L’objet de ce travail est d’étudier l’influence de l’anisotropie structurale, induite lors de la mise en forme d’un Polylactide (PLA), sur les dynamiques moléculaires de la phase amorphe. Deux procédés de mise en oeuvre sont retenus : l’électrofilage et la cristallisation induite par flux. Le premier permet d’aboutir à un système non-cristallin, lorsque le deuxième permet d’aboutir à un système semi-cristallin. Pour chaque système, une étude microstructurale est préalablement réalisée pour mettre en avant l’anisotropie structurale induite lors de la mise en oeuvre. Pour ce faire différentes techniques d’analyses sont utilisées : microscopie optique, microscopie électronique, diffraction des rayons X, calorimétrie à balayage différentielle (DSC) et calorimétrie à balayage rapide (FSC). L’utilisation de la FSC s’avère précieuse. Du fait des vitesses extrêmement rapide (1000 K.s-1) et de la diminution importante de la masse (dizaine de nanogrammes), la transition vitreuse et la cinétique de vieillissement physique sont au préalable étudiées dans le cas d’un PLA amorphe. Il est montré que les vitesses de refroidissement atteignable en FSC permettent d’accélérer les cinétiques de vieillissement physique. Les dynamiques moléculaires sont ensuite étudiées à travers le concept de coopérativité et le phénomène de vieillissement physique. Il est montré que l’orientation préférentielle induite dans le système non-cristallin aboutit à la formation de mésophase qui augmente la coopérativité, autrement dit les interactions intermoléculaires. Dans le cas du système semi-cristallin, les dynamiques moléculaires sont influencées par le couplage amorphe/cristal et le confinement des cristaux, et non pas par l’anisotropie structurale induite avant cristallisation. / The aim of this work is to investigate the molecular dynamics of Polylactide (PLA) subjected to structural anisotropy during its processing. To do so, two experimental set-ups were used: electrospinning and flow induced crystallization. The first one leads to non-crystalline system, while the second one leads to semi-crystalline system. For each system, the microstructure is investigated to highlight the structural anisotropy induced during the processing. Different experimental techniques are used: optical microscopy, electronic microscopy, X-ray diffraction, differential scanning calorimetry (DSC) and fast scanning calorimetry (FSC). FSC proves to be useful. Due to the high scanning rates (1000 K.s-1) and the decrease of the sample mass (few tens of nanogrammes), glass transition and physical aging kinetics are beforehand investigated in the case of a wholly amorphous PLA. It is shown that high cooling rates available by FSC allow to accelerate physical aging kinetics. Molecular dynamics are then investigated through concept of cooperativity and phenomenon of physical aging. It is shown that preferential orientation induced during electrospinning leads to the formation of mesophase, which increase cooperativity, namely the intermolecular interactions. With regard to semi-crystalline system, molecular dynamics are only affected by the coupling between amorphous/crystal and the confinement effect of the crystals, rather than the structural anisotropy induced before the crystallization step.

This project investigates the moisture barrier properties of bio-based polymers and ways of improving them. The first section addresses the effect of crystallinity on the water permeability of poly(lactic acid) (PLA). The second section investigates PLA/talc composites and PLA/ montmorillonite nanocomposites. The third section is focused on a new polymer, polybutylene succinate (PBS), and its nanocomposites with montmorillonite. In the first section, the water vapour transmission rates (WVTR) through samples of polylactic acid of different crystallinities have been measured. Three different grades of commercial PLA were used with different ratios of L-lactide and D-lactide to give a range of crystallinities from 0 to 50%. Sheets of PLA were prepared by melt compounding followed by compression moulding and annealing at different temperatures and for different times to give the range of crystallinities required. Crystallinity was measured by differential scanning calorimetry (DSC) and the morphology of the samples was observed under crossed polars in a transmitted light microscope. Water vapour transmission rates through the films were measured at 38°C and at a relative humidity of 90%. It was found that the measured values of WVTR decreased linearly with increasing crystallinity of the PLA from 0 to 50%. The results are discussed in terms of the effect of crystallinity on solubility and shown to fit the tortuous path model. The model was also successfully used to explain published data on water permeability of polyethylene terephthalate. In the second section, a series of PLA/talc composites and PLA/ montmorillonite nanocomposites were prepared by melt compounding followed by compression moulding. The morphologies of the composites were investigated using transmission electron microscopy (TEM) and wide-angle X-ray diffraction (WAXD) and it was found that the fillers were well dispersed in the polymer matrix. The average aspect ratio of the compounded talc was found to be 8, and that of the nanoclay was found to be 50. Water vapour transmission rates (WVTR) through the films were measured at 38°C and at a relative humidity of 90%. It was found that the measured values of WVTR decreased with increasing filler content and the results gave good agreement with predictions from the Nielsen tortuous path model. In the third section, PBS/ montmorillonite nanocomposites were prepared by melt compounding followed by compression moulding. The melting and crystallisation behaviour of the pure PBS samples were investigated using differential scanning calorimetry (DSC) and cross polarised optical microscopy. A slight decrease of the degree of crystallinity was found in PBS containing 5% nanoclay. The morphology of the composites was investigated using transmission electron microscopy (TEM) and wide-angle X-ray diffraction (WAXD) and it was confirmed that that composite structures were intercalated. Water vapour transmission rates (WVTR) through the PBS sheets were measured using a MOCON Permatran-W®398. The measured values of WVTR decreased with increasing nanoclay content. However, the experimental values were all higher than the values predicted by the Nielsen tortuosity model. This result shows that in the case of PBS, which is a highly crystalline polymer, the nanoclay is not as well dispersed and is not as effective in reducing water vapour permeability as in the case of PLA.

Le rotomoulage est une technique de transformation des polymères thermoplastiques qui souffre encore aujourd'hui d'un certain empirisme. Depuis de nombreuses années, la simulation du procédé de rotomoulage est considérée comme une nécessité à l'introduction de nouveaux matériaux et à l'élargissement de ses domaines applications. Ces travaux s'inscrivent à la suite de nombreuses études visant à développer un logiciel de simulation permettant de prédire le comportement de la matière en condition de mise en œuvre.L'objectif de cette thèse est de s'intéresser plus particulièrement à la simulation de la phase de refroidissement. Pour cela, il est nécessaire de mettre au point un modèle décrivant la cinétique de cristallisation et pouvant tenir compte des contraintes liées aux conditions thermiques extrêmes dans lequel se déroule le procédé (température, présence d'oxygène, temps de cycle long), lesquelles peuvent avoir une influence sur la thermostabilité du polymère. Dans le cadre de cette étude, le choix s'est porté sur le Polylactide (PLA). Le PLA présente une faible stabilité thermique et une cinétique de cristallisation lente, ce qui facilite l'observation de ces deux phénomènes. Dans un premier temps, la thermodégradation du PLA a été étudiée et un modèle visant à décrire son évolution dans des conditions proches de celles du procédé, a été mis en place. Puis, une étude de cristallisation considérant l'influence de la masse moléculaire et du polymorphisme du PLA, a été réalisée afin de modéliser sa cinétique. Enfin, un couplage des deux modèles a été envisagé dans l'optique de les intégrer à une simulation globale des transferts thermiques impliqués dans le procédé de rotomoulage. / Rotational molding is a thermoplastic polymer processing technology which has been, for many years, suffering from a kind of empiricism.The simulation of rotational molding is believed to be the key to introduce new materials and more diversity in its applications. This work follows several studies aimed to develop a simulation software which would predict the material behavior in processing conditions.Consequently, this thesis will focus specifically on the simulation of the cooling phase. This type of simulation requires kinetic crystallization modeling, acknowledging the influence that the extreme thermal conditions of the rotomolding process can have on the thermal stability of the material. In this study we chose to work with Polylactic acid (PLA), a material suffering poor thermal stability and presenting with slow kinetic crystallization, making it suitable to observe these phenomenona. First, the thermal degradation of PLA has been studied and a model describing its behavior, under similar conditions to processing, has been proposed. Then, a crystallization study including the influence of the molecular weight, as well as the polymorphism of PLA, has been completed and the kinetic crystallization modeling has been performed. Finally, the integration of both models in a global simulation of the thermal transfers describing the rotomolding process has been investigated.

Current plastics are mostly derived from petrochemical sources, as it is a finite resource renewable replacements are sought after. Polymers derived from cyclic esters such as; lactide, valerolactone and caprolactone are of interest. An industrially viable method of producing stereocontrolled polylactide (PLA) from rac-lactide is desired. Previous work on poly(cyclic esters) is overviewed in chapter 1 with an emphasis upon PLA. Chapter 2 reports the coordination of Ti(OiPr)4 to homo/piperazine bridged bis(phenol) (salan) ligands. Under ambient conditions bimetallic structures were produced and a steric dependent equilibrium system is discussed. Forcing conditions resulted in monometallic homopiperazine salan complexes. Their application for the ring-opening-polymerisation (ROP) of rac-lactide is investigated. Homo/piperazine salan titanium catecholates were synthesised and their cytotoxicity investigated by collaborators. Chapter 3 details the synthesis of monometallic homopiperazine salan zirconium/hafnium isopropoxide complexes. Their utility for the ROP of rac-lactide in solution and solvent free systems are discussed. Bimetallic or tetrametallic solid state structures from attempts to coordinate Zr(IV)/Hf(IV) metals to piperazine salan ligands are also discussed. Chapter 4 discusses the complexation of AlMe3 with homopiperazine salan ligands. The resulting monometallic complexes were inactive for the ROP of lactide. Benzyl alcohol derivatives were synthesised and trialled for solvent free ROP of rac-lactide, δ-valerolactone, ε-caprolactone. Co-polymerisations were investigated and a tri-block polymer of poly(ε-caprolactone/δ-valerolactone/rac-lactide) was prepared. Chapter 5, trans-1,4-DACH salen ligands were synthesised and investigated as ligands with Al(III), Ti(IV), Zr(IV), and Zn(II) metal centres. Bimetallic Al(III) and Ti(IV) structures were characterised and trialled for the ROP of rac-lactide. Isotactic PLA was reported for aluminium complexes, dependent upon phenoxy substituents, and these polymerisations were shown to be immortal in nature. Chapter 6 details the synthesis of trans-1,2-DACH salalen ligands which were complexed to AlMe3, these initiators were investigated for the solution ROP of rac-lactide. The further synthesis of benzyloxy derivatives is also reported and they were utilised for solution and solvent free polymerisations of rac-lactide. The initiator’s behaviour is discussed with respect to varying amine and imine groups.

Understanding, and ultimately, predicting the degradation of bioresorbable composites made of biodegradable polyesters and calcium-based ceramics is paramount in order to fully unlock the potential of these materials, which are heavily used in orthopaedic applications and also being considered for stents. A modelling framework which characterises the degradation of bioresorbable composites was generated by generalising a computational model previously reported in literature. The framework uses mathematical expressions to represent the interwoven phenomena present during degradation. Three ceramic-specific models were then created by particularising the framework for three common calcium-based fillers, namely tricalcium phosphate (TCP), hydroxyapatite (HA) and calcium carbonate (CC). In these models, the degradation of a bioresorbable composite is described with four parameters: the non-catalytic and auto-catalytic polymer degradation rates, $k_1$ and $k_2'$ respectively and the ceramic dissolution rate and exponent, $A_\text{d}$ and $\theta$ respectively. A comprehensive data mining exercise was carried out by surveying the existing literature in order to obtain quantitative degradation data for bioresorbable composites containing TCP, HA and CC. This resulted in a database with a variety of case studies. Subsequently, each case study was analysed using the corresponding ceramic-specific model returning a set of values for the four degradation constants. Both cases with agreement and disagreement between model prediction and experimental data were studied. 76% of the 107 analysed case studies displayed the expected behaviour. In general terms, the analysis of the harvested data with the models showed that a wide range of degradation behaviours can be attained using different polymeric matrix - ceramic filler combinations. Furthermore, the existence of discrepancies in degradation behaviour between a priori similar bioresorbable composites became apparent, highlighting the high number of hidden factors affecting composite degradation such as polymer tacticity or ceramic impurities. The analysis of the case studies also highlighted that the ceramic dissolution rate needed to depict the portrayed degradation behaviours is significantly higher than that reported for ceramics alone in dissolution studies under physiological conditions, indicating that studies of the filler elements alone do not provide a complete picture. Lastly, the computational analysis provided insight into the complex influence of factors such as sample porosity and degradation protocol in the degradation behaviour. In addition to the computational analysis of literature data, an experimental degradation study was carried out with nanocomposites made of calcium carbonate and poly(D,L-lactide-co-glycolide). This study showed the existence of a clear buering effect with the addition of the ceramic filler and confirmed the assumptions employed in the modelling framework in this particular bioresorbable composite. The detailed nature and modest size of these data enabled a more precise and thorough analysis using the CC composites degradation model. In summary, the modelling framework is able to capture the main degradation behaviour of bioresorbable composites and also point to factors responsible for dissimilar behaviours. The degradation maps generated with the values of $k_1$, $k_2'$, $A_\text{d}$ and $\theta$ output by the models appear to be a good tool to summarise, classify and facilitate the analysis and search of specific bioresorbable composites.

O Poli (ácido lático), PLA, e a Policaprolactona, PCL, são dois poliésteres termoplásticos alifáticos, conhecidos por suas capacidades de biodegradabilidade e bioreabsoção e, nos últimos anos, têm sido amplamente estudados como alternativas aos metais em bioimplantes. Por terem características mecânicas distintas, muitas vezes estes materiais são utilizados em blendas poliméricas, visando obter uma combinação construtiva entre tais propriedades; o PLA é mais rígido, tem maior resistência à tração, contudo é frágil; o PCL tem menor rigidez, contudo apresenta maior tenacidade, além de ser extremamente dúctil. A combinação destas propriedades em uma blenda torna a dupla PLA/PCL especialmente atraente à utilização em stents coronarianos, no qual o uso do PLA como único componente do stent pode causar complicações ao paciente, devido à necessidade de aquecimento do material acima de sua temperatura de transição vítrea (ao redor dos 60°C) para que ele possa ser inflado sem risco de uma catastrófica falha. Entretanto, tal aquecimento pode causar necrose dos tecidos coronarianos. Assim sendo, a inclusão do PCL na blenda tem como principal objetivo diminuir a temperatura de transição vítrea do conjunto do PLA. Este estudo teve como principal foco a análise de como o acréscimo de PCL e de dois diferentes tipos de compatibilizantes impactou no comportamento térmico e mecânico das blendas. Para tal, testes dos vinte tipos de blendas desenvolvidas foram submetidos a análises de DSC, DMTA e a ensaios de tração e impacto. Os últimos dois são de fundamental importância, pois o PLA tem pouca ductilidade e resistência ao impacto. Além desses testes, foram efetuadas também análises MEV, com intuito de verificar as modificações morfológicas das blendas ao adicionar-se tanto os compatibilizantes, quanto PCL às formulações. Ensaios espectroscópicos na região do infravermelho também foram conduzidos, a fim de analisar-se, além das estruturas químicas dos componentes da blenda, as interações entre eles e as modificações espectrais causadas por ela. Testes preliminares, como o GPC e a termogravimetria, também estão presentes. Com isso foi possível, além de fazer a determinação da massa molar dos componentes da blenda, ter acesso a dados acerca da degradação térmica dos polímeros utilizados. Ademais, a fim de analisar-se preliminarmente o potencial das blendas desenvolvidas como biomaterial, foram efetuados testes de Citotoxidade em formulações selecionadas. Como resultado da intensa investigação sobre as propriedades das blendas PLA/PCL, compatibilizadas ou não, foi verificado grande aumento de ductilidade nas formulações, sem perda apreciável de resistência mecânica. Em muitas das blendas, houve também expressivo aumento na tenacidade. Em contrapartida, não foram verificadas alterações significativas no perfil térmico das amostras, conforme DMTA e DSC. / The Polylactide, PLA, and the Polycaprolactone, PCL, are two thermoplastic aliphatic polyesters, known for their biodegradability and bioresorption abilities and, in the latest years, they have been extensively studied as alternatives to metals in bioimplants. Since they have distinct mechanical properties, these materials are many times used in polymeric blends, in order to obtain a constructive combination of the mechanical properties; the Polylactide is more rigid and has better tensile resistance, however it is brittle; on the other hand, the Polycaprolactone has lower rigidity, but it has better toughness, in addition to its great ductility. The combination of these properties in a blend makes the PLA/PCL configuration especially attractive to the use in coronary stents, on which the use of the PLA as only component may cause serious complications to the patient, due to its need to be warmed above its glass transition temperature (around 60°C) in order to be inflated without the risk of any catastrophic failure. However, this heating might cause necrosis of the coronary tissue. The inclusion of the PCL on the blend has, as a main goal, the objective of, in addition to lowering the glass transition temperature on the aggregate, is to allow the expansion of the material with no risk of failure. This study focused on how the addition of PCL and two different kinds of compatibilizers alters the thermal and mechanical behavior of the blends. To do so, tests were performed on the twenty types of blends developed, e.g. DSC, DMTA, tensile and impact tests. The latter two are of critical importance, because the Polylactide has little toughness and ductility. Furthermore, SEM was also performed in order to verify the morphological changes caused by increasing the PCL concentration on the blends, as well as the addition of the compatibilizers. Infrared spectroscopic analysis was also conducted on the blends, thus the chemical structures of the main components of the blends could be assessed, as well as the interactions and the spectral changes caused by it. Preliminary tests, for example, GPC and thermogravimetry were also conducted. With this data, it was possible to determine the molar mass of the blends components and assess the thermal degradation profile of the materials used. Moreover, preliminary tests were conducted in order to determine the potential some selected blends have as biomaterials. As the result of this deep research on the PLA/PCL blends properties, compatibilized or not, it was possible to achieve relevant increase in the ductility and toughness of the formulations, with no significant loss in terms of mechanical resistance. On the other hand, no significant changes on the thermal profile of the blends were observed, according to DMTA and DSC tests.

L'utilisation de polymères biodégradables synthétiques connaît un grand essor depuis une dizaine d'années. Parmi ces polymères, les polyesters occupent une place privilégiée car ils sont biocompatibles : ils sont d'origine naturelle ou d'origine synthétique. Dans tous les cas, on peut les préparer par polymérisation par ouverture de cycle (ROP) à partir de lactones1. <br /> L'utilisation des lactones est parfois limitée à cause de leur faible polymérisabilité. Cette dernière est contournée par l'utilisation de systèmes catalytiques très réactifs souvent à base de métaux qui ne sont pas toujours compatibles avec une application en biologie (pharmacologie, environnement)2. Une approche pour pallier ce problème consiste à activer ‘chimiquement' ces monomères pour en tirer un avantage dans le processus de polymérisation. Le L-lacOCA est ainsi un analogue du L-lactide qui possède une fonction O-carboxyanhydride (OCA). Ce monomère est beaucoup plus réactif que la dilactone cyclique équivalente : il polymérise de façon contrôlée et vivante dans des conditions catalytiques plus douces3. <br /> Ce travail commence par une étude théorique de la ROP du L-lacOCA et du L-lactide catalysée par la 4-diméthylaminopyridine (DMAP) et en présence d'un alcool. Le mécanisme de la polymérisation ainsi révélé consiste en une activation basique de l'amorceur par la DMAP. Pour ce catalyseur, il y a mise en évidence pour la première fois d'un mode d'action bifonctionnel inusuel qui met en jeu une liaison hydrogène de faible énergie4.<br /> La deuxième partie du manuscrit décrit le développement de la ROP du L-lacOCA avec un systême catalytique alternatif écocompatible : la catalyse enzymatique. Jusqu'à maintenant, les enzymes réalisent difficilement la ROP du lactide. Avec deux lipases, la Novozyme 435 et la lipase PS, il a été possible d'obtenir du polylactide de haut poids moléculaire à partir du monomère activé. Dans le cas de la Novozyme 435, la polymérisation est contrôlée et possède un caractère vivant.<br /> Dans une dernière partie, nous avons essayé d'étendre le principe d'activation du motif OCA à d'autres monomères. Nous avons étudié la ROP des β-OCAs, les O-carboxyanhydrides à 6 chaînons qui pourraient donner accès aux polymères naturels comme le PHB. Trois monomères de ce type, le PivOCA, le MepOCA et le ButOCA ont été synthétisés. L'étude de leurs réactivités a mis en avant un problème de sélectivité entre les deux carbonyls du motif OCA lors d'une attaque nucléophile. A cause de réactions secondaires, les essais de ROP ont montré qu'il était difficile d'accéder proprement à des polyesters.<br />Références<br />1. Biopolymers, Wiley VCH, 2003, Vol. 3a-3b-4.<br />2. O. Dechy-Cabaret, B. Martin-Vaca, D. Bourissou, Chem. Rev., 2004 (104) 6147.<br />3. O. Thillaye du Boullay, E. Marchal, B. Martin-Vaca, F. P. Cossio and D. Bourissou., J. Am. Chem. Soc., 2006 (128) 16442.<br />4. C. Bonduelle, B. Martin-Vaca, F.P. Cossio, D. Bourissou, Chem. Eur. J., 2008 , 14, 5304.

Thèse numérisée par la Division de la gestion de documents et des archives de l'Université de Montréal

O Poli (ácido lático), PLA, e a Policaprolactona, PCL, são dois poliésteres termoplásticos alifáticos, conhecidos por suas capacidades de biodegradabilidade e bioreabsoção e, nos últimos anos, têm sido amplamente estudados como alternativas aos metais em bioimplantes. Por terem características mecânicas distintas, muitas vezes estes materiais são utilizados em blendas poliméricas, visando obter uma combinação construtiva entre tais propriedades; o PLA é mais rígido, tem maior resistência à tração, contudo é frágil; o PCL tem menor rigidez, contudo apresenta maior tenacidade, além de ser extremamente dúctil. A combinação destas propriedades em uma blenda torna a dupla PLA/PCL especialmente atraente à utilização em stents coronarianos, no qual o uso do PLA como único componente do stent pode causar complicações ao paciente, devido à necessidade de aquecimento do material acima de sua temperatura de transição vítrea (ao redor dos 60°C) para que ele possa ser inflado sem risco de uma catastrófica falha. Entretanto, tal aquecimento pode causar necrose dos tecidos coronarianos. Assim sendo, a inclusão do PCL na blenda tem como principal objetivo diminuir a temperatura de transição vítrea do conjunto do PLA. Este estudo teve como principal foco a análise de como o acréscimo de PCL e de dois diferentes tipos de compatibilizantes impactou no comportamento térmico e mecânico das blendas. Para tal, testes dos vinte tipos de blendas desenvolvidas foram submetidos a análises de DSC, DMTA e a ensaios de tração e impacto. Os últimos dois são de fundamental importância, pois o PLA tem pouca ductilidade e resistência ao impacto. Além desses testes, foram efetuadas também análises MEV, com intuito de verificar as modificações morfológicas das blendas ao adicionar-se tanto os compatibilizantes, quanto PCL às formulações. Ensaios espectroscópicos na região do infravermelho também foram conduzidos, a fim de analisar-se, além das estruturas químicas dos componentes da blenda, as interações entre eles e as modificações espectrais causadas por ela. Testes preliminares, como o GPC e a termogravimetria, também estão presentes. Com isso foi possível, além de fazer a determinação da massa molar dos componentes da blenda, ter acesso a dados acerca da degradação térmica dos polímeros utilizados. Ademais, a fim de analisar-se preliminarmente o potencial das blendas desenvolvidas como biomaterial, foram efetuados testes de Citotoxidade em formulações selecionadas. Como resultado da intensa investigação sobre as propriedades das blendas PLA/PCL, compatibilizadas ou não, foi verificado grande aumento de ductilidade nas formulações, sem perda apreciável de resistência mecânica. Em muitas das blendas, houve também expressivo aumento na tenacidade. Em contrapartida, não foram verificadas alterações significativas no perfil térmico das amostras, conforme DMTA e DSC. / The Polylactide, PLA, and the Polycaprolactone, PCL, are two thermoplastic aliphatic polyesters, known for their biodegradability and bioresorption abilities and, in the latest years, they have been extensively studied as alternatives to metals in bioimplants. Since they have distinct mechanical properties, these materials are many times used in polymeric blends, in order to obtain a constructive combination of the mechanical properties; the Polylactide is more rigid and has better tensile resistance, however it is brittle; on the other hand, the Polycaprolactone has lower rigidity, but it has better toughness, in addition to its great ductility. The combination of these properties in a blend makes the PLA/PCL configuration especially attractive to the use in coronary stents, on which the use of the PLA as only component may cause serious complications to the patient, due to its need to be warmed above its glass transition temperature (around 60°C) in order to be inflated without the risk of any catastrophic failure. However, this heating might cause necrosis of the coronary tissue. The inclusion of the PCL on the blend has, as a main goal, the objective of, in addition to lowering the glass transition temperature on the aggregate, is to allow the expansion of the material with no risk of failure. This study focused on how the addition of PCL and two different kinds of compatibilizers alters the thermal and mechanical behavior of the blends. To do so, tests were performed on the twenty types of blends developed, e.g. DSC, DMTA, tensile and impact tests. The latter two are of critical importance, because the Polylactide has little toughness and ductility. Furthermore, SEM was also performed in order to verify the morphological changes caused by increasing the PCL concentration on the blends, as well as the addition of the compatibilizers. Infrared spectroscopic analysis was also conducted on the blends, thus the chemical structures of the main components of the blends could be assessed, as well as the interactions and the spectral changes caused by it. Preliminary tests, for example, GPC and thermogravimetry were also conducted. With this data, it was possible to determine the molar mass of the blends components and assess the thermal degradation profile of the materials used. Moreover, preliminary tests were conducted in order to determine the potential some selected blends have as biomaterials. As the result of this deep research on the PLA/PCL blends properties, compatibilized or not, it was possible to achieve relevant increase in the ductility and toughness of the formulations, with no significant loss in terms of mechanical resistance. On the other hand, no significant changes on the thermal profile of the blends were observed, according to DMTA and DSC tests.

No description available.