody. Modelling of EIS data gave equivalent circuits which showed that the electron transfer resistance increased from 0.458 k&Omega / for Pt/PANi-PSSA electrode to 1066 k&Omega / for Pt/PANi-PSSA/AFB1-Ab immunosensor, indicating that immobilization of the antibody and incubation in BSA introduced an electron transfer barrier. The AFB1 immunosensor had a detection limit of 0.1 mg/L and a sensitivity of 869.6 k &Omega / L/mg.</p>