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Contribution à l'étude de la structure et de la texture du PLA : Effet de la dégradation hydrothermale / Contribution to the study of the structure and the texture of the PLA : Effect of the hydrothermal degradationSambha'a, Lionel 24 February 2011 (has links)
Le risque d'épuisement de ressources naturelles fossiles à partir desquelles nombres d'oléfines sont fabriqués, a permis le développement de nouveaux matériaux polymères, 100% renouvelables dénommés biopolymères. L'acide poly lactique est sans doute le plus prometteur d'entre eux. D'origine naturelle, ce polyester est synthétisé à partir d'aliments riches en amidon tels que le maïs, la betterave ou la pomme de terre. Son caractère biodégradable lui offre un large éventail d'applications dans les domaines aussi variés et divers que la médecine, le bâtiment, l'industrie automobile, le biomédicale ou encore le textile habillement. Ce travail consiste à étudier la structure et la texture de l'isomère mixte (PDLA) et de déterminer l'incidence de sa morphologie sur les propriétés mécaniques et tinctoriales requises pour des applications textiles. Nous avons par des méthodes spectrales, caractérisé le polymère afin d'en déterminer entre autre, la composition massique, et la stéréorégularité, paramètres très importants ayant une forte influence sur les propriétés mécaniques du polymère, notamment la stabilité thermique ou la résistance à l'hydrolyse. Nos expériences menées sur la stabilité thermique du polymère révèlent que le polymère est susceptible de s'hydrolyser sous l'action combinée de l'eau, de la température et du pH, entraînant ainsi une diminution de la masse moléculaire, donc, une perte de propriétés mécaniques de la fibre.Le PLA est également un polymère qui supporte mal la teinture, et seuls les colorants dispersés sont susceptibles de teinte cette fibre sous certaines conditions. L'étude de la cinétique de fixation de trois colorants dispersés sur la fibre de PLA à permis d'établir une relation entre la structure du colorant et ses propriétés tinctoriales. / The risk of exhaustion of fossil natural resources from which count of polymers are made, allowed the development of new polymer materials, renewable 100 % were called biopolymer. The poly acid lactic is doubtless the most promising of them. Of natural origin, this polyester is synthetized from food rich in starch such as the corn, the beet or the potato. His biodegradable character offers him a wide range of applications in many field as medicine, building, car industry, biomedical or textile clothing. This work consists in studying the structure and the texture of the mixed isomer (PDLA) and to determine the incidence of its morphology on the mechanical properties required for textiles applications.We have by spectral methods, characterized the polymer ,in arder to determine, the molecular weight,composition, and monomers distribution, very important parameter, having a strong influence on the mechanical properties of the polymer, in particular the thermal stability or the resistance in the hydrolysis. Our experiments led on the thermal stability of the polymer reveal that the polymer may hydrolyser under the combined effect of temperature, moisture and by the pH, then, a decrease of the molecular weight, thus, a Joss ofmechanical properties of the fiber.The PLA is also a polymer which can be dye only with certain disperses dyes under particulars conditions.The study of the kinetics of fixation of three disperses dyes scattered on PLA fiber permit to establish a relation between the structure of the disperses dyes and its dyeing properties.
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Etude et modélisation de la cristallisation du Polylactide (PLA) en vue de l'optimisation du procédé de rotomoulage / Polylactic acid (PLA) crystallisation study and modeling for rotomolding process optimizationAressy, Matthieu 19 December 2013 (has links)
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.
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Síntese e caracterização de polímeros biodegradáveis para liberação controlada de dexametasona / Synthesis and characterization of biodegradab polymers for controlled dexamethasone releaseColtro, Monise Cristina Ribeiro Casanova 01 December 2014 (has links)
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Previous issue date: 2014-12-01 / Conselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPq / Bioabsorbable and biodegradable polymers are extremely importante in medical applications such as sutures and controlled drug realease systems because they do not produce toxic products. In this sense, several researches prepare and characterize polylactic acid but do not apply it or vice-versa. The present work aimed to prepare and characterize polylactic acid and perform in vitro and in vivo tests in inflammaded knees of sheeps. In this work, the polymers PLLA and PDLLA were sinthesized by melt policondensation method. In order to reach a higher molecular weight of polymers, catalysts were used based on zinc and tin supported on sulfonated styrene-divinylbenzene (Sty-DVB) copolymers. The Sty-DVB copolymer was synthesized through suspension polymerization in the presence of inert diluents. The Sty-DVB copolymer was sulfonated with concentrated sulfuric acid in the presence of dichloroethane. The original and sulfonated copolymer, as well, the supported catalysts were characterized by nitrogen physical adsorption, FTIR, EDS, scanning electron microscopy, X-ray diffraction, atomic absorption spectrometry and thermogravimetric analysis. PLLA and PDLLA were characterized by inherent viscosity measurements, X-ray diffraction, thermogravimetric analysis and nuclear magnetic resonance of 1H and 13C. PDLLA nanospheres were prepared through nanoprecipitation method without and with the incorporation of dexamethasone, an anti-inflammatory drug. The polymeric nanospheres were characterized by dynamic light scattering to measure medium diameter and polydispersity index, as well, zeta potential The encapsulation efficiency, the drug loading, the yield as well as controlled release drug profile in dialyses membrane were obtained by high performance liquid chromatography analyzes. Tin was supported on sulfonated Sty-DVB copolymer as SnO2, while zinc was detected by EDS analysis without the possibility of compound type identification. Tin supported catalyst was more efficient than zinc containing catalyst. PDLLA nanospheres containing encapsulated dexamethasone with medium diameter of 80 nm and polydispersity index near 0.110 were obtained with excellent reproducibility. Encapsulation efficiency, dexamethasone load in PDLLA and yield were 75 %, 3.5 % and 78 %, respectively. In vivo tests showed the visual apparence on recuperation of inflamed sheep knees treated with PDLLA nanoespheres were excelente compared to the ones treated with comercial dexametasone. / Polímeros biodegradáveis e bioabsorvíveis são de extrema importância em aplicações médicas em suturas ou como carreadores de fármacos devido a produção de resíduos não tóxicos. Neste sentido, vários trabalhos sintetizam e caracterizam o poliácido lático mas não fazem nenhuma aplicação in vitro e in vivo e vice-versa. Assim este trabalho visou sintetizar e caracterizar o poliácido lático e realizar testes de liberação in vitro e testes de liberação in vivo em joelhos inflamados por ruptura de ligamento de ovelhas. Neste trabalho sintetizou-se os polímeros PLLA e PDLLA pelo método de policondensação em estado fundido. Para garantir o alcance de um peso molecular maior, fez-se o uso de catalisadores de zinco e estanho suportado em copolímero estireno-divinilbenzeno (Sty-DVB) sulfonado. O copolímero Sty-DVB foi preparado por polimerização em suspensão na presença de diluentes inertes. O copolímero Sty-DVB foi sulfonado com ácido sulfúrico concentrado na presença de dicloroetano. O copolímero original e sulfonado, bem como, os catalisadores suportados foram caracterizados por medidas de adsorção física de nitrogênio, espectroscopia na região de infravermelho, espectrometria de energia dispersiva (EDS), microscopia eletrônica de varredura, difração de raios-X, espectrometria absorção atômica e termogravimetria. Os polímeros PLLA e PDLLA foram caracterizados por medidas de viscosidade inerente, difração de raios X, termogravimetria e ressonância magnética nuclear de 1H e 13C. Nanoesferas de PDLLA foram preparadas pelo método de nanoprecipitação sem e com o farmáco anti-inflamatório dexametasona. As nanoesferas foram caracterizadas por espalhamento de luz dinâmico para medir o diâmetro médio e o índice de polidispersão, bem como, o potencial zeta. A eficiência de encapsulamento do fármaco, a carga do fármaco, o rendimento bem como o perfil de liberação do fármaco em teste in vitro em membrana de diálise foram obtidos por análises de cromatografia líquida de alta eficiência. O estanho foi suportado no copolímero Sty-DVB sulfonado na forma de SnO2, enquanto para o zinco a sua presença foi detectada pela análise de EDS sem que fosse possível identificar o tipo de composto adsorvido. O catalisador com estanho suportado foi mais eficiente que o catalisador contendo zinco. Nanoesferas de PDLLA contendo dexametasona encapsulada com diâmetro médio de 80 nm e polidispersão de aproximadamente 0,110 foram obtidas com excelente reprodutibilidade. A eficiência de encapsulamento, a carga de dexametasona no PDLLA e o rendimento form 75%, 3,5% e 78 %, respectivamente. Os testes in vivo preliminares mostraram que a aparência visual da recuperação do ligamento em joelhos tratados com nanoesferas de PDLLA com dexametasona foram extremamente melhores que os joelhos tratados com dexametasona comercial.
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Mechanical characterization of DuraPulp by means of micromechanical modellingAl-Darwash, Mustafa, Nuss, Emanuel January 2015 (has links)
Södra DuraPulp is a relatively new eco-composite, made from natural wood fibers and polylactic acid (PLA), which comes from corn starch. Until now, there are only few applications for DuraPulp, mainly in the area of design. To find new fields of application, more knowledge about its mechanical material properties are of great interest.This study deals with characterizing the mechanical properties of DuraPulp in an analytical way by means of micromechanical modelling and evaluation with help of Matlab. The mechanical properties for PLA were taken from scientific literature. Not all properties of the wood fibers could be found in literature (particularly Poisson’s ratios were unavailable). Therefore, they partly had to be assumed within reasonable boundaries. These assumptions are later validated regarding their influence on the final product.Figures and tables were used to present and compare the in- and out-of-plane E-Moduli, shear moduli and Poisson’s ratios of DuraPulp. The calculated in-plane E-Moduli were then compared to those obtained from an earlier study, where DuraPulp was tested in tension. The results showed that experimental and analytical values are very similar to each other. / Södra DuraPulp är en relativt ny eco-komposit, tillverkat av naturliga trä fibrer och polylactic syra som kommer från majsstärkelser. I dagsläget finns det få användningsområden för DuraPulp, huvudsakligen används det inom design. För att expandera användningsområdet behövs det mer kunskaper angående de mekaniska egenskaperna för materialet. Studien handlar om att karakterisera de mekaniska egenskaperna för DuraPulp på ett analytiskt sätt i form av mikro-mekanisk modellering och evaluering med hjälp av Matlab. De huvudsakliga mekaniska egenskaperna för PLA kunde hämtas från flera vetenskapliga källor, men de motsvarande mekaniska egenskaperna för fibrer kunde inte alla valideras. Delvis antogs dem i rimliga gränser och deras inverkan validerades med hjälp av en parameter studie.Figurer och tabeller användes för att presentera och jämföra in- och ut-plan E-Moduler, skjuvmoduler och tvärkontraktionstalen av DuraPulp. De beräknade in-plan E-modulerna för DuraPulp jämfördes med motsvarande E-moduler från en tidigare studie där DuraPulp genomgick dragtest. Resultatet visade att analytiska och experimentella värden överensstämmer bra med varandra.
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Παρασκευή νανοσύνθετων υλικών που βασίζονται σε βιο-αποικοδομήσιμα πολυμερή με εγκλείσματα οργανικών νανοσωματιδίωνΠαύλου, Χρήστος 22 August 2014 (has links)
Η παρούσα εργασία αναφέρεται σε νανοσύνθετα βιο-αποικοδομήσιμα οργανικά πολυμερή, με κύρια πολυμερική μήτρα το πολυγαλακτικό οξύ (PLA). Η ερευνητική κοινότητα δείχνει μεγάλο ενδιαφέρον για την χρήση και την ανάπτυξη των βιοδιασπώμενων πολυμερών. Με αυτά αναμένεται να μειωθούν οι επιπτώσεις των πλαστικών υλικών στο περιβάλλον. Στην βιβλιογραφία υπάρχει μεγάλη δραστηριότητα για την ανάλυση του ανθρακικού αποτυπώματος των διασπώμενων πολυμερών. Επίσης, η ερευνητική κοινότητα εστιάζει την προσοχή της και στην μελέτη των ιδιοτήτων των βιοδιασπώμενων πολυμερών. Στο μέλλον αναμένεται να μπορέσουν να χρησιμοποιηθούν σε τομείς που τώρα, λόγω των περιορισμένων μήχανικών τους ιδιοτήτων δεν εφαρμόζονται.
Βασικό αντικείμενο μελέτης στην εργασία αυτή ήταν η αλληλεπίδραση οργανικών σφαιρικών νανοσωματιδίων από πολυ(οξικό βινυλεστέρα) με το πολυγαλακτικό οξυ. Για να δημιουργηθεί μια εικόνα της συμπεριφοράς του πολυγαλκατικού οξέος σαν πολυμερική μήτρα, συντέθηκαν και αξιολογήθηκαν μίγματα απο ομοπολυμερή πολυ(οξικού βινυλεστέρα) (PVAc) πολυβινυλικης αλκοόλης (PVOH) και πολυαμιδίου (PA11, PA12). Ύστερα παρασκευάσθηκαν νανοσύνθετα φιλμ απο νανοσωματίδια δικτυωμένου πολυστυρολίου (NPs-PS), δικτυωμένου πολυ(οξικού βινυλεστέρα) (NPs-PVAc) και νανοσωματίδια δικτυωμένης παλυ(βινυλικής αλκοόλης) (με βαθμούς υδρόλυσης H.D.: 100, 50, 48 και 38%). Εν συνεχεία, στην πολυμερική μήτρα απο PLA εισήχθησαν νανοδομές δικτυωμένου πολυ(στυρενοσουλφονικού δεκαέξυλου τριμεθυλαμμωνίου) (PSSAmC16-ΑΝ) σε διάφορες αναλογίες (1, 2, και 5%) και νανοδομημένα δίκτυα δικτυωμένου πολυστυρολίου (PS-NN). Τέλος οι μηχανικές ιδιότητες όλων των φιλμ αξιολογήθηκαν μέσω δοκιμής τάσης-εφελκυσμού και τα μορφολογικά τους χαρακτηριστικά μελετήθηκαν μέσω της ηλεκτρονιακής μικροσκοπίας σάρωσης SEM. / The scientific community shows great interest in the use and development of biodegradable polymers, due to their low impact on the environment. In literature there is plenty of research activity on the analysis of biodegradable polymers in comparison to the CO2 emission during the life cycle of polymer products. The carbon footprint of biodegradable polymers is far smaller than those of conventional polymers. The biodegradable materials are so desirable because these are expected to overcome significant problems such as environmental pollution, waste management issues which are created by plastics, as well as their oil dependence. Thus, the research community is focused on the study of the properties of biodegradable polymers and their potential use in applications where their design is mainly limited by the material's mechanical properties, such as modulus, strength and other characteristic properties of the behavior of the polymers (such as miscibility, optical transparency and barrier properties).
In the present work blends of PLA with the homopolymers polystyrene (PS), polyvinyl acetate (PVAc) and polyamides (PA11, PA12) were made and the quality of the synthesized films was assessed. In a further step, spherical organic nanoparticles of PS, PVAc (either non-hydrolyzed or hydrolyzed with hydrolysis degree H.D.: 100, 50, 48 and 38%) as well as assymetric nanostructures of polystyrene sulfonate ammonium salt (PSSAmC16-AN) and PS-NN were incorporated into the PLA matrix in various percentages (1, 2, and 5%). Afterwards the mecahanical properties of the blends were evaluated by stress-strain measurements, whereas their morphological characteristics were tested through scanning electron microscopy (SEM).
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Improvement of compatibility of poly(lactic acid) blended with natural rubber by modified natural rubberChumeka, Wannapa 11 December 2013 (has links) (PDF)
The aim of this research work was to improve the compatibility of polymer blends made from poly(lactic acid) and natural rubber (PLA/NR blends) by using modified natural rubber as a compatibilizer. Natural rubber was chemically modified into two categories: natural rubber grafted poly(vinyl acetate) copolymer (NR-g-PVAc) and block copolymers (PLA-NR diblock copolymer and PLA-NR-PLA triblock copolymer). PLA/NR blends were prepared by melting blending in a twin screw extruder and compression molded to obtain a 2-mm thick sheet. The blends contained 10-20 wt% of NR and modified NR, and the impact strength and tensile properties were investigated. The compatibilization effect was determined by DMTA, DSC and SEM. NR-g-PVAc was synthesized by emulsion polymerization to obtain different PVAc graft contents (1%, 5% and 12%). Characterization by DMTA showed an enhancement in miscibility of the PLA/NR-g-PVAc blends. NR-g-PVAc could be used as a toughening agent of PLA and as a compatibilizer of the PLA/NR blend. The block copolymers were synthesized following two routes: (1) hydroxyl telechelic natural rubber (HTNR) and lactide and (2) HTNR and PLA prepolymer. In the former route, lactide was in situ polymerized via a ring opening polymerization to be a PLA block segment during block copolymerization. In the latter route PLA prepolymer was synthesized by a condensation polymerization of L-lactic acid prior to block copolymerization. Both block copolymers acted as good compatibilizers for the PLA/NR blend by increasing the impact strength and decreasing the NR particle size. Triblock copolymers provided higher impact strength than diblock copolymers, and they were a less effective compatibilizer than NR-g-PVAc. In contrast to NR and NR-g-PVAc, the block copolymer was not a good toughening agent for PLA.
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Microbial-derived cellulose-reinforced biocomposites : a thesis submitted in partial fulfilment of the requirements for the degree of Master of Engineering in the Department of Mechanical Engineering, Engineering School, University of Canterbury, Christchurch, New Zealand /Piao, Haiyuan. January 1900 (has links)
Thesis (M.E.)--University of Canterbury, 2006. / Typescript (photocopy). "31st May 2006." Includes bibliographical references (leaves 126-133). Also available via the World Wide Web.
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Processing and properties of nanocomposites based on polylactic acid, chitin and celluloseHerrera Vargas, Natalia January 2017 (has links)
The production of bio-based and biodegradable nanocomposites has gained attention during recent years for environmental reasons; however, the large-scale production of these nanocomposites still poses challenges. The objective of this work has been to prepare bio-based and biodegradable nanocomposites via liquid-assisted extrusion and to gain a deeper understanding of the process and the relationship between the process, composition, structure and properties. Extrusion is a common industrial process and thus, the development of this technique for the preparation of bionanocomposites can promote the commercialization of these materials in future. In this work, nanocomposites based on polylactic acid (PLA), cellulose nanofibers (CNF), cellulose nanocrystals (CNC), and chitin nanocrystals (ChNC) with varying nanomaterial content were prepared via liquid-assisted extrusion using a plasticizer as a dispersing and processing aid. This process consists of dispersing the nanomaterial in a liquid composed of water, a plasticizer and/or a solvent, and then feeding this suspension directly into the extruder during the process. To be able to carry out this process successfully, parameters such as the amount of liquid, the liquid feeding rate or the water-to-solvent ratio, among others, should be taken in account. CNF and ChNC were produced from banana rachis waste and crustacean waste, respectively, whereas CNC were available as a commercial product. Glycerol triacetate (GTA) and triethyl citrate (TEC) were used as plasticizers, dispersing and processing aids. The effects of the liquids used during extrusion, the plasticizers and the nanomaterials in the PLA properties were studied. Furthermore, the effects of the cooling rate during the compression molding and the solid-state drawing on the properties of the PLA nanocomposites were investigated. Additionally, the effect of ChNC on the processing and properties of blown films was evaluated. The results presented in this work demonstrated that the use of water and a solvent during the liquid-assisted extrusion did not decrease the molecular weight of the PLA. It was also found that the feeding of nanomaterials in aqueous or aqueous/solvent suspension resulted in PLA micro-composite with lower mechanical properties than PLA. However, when a nanomaterial was fed together with a plasticizer, its dispersion and distribution into the PLA were progressively improved with increasing plasticizer content. The plasticized PLA nanocomposites showed improved properties compared to their respective counterpart without nanomaterials when the plasticizer content was ≥7.5 wt%. Furthermore, it was demonstrated that the properties of PLA can be tailored through the composition of the nanocomposite or during the processing. It was observed that the modification of PLA with only plasticizer in high amounts (20 wt%) resulted in enhanced elongation at break and toughness but it had negative effects on the thermal and mechanical properties; however, the incorporation of nanomaterials minimized these effects. The addition of a small amount of nanomaterial (1 wt%), either CNF, CNC or ChNC, to plasticized PLA resulted in enhanced mechanical properties. It was also demonstrated that the cooling rate during compression molding and the solid-state drawing significantly affected the crystallinity of the PLA nanocomposites and, thus, their final properties. The fast cooling rate during compression molding resulted in more flexible and transparent materials than when a slow cooling rate was used, and as a result, PLA films with different mechanical properties were obtained. The drawing of the PLA/CNF nanocomposite at a drawing temperature slightly above the Tg, a high draw speed and at the highest drawing ratio, resulted in the highest mechanical properties. It was also found that the increased toughness after adding CNF to the plasticized PLA or after drawing the PLA/CNF nanocomposite, was attributed to the occurrence of massive crazing effect as a result of the presence of CNF and its effect on the crystallinity and/or on the spherulite growth. Finally, 6 kg of plasticized PLA nanocomposite with 5 wt% of ChNC was prepared and used as a masterbatch to produce bio-nanocomposite blown films. The nanocomposite material showed easier processability during the film-blowing process when compared with the reference material without nanocrystals. In addition, the nanocomposite blown films exhibited higher tear and puncture strength, lower fungal activity and lower electrostatic attraction properties, which are favorable in packaging applications. In conclusion, this thesis shows that the liquid-assisted extrusion process is an excellent approach for producing PLA nanocomposites using cellulose and chitin nanomaterials. The results indicated that the addition of these nanomaterials, together with a plasticizer and further processing, can result in PLA nanocomposites with varied properties that can be used for packing applications. It was also shown that the processing technique presented can be a step forward for the large-scale production of bionanocomposites.
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Mechanical behavior of a bio-based composite : influences of production conditionsHosseini Moghadam, Seyed Mazdak, Alshihabi, Mohamed January 2016 (has links)
Some mechanical properties of DuraPulp, a bio-based, bio-degradable composite made from polylactic acid (PLA) and pulp fibers, were determined. Focus was put on the conditions during productions whereby three different press times were studied. Additionally, two different material compositions (PLA to fiber ratios) were used. Uniaxial tensile tests with two different load rates, one and 50 mm/min, were performed. An increase in maximum strength and E-modulus of DuraPulp was observed by increasing the press time, while PLA content decreased the maximum strength and E modulus.
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Étude des scénarios de fin de vie des biocomposites : vieillissement et retransformation de biocomposites PP/farine de bois et PLA/fibres de lin / Study of biocomposite end-of-life scenariosSoccalingame, Lata 09 December 2014 (has links)
Les matériaux biocomposites, en particulier les composites matrice thermoplastique biosourcée ou non renforcée de charges ou de fibres végétales, connaissent actuellement un essor significatif et présentent pour l'avenir un gisement grandissant de matières en fin de vie. En conséquence, l'étude du comportement de ces matériaux au regard de différents scénarios de fin de vie que sont le recyclage mécanique, le compostage et l'incinération constitue un enjeu scientifique et technologique important. Le premier objectif de cette thèse est d'étudier la fin de vie par retransformation (cycles successifs d'injection et de broyage) de biocomposites à matrice polypropylène (PP) chargé de farine de bois. L'impact de la taille des particules de bois et d'un agent de couplage a été évalué. Une très bonne stabilité mécanique jusqu'à 7 cycles de retransformation a été observée malgré des dégradations des différents composants du matériau. Le comportement face à la retransformation après vieillissement artificiel accéléré ou après une exposition naturelle en extérieur a été étudié. La tendance majeure dégagée est un phénomène de « régénération » des propriétés mécaniques par retransformation, et cela malgré des dégradations importantes après vieillissement. Il a été également été observé que l'ajout de bois a tendance à limiter la photodégradation du PP. Le second objectif est d'étudier la fin de vie de biocomposites à matrice acide polylactique (PLA) renforcé de fibres de lin. L'impact de différents paramètres de formulation, de la technique de mise en œuvre et d'un vieillissement hygrothermique sur la retransformation de ces matériaux a été évalué. Les mêmes phénomènes de « régénération » sont observés, ce qui montre l'effet bénéfique de la retransformation. La fin de vie par compostage et par biodégradation est traitée. Des mesures d'énergies de combustion ont enfin permis d'estimer le potentiel de valorisation par incinération qui serait en lien avec le niveau de dégradation du PLA. / Nowadays, biocomposite materials are booming and will be a growing end-of-life issue for the future. They are based on a thermoplastic matrix (oil-based or bio-based) reinforced with vegetable fillers or fibers. Consequently, the study of their end of life through recycling, composting and incineration is a scientific and technologic challenge.The first goal of this thesis is to study the reprocessing end of life (successive injection and grinding cycles) of polypropylene (PP) based biocomposites filled with wood flour. The impact of the wood particle size and a coupling agent was assessed. Thus, a very good mechanical stability was observed up to 7 reprocessing cycles despite some degradation from the material components. Then, the reprocessing after artificial or natural UV weathering was carried out. The major trend is a “regeneration” phenomenon of mechanical properties after reprocessing in spite of strong degradations after UV weathering. Moreover, the addition of wood filler tends to restrain the PP photochemical degradation.The second goal is to study the end of life of polylactic acid (PLA) based biocomposites reinforced with flax fibers. The impact of the composition, the processing technic and humidity weathering on the reprocessing was assessed. Similar “regeneration” phenomena were observed leading to conclude to the beneficial effect of reprocessing. Then composting and biodegradation aspects were investigated. Heat release rate measurements enabled to estimate the incineration potential which could be linked to the PLA degradation rate.
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