Les polylactides (PLA) sont une famille de polymères biodégradables et biocompatibles de la famille des polyesters aliphatiques. Lorsque le PLA est dans un milieu humide et à une température excédant le 60°C, il se dépolymérise rapidement par hydrolyse, étape préalable à la biodégradation du PLA. Le PLA est utilisé dans le domaine biomédical et dans la fabrication de nombreux produits destinés, entre autres, à l’usage alimentaire tels que des emballages, des ustensiles et de la vaisselle jetable. Cependant, quand des applications à longue durée de vie sont visées, sa dégradation peut devenir une propriété non désirable. À cet égard, le mélanger avec un autre polymère est une des alternatives les plus simples et peu coûteuses afin de limiter cette dégradation. Le polyméthacrylate de méthyle (PMMA), un polymère thermoplastique et biocompatible avec de bonnes propriétés mécaniques et thermiques, est un candidat potentiel. Ce travail de recherche, divisé en deux étapes, consiste en l’étude de l’hydrolyse du PLA puis celle des mélanges PLA/PMMA aux températures supérieures à leur température de transition vitreuse, cela en milieu neutre, en milieu alcalin et, en certains cas, en milieu acide. La première étape de ce travail comprend l’étude de l’hydrolyse du PLA en fonction de sa capacité à cristalliser ainsi que de la température et de l’acidité du milieu d’hydrolyse en phase aqueuse. Pour l’effet de composition, deux PLA commerciaux qui différaient dans leurs ratios de compositions d’énantiomères L- et D- ont été sélectionnés. Le premier de ces PLA avait la capacité de cristalliser jusqu’à un taux d’environ 40% alors que le second était complètement amorphe. L’hydrolyse a été effectuée dans l’eau distillée (pH égal à 5.3) à 60, 70 et 80 °C pour évaluer l’effet de la température. Ensuite, les PLA ont été soumis à l’hydrolyse en milieu acide (pH égal à 1) et alcalin (pH égal à 12) à une température constante de 70°C afin d’évaluer l’effet de l’acidité et l’alcalinité du milieu. L’hydrolyse a été réalisée en suivant l’évolution de la perte de masse, du pourcentage d’eau absorbée, de l’évolution de la distribution de masse molaire et finalement de la température de fusion et du changement d’enthalpie qui y est associé. Les résultats ont montré que l’hydrolyse en milieu acide et neutre procède par un mécanisme d’érosion massique (i.e. érosion dans le cœur de l’échantillon) tandis qu’en milieu alcalin, l’hydrolyse du PLA suit principalement un mécanisme d’érosion surfacique. La cinétique de l’hydrolyse a été modélisée avec succès à l’aide d’un modèle exponentiel à deux étapes qui prend en compte chaque étape du mécanisme d’érosion. Indépendamment de leur composition énantiomérique et même si tous les échantillons étaient amorphes au début des essais, ils ont cristallisé rapidement durant l’hydrolyse. Dans une deuxième étape, l’hydrolyse des mélanges PLA/PMMA a été étudiée. L’ajout du PMMA avait pour but de ralentir la progression de l’hydrolyse puisque ce matériau est un polymère d’addition insensible à l’hydrolyse. Les mélanges préparés par extrusion ont été soumis à l’hydrolyse en milieu neutre et en milieu alcalin à 80°C durant 30 et 5 jours, respectivement. Le milieu acide n’a pas été utilisé, car, dans la première étape du travail, le comportement en hydrolyse y a été trouvé similaire à celui en milieu neutre. Les résultats montrent que le PMMA n’a aucune influence sur le développement de la cristallinité durant l’hydrolyse car le PLA a cristallisé rapidement dans les deux milieux. La réduction de la masse molaire durant l’hydrolyse a causé une réduction de la température et de l’enthalpie de fusion du PLA. La présence du PMMA a fortement amélioré l’intégrité structurelle des mélanges. À cet effet, une teneur aussi faible que 5% de PMMA retardait significativement la fragmentation des échantillons par comparaison au PLA pur. Néanmoins, le PMMA n’a eu aucune influence sur la diffusion de l’eau dans la matrice polymérique. De plus, la présence du PMMA n’a joué aucun rôle sur la cinétique de l’hydrolyse du PLA lorsque le mécanisme en cause était l’érosion massique (i.e. milieu neutre). Par contre, en milieu alcalin, où le mécanisme d’érosion surfacique est prédominant, la perte de masse et la cinétique de l’hydrolyse ont été fortement ralenties par la présence du PMMA. L’enlèvement sélectif du PLA durant l’hydrolyse a laissé une structure poreuse interconnectée d’échelle nanométrique qui n’avait été observée auparavant.

Yes / Highly oriented long-chain-branched poly (lactic acid) (LCB-PLA) was prepared and the structure evolution was studied in the process of solid die drawing by compared with poly (lactic acid) (PLA). During drawing, samples underwent not only die drawing process but also free drawing process. Drawing speed presented a prominent effect on the free drawing process, while die thickness showed a more obvious influence on the die drawing process. For PLA, free drawing process mainly contributed to its final orientation degree and crystallinity, and thus the mechanical properties of PLA were greatly influenced by drawing speed. However, for LCB-PLA, die drawing process made a greater contribution to the final orientation degree and crystallinity, and its mechanical properties were mainly affected by die thickness. Under the same drawing condition, the tensile strength and modulus of LCB-PLA were always higher than those of PLA, and reached up to 228 MPa and 7.2 GPa, respectively, which basically met the requirement for born fixation materials. Samples which only underwent die drawing showed obvious “sandwich” structure, and the thickness of the oriented skin layer for LCB-PLA was thicker than that for PLA, suggesting that shear-induced orientation can be easily retained due to the enhanced entanglement between long branched chains. After drawing, LCB-PLA samples showed smaller lamellae size (Llateral) but larger long period (Lac) compared with PLA, suggesting that the low chain mobility restricted the motion of chain slipping of LCB-PLA and thus resulted in the fragmentation of neighboring crystal lamella by chain stretched-out.

PLA (Atkarpomis tiesinių agregatų) formalizavimo metodas gali būti naudojamas sistemų formalių specifikacijų sudarinėjimui. Sistemų formalios specifikacijos gali būti užrašomos tekstiniu pavidalu, tačiau tai yra labai varginantis procesas, ko pasėkoje gautas rezultatas yra vaizdiniai neinformatyvus ir vartotojai negali lengvai perprasti sistemos specifikacijos. Šiame dokumente pateikiamas būdas vizualiai ir pakankamai lengvai užrašyti sistemų formalias specifikacijas naudojant PLA formalizavimo metodą. Šiame dokumente taip pat pristatomas grafinis redaktorius – sudėtingų formalių specifikacijų integruotos analizės automatizavimo sistemos posistemė, skirta agregatinių specifikacij�� kūrimui ir redagavimui. / PLA method can be used to formally specify systems. Systems specifications are written as text, what is exhaustive and understandable, but unfortunately are not visual, and user can’t quickly acquaintance with the formalized system. This article presents a way to visually and quite easily write systems specifications using PLA formalization method. This article also presents a software tool to accomplish this task. That’s graphical editor – a subsystem of a formal complex systems integrated analysis automatization system (FSA).

Submitted by JOÃO DOMINGOS AUGUSTO DOS SANTOS PEREIRA (jdapereira1@yahoo.com.br) on 2016-06-22T14:29:05Z No. of bitstreams: 1 Tese-Joao-Final-1506.pdf: 5514546 bytes, checksum: 2745243ab942ec11ef93c6cdc29078f4 (MD5) / Approved for entry into archive by Juliano Benedito Ferreira (julianoferreira@reitoria.unesp.br) on 2016-06-24T19:02:25Z (GMT) No. of bitstreams: 1 pereira_jda_dr_bauru.pdf: 5514546 bytes, checksum: 2745243ab942ec11ef93c6cdc29078f4 (MD5) / Made available in DSpace on 2016-06-24T19:02:25Z (GMT). No. of bitstreams: 1 pereira_jda_dr_bauru.pdf: 5514546 bytes, checksum: 2745243ab942ec11ef93c6cdc29078f4 (MD5) Previous issue date: 2016-04-29 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Espumas de PLA/Amido e PLA/Amido/Sepiolita (SEP) com distintas composições foram produzidas. As amostras foram caracterizadas pelas seguintes técnicas: i) microscopia eletrônica de varredura (MEV); ii) medidas de densidade (ρ); iii) calorimetria diferencial exploratória (DSC), iv) análise mecânica (flexão e tração); v) análise térmica dinâmico mecânica (DMTA); vi) testes in vivo. Nas imagens de MEV, tanto nos precursores quanto nas espumas, a interface entre as fases foi eminentemente física com duas fases distintas e houve ocorrência de lacunas entre elas, sendo que um aumento no tamanho das lacunas foi observado nas espumas. Observou-se que nas amostras com SEP ocorreu uma maior geração de células com menores dimensões e mais compactas. Isto demonstra que a SEP apresentou, assim como os grânulos de amido, o comportamento de agente de nucleação. Nas medidas de ρ os menores valores ocorreram com as amostras originárias do autoclave e do banho de glicerina, respectivamente. Essas diminuições foram consistentes com a expansão da matriz de PLA observada nas imagens de MEV. Nas medidas de DSC, em geral, a adição do amido ao PLA implicou no aumento da Xc. Tal efeito sucedeu-se devido a interface entre o amido e o PLA ser mais energética, o que facilitou a formação de cristais na matriz de PLA. Nos compósitos contendo SEP, em geral, maiores valores de Xc foram observados quando comparados com as blendas de PLA/amido nas mesmas proporções de materiais. Esse comportamento provavelmente está associado ao efeito da SEP como agente nucleante no PLA. Na análise mecânica, tanto no ensaio de flexão quanto no de tração, com o aumento do conteúdo de amido nas blendas menores foram a resistência e a deformação máxima, bem como a tensão e a deformação de ruptura. Adicionalmente, o mesmo comportamento de diminuição foi mantido para os compósitos com a SEP. No entanto, no ensaio de tração, essas amostras apresentaram medidas com valores maiores do que o das blendas. Nos resultados observados via DMTA, em geral, a adição do amido e da SEP diminuíram a rigidez da matriz PLA, ou seja, valores de E' menores nas blendas e nos compósitos do que nas amostras de PLA puro. No estudo in vivo, aprovado pela Comissão de Ética no Uso de Animais da FCT/UNESP, Presidente Prudente, São Paulo, Brasil (processo nº 02/2014), foram utilizados 18 ratos machos da linhagem Wistar (Rattus novergicus, variedade albina, Rodentia, Mammalia) com idade de 120 dias, obtidos junto à Universidade do Oeste Paulista (UNOESTE). Os animais foram submetidos a processo cirúrgico para a implantação das amostras e após 40 semanas, contadas a partir da data da cirurgia de implantação, as amostras foram removidas. Para a análise da morfologia estrutural das amostras e tecidos removidos, medidas de MEV e microscopia ótica (MO) foram realizadas, respectivamente. Observou-se pela técnica de MEV que as superfícies das amostras pós implante apresentaram um padrão de recobrimento por tecido biológico com morfologia capsular. Nas fotomicrografias obtidas pela MO estruturas como fibras musculares, tecido adiposo (TA) e conjuntivo denso (TCD) foram observados. Além disso, em algumas fotomicrografias foram observados poucos pontos focais de infiltrado inflamatório. Próximo ao tecido muscular foi observada a presença de TA permeado de TCD, caracterizando como um tecido capsular. / Foams of PLA/Starch and PLA/Starch/Sepiolite (SEP) with different compositions were produced. The following techniques were used in the samples characterization: i) scanning electron microscopy (SEM); ii) density (ρ) measures; iii) differential scanning calorimetry (DSC), iv) mechanical analysis (flexion and traction); v) dynamic mechanical thermal analysis (DMTA); vi) in vivo test. In the SEM images, in both foams and precursors, the interface between the phases was eminently physic with two distinct phases with gaps between them, and an increase in size of the gaps was observed in the foam. It was observed that in the samples with SEP occurred greater generation of smaller cell and more compact. This demonstrates that SEP presented, as well as the starch granules, the nucleating agent behavior. In ρ measures the lowest values were found in samples originating from the autoclave and glycerine bath, respectively. These decreases were consistent with the expansion of PLA matrix observed in the SEM images. In the DSC measurements in general, the starch addition to PLA resulted in increased Xc. This effect happened because the interface between starch and PLA be more energetic, which facilitated the crystals formation in the PLA matrix. In composites containing SEP, generally larger Xc values were observed when compared with the PLA/starch blends in the same proportions materials. This behavior is probably related to the effect of the SEP as a nucleating agent in the PLA. In the mechanical analysis, flexion and traction, with increasing starch content in the blends lower resistance and maximum deformation as the tension and rupture deformation were obtained. Additionally, the same decrease in performance was maintained for composites SEP. However, in the tensile test, these samples showed values greater than the blends. In the results observed via DMTA, in general, the addition of starch and SEP resulted in a stiffness decrease of PLA matrix, that is, E' lower values for blends and composites when compared with pure PLA samples. In the in vivo study, approved by the Ethics Committee on Animal Use the FCT/UNESP, Presidente Prudente, São Paulo, Brazil (process No. 02/2014), 18 rats Wistar (Rattus norvegicus, albino variety, Rodentia, Mammalia) were used with age of 120 days, obtained from the Universidade do Oeste Paulista (UNOESTE). The animals underwent surgical procedure for samples implantation, after 40 weeks counted from the implantation surgery date, the samples were removed. For structural analysis of removed samples and tissues SEM morphology measurements and optical microscopy (OM) were performed respectively. It was observed by SEM technique that the surfaces of post-implant samples showed a pattern coating by biological tissue with capsular morphology. In the photomicrographs obtained by OM, structures such as muscle fibers; adipose tissue (AT) and dense connective (TDC) were observed. Furthermore, in photomicrographs were observed in some few focal inflammatory infiltrate. Next to the muscle tissue was observed the presence of AT permeated by the TDC, featuring as capsular tissue. / Foams of PLA/Starch and PLA/Starch/Sepiolite (SEP) with different compositions were produced. The following techniques were used in the samples characterization: i) scanning electron microscopy (SEM); ii) density (ρ) measures; iii) differential scanning calorimetry (DSC), iv) mechanical analysis (flexion and traction); v) dynamic mechanical thermal analysis (DMTA); vi) in vivo test. In the SEM images, in both foams and precursors, the interface between the phases was eminently physic with two distinct phases with gaps between them, and an increase in size of the gaps was observed in the foam. It was observed that in the samples with SEP occurred greater generation of smaller cell and more compact. This demonstrates that SEP presented, as well as the starch granules, the nucleating agent behavior. In ρ measures the lowest values were found in samples originating from the autoclave and glycerine bath, respectively. These decreases were consistent with the expansion of PLA matrix observed in the SEM images. In the DSC measurements in general, the starch addition to PLA resulted in increased Xc. This effect happened because the interface between starch and PLA be more energetic, which facilitated the crystals formation in the PLA matrix. In composites containing SEP, generally larger Xc values were observed when compared with the PLA/starch blends in the same proportions materials. This behavior is probably related to the effect of the SEP as a nucleating agent in the PLA. In the mechanical analysis, flexion and traction, with increasing starch content in the blends lower resistance and maximum deformation as the tension and rupture deformation were obtained. Additionally, the same decrease in performance was maintained for composites SEP. However, in the tensile test, these samples showed values greater than the blends. In the results observed via DMTA, in general, the addition of starch and SEP resulted in a stiffness decrease of PLA matrix, that is, E' lower values for blends and composites when compared with pure PLA samples. In the in vivo study, approved by the Ethics Committee on Animal Use the FCT/UNESP, Presidente Prudente, São Paulo, Brazil (process No. 02/2014), 18 rats Wistar (Rattus norvegicus, albino variety, Rodentia, Mammalia) were used with age of 120 days, obtained from the Universidade do Oeste Paulista (UNOESTE). The animals underwent surgical procedure for samples implantation, after 40 weeks counted from the implantation surgery date, the samples were removed. For structural analysis of removed samples and tissues SEM morphology measurements and optical microscopy (OM) were performed respectively. It was observed by SEM technique that the surfaces of post-implant samples showed a pattern coating by biological tissue with capsular morphology. In the photomicrographs obtained by OM, structures such as muscle fibers; adipose tissue (AT) and dense connective (TDC) were observed. Furthermore, in photomicrographs were observed in some few focal inflammatory infiltrate. Next to the muscle tissue was observed the presence of AT permeated by the TDC, featuring as capsular tissue.

Yes / Sheet specimens of a PLLA-based polymer have been extended at a temperature near to the glass transition in both uniaxial and planar tension, with stress relaxation observed for some time after reaching the final strain. Both axial and transverse stresses were recorded in the planar experiments. In all cases during loading, yielding at small strain was followed by a drop in true stress and then strain hardening. This was followed by stress relaxation at constant strain, during which stress dropped to reach an effectively constant level. Stresses were modelled as steady state and transient components. Steady-state components were identified with the long-term stress in stress relaxation and associated with an elastic component of the model. Transient stresses were modelled using Eyring mechanisms. The greater part of the stress during strain hardening was associated with dissipative Eyring processes. The model was successful in predicting stresses in both uniaxial and planar extension over a limited range of strain rate.

Šiame magistriniame darbe yra aptariama logistikos svarba prekybinėse įmonėse. Atliekamas sandėliavimo ir transportavimo, bei efektyvaus klientų užsakymų tenkinimo naudojant informacines technologijas optimizavimo tyrimas. Panašių programų analizė. Neformaliai ir formaliai Z kalba sandėlių sistemos aprašymas. Bendro prekybos centro ir sandėlio PLA modelio parengimas su agregacine schema ir koncepciniu modeliu, formalia specifikacija. Taip pat išskirtos perėjimų ir išėjimų operacijos. Vėliau bendrojo PLA modelio pritaikymas sandėlių ir prekybos centrų logistikos schemai, agregacinės schemos paruošimas. Formaliųjų Z ir PLA metodų apjungimas kuriant imitacinius modelius, bei imitacinio modelio paruošimas ir jo analizė. Z ir PLA matodų pranašumai ir trūkumai kuriant imitacinius modelius. Išvadose darbo pasiekti rezultatai. / In this graduate work is consideration about logistic importance in commercial companies. Optimization analysis about warehouse and transport functions, effeteness of clients requests using information technologies. The similar programs analysis. Not formally and formally Z language warehouse system descripting. General super market and warehouse PLA model preparation with aggregate scheme and with conceptual model and with formal specification. Also transitions and output operations. Then this general model use for super markets and warehouses and make aggregate scheme. Then integrate efficiency of logistic centres evaluated function. Formal Z and PLA metods coupling to create warehouse imitation model. In conclusion presented analysis work results.

No description available.

Mémoire numérisé par la Direction des bibliothèques de l'Université de Montréal.

Étude du compilateur de PLA pour une génération automatique de partie contrôle de microprocesseurs. Cet outil accepte la description de l'algorithme d'interprétation de l'automate à travers un langage intermédiaire. La possibilité de réalisation d'un automate de Moore ou Mealy pour un même automate est une facilité importante de cet outil qui permet de générer les actions conditionnées par simplification de l'algorithme d'interprétation de l'automate. Présentation en annexe de la stratégie de conception et de prise en compte de la priorité de signaux du micro MC 6800

This thesis illustrates a comprehensive study on the PVT, solubility and surface tension properties of polylactic acid (PLA) with dissolved CO2 based on thermodynamic models. The solubility of CO2 in PLA melt was calculated by means of a gravimetric method, using a Magnetic Suspension Balance (MSB). The swelling volume of the polymer/gas mixture due to dissolution of gas was compensated for by direct measurement through a view cell or by theoretical models such as Simha Somcynsky (SS) - Equation of State (EOS) and Sanchez Lacombe (SL) - Equation of State (EOS). Three grades of PLA (i.e., PLA3001D, PLA8051D, and PLA4060D) were chosen. It was observed that the pressure, temperature, D-content and Molecular weight variance had an effect on the swelling and solubility. The surface Tension of PLA/CO₂ mixture was also calculated from the captured image using the Axsymmetric Drop Shape Analysis (ADSA). The effects of varying the pressure, temperature, and molecular weight on surface tension were investigated.