The context of this thesis is a research project focused on the investigation of a renewable biopolymer-poly(lactic acid) (PLA) as a potential replacement of petroleum-based polymers in advanced nanocomposites reinforced with Microfibrillated cellulose (MFC). MFC is extracted from wood, which is a renewable, sustainable, carbon neutral and recyclable material. This advanced MFC-PLA bio- based composite material is expected to allow for the substitution of petroleum-based plastics in various markets and applications. The specific objectives of the thesis are: 1) to describe the morphological characterization of MFC used for prototype MFC-PLA composites, and 2) to determine the mechanical properties of the prototype MFC-PLA nanocomposites formulation generated in form of thin transparent films. In order to meet this objective it was necessary to: 2.1) develop a methodology for optical strain measurement in transparent thin films; and 2.2) develop an effective methodology for obtaining multiple mechanical properties from small number of specimens of prototype materials subjected to tensile tests. Two types of MFC, one obtained by courtesy of University of Maine and the other purchased from Innventia AB company, were investigated under a field emission scanning electron microscopy (FESEM). The micrographs obtained from FESEM showed that both types of MFC were of complex hierarchical structures, which did not allow qualitative characterization of the morphological features in terms of particulate composites nor cellular solids. Since prototype formulations of MFC-PLA composites were generated in small amounts (typically one Petri dish) in a form of thin transparent films, there was a need for quick and efficient assessment of their key mechanical properties that would provide feedback and guide further prototyping work. An optical measurement method based on digital image correlation (DIC) principle was developed to measure the deformation and strains of the tensile film samples. In our study, the accuracy and precision of the measurement of deformation were ±1.5 µm and 0.4 µm respectively. The corresponding accuracy and precision in terms of strains were ±30 µstrain and 75 µstrain respectively. This method can be successfully used to determine the critical mechanical properties, such as elastic modulus, toughness and Poisson's ratio, of transparent thin films by a single tensile test, all of which require precise strain measurement. In addition, this optical measurement method makes it possible to significantly simplify the testing for measuring essential work of fracture (EWF), an important material property of thin transparent films. In traditional method, measurement of EWF requires large amount of notched specimens. However, our study showed that only a small amount of notched specimens were needed to measure the EWF of a material. This method could not be successfully used to determine EWF from un-notched tensile specimens. / Graduation date: 2012 / Folder labeled "UMaine MFC aerogel" contains SEM micrographs of MFC from University of Maine (referred as type A MFC in the thesis). Two pieces of leaf-like flakes at different locations were cut by Focused Ion Beam (FIB) in order to observe the internal structure of the flakes. Folder "FIB_01 ": a series of SEM micrographs of FIB-cut flake at different magnification levels. Folder "FIB_02 ": another series of SEM micrographs of FIB-cut flake at various magnification levels. Folder labeled "Swedish MFC aerogel" contains SEM micrographs of MFC from Innventia AB company, Sweden (referred as type B MFC in the thesis). There is a series of SEM micrographs of type B MFC aerogel at various magnification levels in this folder.

The objective of this research project was to evaluate the mechanical, morphological, and permeability properties of electrospun blends of polydioxanone and poly(lactic acid) for application as vascular grafts. Mechanical analysis was performed by uniaxial tensile testing to examine the peak load, peak stress, elastic modulus, and strain at break of the fibrous materials. The morphological characteristics of the polymer blends were analyzed using phase contrast microscopy, scanning electron microscopy, and image analysis software. Scanning electron microscopy and image analysis software were used to assess fiber diameter and pore size of electrospun scaffolds. Scaffold permeability measurements were also used to calculate fiber diameter and pore size, and the values were compared to those obtained using image analysis. The material property results acquired from the research suggest that the electrospun polymer blends have potential for use in vascular graft applications.

The blending of lignin as a component in a thermoplastic blend poses a challenge in the form of dispersion and compatibility. Polyesters such as poly(lactic acid) and poly(butylene adipate-co-terephthalate) offer the best opportunity of compatibility in melt blending with lignin due to their ability to form hydrogen bonds. The fractionation of lignin into more homogeneous fractions offers better dispersion and more consistent properties, retaining the toughness of the original polymer in addition to bridging stress transfer between PLA and PBAT. Functionalization of lignin was done by lactic acid grafting. The resulting blend of PLA/PBAT/modified fractionated lignin showed improved interaction between lignin and PLA, but reduced compatibility between lignin and PBAT. This thesis provides a deeper understanding on the effect of lignin heterogeneity, its fractions, and the functionalization of lignin on lignin and bioplastic blends to further the use of a largely produced industrial by-product in high value applications. / Natural Sciences and Engineering Research Council (NSERC) – Lignoworks Biomaterials and Chemicals Strategic Research Network, Canadian Foundation for Innovation (CFI), Ontario Ministry of Agriculture, Food and Rural Affairs (OMAFRA)

Le poly(acide lactique), PLA, est un polymère biocompatible et biodégradable, qui peut être produit à partir de ressources renouvelables. En conséquence, il a soulevé une attention toute particulière en tant que remplacement éventuel des polymères à base de pétrole. C’est un polyester aliphatique ayant des propriétés telles que module élevé, haute résistance, biocompatibilité et est donc un matériau prometteur pour diverses applications telles que les implants, l’encapsulation de médicaments et l'emballage. A cause de sa faible température de transition vitreuse, le PLA a une faible résistance thermique et les applications sont donc limitées à celles qui ne sont pas associées à des températures élevées. En outre, ce polymère souffre d'un faible degré de cristallinité. L'augmentation du taux de cristallinité dans de nombreuses techniques de mise en forme, telles que le moulage par injection, est nécessaire. Il y a plusieurs façons d'augmenter le niveau de cristallinité du PLA. Ces procédés comprennent l'utilisation d'agents nucléants, de plastifiants, ou de combinaisons d'agents plastifiants et de nucléation. La cristallisation du PLA à l'état fondu se présente sous deux formes cristallines légèrement différentes connues sous les noms α et α'. Cette étude compare la capacité d'auto-nucléation de ces deux formes cristallines par auto-nucléation. Ceci est réalisé en comparant les températures de cristallisation lors du refroidissement des échantillons préalablement cristallisés à diverses températures, puis de nouveau chauffé à une température dans la plage de fusion partielle du PLA. Dans la deuxième étape, l'effet des paramètres cinétiques et le poids moléculaire du PLA sur l'efficacité de nucléation des PLA phases cristallines a été étudié. Cette partie de l’étude ouvre une nouvelle voie pour comprendre le rôle des modifications cristallines du PLA qui mènent aux conditions optimales pour la cristallisation du PLA. La mise en forme des polymères implique des contraintes de cisaillement et d’élongation, ce qui implique une cristallisation induite par l’écoulement et la solidification qui s’en suit. Les propriétés mécaniques des produits finals dépendent du degré de cristallisation et de la nature des cristaux formés. Par conséquent, l'optimisation du procédé nécessite une bonne compréhension de la façon dont l’écoulement influence la cristallisation. Le type d'écoulement peut jouer un rôle important sur la cristallisation. Par exemple, l'écoulement élongationnel provoque l’orientation et l’étirement des molécules dans le sens de l'extension, comme dans le cas de la mise en forme de fibres et le soufflage de film, en aidant le processus de cristallisation induite par l'écoulement. Une littérature abondante existe sur la ii cristallisation des thermoplastiques classiques induite par l'écoulement. Cela dit, moins d'attention a été accordée à l'effet de l'écoulement de cisaillement et d'allongement sur la cristallisation du PLA. Comme étudié dans la dernière partie de ce document, l'effet du poids moléculaire sur la cristallisation induite par cisaillement du PLA est rapporté. Pour cela, trois différents PLA à faible, moyen et haut poids moléculaire ont été préparés par réaction d'hydrolyse. Ensuite, en utilisant un rhéomètre oscillatoire, l’effet du cisaillement sur la cinétique de cristallisation du PLA a été examiné. / Abstract : Poly(lactic acid), PLA, is a biocompatible and biodegradable polymer that can be produced from renewable resources. As a result, it has raised particular attention as a potential replacement for petroleum-based polymers. It is an aliphatic polyester with properties such as high modulus, high strength, and biocompatibility and is thus a promising material for various applications such as implants, drug encapsulation, and packaging. In the wake of low glass transition temperature, PLA has a low heat resistance and its application is limited to those not associated with high temperatures. In addition, this polymer suffers from a low degree of crystalinity. Increasing the crystallization rate in many processing operations, such as injection molding, is required. So far, many routes have been found to improve the crystallinity of PLA. These methods include using nucleating agents, plasticizers, and combination of nucleating agents and plasticizers together. PLA crystallization in the melt state results in two slightly different crystalline forms known as α and α’forms. This thesis compares the self-nucleation ability of these two crystal forms by self-nucleation. This is achieved by comparing crystallization temperatures upon cooling for samples previously crystallized at various temperatures and then re-heated to a temperature in the partial melting range for PLA. In the second step, we study the effect of molecular weight of PLA on the nucleation efficiency of PLA crystalline phases. This part of the investigation opens a new pathway to understand the role of PLA crystalline phases on the optimal condition for its crystallization kinetics. Polymer processing operations involve mixed shear and elongational flows and cause polymer molecules to experience flow-induced crystallization during flow and subsequent solidification. The mechanical properties of the final products are significantly dependent upon the degree of crystallization and types of formed crystals. Therefore, optimization of any polymer process requires a good understanding of how flow influences crystallization. The type of flow can play a significant role in affecting crystallization. For example, elongational flow causes molecules to orient and stretch in the direction of extension, as in the case of fiber spinning and film blowing, helping the process of flow-induced crystallization. An extensive body of literature exists on flow-induced crystallization of conventional thermoplastics. Having said that, less attention has been paid to the effect of shear and elongational flow on the PLA crystallization kinetics. As investigated in the final part of this thesis, the effect of iv molecular weight on the shear-induced crystallization of PLA is reported. For this, low, medium and high molecular-weight PLAs were prepared from a high molecular weight one by a hydrolysis reaction. Next, by means of a simple rotational rheometry, effect of the shear flow was examined on the crystallization kinetics of these three PLAs.

Doctor of Philosophy / Department of Grain Science and Industry / X. Susan Sun / Poly(lactic acid) (PLA), a synthetic biopolymer, is a promising substitute of some petroleum-based polymers due to its mechanical and biodegradable properties. But, because of the high cost of PLA (compared to those petroleum plastics for disposable application), starch has been incorporated into PLA to reduce cost and accelerate the biodegradability rate of the composites. But, the addition of starch as filler to PLA decreased mechanical performance of the composite. The addition of methylenediphenyl diisocyanate (MDI) into PLA/starch blends improved drastically the mechanical properties of the composite. Results from thermal-degradation analysis showed that PLA had the highest Arrhenius activation energy and strongest thermal endurance of all samples, followed by PLA/starch/MDI and PLA/starch. Aged samples exposed to fluctuating humidity storage conditions significantly decreased their performance. But, storing the samples in plastic bags could minimize degradation of properties. PLA and its composites with starch would not significantly affect application function when they are stored in controlled environment. PLA and PLA/starch based composites sealed in plastic bags can be stored in fluctuating humidity conditions (30-90% RH) for up to 30 days. Tensile strength, elongation, and damping increased with average particle size of starch granules (APS). But, declination of these properties was detected with APS larger than 45 mm. Crystallinity increased as the APS decreased. Young’s modulus, storage modulus, and moisture absorption were not significantly affected by the starch APS. The use of MDI as a coupling agent altered the role of starch APS on those properties of poly(lactic acid)/starch composite. The oxidation of the primary alcohol group on C6 of starch molecules up to 10% degree of substitution did not significantly affect the mechanical properties of PLA/starch/MDI, but the composites showed a reduced inelastic deformation (tensile curve) and significant increase in storage modulus and damping. Results suggest that a substitution of hydroxyl group on C6 of starch molecules for carboxyl group (up to 10%) increased the strengthening effect of MDI enough to reduce inelastic deformation of the composites upon load, but not enough to enhance mechanical properties.

Le psoriasis est une dermatose inflammatoire chronique affectant 2 à 3 % de la population européenne. Les cytokines pro-inflammatoires ont un rôle crucial dans la pathogénèse du psoriasis. Parmi les voies de signalisation cytokinique, l'étude de la voie JAK/STAT a conduit au développement de traitements systémiques efficaces. Cependant, les essais cliniques évaluant les inhibiteurs JAK/STAT impliquent en grande majorité des administrations orales, la voie topique restant marginale. Le développement de formulations innovantes pour application topique contenant des inhibiteurs JAK/STAT semble être une stratégie prometteuse dans le cadre du psoriasis. Les nanoparticules de poly(acide lactique) (NP PLA) développées au laboratoire ont été étudiées pour la délivrance topique de principes actifs. Ce sont des vecteurs efficaces, qui s'accumulent dans les follicules pileux. De plus, l'encapsulation d'actifs dans des NP PLA permet une libération spécifique au niveau du site d'action, et donc une réduction de la toxicité. L'objectif de ce travail est d'élaborer des formulations semi-solides de NP PLA contenant un inhibiteur JAK/STAT pour le traitement topique du psoriasis, tout en caractérisant un modèle in vivo de psoriasis induit par applications d'Imiquimod. Cette caractérisation des lésions psoriasiformes permettra l'évaluation in vivo des nanoformulations topiques contenant des inhibiteurs JAK/STAT. Cinq formulations ont été élaborées puis caractérisées afin de répondre aux attentes galéniques pour une application topique. L'intégrité des NP PLA a été vérifiée, et la pénétration/perméation de molécules modèles à travers de la peau de souris inflammée a été évaluée / Psoriasis is a chronic inflammatory skin disease, affecting 2 to 3 % of European population. Inflammatory cytokines play a crucial role in the pathogenesis of psoriasis. Among cytokines signaling pathways, JAK/STAT pathway has been widely investigated, leading to the development of efficient systemic agents. However, current clinical trials evaluating JAK/Sat inhibitors mainly involve oral administrations, with few investigations on topical route. Developing innovative drug delivery systems for topical application of JAK/STAT inhibitors seems a promising strategy for psoriasis treatment. Poly(lactic acid) nanoparticles (PLA NPs) developed in the laboratory have been widely investigated for topical drug delivery and are efficient carriers for local dermatotherapy, especially through hair follicles. Moreover, drug encapsulation in PLA NPs for topical delivery allows a specific delivery to the site of action, and thus a decreased toxicity.The aim of this work was to elaborate semi-solid formulations of PLA NPs containing JAK/STAT inhibitors for topical treatment of psoriasis, while characterizing an in vivo model of Imiquimod-induced psoriasis in mice. This characterization of psoriasis-like skin lesions in Imiquimod treated mice provided key tools for in vivo evaluation of topical nanoformulations containing JAK/STAT inhibitors. Five formulations have been developed and then characterized in order to meet galenic criteria for topical drug administration. PLA NPs integrity was assessed, and penetration/permeation profiles of model dugs through inflamed mice skin were determined

Orientadores: Ana Rita Morales, Otávio Cavalett / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química / Made available in DSpace on 2018-08-27T19:01:47Z (GMT). No. of bitstreams: 1 CosatedeAndrade_MarinaFernandes_M.pdf: 2991365 bytes, checksum: df7e463a288c5c88feea3df3157d956a (MD5) Previous issue date: 2015 / Resumo: Este projeto teve como objetivo realizar uma Avaliação do Ciclo de Vida comparando três formas de destinação do poli(ácido láctico) (PLA) e estudar a reciclagem deste polímero, que pode ser mecânica ou química. A reciclagem mecânica foi realizada por duas extrusões do PLA. No segundo processamento, o polímero proveniente da primeira extrusão foi dividido em duas partes, sendo que uma porção recebeu adição de um extensor de cadeia comercial. As amostras obtidas foram caracterizadas por Calorimetria Diferencial Exploratória (DSC), Cromatografia por Permeação em Gel (GPC), Índice de Fluidez, Análise Termogravimétrica (TGA), ensaio de resistência ao impacto Izod e ensaio de tração. Os resultados obtidos mostraram que o número de extrusões diminuiu a massa molar, o índice de fluidez e a estabilidade térmica e aumentou a cristalinidade do polímero. A presença do extensor de cadeia causou a recuperação dessas propriedades. Além disso, o módulo de elasticidade e o alongamento na ruptura sofreram alterações importantes com o aumento da cristalinidade do material. A reciclagem química foi realizada pela hidrólise do PLA, que gera ácido láctico, e posteriormente pela polimerização do ácido láctico, em que é obtido novamente PLA, através da policondensação direta. O ácido láctico foi caracterizado por Cromatografia Líquida de Alta Eficiência (HPLC) e o rendimento da reação obtido foi acima de 95%. O PLA polimerizado foi identificado por Espectroscopia do Infravermelho por Transformada de Fourier (FTIR) e sua massa molar foi medida por Cromatografia por Permeação em Gel (GPC). Os resultados da Avaliação do Ciclo de Vida para os métodos e categorias estudados mostraram que a reciclagem mecânica apresentou o menor impacto ambiental, seguida pela reciclagem química e pela compostagem. Dentre as formas de reciclagem, o insumo mais importante foi o consumo de energia elétrica / Abstract: This project aimed to conduct a Life Cycle Assessment comparing three forms of poly(lactic acid) (PLA) disposal and to study the mechanical and chemical recycling of this polymer. Mechanical recycling was performed by two extrusions of PLA. In the second extrusion, part of the material was processed with a commercial chain extender. The samples were characterized by Differential Scanning Calorimetry (DSC), Gel Permeation Chromatography (GPC), Melt Flow Index, Thermogravimetric Analysis (TGA), Izod test and Tensile test. The results showed that the molecular weight, Melt Flow Index and thermal stability decreased and the crystallinity degree of the polymer increased with the extrusion number. The presence of a chain extender recovered these properties. Furthermore, Young modulus and elongation at break undergo important changes with the crystallinity increase. The chemical recycling was performed by hydrolysis reaction, which produced lactic acid. PLA was obtained through the direct condensation polymerization from lactic acid monomer. Lactic acid was characterized by High Performance Liquid Chromatography (HPLC) and the reaction yield was above 95%. The polymerized PLA was identified by Fourier Transform Infrared Spectroscopy (FTIR) and Gel Permeation Chromatography (GPC). Considering the methods and impact categories studied, the Life Cycle Assessment showed that mechanical recycling had the lowest environmental impact, followed by chemical recycling and composting. Among the forms of recycling, the most important input was the electricity consumption / Mestrado / Ciencia e Tecnologia de Materiais / Mestra em Engenharia Química

[EN] The current PhD thesis deals with the development and characterization of novel nanocomposites based on biodegradable poly(mannitol sebacate) (PMS) matrices with tailored properties and shape-memory capabilities for biomedical applications. Two types of fillers -cellulose nanocrystals (CNC) and electrospun poly(lactic acid) nanofibers (NF-PLA)- were used as reinforcement in order to induce and/or enhance the shape-memory properties of PMS matrices. Also, different crosslinking profiles and stoichiometric ratios between mannitol and sebacic acid (1:1 and 1:2) were studied and evaluated to obtain samples with low and high degrees of crosslinking. An appropriate combination of the crosslinking profile and the monomer ratio for PMS matrix, as well as the addition of low content of CNC, allowed the development of PMS/CNC nanocomposites with a wide range of mechanical properties and degradation profiles. On the other hand, highly oriented poly(lactic acid) (PLA) nanofiber mats obtained by electrospinning were embedded in the PMS matrices. An enhancement of up to 53-fold in the Young's modulus was observed for PMS/NF-PLA nanocomposites filled with 15 wt% of PLA nanofibers. The incorporation of fillers (CNC and NF-PLA) allowed the development of thermally active shape-memory nanocomposites with an enhancement of parameters such as recovery stress and shape fixity. The electrospun PLA-reinforced nanocomposites, offered the best balance of mechanical and thermal properties, as well as a greater control of the transition temperature for switching the change of shape, within a useful range of temperatures. Owing to that, these materials may be of interest as smart responsive systems in long-term biomedical applications. / [ES] La presente tesis doctoral, se centra en el desarrollo y caracterización de nuevos nanocompuestos biodegradables, a partir de matrices de poli(mannitol sebacato) (PMS) con propiedades a medida y capacidades de memoria de forma para aplicaciones biomédicas. Dos tipos de cargas -nanocristales de celulosa (CNC) y nanofibras de ácido poliláctico (NF-PLA) obtenidas mediante electrospinning- se han utilizado como refuerzo, con la finalidad de inducir y/o mejorar las propiedades de memoria de forma en matrices de PMS. Se han estudiado y evaluado diferentes tratamientos de curado y ratios de reacción entre el mannitol y ácido sebácico (1:1 y 1:2), con la finalidad de obtener muestras con bajo y alto grado de reticulación. Una combinación adecuada del tratamiento de curado y el ratio entre monómeros del PMS, así como la adición de bajos contenidos de CNC, permitió desarrollar nanocompuestos de PMS/CNC con un amplio rango de propiedades mecánicas y perfiles de degradación. Por otro lado, se han producido mats de nanofibras de ácido poliláctico (PLA) con alta orientación mediante la técnica de electrospinning, para embeberse en matrices de PMS, observándose una mejora de hasta 53 veces en el módulo de Young para nanocompuestos de PMS/NF-PLA con un 15% en peso de nanofibras. La incorporación de cargas (CNC y NF-PLA) permitió el desarrollo de nanocompuestos con memoria de forma activada térmicamente, con una mejora de parámetros tales como la fuerza de recuperación y la capacidad de fijación. Los nanocompuestos reforzados con NF-PLA obtenidas por electrospinning, ofrecieron el mejor balance de propiedades mecánicas y térmicas, así como un mayor control de la temperatura de transición para la activación del cambio de forma en un intervalo útil de temperaturas. Por todo ello, estos materiales pueden resultar de interés como sistemas activos en aplicaciones biomédicas de larga duración. / [CAT] La present tesi doctoral se centra en el desenvolupament i caracterització de nous nanocompostos biodegradables a partir de matrius de poli(mannitol sebacato) (PMS) amb propietats a mesura i capacitats de memòria de forma per a aplicacions biomèdiques. Dos tipus de càrregues -nanocristals de cel·lulosa (CNC) i nanofibres d'àcid polilàctic (NF-PLA) obtingudes mitjançant electrospinning- s'han utilitzat com a reforç amb la finalitat d'induir i/o millorar les propietats de memòria de forma en matrius de PMS. S'han estudiat i avaluat diferents tractaments de curat i ràtios de reacció entre el mannitol i àcid sebàcic (1:1 i 1:2) amb la finalitat d'obtenir mostres amb baix i alt grau de reticulació. Una combinació adequada del tractament de curat i el ràtio entre monòmers del PMS, així com l'addició de baixos continguts de CNC, va permetre desenvolupar nanocompostos de PMS/CNC amb un ampli rang de propietats mecàniques i perfils de degradació. D'altra banda, s'han produït mats de nanofibres d'àcid polilàctic (PLA) amb alta orientació mitjançant la tècnica de electrospinning, per embeure's en matrius de PMS, observant-se una millora de fins a 53 vegades en el mòdul de Young per nanocompostos de PMS/NF-PLA amb un 15% en pes de nanofibres. La incorporació de càrregues (CNC i NF-PLA) va permetre el desenvolupament de nanocompostos amb memòria de forma activada tèrmicament, amb una millora de paràmetres tals com la força de recuperació i la capacitat de fixació. Els nanocompostos reforçats amb NF-PLA obtingudes per electrospinning, van oferir el millor balanç de propietats mecàniques i tèrmiques, així com un major control de la temperatura de transició per a l'activació del canvi de forma en un interval útil de temperatures. Per tot això, aquests materials poden resultar d'interés com a sistemes actius en aplicacions biomèdiques de llarga durada. / Sonseca Olalla, A. (2015). DEVELOPMENT OF SHAPE-MEMORY COMPOSITES BASED ON A BIODEGRADABLE POLYESTER ELASTOMER [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/54129 / TESIS

RESUMEN El objetivo de esta tesis fue la obtención y caracterización de films biodegradables con características antimicrobianas y/o antioxidantes a partir de quitosano (CH). Para modular sus propiedades y mejorar su funcionalidad, se estudió la combinación con otras matrices poliméricas: almidón de trigo (WS), polivinil alcohol (PVA) y ácido poliláctico (PLA). Además se incorporaron aceites esenciales (EO) de tomillo (Th) o albahaca (B), ¿-tocoferol (Tp) y ácido cítrico (CA). Se evaluó el efecto del tratamiento de homogenización de las dispersiones formadoras de films (FFD) en films de quitosano con EO en diferentes proporciones. La microfluidización dio lugar a una reducción en el tamaño de gota, a una mayor carga superficial de las mismas y una menor viscosidad de las dispersiones. Además, intensificó todos los efectos provocados por la incorporación de EO sobre las propiedades mecánicas de los films debido a potenciación de las interacciones con el polímero. A baja proporción de EO, la microfluidización mejoró las propiedades de barrera al vapor de agua de los films, pero no tuvo un impacto significativo en la permeabilidad al oxígeno. Los films ejercieron un papel protector frente a la oxidación en grasa de cerdo. La presencia de EO en los films, a pesar de aumentar la permeabilidad al oxígeno, dio lugar a una menor velocidad de oxidación de las muestras (especialmente a alta humedad relativa), probablemente por el efecto antioxidante de los componentes de los EO. Los films de quitosano se mostraron efectivos en el control del deterioro microbiano cuando se aplicaron en carne de cerdo picada, pero la incorporación de los EO no mejoró su actividad antimicrobiana. Se incorporó CH en films de WS en diferentes proporciones. La adición de CH en cantidades crecientes dio lugar a un aumento en la viscosidad y estabilidad de las FFD. Ambos polímeros mostraron un alto grado de compatibilidad lo que dio lugar a una microestructura homogénea. El aumento de la proporción de CH dio lugar a films con mejores propiedades mecánicas ya que el CH pareció inhibir la retrogradación del almidón. Los films WS:CH dieron lugar a una reducción de la carga microbiana cuando se aplicaron en muestras de carne de cerdo picada. Se incorporaron diferentes antioxidantes (aceite esencial de tomillo y albahaca, ácido cítrico y ¿-tocoferol) en films mezcla de WS (80%) y CH (20%). Los films presentaron una microestructura heterogénea por la inmiscibilidad de componentes, principalmente el film con ¿-tocoferol que presentó separación de fases. Esto llevó asociado una superficie más rugosa, con menor brillo y, en el caso del ¿-tocoferol, un color más amarillo. No obstante la incorporación de antioxidantes conllevó un aumento de la transparencia y una disminución de la permeabilidad al oxígeno. El CA provocó un aumento en el módulo de elasticidad y un descenso de la extensibilidad de los films. La incorporación de CH en matrices de PVA dio lugar a films altamente homogéneos, debido a la compatibilidad de ambos polímeros. Se obtuvieron films más resistentes y rígidos, pero menos extensibles. Se observó una reducción del grado de cristalinidad y un aumento de la estabilidad térmica, además de una reducción de la trasmisión de la luz UV. Así mismo, cuando se aplicaron a muestras de carne de cerdo picada presentaron una acción antimicrobiana. La incorporación de CH en una matriz de PLA mediante extrusión no afectó al comportamiento térmico del PLA ni a su grado de cristalinidad. Ambos polímeros se mostraron incompatibles. La reducción del tamaño de las partículas de CH minimizó el impacto negativo sobre las propiedades mecánicas y de barrera al vapor de agua. En su aplicación a muestras de carne de cerdo picada, la presencia de CH mejoró las propiedades antimicrobianas de los films. / Bonilla Lagos, MJ. (2013). Desarrollo de films y recubrimientos comestibles bio-activos como soporte de agentes antioxidantes y antimicrobianos [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/28370 / TESIS

Teoretická část předložené dizertační práce popisuje princip radikálového roubování a faktory ovlivňující reakční průběh. Radikálové roubování poly(mléčné kyseliny) (PLA) reaktivní modifikací je vhodnou technikou přípravy biodegradabilních polymerních materiálů s rozličnými vlastnostmi. Současný stav problematiky modifikace poly(mléčné kyseliny) radikálovým roubováním v tavenině je obsahem literární rešerše včetně možných aplikací. Experimentální část se zabývá modifikací PLA anhydridem kyseliny itakonové (IAH) radikálovým roubováním v tavenině. Reakce byla iniciována 2,5-bis(tert-butylperoxy)-2,5-dimethylhexanem (L101). V první části je průběh radikálového roubování pozorován “in situ” pomocí diferenciální kompenzační kalorimetrie (DSC) a termogravimetrické analýzy (TGA). Exotermní pík na DSC záznamu odpovídá průběhu radikálové reakce, na jehož základě lze definovat aktivační energii reakce. Průběh TGA křivky “in situ” radikálové reakce umožňil detekovat vedlejší produkty vznikající v průběhu radikálové modifikace. Ve druhé části byla PLA funkcionalizována reakcí v diskontinuálním laboratorním mixéru za reakčních podmínek navržených dle poločasu rozpadu zvoleného iniciátoru a zpracovatelských podmínek PLA. Reakční teplota 190 °C byla stanovena výpočtem z Arrheniovy rovnice pro reakční čas 6 min. Uvedené reakční parametry byly zvoleny s ohledem na kinetiku rozkladu L101 a potlačení degradace PLA. Infračervená spektroskopie (FTIR) potvrdila navázání IAH na PLA řetězec na základě výskytu –CH2 vibrací s absorpčními pásy při vlnočtu 2860 a 2920 cm-1. Vzrůstající intensita absorpčního pásu 1750 cm-1 potvrdila přítomnost minoritních C=O vibrací anhydridového kruhu překrytých dominantními C=O vibracemi PLA řetězce. Nukleární magnetická rezonance (1H-NMR) nepotvrdila roubování oligomerního IAH na PLA. Koncentrace reaktantů ve zvoleném rozsahu (0.5–10 hm % IAH, 0.1–2 hm % L101) byla použita pro posouzení jejího vlivu na obsah naroubovaného IAH a míru vedlejších reakcí, např. -štěpení, větvení a síťování. Při vysoké koncentraci IAH a L101 byla potvrzena homopolymerace IAH i přes její zanedbávání v tématicky podobných studiích. Tvrzení o IAH homopolymeraci bylo podpořena výsledky kolorimetrické analýzy, charakterizací vzorků připravených polymerací IAH za podmínek radikálového roubování a termickou stabilitou frakcí extrahovaných z PLA-g-IAH. Radikálovou modifikací PLA došlo ke zvýšení flexibility polymerních řetězců díky objemné struktuře IAH navázané na PLA řetězci, což se projevilo poklesem teploty skelného přechodu (Tg). Zvýšený obsah amorfní fáze, hydrofilní chování, rozvětvená struktura a štěpení řetězců má pozitivní vliv na zvýšenou biodegradabilitu PLA-g-IAH v porovnání s nemodifikovanou PLA. Neradikálová degradace, probíhající v průběhu zpracování PLA, byla prokázána změnou tokových vlastností taveniny. Tento nežádoucí jev byl potlačen přídavkem tzv. “prodlužovače řetězců” obsahujícího reaktivní epoxy skupiny. Reakce mezi epoxy skupinami a karboxylovými skupinami byla potvrzena pomocí FTIR a změnou reologických vlastností PLA-g-IAH.