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Neste trabalho foram obtidos nanocompósitos contendo 0, 1, 2, 5 e 10% (m/m) de argila organofílica montmorilonita cloisite 30B, contendo terminações hidroxila, por processamento reativo entre um pré-polímero com terminações isocianato e o 1,4-butanodiol, utilizando-se um misturador fechado. Os resultados mostraram que os poliuretanos termoplásticos sintetizados foram obtidos com sucesso. A adição de montmorilonita nos TPUs ocasionou a formação de folhas de argila dispersas de maneira intercalada, parcialmente esfoliada, esfoliada e aglomerados na matriz do TPU. Com a adição da argila houve modificações nos comportamentos de cristalização, estabilidade térmcica e mecanismo de degradação, assim como um aumento nos valores de energia aparente de ativação deste processo. A mobilidade de alguns segmentos poliméricos também foi alterada com a adição da argila. Portanto modificações morfológicas e viscoelásticas foram observadas para os nanocompósitos em dependência da quantidade de argila organofílica empregada, assim como a adição da organoargila alterou o comportamento térmico do poliuretano termoplástico, tornando os nanocompósitos mais suscetíveis a mudanças nos processos de fusão e cristalização em função da exposição a temperaturas elevadas. / In this study, were obtained nanocomposites containing 0, 1, 2, 5 and 10% (w/w) of organophilic clay montmorillonite Cloisite 30B, containing hydroxyl terminations, by reactive processing between a prepolymer with isocyanate terminations and 1,4-butanediol, using a closed mixer. The analysis showed that the obtained thermoplastic polyurethanes were synthesized successfully. The addition of the montmorillonite in the TPUs resulted in the formation of sheets of clay dispersed in order intercalated, partially exfoliated, exfoliated and agglomerate in the TPU matrix. With the addition of clay there were changes in the behavior of crystallization, thermal stability and degradation mechanism, as well as an increase in the values of the apparent activation energy of this process. The mobility of certain polymer segments was also changed with the addition of the clay. Therefore viscoelastic and morphological changes were observed in the nanocomposites in dependence on the amount of organophilic clay used, as well as the addition of the organophilic decreased the thermal stability of the thermoplastic polyurethane, making nanocomposites more susceptible to changes in the melting and crystallization processes due to exposure to elevated temperatures.

Neste trabalho foram obtidos nanocompósitos contendo 0, 1, 2, 5 e 10% (m/m) de argila organofílica montmorilonita cloisite 30B, contendo terminações hidroxila, por processamento reativo entre um pré-polímero com terminações isocianato e o 1,4-butanodiol, utilizando-se um misturador fechado. Os resultados mostraram que os poliuretanos termoplásticos sintetizados foram obtidos com sucesso. A adição de montmorilonita nos TPUs ocasionou a formação de folhas de argila dispersas de maneira intercalada, parcialmente esfoliada, esfoliada e aglomerados na matriz do TPU. Com a adição da argila houve modificações nos comportamentos de cristalização, estabilidade térmcica e mecanismo de degradação, assim como um aumento nos valores de energia aparente de ativação deste processo. A mobilidade de alguns segmentos poliméricos também foi alterada com a adição da argila. Portanto modificações morfológicas e viscoelásticas foram observadas para os nanocompósitos em dependência da quantidade de argila organofílica empregada, assim como a adição da organoargila alterou o comportamento térmico do poliuretano termoplástico, tornando os nanocompósitos mais suscetíveis a mudanças nos processos de fusão e cristalização em função da exposição a temperaturas elevadas. / In this study, were obtained nanocomposites containing 0, 1, 2, 5 and 10% (w/w) of organophilic clay montmorillonite Cloisite 30B, containing hydroxyl terminations, by reactive processing between a prepolymer with isocyanate terminations and 1,4-butanediol, using a closed mixer. The analysis showed that the obtained thermoplastic polyurethanes were synthesized successfully. The addition of the montmorillonite in the TPUs resulted in the formation of sheets of clay dispersed in order intercalated, partially exfoliated, exfoliated and agglomerate in the TPU matrix. With the addition of clay there were changes in the behavior of crystallization, thermal stability and degradation mechanism, as well as an increase in the values of the apparent activation energy of this process. The mobility of certain polymer segments was also changed with the addition of the clay. Therefore viscoelastic and morphological changes were observed in the nanocomposites in dependence on the amount of organophilic clay used, as well as the addition of the organophilic decreased the thermal stability of the thermoplastic polyurethane, making nanocomposites more susceptible to changes in the melting and crystallization processes due to exposure to elevated temperatures.

Neste trabalho foram obtidos nanocompósitos contendo 0, 1, 2, 5 e 10% (m/m) de argila organofílica montmorilonita cloisite 30B, contendo terminações hidroxila, por processamento reativo entre um pré-polímero com terminações isocianato e o 1,4-butanodiol, utilizando-se um misturador fechado. Os resultados mostraram que os poliuretanos termoplásticos sintetizados foram obtidos com sucesso. A adição de montmorilonita nos TPUs ocasionou a formação de folhas de argila dispersas de maneira intercalada, parcialmente esfoliada, esfoliada e aglomerados na matriz do TPU. Com a adição da argila houve modificações nos comportamentos de cristalização, estabilidade térmcica e mecanismo de degradação, assim como um aumento nos valores de energia aparente de ativação deste processo. A mobilidade de alguns segmentos poliméricos também foi alterada com a adição da argila. Portanto modificações morfológicas e viscoelásticas foram observadas para os nanocompósitos em dependência da quantidade de argila organofílica empregada, assim como a adição da organoargila alterou o comportamento térmico do poliuretano termoplástico, tornando os nanocompósitos mais suscetíveis a mudanças nos processos de fusão e cristalização em função da exposição a temperaturas elevadas. / In this study, were obtained nanocomposites containing 0, 1, 2, 5 and 10% (w/w) of organophilic clay montmorillonite Cloisite 30B, containing hydroxyl terminations, by reactive processing between a prepolymer with isocyanate terminations and 1,4-butanediol, using a closed mixer. The analysis showed that the obtained thermoplastic polyurethanes were synthesized successfully. The addition of the montmorillonite in the TPUs resulted in the formation of sheets of clay dispersed in order intercalated, partially exfoliated, exfoliated and agglomerate in the TPU matrix. With the addition of clay there were changes in the behavior of crystallization, thermal stability and degradation mechanism, as well as an increase in the values of the apparent activation energy of this process. The mobility of certain polymer segments was also changed with the addition of the clay. Therefore viscoelastic and morphological changes were observed in the nanocomposites in dependence on the amount of organophilic clay used, as well as the addition of the organophilic decreased the thermal stability of the thermoplastic polyurethane, making nanocomposites more susceptible to changes in the melting and crystallization processes due to exposure to elevated temperatures.

<p>U ovoj doktorskoj disertaciji je ispitan uticaj montmorilonita i<br />termoplastičnih segmentiranih poliuretana na kinetiku reakcija<br />umrežavanja, strukturu i svojstva funkcionalnih hibridnih<br />materijala na osnovu epoksidnih smola. Pripremljene su dve<br />serije uzoraka hibridnih materijala: prva na osnovu epoksidne<br />smole sa različitim sadržajem organski modifikovanog<br />montmorilonita (0, 1, 3, 5 i 10 mas.%) umrežene sa<br />umreživačem Jeffamine D-230; druga serija je sintetisana na<br />osnovu epoksidne smole, sa različitim sadržajem (10, 15 i 20<br />mas.%) termoplastičnog poliuretanskog elastomera sa<br />različitim sadržajem tvrdih segmenata (20, 25 i 30 mas.%)<br />sintetisanih na osnovu alifatičnog polikarbonatnog diola i<br />heksametilendiizocijanata i produživača lanca butandiola, kao<br />i katalizatora dibutiltin dilaurata; kao i bez dodatog elastomera<br />umrežene sa diaminom Jeffamine D-2000. Umrežavanje<br />reaktivnih sistema sa projektovanim sirovinskim sastavom je<br />praćeno diferencijalnom skenirajućom kalorimetrijom (DSC).<br />Modeli izokonverzije primenjeni su da se ustanovi da li<br />dodatak punila utiče na reakciju umrežavanja hibridnih<br />materijala. Sintetisani materijali su analizirani dinamičkomehaničkom<br />analizom (DMA), mikroskopijom atomskih sila<br />(AFM), kao i TG-DSC i TG-MS metodama i određena su<br />mehanička svojstva (zatezna čvrstoća, prekidno izduženje i<br />tvrdoća po &Scaron;oru A). Epoksidni materijal sa 10 mas.% organski<br />modifikovanog montmorilonita ima značajno niže vrednosti<br />energija aktivacije za definisane stepene reagovanja, čime je<br />potvrđen katalitički efekat gline sa slojevitom strukturom kada<br />je prisutna u reakcionoj sme&scaron;i u dovoljnoj količini. Uticaj<br />otežane difuzije pri kraju reakcije je izraženiji u prisustvu<br />montmorilonita, čime je pokazano da njegovo prisustvo utiče<br />na ceo mehanizam umrežavanja. Utvrđeno je da na vrednosti<br />G&#39;, pored udela montmorilonita, utiče i stepen dispergovanja<br />čestica unutar polimerne matrice. Zaključeno je da dodatak<br />punila do 3 mas. % utiče povoljno na ispitana mehanička<br />svojstva, dok pri sadržaju od 5 i 10 mas. % dolazi do<br />aglomeracije čestica punila, &scaron;to negativno utiče na ispitana<br />svojstva, osim tvrdoće, koja se povećava linearno sa dodatkom<br />punila montmorilonita. Na osnovu rezultata TG analize<br />zaključeno je da je sa porastom udela montmorilonita u<br />epoksidnoj matrici termička stabilnost uzoraka ispitivanih u<br />atmosferi vazduha neznatno pobolj&scaron;ana, dok u inertnoj<br />atmosferi nema uticaja na termičku stabilnost, niti na<br />mehanizam raspada hibridnih materijala na osnovu epoksidnih<br />smola sa različitim udelima montmorilonita. Kod sistema kod<br />kojih je dodavan termoplastični poliuretanski elastomer,<br />zaključeno je da pri većem sadržaju segmentiranih poliuretana<br />u epoksidnoj matrici (10 i 15 mas.%) proces umrežavanja<br />započinje na nižim temperaturama i maksimalna brzina se<br />ostvaruje na nižim temperaturama, a najveća vrednost<br />promena ukupne entalpije reakcije umrežavanja je određena za<br />hibridni materijal sa poliuretanom koji u svojoj strukturi ima<br />30 mas.% tvrdih segmenata. Zatezna čvrstoća hibridnih<br />materijala raste sa porastom udela tvrdih segmenata u strukturi<br />poliuretana, kao i sa porastom masenog udela poliuretanskog<br />elastomera u epoksidnoj matrici. Dodatkom termoplastičnih<br />segmentiranih poliuretana značajno je povećano prekidno<br />izduženje epoksidnih smola. Sa porastom udela tvrdih<br />segmenata kod poliuretana dodatih u istom masenom procentu<br />u epoksidnu matricu, tvrdoća raste. Ustanovljeno je da na<br />konačna svojstva hibridnih materijala utiče izbor polaznih<br />komponenti, način ume&scaron;avanja punila u matricu i uslovi pri<br />kojima se vr&scaron;i umrežavanje. Zaključeno je da je dobro<br />poznavanje kinetičkih parametara reakcije umrežavanja važno<br />za pravilan odabir optimalnih uslova za proizvodnju i preradu<br />hibridnih materijala u industrijskim uslovima.</p> / <p>In this thesis the influence of clay fillers and thermoplastic<br />segmented polyurethanes on the curing kinetics, structure and<br />properties of functional hybrid materials based on epoxy resins<br />was assessed. Two sets of hybrid material samples were<br />prepared. First type of samples was based on epoxy resin with<br />a different content of organically modified montmorillonite (0,<br />1, 3, 5 and 10 wt. %) and crosslinking with hardener Jeffamine<br />D-230. Second type of samples was based on epoxy resin,<br />having different content (10, 15 and 20 wt. %) of thermoplastic<br />segmented polyurethane with different content of hard<br />segments (20, 25 and 30 wt. %) based on aliphatic<br />polycarbonate macrodiols and hexamethylene diisocyanate,<br />with chain extender 1,4-butanediol and the catalyst, dibutyltin<br />dilaurate, and also a sample without added elastomeric<br />polyurethane and crosslinking with hardener Jeffamine D-<br />2000. The curing of the hybrid materials based on epoxy resins<br />systems were investigated by non-isothermal differential<br />scanning calorimetry (DSC). The kinetic study by<br />isoconversion models has been carried out using data from<br />DSC. The synthesized materials were analyzed by dynamicmechanical<br />analysis (DMA), atomic force microscopy (AFM)<br />as well as TG-DSC and TG-MS methods and mechanical<br />properties (tensile strength, elongation and hardness at Shore<br />A) were determined. Epoxy based hybrid material with 10 wt.<br />% of the organically modified montmorillonite has<br />significantly lower activation energy values for the defined<br />reaction rates, thereby confirming the catalytic effect of the<br />clay with the layered structure when present in the reaction<br />mixture in sufficient quantity. The diffusion effects at the end<br />of the reaction are more pronounced in the presence of<br />montmorillonite, which indicates that its presence affects the<br />entire curing mechanism. It was found that G&#39;, along with<br />montmorillonite content, is affected by the degree of particle<br />dispersion inside the polymer matrix. It was concluded that the<br />addition of montmorillonite up to 3 wt. % improves<br />investigated mechanical properties, while the samples with 5<br />and 10 wt. % of montmorillonite resulted in agglomeration of<br />the filler particles, which negatively influenced the<br />investigated properties, except for the hardness which<br />increases linearly with the addition of montmorillonite. TG<br />analysis shows that the increase of montmorillonite content in<br />the epoxy matrix slightly improves the thermal stability in the<br />air, while in the inert atmosphere there is no influence on the<br />thermal stability nor on the mechanism of the decomposition<br />of epoxy based hybrid materials. In the system with a<br />thermoplastic polyurethane filler, it was concluded that hybrid<br />materials with a higher content of segmented polyurethane (10<br />and 15 wt. %), curing process starts at lower temperatures and<br />the maximum speed is achieved at lower temperatures and the<br />highest value of changes in total enthalpy of the crosslinking<br />reaction is determined for the epoxy hybrid material with<br />polyurethanes containing 30 wt. % of hard segments. Tensile<br />strength of hybrid materials increases with the increase of hard<br />segments content in the polyurethane elastomer as well as with<br />the increase of polyurethane content in the epoxy matrix. The<br />addition of thermoplastic segmented polyurethanes<br />significantly increased the elongation at break of prepared<br />epoxy resins hybrid materials. The increase of the hard<br />segments content in polyurethane, in the same ratio, improves<br />hardness of epoxy based hybrid material. It was concluded that<br />the final properties of hybrid materials are influenced by the<br />selection of initial compounds, methods of processing and the<br />curing conditions. It was concluded, as well that knowing the<br />kinetic parameters of curing reaction is important for the<br />proper selection of optimal parameters for production and<br />processing of hybrid materials in industrial conditions.</p>

Des polyuréthanes thermoplastiques (TPU) contenant des segments rigides et segments souples d’architecture moléculaire variable sont synthétisés en deux étapes, dont la première fait intervenir un pré-polymère polyuréthane. La microstructure de ces polymères montre qu’une séparation de phases intervient entre segments souples et rigides selon la nature des segments utilisés. Les segments rigides peuvent s’organiser sous deux formes, l’une amorphe et l’autre organisée sous forme d’entités cristallines. La morphologie des TPU dépend de la structure chimique du segment rigide employé. L’incompatibilité entre segments souples et rigides a été mise en évidence à partir de l’analyse des paramètres de solubilité complétée des caractérisations à différentes échelles par des techniques de microscopie (électronique et AFM) et de diffusion des rayons X. Ces polyuréthanes thermoplastiques sont ensuite utilisés pour préparer des mélanges bitume –polymère. Les interactions entre segments du polymère et fractions du bitume sont étudiées en considérant les paramètres de solubilité de chacun d’eux et des mesures de gonflement afin de juger de la miscibilité entre les composés. Des huiles modèles sont employées dans le but de mimer certaines fractions huileuses du bitume, et les segments souples et rigides sont synthétisés séparément afin d’étudier les propriétés de chacune des phases en présence dans le mélange bitume – polymère. La morphologie multi-échelle des mélanges est étudiée en lien avec les propriétés rhéologiques et la structure du polymère utilisé. L’ajout de polymère dans le bitume permet de modifier les propriétés viscoélastiques du bitume au-delà de sa transition vitreuse grâce au gonflement sélectif du polymère par les fractions huileuses. Après avoir mis en évidence et analysé le gonflement sélectif grâce à la prise en considération des paramètres de solubilité et mesuré les tensions interfaciales, nous montrons que la présence d’une phase continue riche en polymère contenant des segments rigides semi-cristallins dans les mélanges conduit à retarder l’écoulement du matériau bitumineux à plus hautes températures. La composition en huile de cette phase riche en polymère dépendra de son affinité avec les fractions du bitume et donc de la structure chimique du polymère. De plus, la teneur du polymère en segments rigides semi-cristallins est aussi un levier permettant d’intervenir sur son affinité avec le bitume et par conséquent sur les propriétés rhéologiques du mélange bitume-polymère. / Thermoplastic polyurethane (TPU) containing hard and soft segments with variable molecular architecture are synthesized in two steps, the first one including a polyurethane pre-polymer. The microstructure of theses polymers shows phase separation occurring between soft and hard segments according to the nature of the segments. Hard segments can organize under two forms, either amorphous or crystalline. The morphology of TPU depends on the chemical structure of the hard segment involved. Incompatibility between soft and hard segments was highlighted from solubility parameters analysis, complete with characterization at various scales with microscopy (electron and AFM) and X-ray scattering technics. Theses thermoplastic polyurethanes are used to prepare bitumen-polymer blends. Interactions between the polymer segments and bitumen fractions are studied, considering solubility parameters of each of them and swelling measurements in order to study miscibility between the compounds. Model oils are used in the aims of mimicking some oily fractions of bitumen, and soft and hard segments are separately synthesized to study properties of each phases in the bitumen-polymer mixture. Multi-scale morphology of the blends is studied in connection with rheological properties and structure of the used polymer. The addition of polymer in bitumen allows to modify viscoelastic properties of bitumen beyond its glass transition due to the selective swelling of the polymer by the oily fractions. Having highlighted and analyzed the selective swelling by considering solubility parameters and interfacial tension measurements, we show that the presence of a continuous polymer-rich phase containing semi-crystalline hard segments in the blends leads to delay the flow of the bituminous material at highest temperatures. The oil composition of this polymer-rich phase will depend on its affinity with the fractions of bitumen and thus on the chemical structure of the polymer. In addition, semi-crystalline hard segment content of the polymer is also a key parameter allowing to adjust its affinity with bitumen and consequently on rheological properties of the bitumen-polymer mixture.