Made available in DSpace on 2014-12-17T14:07:18Z (GMT). No. of bitstreams: 1 BeatrizSSNM_DISSERT.pdf: 3822050 bytes, checksum: cb23d4096043d3edf7fed1c6cb6c7f6a (MD5) Previous issue date: 2013-11-01 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico / The environmental impact caused by the disposal of non-biodegradable polymer packaging on the environment, as well as the high price and scarcity of oil, caused increase of searches in the area of biodegradable polymers from renewable resources were developed. The poly (lactic acid) (PLA) is a promising polymer in the market, with a large availability of raw material for the production of its monomer, as well as good processability. The aimed of this study was synthesis PLA by direct polycondesation of lactic acid, using the tool of experimental design (DOE) (central composite rotatable design (CCRD)) to optimize the conditions of synthesis. The polymer obtained was characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), viscosimetric analysis, differential scanning calorimeter (DSC) and size exclusion chromatography (SEC). The results confirmed the formation of a poly (lactic acid) semicrystalline in the syntheses performed. Through the central composite rotatable design was possible to optimize the crystallization temperature (Tc) and crystallinity degree (Xc). The crystallization temperature maximum was found for percentage of catalyst around the central point (0,3 (%W)) and values of time ranging from the central point (6h) to the upper level (+1) (8h). The crystallization temperature maximum was found for the total synthesis time of 4h (-1) and percentage of catalyst 0,1(W%) (-1). The results of size exclusion chromatography (SEC) showed higher molecular weights to 0,3 (W%) percent of catalyst and total time synthesis of 3,2h / Os impactos ambientais causados pelo descarte de embalagens polim?ricas n?o biodegrad?veis no meio ambiente, assim como o alto pre?o e escassez do petr?leo, fizeram com que pesquisas crescentes na ?rea de pol?meros biodegrad?veis provenientes de fontes renov?veis fossem desenvolvidas. O poli (?cido l?ctico) (PLA) ? um pol?mero promissor nesse mercado, com uma grande disponibilidade de mat?ria-prima para produ??o do seu mon?mero, assim como tamb?m boa processabilidade. Dessa forma, este trabalho teve como objetivo a s?ntese por policondensa??o direta do poli (?cido L?ctico) a partir do ?cido-L-l?ctico utilizando a ferramenta de planejamento fatorial, por meio de um delineamento composto central rotacional (DCCR), visando otimizar as condi??es de s?ntese. O pol?mero obtido foi caracterizado por microscopia eletr?nica de varredura (MEV), espectroscopia na regi?o do infravermelho (FTIR), an?lise viscosim?trica, calorimetria explorat?ria diferencial (DSC) e cromatografia por exclus?o de tamanho (SEC). Os resultados obtidos confirmaram a forma??o do poli (?cido l?ctico) semicristalino em todas as s?nteses realizadas. Atrav?s do delineamento composto central rotacional foi poss?vel a otimiza??o da temperatura de cristaliza??o (Tc) e do grau cristalinidade (Xc). A temperatura de cristaliza??o m?xima foi obtida para percentuais de catalisador em torno do ponto central (0,3(W%)) e valores de tempo variando do ponto central (6h) ao n?vel superior (+1) (8h). O grau de cristalinidade (Xc) m?ximo foi obtido para o tempo total de s?ntese de 4h (-1) e percentual de catalisador de 0,1 (W%) (-1). A an?lise de cromatografia por exclus?o de tamanho (SEC) forneceu resultados de maiores massas molares dentre todos os pol?meros sintetizados, para o percentual de catalisador (octoato de estanho) de 0,3(W%) e tempo total de s?ntese de 3,2h

Since the industrial revolution the rise of the global economy depends on using more amounts of fossil fuels. Currently oil is the leading feedstock for the production of various kinds of plastic products, from packaging materials to machine parts. However, even this advanced technology, such as plastic, awarded several Nobel prizes, has its drawbacks. The big disadvantage is their very slow degradation (tens to thousands of years), thereby the accumulation of waste is increasing. Another disadvantage is its production from non-renewable materials (oil). Therefore, the developed economies, including the European Union (EU), are trying to find new alternatives to conventional plastics using biotechnology manufacturers to called bioplastics, which are made from renewable materials. This thesis deals with the use of bioplastics in the market. Using the questionnaires is creating survey of market among producers of bioplastics and consumers, combined with a personal interview with the promoters of bioplastics. Results processed by this methodology showed that the biggest factor, which influence the promotion of bioplastics, is too high price. This is the main reason why the public is so little informed about them. If the price of production decreases, promotion and use of bioplastics will be probably to increase.

O amido termoplástico (TPS) é um material biodegradável, de baixo custo, com grande potencial para aplicação na composição de plásticos biodegradáveis. Muitos estudos têm sido realizados no sentido de melhorar algumas de suas propriedades, principalmente a sua baixa resistência mecânica, elevada hidrofilicidade, e baixa miscibilidade com polímeros comerciais, fatores que dificultam a ampliação da utilização desse material como plástico biodegradável. Uma alternativa para melhorar tais propriedades, é a produção de blendas destes materiais com outros polímeros. Contudo, quando a natureza química dos materiais a serem combinados é muito diversa, faz-se necessário compatibilizar os materiais, em geral obtida pela adição de agentes compatibilizantes ou promovendo reações durante a extrusão, processo denominado compatibilização reativa. No trabalho, diferentes alternativas foram investigadas com o intuito de aumentar o potencial de aplicação do amido, entre elas: o efeito do ácido cítrico na modificação do amido; o uso da ureia para estabilização da massa molar do amido via extrusão reativa permitindo seu reprocessamento; a modificação do amido com ácido cítrico e ou 4,4\'-difenil metano diisocianato e o uso de dois processos de extrusão reativa para produção do amido termoplástico; a produção de blendas de amido com poli(butileno adpato co-tereftalato) e poli(ácido lático); a produção do amido termoplástico com reticulação termorreversível pela incorporação de reações de Diels-Alder. Foram feitas diversas caracterizações entre elas, análise das propriedades térmicas por meio das técnicas de termogravimetria (TGA), calorimetria exploratória diferencial (DSC), análise dinâmicomecânica (DMA) ensaios mecânicos, absorção de umidade, espectroscopia de infravermelho por transformada de Fourier (FTIR), microscopia eletrônica de varredura (MEV), análises reológicas, cromatografia (HPSEC) e viscosimetria. Os resultados das investigações contribuíram para o desenvolvimento de novos polímeros termoplásticos ou termorrígidos a base de amido de milho e esclareceram questões não abordadas na literatura, sobre a modificação do amido via processo de extrusão reativa. / Thermoplastic starch (TPS) is a biodegradable material, inexpensive, with high potential of usage in the biodegradable plastics composition. Many studies have been performed to improve some properties, mainly its low mechanical strength, high hydrophilicity and low miscibility with commercial polymers, factors that hinder the usage expansion such material as plastic. An alternative to improve these properties is the polymer blends of starch production with other polymers. However, when the materials chemical nature is quite variable then is necessary to make the polymers compatible. Usually, the reactive compatibility is obtained by the addition of coupling agents or promoting reactions during extrusion. In the present study, new alternatives were studied in order to increase the starch application potential including: the citric acid effect on starch modification; use of urea to stabilize the starch molecular weight by reactive extrusion allowing its reprocessing; the starch modification with citric acid and 4,4\'-diphenyl methane diisocyanate and the use of two reactive extrusion processes for thermoplastic starch producing; starch blends production with poly (butylene adipate co-terephthalate) and poly (lactic acid); the starch modification by incorporating crosslinking thermoreversible Diels-Alder adduct. Several characterizations were made including thermal analysis by means of thermogravimetry (TGA), differential scanning calorimetry (DSC), dynamical mechanical analysis (DMA) mechanical testing, moisture absorption, Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), rheology analysis, chromatography (HPSEC) and viscometry. The research results have contributed to the development of new thermoplastic polymers or thermosetting from corn starch and helped to clarify issues not addressed in the literature about the starch modification by reactive extrusion process.

Made available in DSpace on 2016-08-17T18:39:44Z (GMT). No. of bitstreams: 1 4583.pdf: 2193987 bytes, checksum: a9b3822b8425223d19c05e613a4895db (MD5) Previous issue date: 2012-05-29 / The biological contamination causes a great depth of concern in the polymers industry, whose materials are used for food packaging. Most of the bacteria are associated to a biofilm; complex microbial ecosystem, well structured; thus, it is essential to search for alternatives which can provide the reduction of biofilm accumulation on the surface. One of the alternatives is the usage of nanomaterial for such control. One example of such material is the silver nanoparticle. The human activities produce a lot of residue which have hard decomposition. Research and production with biodegradable plastic open space to a new market by being driven to ecological awareness. One example of such plastic is Poli (lactic acid) (PLA). The aim of such research was to evaluate the anti-bacterial, biodegradable and inhibitory action in the shaping of biofilms on the modified PLA with silver nanoparticle in concentrations of 0,3, 0,5, 1,0 and 1,5 %. Standard strain Staphylococcus aureus and Escherichia coli were used for the antibacterial activity evaluation, through the Japanese regulation JIS Z 2801:2000. For the biofilm inhibition evaluation, the samples were incubated with biofilm forming strains from S. aureus, E. coli and Pseudomonas aeruginosa in a constant shaking and evaluated in 1, 3 and 7 days. The samples were buried with a humidity air system for observation of natural degradation in organic soil, in favor of its bacterial growing for 328 days. The results show that the silver antibacterial action was around 70% for E. coli and a small inhibition of biofilm was observed on the third day for E. coli and P. aeruginosa. The PLA natural biodegradation was stable for the mass loss as well as he significantly loss of molar mass. The analysis of the compound presented good distribution and bad dispersion, which could have influenced on the antibacterial activity. New process methods for the nanoparticle incorporation must be carried out for better dispersion and availability of PLA silver surface. / A contaminação biológica causa grande preocupação na indústria de polímeros, cujos materiais são usados para embalagens de alimentos. A maior parte das bactérias se encontra associadas a um biofilme; complexo ecossistema microbiano, bem estruturado; sendo assim, é essencial buscar alternativas que proporcionem a redução do acúmulo de biofilme nas superfícies. Uma das alternativas é o uso de nanomateriais para tal controle. Um exemplo deste material é a nanopartícula de prata. As atividades humanas produzem muito resíduos de difícil decomposição. Impulsionada pela consciência ecológica, as pesquisas e produção com plásticos biodegradáveis ganham espaço. Exemplo de tal plástico é o Poli (ácido lático) (PLA). O objetivo desta pesquisa foi avaliar a ação antibacteriana, biodegradante e a inibitória na formação dos biofilmes sobre o PLA modificado com nanopartícula de prata nas concentrações de 0,3, 0,5, 1,0 e 1,5 %. Foram utilizadas cepas padrão de Staphylococcus aureus e Escherichia coli para a avaliação da atividade antibacteriana, através da norma japonesa JIS Z 2801:2000. Para a avaliação da inibição do biofilme as amostras foram incubadas com cepas formadoras de biofilme de S. aureus, E. coli e Pseudomonas aeruginosa em constante agitação e avaliadas em 1, 3 e 7 dias. Para a observação da degradação natural em solo orgânico as amostras foram enterradas com um sistema de ar e umidade, favorável ao crescimento bacteriano por 328 dias. Os resultados mostraram que a ação antibacteriana da prata foi de aproximadamente 70 % para E. coli e uma pequena inibição do biofilme foi observada no terceiro dia para E. coli e P. aeruginosa. A biodegradação natural do PLA foi estável para a perda de massa e foi observada redução significativa de massa molar. A análise do composto apresentou boa distribuição e má dispersão, que pode ter influenciado na atividade antibacteriana. Novos métodos de processamento para a incorporação das nanopartículas devem ser realizados para melhor dispersão e disponibilidade da prata na superfície do PLA.

Made available in DSpace on 2014-12-17T14:58:24Z (GMT). No. of bitstreams: 1 LucianiPRCB_DISSERT.pdf: 1590576 bytes, checksum: b6a8be3214f47da9445a11624c33de1c (MD5) Previous issue date: 2013-08-08 / Some fibrous materials, for having properties such as biocompatibility, strength and flexibility, are of great interest for medical and pharmaceutical applications. Among these materials, the fabric made from polylactic acid (PLA) has received special attention, and beside to present these features, is derived from biological source, antimicrobial and bioabsorbable. One of the limitations of PLA is its low wettability and capillarity. Due to this, it is necessary to perform surface modification of the knitted fabric, increasing its hydrophilicity. This work aims to realize the plasma treatment at low pressure in order to increase the surface energy of the polymer. The work was divided into three steps: i) Influence of the gas ratio (oxygen and nitrogen) in the surface modification of PLA fabric after the plasma treatment, ii) physical characterization and physicochemical surface tissue; iii) Evaluation of the effect from current and gas ratio in the capillary rise of tissues and iv) Study of capillarity in yarns and fabrics. The results showed that better gas ratios were the atmospheres: 100% oxygen; 100% nitrogen and 50% oxygen and 50% nitrogen. The surface characterization showed changes in topography and introduction of polar groups which increased the wettability of the fabric. In another part of this study, it was found that the atmosphere containing only nitrogen gas showed the most capillary rise to a current of 0.15 A. The results in capillary yarns and fabrics showed that the thread reached equilibrium in a time much less than the fabric to an atmosphere of 100% nitrogen and 0.15 A. Current Plasma technology was effective to increase the hydrophilicity of PLA fabric, providing surface characteristics favorable for future application in the biomedical field / Alguns materiais fibrosos, por apresentarem propriedades como biocompatibilidade, resist?ncia e flexibilidade, s?o de grande interesse para aplica??es m?dicas e farmac?uticas. Dentre estes materiais, o tecido produzido com ?cido poli l?ctico (PLA) tem recebido aten??o especial por, al?m de apresentar estas caracter?sticas, ? derivado de fonte biol?gica e bioabsorv?vel. Uma das limita??es do PLA ? sua baixa molhabilidade e capilaridade. Devido a isto, torna-se necess?rio realizar modifica??o superficial do tecido de malha, aumentando sua hidrofilicidade. O presente trabalho tem como objetivo realizar o tratamento a plasma a baixa press?o com a finalidade de aumentar a energia superficial do fio e da malha. O trabalho foi divido em tr?s etapas: i) Influ?ncia da raz?o de g?s (oxig?nio e nitrog?nio) na modifica??o superficial do tecido de PLA ap?s tratamento a plasma; ii) caracteriza??o f?sica e f?sico-qu?mica da superf?cie do tecido; iii) avalia??o do efeito da corrente e raz?o de g?s na ascens?o capilar de tecidos e iv) estudo da capilaridade em fios e tecidos. Os resultados mostraram que as melhores raz?es de gases foram em atmosfera 100% oxig?nio, 100% nitrog?nio e 50% oxig?nio e 50% nitrog?nio utilizando uma corrente de 0,15 A . A caracteriza??o superficial mostrou mudan?as na topografia e introdu??o de grupos polares o que aumentou a molhabilidade do tecido de malha. Em outra etapa desse estudo, constatou-se que a utiliza??o atmosfera gasosa contendo apenas nitrog?nio foi a que apresentou a maior ascens?o capilar para uma corrente de 0,15 A. Os resultados de capilaridade em fios e tecidos mostraram que o fio atingiu o equil?brio em um tempo bem menor que o tecido para uma atmosfera de 100% nitrog?nio e corrente de 0,15 A. A tecnologia de plasma mostrou-se eficaz para aumentar a hidrofilicidade do tecido de malha de PLA, proporcionando caracter?sticas superficiais favor?veis para futura aplica??o na ?rea biom?dica

I och med att additiv tillverkning blir allt vanligare i dagens samhälle kommer dess ekologiska, samt ekonomiska effekter bli alltmer tydliga och viktiga att ta i beaktning. Tekniken utvecklas och är numera tillgänglig för i stort sett alla. Detta har gjort att 3D-skrivare bland privatpersoner blivit vanligt förekommande. Det har lett till att mer filament går åt till användning av 3D-skrivare, vilket också leder till att mer material går till spillo. Ett av de vanligaste filamentmaterialen inom detta område är PLA. PLA har många fördelar när det kommer till 3D-skrivning, en av nackdelarna är dock svårigheten med att ta till vara på spillmaterialet då det är svårt att återvinna. Detta bidrar till ett ökat behov av att kunna återvinna filamentet själv, och vad kan då vara bättre än att göra det till nytt filament som kan användas igen? Detta är bra ur både ekonomiska och ekologiska hållbarhetsaspekter. Av denna anledning har en extruderingsmaskin designats så att privatpersoner och mindre aktörer ska kunna bygga en egen. På så sätt kan de ta hand om sitt spillmaterial på ett vis som närmar sig en cirkulär ekonomi. Projektet inleddes med en bakgrundsundersökning för att undersöka befintliga lösningsalternativ som redan finns och för att få tips och inspiration. Sedan genomfördes en idégenereringsprocess för att ta fram så många idéer som möjligt för att därigenom förbättra möjligheterna till att hitta en exceptionell lösning. När ett koncept hade valts gjordes jämförelser mellan olika komponenter. Sedan gjordes beräkningar på de valda komponenterna. Detta för att kunna dimensionera dem, delvis för att vara säker på att den håller, men även för att veta hur mycket värme och mekanisk energi som kommer att behöva tillföras i maskinen för att den ska fungera som tänkt. Ett komplett designförslag har tagits fram tillsammans med dimensioner på komponenter för att underlätta för ett eventuellt privat byggprojekt av denna extruderingsmaskin. Vissa ändringar kan göras beroende på budget och tillgänglighet av komponenter. De ändringar som görs kan leda till att även beräkningar behöver göras om eller justeras. Flera av måtten och dimensionerna på vissa komponenter kan ses som överdrivna, detta är på grund av att de ska klara det högsta tryck och krafter som kan uppstå. Dessa uppstår enbart när det satt stopp i matrisen. Att det sätter stopp helt och hållet kommer troligtvis vara ovanligt, men om det händer är det viktigt att maskinen klarar av ett sådant stopp. Till sist kommer alla inställningar behöva justeras och testas på egen hand. Detta är på grund av att maskinen inte har byggts, utan enbart är ett koncept. Dessutom kommer den troligtvis fungera lite annorlunda för alla som bygger den då det kommer att vara skillnader i montering och komponenter. / In today's society additive manufacturing is getting more and more common. The technique is developing and is within reach for almost everyone. It is within the private sector the biggest growth of popularity can be seen. The increased usage of this technology has led to increased usage of plastic within this field. This means that the waste has increased as well. One of the most common materials for 3D-printing is PLA, this is because of a few different benefits. Although it has its cons, one of the bigger drawbacks is that it is hard to recycle. There are very few recycling facilities that can take care of PLA. This means that it is necessary to find another way to handle the otherwise wasted PLA. One way to do this is by making it possible for people to do it themselves, therefore the goal of this project, to develop an extruder for individuals. The extruder is supposed to use old PLA-prints to make new filament. This is good from an ecological perspective as well as an economic one. The extruder is designed to make it possible for the user to assemble it on their own. The project started with a background search, this was to get a better picture of the problem, but also to see what alternative solutions already exists. After this the phase of brainstorming as many ideas as possible started. When a concept had been chosen it was developed even further and calculations were done to ensure that it would work as intended. The calculations contained aspects such as strength of the base and pipe, but also the amount of energy needed from the motor and heaters to fulfill their respective functions. A complete design proposal for the extruder has been established, this together with supporting calculations and measurements for the different components. A few changes can be done to modify the machine for individual needs, however the calculations might have to be adapted depending on the changes that are made. A few of the dimensions on certain components might seem exaggerated. This is because they need to be able to handle the highest pressures and forces that may occur. These pressures and forces are only reached when the machine gets clogged up. The machine clogging should be unusual, but once it happens it might break without proper dimensions. At last smaller adjustments might have to be made by the user. This is because the machine has not been built, it is just a concept. Also, there will be differences depending on what specific component is chosen and the individual assembling process.

Tesis por compendio / [ES] La presente tesis doctoral tiene como principal objetivo el desarrollo de materiales poliméricos que sean respetuosos con el medio ambiente y favorezcan modelos de economía circular, centrando las líneas de investigación en el reaprovechamiento de residuos de la industria del mango y en la utilización de ácido poliláctico (PLA) como principal matriz polimérica. Para ello se emplean diferentes técnicas de procesado como el electrospinning, la extrusión, la inyección o la producción de films por disolución. Además, se plantea la utilización de diferentes aditivos como plastificantes y cargas lignocelulósicas de origen renovable para mejorar las propiedades de estos materiales sin comprometer su alto potencial medioambiental. El primer bloque de la tesis centra sus esfuerzos en el reaprovechamiento de diferentes residuos del mango (uno de los cultivos más populares del mundo), como la piel y el kernel, para desarrollar diferentes materiales con un gran contenido natural. Dentro de los estudios realizados en este bloque se incluye la extracción de almidón a partir del kernel de mango para la posterior fabricación de nanofibras por electrospinning, con gran aplicación en el sector médico. Otros estudios realizados proponen la combinación de matrices poliméricas como el biopolipropileno y el PLA, en combinación con harina de piel de mango y harina de hueso de mango, respectivamente, mediante procesos de extrusión, extrusión reactiva (REX) e inyección. En el caso del biopolipropileno se utilizan además agentes compatibilizantes basados en ácido itacónico para aumentar la adhesión entre las partículas lignocelulósicas de la piel del mango con la matriz polimérica, la cual es altamente apolar. Por otro lado, a las formulaciones de PLA y harina de hueso de mango se le añaden plastificantes como la triacetina y la tributirina para aumentar las propiedades dúctiles del PLA. Un cuarto estudio se enfoca en la producción de films de glicerol con harina de hueso de mango, rica en almidón, para observar cómo afecta el tamaño de partícula de la harina sobre las propiedades de los films. Por último, se propone el desarrollo de materiales termoplásticos ricos en almidón utilizando harina de kernel de mango en combinación con diferentes plastificantes como glicerol, sorbitol y urea. Estos materiales ricos en almidón son procesados por extrusión e inyección y son completamente biodegradables y de origen natural. El segundo y último bloque de la tesis está enfocado a la utilización del ácido poliláctico obtenido de fuentes renovables en procesos de extrusión e inyección. Este poliéster es un polímero biodegradable cuya principal desventaja es su gran fragilidad. Por ello, se han empleado diferentes tipos de plastificantes naturales para incrementar las propiedades dúctiles del PLA. En un primer trabajo, se combina el PLA con α-terpinil acetato, un plastificante de origen renovable. Además, se añade piel de mandarina molida como carga natural para evaluar si este plastificante es capaz de aumentar la ductilidad de mezclas de PLA con cargas lignocelulósicas, obtenido resultados muy positivos. Un segundo trabajo plantea la combinación de PLA con dietil-L-tartrato, un plastificante obtenido del ácido tartárico, encontrado en la uva y el tamarindo, obteniendo elongaciones de más de un 300%. Por último, dos estudios más plantean la combinación de PLA con terpenoides, más concretamente ésteres de geranilo y linalilo. En este sentido, uno de los trabajos se centra en variar la proporción de acetato de linalilo y acetato de geranilo en las composiciones, mientras que el otro trabajo evalúa como afecta la longitud de cadena de los ésteres de geranilo a la plastificación del PLA. Todos los plastificantes utilizados en este bloque ofrecieron resultados muy prometedores, con alargamientos a la rotura superiores al 200% en materiales completamente naturales y biodegradables con gran aplicación en el sector alimentario y del envase y embalaje. / [CA] La present tesi doctoral té com a principal objectiu el desenvolupament de materials polimèrics que siguen respectuosos amb el medi ambient i afavorisquen models d'economia circular, centrant les línies d'investigació en el reaprofitament de residus de la indústria del mango i en la utilització d'àcid polilàctic (PLA) com a principal matriu polimèrica. Per a això s'empren diferents tècniques de processament com l'electrospinning, l'extrusió, la injecció o la producció de films per dissolució. A més, es planteja la utilització de diferents additius com a plastificants i càrregues lignocelulòsiques d'origen renovable per a millorar les propietats d'aquests materials sense comprometre el seu alt potencial mediambiental. El primer bloc de la tesi centra els seus esforços en el reaprofitament de diferents residus del mango (un dels cultius més populars del món), com la pell i el kernel, per a desenvolupar diferents materials amb un gran contingut natural. Dins dels estudis realitzats en aquest bloc s'inclou l'extracció de midó a partir del kernel de mango per a la posterior fabricació de nanofibers per electrospinning, amb gran aplicació en el sector mèdic. Altres estudis realitzats proposen la combinació de matrius polimèriques com el biopolipropilè i el PLA, en combinació amb farina de pell de mango i farina d'os de mango, respectivament, mitjançant processos d'extrusió, extrusió reactiva (REX) i injecció. En el cas del biopolipropilè s'utilitzen a més agents compatibilitzants basats en àcid itacònic per a augmentar l'adhesió entre les partícules lignocelulòsiques de la pell del mango amb la matriu polimèrica, la qual és altament apolar. D'altra banda, a les formulacions de PLA i farina d'os de mango se li afigen plastificants com la triacetina i la tributirina per a augmentar les propietats dúctils del PLA. Un quart estudi s'enfoca en la producció de films de glicerol amb farina d'os de mango, rica en midó, per a observar com afecta la grandària de partícula de la farina sobre les propietats dels films. Finalment, es proposa el desenvolupament de materials termoplàstics rics en midó utilitzant farina de kernel de mango en combinació amb diferents plastificants com glicerol, sorbitol i urea. Aquests materials rics en midó són processats per extrusió i injecció i són completament biodegradables i d'origen natural. El segon i últim bloc de la tesi està enfocat a la utilització de l'àcid polilàctic obtingut de fonts renovables en processos d'extrusió i injecció. Aquest polièster és un polímer biodegradable el principal desavantatge del qual és la seua gran fragilitat. Per això, s'han emprat diferents tipus de plastificants naturals per a incrementar les propietats dúctils del PLA. En un primer treball, es combina el PLA amb α-terpinil acetat, un plastificant d'origen renovable. A més, s'afig pell de mandarina molta com a càrrega natural per a avaluar si aquest plastificant és capaç d'augmentar la ductilitat de mescles de PLA amb càrregues lignocelulòsiques, obtenint resultats molt positius. Un segon treball planteja la combinació de PLA amb dietil-L-tartrat, un plastificant obtingut de l'àcid tartàric, trobat en el raïm i el tamarinde, obtenint elongacions de més d'un 300%. Finalment, dos estudis més plantegen la combinació de PLA amb terpenoids, més concretament èsters de geranil i linalil. En aquest sentit, un dels treballs se centra en variar la proporció d'acetat de linalil i acetat de geranil en les composicions, mentre que l'altre treball avalua com afecta la longitud de cadena dels èsters de geranil a la plastificació del PLA. Tots els plastificants utilitzats en aquest bloc van oferir resultats molt prometedors, amb allargaments al trencament superiors al 200% en materials completament naturals i biodegradables amb gran aplicació en el sector alimentari i de l'envàs i embalatge. / [EN] The present doctoral thesis has as its main objective the development of polymeric materials that are environmentally friendly and promote circular economy models, focusing research on the reuse of waste from the mango industry and the use of polylactic acid (PLA) as the main polymer matrix. Various processing techniques such as electrospinning, extrusion, injection, or cast film are employed for this purpose. In addition, the use of different additives such as plasticizers and lignocellulosic fillers of renewable origin is proposed to improve the properties of these materials without compromising their high environmental potential. The first part of the thesis focuses on the reuse of various mango waste products (one of the most popular crops in the world), such as peel and kernel, to develop different materials with a high natural content. Studies in this section include the extraction of starch from mango kernels for the subsequent production of nanofibers by electrospinning, which have significant applications in the medical sector. Other studies propose the combination of polymeric matrices such as biopolypropylene and PLA, in combination with mango peel flour and mango kernel flour, respectively, through extrusion, reactive extrusion (REX), and injection processes. In the case of biopolypropylene, compatibilizing agents based on itaconic acid are also used to increase the adhesion between lignocellulosic particles from mango peel and the highly apolar polymer matrix. On the other hand, PLA formulations with mango kernel flour are supplemented with plasticizers such as triacetin and tributyrin to enhance the ductile properties of PLA. A fourth study focuses on the production of glycerol films with mango kernel flour, rich in starch, to observe how the particle size of the flour affects the film properties. Finally, the development of starch-rich thermoplastic materials is proposed using mango kernel flour in combination with different plasticizers such as glycerol, sorbitol, and urea. These starch-rich materials are processed by extrusion and injection and are completely biodegradable and of natural origin. The second and final part of the thesis is focused on the use of polylactic acid obtained from renewable sources in extrusion and injection processes. This biodegradable polyester has the main disadvantage of being very brittle. Therefore, different types of natural plasticizers have been used to increase the ductile properties of PLA. In the first study, PLA is combined with α-terpinyl acetate, a renewable plasticizer. In addition, ground tangerine peel is added as a natural filler to evaluate if this plasticizer can increase the ductility of PLA blends with lignocellulosic fillers, yielding very positive results. A second study proposes the combination of PLA with diethyl-L-tartrate, a plasticizer obtained from tartaric acid, found in grapes and tamarind, resulting in elongations of more than 300%. Finally, two more studies propose the combination of PLA with terpenoids, specifically geranyl and linalyl esters. In this regard, one of the works focuses on varying the proportion of linalyl acetate and geranyl acetate in the compositions, while the other study evaluates how the chain length of geranyl esters affects PLA plasticization. All the plasticizers used in this section offered very promising results, with elongations at break exceeding 200% in completely natural and biodegradable materials with significant applications in the food and packaging sectors. / This research is a part of the grant PID2020-116496RB-C22, funded by MCIN/AEI/10.13039/501100011033 and the grant TED2021-131762A-I00, funded by MCIN/AEI/10.13039/501100011033 and by the European Union “NextGenerationEU”/PRTR. Authors also thank Generalitat Valenciana-GVA for funding this research through the grant numbers AICO/2021/025 and CIGE/2021/094. Funded with Aid for First Research Projects (PAID-06-22), Vice-rectorate for Research of the Universitat Politècnica de València (UPV). J. I.-M. wants to thank FPU19/01759 grant funded by MCIN/AEI/10.13039/501100011033 and by ESF Investing in your future. J. G.-C. wants to thank FPU20/01732 grant funded by MCIN/AEI/10.13039/ 501100011033 and by ESF Investing in your future. / Gómez Caturla, J. (2024). Desarrollo y caracterización de polímeros de alto rendimiento medioambiental derivados de residuos agroindustriales y aditivos de origen renovable [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/203217 / Compendio

Univ., Diss.--Kiel, 2002.

Les nanoparticules polymériques biodégradable (NPs) sont apparues ces dernières années comme des systèmes prometteurs pour le ciblage et la libération contrôlée de médicaments. La première partie de cette étude visait à développer des NPs biodégradables préparées à partir de copolymères fonctionnalisés de l’acide lactique (poly (D,L)lactide ou PLA). Les polymères ont été étudiés comme systèmes de libération de médicaments dans le but d'améliorer les performances des NPs de PLA conventionnelles. L'effet de la fonctionnalisation du PLA par insertion de groupements chimiques dans la chaîne du polymère sur les propriétés physico-chimiques des NPs a été étudié. En outre, l'effet de l'architecture du polymère (mode d'organisation des chaînes de polymère dans le copolymère obtenu) sur divers aspects de l’administration de médicament a également été étudié. Pour atteindre ces objectifs, divers copolymères à base de PLA ont été synthétisés. Plus précisément il s’agit de 1) copolymères du poly (éthylène glycol) (PEG) greffées sur la chaîne de PLA à 2.5% et 7% mol. / mol. de monomères d'acide lactique (PEG2.5%-g-PLA et PEG7%-g-PLA, respectivement), 2) des groupements d’acide palmitique greffés sur le squelette de PLA à une densité de greffage de 2,5% (palmitique acid2.5%-g-PLA), 3) de copolymère « multibloc » de PLA et de PEG, (PLA-PEG-PLA)n. Dans la deuxième partie, l'effet des différentes densités de greffage sur les propriétés des NPs de PEG-g-PLA (propriétés physico-chimiques et biologiques) a été étudié pour déterminer la densité optimale de greffage PEG nécessaire pour développer la furtivité (« long circulating NPs »). Enfin, les copolymères de PLA fonctionnalisé avec du PEG ayant montré les résultats les plus satisfaisants en regard des divers aspects d’administration de médicaments, (tels que taille et de distribution de taille, charge de surface, chargement de drogue, libération contrôlée de médicaments) ont été sélectionnés pour l'encapsulation de l'itraconazole (ITZ). Le but est dans ce cas d’améliorer sa solubilité dans l'eau, sa biodisponibilité et donc son activité antifongique. Les NPs ont d'abord été préparées à partir de copolymères fonctionnalisés de PLA, puis ensuite analysés pour leurs paramètres physico-chimiques majeurs tels que l'efficacité d'encapsulation, la taille et distribution de taille, la charge de surface, les propriétés thermiques, la chimie de surface, le pourcentage de poly (alcool vinylique) (PVA) adsorbé à la surface, et le profil de libération de médicament. L'analyse de la chimie de surface par la spectroscopie de photoélectrons rayon X (XPS) et la microscopie à force atomique (AFM) ont été utilisés pour étudier l'organisation des chaînes de copolymère dans la formulation des NPs. De manière générale, les copolymères de PLA fonctionnalisés avec le PEG ont montré une amélioration du comportement de libération de médicaments en termes de taille et distribution de taille étroite, d’amélioration de l'efficacité de chargement, de diminution de l'adsorption des protéines plasmatiques sur leurs surfaces, de diminution de l’internalisation par les cellules de type macrophages, et enfin une meilleure activité antifongique des NPs chargées avec ITZ. En ce qui concerne l'analyse de la chimie de surface, l'imagerie de phase en AFM et les résultats de l’XPS ont montré la possibilité de la présence de davantage de chaînes de PEG à la surface des NPs faites de PEG-g-PLA que de NPS faites à partie de (PLA-PEG-PLA)n. Nos résultats démontrent que les propriétés des NPs peuvent être modifiées à la fois par le choix approprié de la composition en polymère mais aussi par l'architecture de ceux-ci. Les résultats suggèrent également que les copolymères de PEG-g-PLA pourraient être utilisés efficacement pour préparer des transporteurs nanométriques améliorant les propriétés de certains médicaments,notamment la solubilité, la stabilité et la biodisponibilité. / Biodegradable polymeric nanoparticles (NPs) have emerged as promising drug delivery carriers for the controlled drug release and targeting. The first part of this study aimed to develop biodegradable NPs from functionalized copolymers of poly (D,L-Lactide) (PLA). Those copolymers were explored as drug delivery systems in attempt to improve the drug delivery performance of conventional PLA NPs. The effect of PLA functionalization (insertion of chemical substituents onto PLA backbone) on the physicochemical properties of the obtained NPs was investigated. Moreover, the effect of polymer architecture (mode of organization of polymer chains in the resultant copolymer) on various drug delivery aspects was also studied. To reach those goals, various PLA based copolymers namely poly(ethylene glycol) (PEG) grafted on PLA backbone at 2.5% & 7% mol/mol of lactic acid monomers (PEG2.5%-g-PLA and PEG7%-g-PLA, respectively), palmitic acid grafted on PLA backbone at 2.5% grafting density (palmitic acid2.5%-g-PLA), and multiblock copolymer of PLA and PEG, (PLA-PEG-PLA)n were synthesized. In the second part, the effect of different PEG grafting densities over PLA backbone on the properties of PEG-g-PLA NPs either physicochemical or biological properties was investigated to reveal the optimal PEG grafting density required to develop stealth particles (long circulating NPs). Finally, functionalized PEG/PLA copolymers that showed the most satisfactory results in terms of various drug delivery aspects, such as size and size distribution, surface charge, drug loading, and controlled drug release were selected for encapsulation of itraconazole (ITZ) to improve its aqueous solubility, bioavailability and hence its antifungal activity. NPs were first prepared from functionalized PLA copolymers then analyzed for their major physicochemical parameters such as encapsulation efficiency, size and size distribution, surface charge, thermal properties, surface chemistry, % poly(vinyl alcohol) (PVA) adsorbed at the surface of NPs, and drug release pattern. Surface chemistry analysis using x-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM) phase imaging were used to study the chain organization behavior of each functionalized copolymer during NPs formulation. Generally speaking, functionalized PEG/PLA copolymers showed improved drug delivery behavior in terms of narrow size and size distribution, enhanced loading efficiency, less plasma protein adsorption onto their surfaces and less macrophage uptake, and finally better antifungal activity for ITZ loaded NPs. For the surface chemistry analysis, AFM phase imaging and XPS studies revealed the possibility of existence of more PEG chains at the surface of PEG-g-PLA NPs than (PLA-PEG-PLA)n during NPs formation. Our results demonstrate that properties of PLA-based NPs can be tuned by proper selection of both polymer composition and polymer architecture. Results also suggest that PEG-g-PLA copolymers could be used efficiently as a nanocarrier to improve various drug properties e.g. solubility, stability, and bioavailability.

Cette thèse rapporte l’étude des propriétés physicochimiques des nanoparticles polymériques et leur impact sur l’interaction avec les cellules vivantes. Nous nous sommes tout spécialement attachés à étudier l’effet des propriétés adhésives et mécaniques des nanoparticules sur leur capacité de pénétration de la membrane cellulaire. Pour ce faire, nous avons tout d’abord utilisé des nanoparticules d’acide polylactique (PLA) fonctionnalisées en surface avec un ligand des sélectines E et P. Le greffage du ligand sur la particule s’est fait par une nouvelle méthode expérimentale garantissant la présence du ligand à la surface de la particule durant toute sa durée de vie. Cette méthode consiste à mélanger un polymère fonctionnalisé avec le ligand avec un autre polymère non fonctionnalisé. La présence du ligand à la surface des nanoparticules formées à partir de ce mélange de polymères a été confirmée par analyse ToF SIMS. Nous avons pu prouver que les particules possédant le ligand greffé à leur surface démontraient une capacité adhésive supérieure à leurs homologues non fonctionnalisés sur des cellules endothéliales HUVEC activées par différentes drogues. De plus, le captage des particules par les cellules HUVEC est modulé par le niveau d’expression des récepteurs selectine E et P et aussi par la quantité de ligand libre. Ces résultats montrent clairement que le greffage du ligand confère aux particules des propriétés adhésives accrues et spécifiques ce qui permet leur usage postérieure comme vecteur pharmaceutique capable de cibler un récepteur particulier à la surface d’une cellule. Nous avons aussi démontré que l’interaction entre les nanoparticules et la membrane cellulaire peut aussi être contrôlée aussi bien par les propriétés mécaniques de la cellule que de la nanoparticule. Dans une première étape, nous avons mesuré à l’aide de l’appareil de forces de surface l’élasticité de cellules macrophagiques déposées sur différents substrats. En contrôlant l’interaction entre la cellule et le substrat sur lequel elle repose nous avons montré qu’il était possible de modifier à ii volonté les propriétés mécaniques cellulaire. Une augmentation de l’élasticité cellulaire s’accompagne d’une augmentation systématique de l’internalisation de nanoparticules de PLA non fonctionnalisées. Ceci suggère un rôle prépondérant des propriétés mécaniques du cortex cellulaire dans le captage des nanoparticules de PLA. Dans une seconde étape, nous avons étudié l’effet des propriétés mécaniques des nanoparticules sur leur capacité de pénétration cellulaire. Pour ce faire, nous avons synthétisé des particules d’hydrogel dont l’élasticité était contrôlée par le degré d’agent réticulant inclus dans leur formulation. Le contrôle des propriétés mécaniques des nanoparticules a été confirmé par la mesure du module de Young des particules par microscopie de force atomique. L’impact des propriétés mécaniques de ces particules sur leur capacité de pénétration dans les cellules vivantes a été étudié sur des cellules macrophagiques de souris. Les résultats ont montré que la cinétique d’internalisation, la quantité de particules internalisées et le mécanisme d’internalisation dépendent tous du module de Young des nanoparticules. Aucune différence dans le trajet intracellulaire des particules n’a pu être observée malgré le fait que différentes voies d’internalisation aient été observées. Ce dernier résultat peut s’expliquer par le fait que les nanoparticules sont internalisées par plusieurs voie simultanément ce qui facilite leur accumulation dans les organelles digestives intracellulaires. Un modèle simple permettant d’expliquer ces résultats a été proposé et discuté. / This thesis reports the study of physical chemical properties of polymeric nanoparticles and their impact on the interaction with living cells. In particular we endeavoured to study the effect of the adhesive and mechanical properties of the vector on its capacity of penetration of the cellular membrane. With this intention, we firstly used nanoparticules of polylactic acid (PLA) functionalized on their surfaces with a ligand of the selectines E and P receptor. The grafting of the ligand on the particle’s surface was carried out thanks to a new experimental method guaranteeing the presence of the active molecule on the surface of the particle during its whole life cycle. This method consists in mixing a polymer functionalized with the ligand with another polymer not functionalized. The presence of the ligand on the surface of the nanoparticules formed starting from this mixture of polymers was confirmed by ToF SIMS analysis. We could show that the particles having the ligand grafted on their surface exhibit a higher adhesive capacity than their non-functionalized counterpart on endothelial cells HUVEC activated by various drugs. Nanoparticles adhesion on cells membrane was modulated by the level of expression of the receptors selectine E and P and also by the quantity of free ligand. These results show clearly that the functionalized particles possess all the characteristics of a pharmaceutical vector capable of targeting a particular receptor on a cell surface. The interaction between nanoparticules and cellular membrane can also be controlled by the mechanical properties of the cell as well as of the nanoparticule. To demonstrate it we have measured the elasticity of macrophagic cells deposited on various substrates using the SFA. We have thus showed that it was possible to control the cell mechanical properties at will by controlling the interaction between the cell and the substrate on which it rests. An increase of the cell elasticity is accompanied by an increase of the internalization of non-functionalized PLA nanoparticules. This suggests a major role of cytocortical mechanical properties in the capture of hard PLA particles. iv Lastly, we studied the effect of the mechanical properties of the nanoparticules on their cellular penetration capacity. With this intention, we synthesized hydrogel particles whose elasticity was controlled by the degree of crosslinking agent included in their formulation. The control of the mechanical properties of the nanoparticules was confirmed by the measurement of the Young modulus of the particles by AFM. The interaction of these particles with macrophagess showed that the mechanical properties of the particles affect various aspects related to the internalization of the nanoparticles. The internalization kinetics, the quantity of internalized particles and the mechanism of internalization depend all on the Young modulus of the nanoparticules. No differences in the intracellular pathway could be observed in spite of the fact that various pathways of internalization were observed for these nanoparticules. This last result can be explained by the fact that the nanoparticules are internalized by several mechanisms of simultaneously which facilitates their accumulation in intracellular digestive organelles. A simple model explaining these results is proposed and discussed.