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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
181

HIGH PRECISION MACHINING AND OPTICAL SURFACE FINISH.

Nsabimana, Leonard 22 July 2022 (has links)
No description available.
182

Performance of Multiple Emission Peak Light Emitting Diode Light Curing Unit: Degree of Conversion and Microhardness of Resin-Based Pit and Fissure Sealant

Ba Armah, Ibrahim 07 1900 (has links)
Background: The light-cured resin-based pit and fissure sealants success and longevity are enhanced by sufficient curing. Multiple emission peak Light Emitting Diode Light Curing Units offer a wider range of wavelengths and different levels of irradiances to ensure sufficient curing.The irradiance is considered a main curing factor that can affect the material properties. Purpose: The aim of this study was to assess the effect of different settings of a multiwave LED LCU on the degree of conversion and microhardness of a pit and fissure sealant comparing the irradiance of 1000 mW/cm2 to 1400 mW/cm2 and 3200 mW/cm2 irradiances of the LCU using manufacturer’s guidelines for curing times at 2, 4 and, 6 mm distances. Methods: A multiwave LED light curing unit was evaluated on three different irradiance levels 1000 mW/cm2 (S), 1400 mW/cm2 (H), and 3200 mW/cm2 (X). A total of 90 samples made from the fissure sealant were fabricated and divided into eighteen groups (n=5/group). Samples were cured following manufacturer’s guidelines of curing times for each curing mode at 2, 4, or 6 mm distance between the light tip and top of samples. The DC was measured using (ATR-FTIR) spectroscopy. The KHN test was performed on five different locations of each specimen using a hardness tester (Leco LM247AT, MI, USA, software; Confident V 2.5.2). Results: The top DC for H-8 was significantly higher than S-10 at 2 and 4mm, H-20 DC was significantly lower than S-30 at only 2mm. The bottom DC for H-8 was significantly higher than S-10 at 2mm only, H-20 DC was significantly lower than S-30 at 4 and 6mm only. H-8 KHN at top surface was significantly lower than S-10 at 2mm only, H-20 was significantly lower than S-30 at 2 and 6mm only. H-8 KHN at bottom surface was significantly lower than S-10 at 4 and 6mm but significantly higher at 2mm. H-20 was significantly lower than S-30 at 2mm but significantly higher at 4 and 6mm. The top DC for X-3 was significantly lower than S-10 at all curing distances with no significant difference at all curing distances between X-9 and S-30. The bottom DC for X-3 was significantly higher than S-10 at all curing distances with no significant difference between X-9 and S-30. X-3 KHN at top surface was significantly lower than S-10s at all curing distances. X-9 was significantly lower than S-30 at 6mm only. X-3 KHN at bottom surface was significantly lower than S-10 at 2 and 4mm only with no significant difference at all curing distances between X-9 and S-30. Conclusions: Using a multiwave LED LCU to polymerize Delton Opaque resin-based fissure sealants will result in an optimal DC and KHN values for any irradiance level if the curing distance is kept at 4 mm or less and with at least two cycles of the shortest curing time recommended by the manufacturer. Using a multiwave LED LCU with 1000, 1400 or 3200 mW/cm2 irradiance levels with shortest curing times recommended resulted in unsatisfactory DC and KHN levels. LED LCU with high and extra high irradiance levels (1400 and 3200 mW/cm2) can result in high DC and KHN levels when used adequately. Xtra Power mode (3200 mW/cm2) used on shortest curing time (3 seconds) resulted in significantly lower mechanical properties and for that reason it is not recommended to be used.
183

Dynamic Modelling and Optimization of Polymerization Processes in Batch and Semi-batch Reactors. Dynamic Modelling and Optimization of Bulk Polymerization of Styrene, Solution Polymerization of MMA and Emulsion Copolymerization of Styrene and MMA in Batch and Semi-batch Reactors using Control Vector Parameterization Techniques.

Ibrahim, W.H.B.W. January 2011 (has links)
Dynamic modelling and optimization of three different processes namely (a) bulk polymerization of styrene, (b) solution polymerization of methyl methacrylate (MMA) and (c) emulsion copolymerization of Styrene and MMA in batch and semi-batch reactors are the focus of this work. In this work, models are presented as sets of differential-algebraic equations describing the process. Different optimization problems such as (a) maximum conversion (Xn), (b) maximum number average molecular weight (Mn) and (c) minimum time to achieve the desired polymer molecular properties (defined as pre-specified values of monomer conversion and number average molecular weight) are formulated. Reactor temperature, jacket temperature, initial initiator concentration, monomer feed rate, initiator feed rate and surfactant feed rate are used as optimization variables in the optimization formulations. The dynamic optimization problems were converted into nonlinear programming problem using the CVP techniques which were solved using efficient SQP (Successive Quadratic Programming) method available within the gPROMS (general PROcess Modelling System) software. The process model used for bulk polystyrene polymerization in batch reactors, using 2, 2 azobisisobutyronitrile catalyst (AIBN) as initiator was improved by including the gel and glass effects. The results obtained from this work when compared with the previous study by other researcher which disregarded the gel and glass effect in their study which show that the batch time operation are significantly reduced while the amount of the initial initiator concentration required increases. Also, the termination rate constant decreases as the concentration of the mixture increases, resulting rapid monomer conversion. The process model used for solution polymerization of methyl methacrylate (MMA) in batch reactors, using AIBN as the initiator and Toluene as the solvent was improved by including the free volume theory to calculate the initiator efficiency, f. The effects of different f was examined and compared with previous work which used a constant value of f 0.53. The results of these studies show that initiator efficiency, f is not constant but decreases with the increase of monomer conversion along the process. The determination of optimal control trajectories for emulsion copolymerization of Styrene and MMA with the objective of maximizing the number average molecular weight (Mn) and overall conversion (Xn) were carried out in batch and semi-batch reactors. The initiator used in this work is Persulfate K2S2O8 and the surfactant is Sodium Dodecyl Sulfate (SDS). Reduction of the pre-batch time increases the Mn but decreases the conversion (Xn). The sooner the addition of monomer into the reactor, the earlier the growth of the polymer chain leading to higher Mn. Besides that, Mn also can be increased by decreasing the initial initiator concentration (Ci0). Less oligomeric radicals will be produced with low Ci0, leading to reduced polymerization loci thus lowering the overall conversion. On the other hand, increases of reaction temperature (Tr) will decrease the Mn since transfer coefficient is increased at higher Tr leading to increase of the monomeric radicals resulting in an increase in termination reaction.
184

Effect of cataract surgery incision location and intraocular lens type on ocular aberrations.

Pesudovs, Konrad, Dietze, Holger H., Stewart, O., Noble, B.A., Cox, Michael J. January 2005 (has links)
No / To determine whether Hartmann-Shack wavefront sensing detects differences in optical performance in vivo between poly(methyl methacrylate) (PMMA) and foldable acrylic intraocular lenses (IOLs) and between clear corneal and scleral tunnel incisions and whether optical differences are manifested as differences in visual performance. SETTING: Department of Optometry, University of Bradford, West Yorkshire, United Kingdom. METHODS: This study comprised 74 subjects; 17 were phakic with no ocular pathology, 20 had implantation of a Pharmacia 722C PMMA IOL through a scleral tunnel, 21 had implantation of an Alcon AcrySof IOL through a scleral tunnel, and 16 had implantation of an AcrySof IOL through a corneal incision. Visual acuity and contrast sensitivity testing, ocular optical quality measurement using Hartmann-Shack wavefront sensing, and corneal surface measurement with a videokeratoscope were performed in all cases. RESULTS: There were significant differences between groups in the total root-mean-square (RMS) wavefront aberration over a 6.0 mm pupil (F=3.91; degrees of freedom=3,70; P<.05) mediated at the 4th-order RMS, specifically spherical and tetrafoil aberrations. The PMMA-scleral group had the least aberrations and the AcrySof-corneal group the most. For a 3.5 mm diameter pupil, the total higher-order RMS wavefront aberration was not significantly different between the groups (P>.05). There were no differences between groups in corneal shape, visual acuity, or contrast sensitivity. CONCLUSIONS: Implantation of the spherical PMMA IOL led to a slight reduction in total wavefront aberration compared to phakic eyes. AcrySof IOLs induced more aberrations, especially spherical aberration. Corneal-based incisions for IOL implantation compounded this increase. Studies of the optical performance of IOLs in vivo should use wavefront sensing as the main outcome measure rather than visual measures, which are readily confounded by multiple factors.
185

Metal catalysed alkylation of carbonyl compounds with formaldehyde

Lorusso, Patrizia January 2015 (has links)
Formaldehyde is a chemical used widely in the manufacture of building materials. A remarkable example is represented by the Lucite two-step Alpha technology for the large scale production of methyl methacrylate (MMA), the essential building block of all acrylic-based products. Esters and ketones are important intermediates in the manufacture of acrylate esters therefore α-hydroxymethylenation of carbonyl compounds using formaldehyde as a one carbon alkylating agent and subsequent dehydration to the corresponding methylenated derivatives has been explored in the current work. We report a novel catalytic approach for the synthesis of methyl methacrylate (MMA) via one-pot α-methylenation of methyl propanoate (a chemical intermediate of the ALPHA process) with formaldehyde, generated in situ by Ru-catalysed dehydrogenation of methanol. Elucidation of the mechanism involved in the catalytic dehydrogenation of methanol along with the collateral alcohol decarbonylation reaction was gained through a combined experimental and DFT study. The development of an alternative process where anhydrous formaldehyde is produced in situ would provide a simplification over the current second step of the ALPHA technology where the formaldehyde is initially produced as formalin, subsequently dehydrated to afford anhydrous formaldehyde in order to ensure high selectivity to MMA. As an alternative approach, ketones, in particular 3-pentanone and 2-butanone, were targeted as potential substrates in order to overcome some of the problems related to competing reactions that occur at the ester group. Hydroxymethylenation, followed by dehydration and Baeyer-Villager oxidation, possibly catalysed by enzymes to reverse the normal selectivity, leads to the formation of acrylate esters. The catalytic reaction is enabled by a gold carbene hydroxide complex in such a way that the substrate undergoes C-H activation and the nascent metal alkyl acts as a nucleophile towards the electrophilic formaldehyde, supplied in the form of alcoform* (solution of paraformaldehyde in methanol).
186

Photo-Curing Through Single Apertures: The Phenomenon and Its Influence On Polymerization

MacPherson, Meoghan Elizabeth January 2013 (has links)
Indiana University-Purdue University Indianapolis (IUPUI) / Reduction of the polymerization shrinkage stress inherent of dimethacrylate-based resin composites has been a work in progress since the phenomenon was first described by Dr. Rafael L. Bowen in 1967. Contemporary efforts to modify the composites or the curing protocols for polymerization have proven a challenging task with controversial results. Influenced by existing mathematical models relating exposure, curing time and depth of cure of resin composites, a novel method for the reduction of polymerization shrinkage stress is proposed. By polymerizing through a single aperture mask, a dental light curing unit is transformed from a planar light source to a point light source, and a fully cured, three-dimensional “bullet” shaped curing front is predicted for the cured resin below. So long as the edges of the bullet do not touch the cavity walls or floor, the shrinkage stress of the bullet is not transferred. Follow-up with an unmasked curing unit then fully polymerizes the restoration. By reducing the volume of uncured composite in contact with the cavity walls and floor, shrinkage stress of the restoration is also reduced. The objective of the present study was to demonstrate this curing phenomenon with a model resin composite using masks with aperture diameters of 0.5, 0.4, and 0.25 mm and curing times of 10, 20, 30, and 40 seconds. The resulting curing front was evaluated quantitatively and qualitatively. From this, mathematical models of the curing front were derived. Selected combinations of aperture mask and curing time were then investigated to evaluate the influence of this phenomenon on the degree of conversion, Knoop hardness, and polymerization shrinkage stress of the same model resin composite. Group differences were analyzed using a one-way ANOVA at 5% significance.
187

Molecular mobility. Structure-property relationship of polymeric materials

Carsí Rosique, Marta 07 January 2016 (has links)
Tesis por compendio / [EN] The present work examines the influence of the chemical structure of polymers on thermal, mechanical and dielectric behavior. The experimental techniques used for the purpose are differential scanning calorimetry, dynamo-mechanical analysis and dielectric spectroscopy. Additionally, in order to confirm the results obtained using the above methods, other techniques such as ray diffraction have also been employed. Chapters 1 and 2 contain the introduction and the objectives, respectively. Chapter 3 briefly describes the experimental techniques used. Chapter 4 contains the findings of the comparative analysis of the response to electrical noise fields for three poly(benzyl methacrylates) with different structures. The analysis was carried out under a wide range of frequencies and temperatures on three poly(benzyl methacrylates) containing two dimethoxy groups in positions 2,5-, 2,3- and 3,4-. The results show that the position of the dimethoxy groups on the aromatic ring has a significant effect on the molecular dynamics of poly(benzyl methacrylate). The spectra obtained were of high complexity and therefore, in order to perform a better analysis, numerical methods for time-frequency transformation including the use of parametric regularization techniques were used. We studied the effect of this structural change on the secondary relaxation processes and relaxation process &#61537;, relating to the glass transition. We also analyzed the effect of the dimethoxy group position on the formation of nanodomains, in which the side chains are predominant, and on the conduction processes of the materials tested. In Chapter 5, the conductivity of rubbery liquids was studied by analyzing poly(2,3-dimethoxybenzyl methacrylate), which exhibits its own particular behavior. The chapter analyzes the principle of time-temperature superposition, employing different interrelated variables. Chapter 6 focuses on how the presence of crosslinking affects the molecular mobility of polymethacrylates containing aliphatic alcohol ether residues. In this case, the effect of crosslinking on the secondary and primary relaxation processes was analyzed. The creation of nanodomains in the side chains as a result of the presence of crosslinking was also studied. / [ES] En este trabajo se presenta un estudio de la influencia de la estructura química de los polímeros en su comportamiento térmico, mecánico y dieléctrico. Las técnicas experimentales empleadas para ello han sido la calorimetría diferencial de barrido, el análisis dinamo-mecánico y la espectroscopia dieléctrica. Adicionalmente, se han empleado otras técnicas como la difracción de rayos, con objeto de corroborar los resultados obtenidos por las primeras. En los Capítulos 1 y 2 se recoge la introducción y los objetivos, respectivamente. El Capítulo 3 presenta una breve descripción de las técnicas experimentales empleadas. En el Capítulo 4 se recogen los resultados obtenidos en el análisis comparativo de la respuesta a campos de perturbación eléctrica en un amplio rango de frecuencias y temperaturas para tres polimetacrilatos de bencilo con dos grupos dimetoxi en posiciones 2,5-, 2,3- y 3,4-. Los resultados obtenidos señalan el importante efecto de la posición de los grupos dimetoxi en el anillo aromático, sobre la dinámica molecular del polimetacrilato de bencilo. Los espectros obtenidos fueron muy complejos, por ello en orden a llevar a cabo un mejor análisis se emplearon métodos numéricos para la transformación tiempo-frecuencia que incluyeron el uso de técnicas de regularización paramétrica. Se ha estudiado el efecto que dicho cambio estructural ejerce tanto sobre los procesos de relajación secundaria como sobre el proceso de relajación &#945;, relacionado con la transición vítrea. Así mismo, se ha analizado el efecto de la posición de los grupos dimetoxi en la formación de iii nanodominios en los que predominan las cadenas laterales, y su efecto en los procesos de conducción de los materiales analizados. En el Capítulo 5 se recoge el estudio de la conductividad de líquidos gomosos tomando como modelo el poli (metacrilato de 2,3-dimetoxibencilo), por su peculiar comportamiento. En este capítulo se ha realizado un análisis del principio de superposición tiempo-temperatura, empleando para ello diferentes variables relacionadas entre sí. En el Capítulo 6 se recoge el efecto de la presencia de entrecruzante en la movilidad molecular de polimetacrilatos que contienen residuos de éteres de alcoholes alifáticos. En este caso, se ha analizado el efecto de la presencia de entrecruzante tanto en los procesos de relajación secundarios, como en el proceso de relajación principal. También se llevó a cabo un análisis del efecto que la presencia de entrecruzante tiene sobre la creación de nanodominios gobernados por las cadenas laterales. / [CA] En aquest treball es presenta un estudi de la influència de l'estructura química dels polímers en el seu comportament tèrmic, mecànic i dielèctric. Les tècniques experimentals utilitzades han sigut la calorimetria diferencial de rastreig, l'anàlisi dinamo-mecànic i l'espectroscòpia dielèctrica. Addicionalment, s'han empleat altres tècniques com la difracció de rajos X a fi de corroborar els resultats obtinguts per les primeres. En els Capítols 1 i 2 s'arreplega la introducció i els objectius, respectivament. Al Capítol 3 es presenta una breu descripció de les tècniques experimentals emprades. En el Capítol 4 es recull els resultats obtinguts en l'anàlisi comparativa de la resposta a camps de pertorbació elèctrica en un ampli rang de freqüències i temperatures de tres polimetacrilats de benzil amb dos grups metoxi en posicions 2,5-, 2,3- i 3,4-. Els resultats obtinguts assenyalen l'important efecte de la posició dels grups metoxi en l'anell aromàtic, sobre la dinàmica molecular del polimetacrilat de benzil. Els espectres obtinguts van ser molt complexos, per aquesta raó per a dur a terme un millor anàlisi es van emprar mètodes numèrics per a la transformació temps-freqüència que van incloure l'ús de tècniques de regularització paramètrica. S'ha estudiat l'efecte que el dit canvi estructural exerceix tant sobre els processos de relaxació secundària com sobre el procés de relaxació &#61537;, relacionat amb la transició vítria. Així mateix, s'ha analitzat l'efecte de la posició dels grups metoxi en la formació de nanodominis en els que predominen les cadenes laterals, i el seu efecte en els processos de conducció dels materials analitzats. En el Capítol 5 s'arreplega l'estudi de la conductivitat de líquids gomosos prenent com a model el poli-(metacrilat de 2,3-dimetoxibencilo), pel seu peculiar comportament. En aquest capítol s'ha realitzat un anàlisi del principi de superposició temps-temperatura, emprant per a això diferents variables relacionades entre sí. En el Capítol 6 s'arreplega l'efecte de la presència d'entrecreuat en la mobilitat molecular de polimetacrilats que contenen residus d'èters d'alcohols alifàtics. En aquest cas, s'ha analitzat l'efecte de la presència d'entrecreuat tant en els processos de relaxació secundaris, com en el procés de relaxació principal. També es va dur a terme un anàlisi de l'efecte que la presència d'entrecreuat químic té sobre la creació de nanodominis governats per les cadenes laterals. / Carsí Rosique, M. (2015). Molecular mobility. Structure-property relationship of polymeric materials [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/59460 / Premios Extraordinarios de tesis doctorales / Compendio
188

Linear block copolymers of L–lactide and 2–dimethylaminoethyl methacrylate : synthesis and properties

Kryuchkov, Maksym 02 1900 (has links)
Part of the research described in this thesis is conducted in collaboration with Centre d' étude et de Recherche sur les Macromolécules (CERM), Université de Liège, Sart-Tilman, Belgium / Les copolymères séquencés amphiphiles sont très prometteurs pour des applications de technologie de pointe en raison de leur capacité à s'auto-assembler dans des structures bien organisées à l'échelle du micro– et du nanométre, et de leur sensibilité à des stimulations de différentes natures. La formation des nanomotifs bien ordonnés dans les films et/ou en masse fournit un substitut à la nanolithographie et est utile pour le design et l'ingénierie de nanomembranes et de matériaux nanoporeux. L'auto–assemblage dans des solvants sélectifs, en incluant la sensibilité au pH et à la température, peut être ajusté pour correspondre aux besoins de différentes applications biomédicales, telles que l’encapsulation et/ou relargage de médicaments, l'ingénierie de tissus, etc. Dans ce contexte, des copolymères séquencés de type L–lactide (LLA) et méthacrylate 2–diméthylaminoéthyl (DMAEMA) sont d’un grand intérêt. Comme le contrôle sur l'auto–assemblage des copolymères séquencés est permis au niveau moléculaire, il est très important de préparer des copolymères bien définis avec des longueurs de bloc prévisibles et de faible polydispersité. Ainsi, une partie de cette étude a été consacrée au développement de procédures synthétiques optimales et à la caractérisation détaillée de copolymères di– et triblocs de LLA et de PDMAEMA. Un outil simple pour déterminer la présence d'homo–PLLA résiduel a été développée; cela a permis de déterminer et d'expliquer plusieurs voies de synthèse indésirables. La dernière inclut la participation possible de l'amorceur bifonctionnel utilisé, et nous avons alors proposé un système alternatif d'amorceur bifonctionnel/catalyseur. La racémisation du LLA par les unités amine de (P)DMAEMA a été observée pendant la polymérisation, limitant ainsi l'utilisation première du bloc PDMAEMA pour la préparation des copolymères PLLA–b–PDMAEMA. Les études thermiques et de cristallisation, en incluant les copolymères séquencés partiellement quaternisés, ont révélé un retard significatif de la vitesse de cristallisation, en présence du bloc de PDMAEMA. Nous avons constaté que les blocs sont miscibles pour de faibles masses molaires et que la miscibilité partielle est maintenue après quaternisation. Selon la longueur et le taux de quaternisation du bloc PDMAEMA, la cristallisation du PLLA a été étudiée dans un environnement restreint et confiné, faiblement ou fortement. La torsion des lamelles cristallines observée pour certains copolymères biséquencés a été accentuée dans les copolymères triséquencés, où la formation de sphérolites annelés a été observée dans toutes les conditions thermiques utilisées. / Multi–functional amphiphilic block copolymers have much promise for various high technology applications thanks to the controlled stimuli–responsive self–assembly into well–organized structures on the micro– and nanometer scales. The formation of well–ordered nanopatterns in films and/or in bulk provides a competitive substitute to nanolithography and is useful in the design and engineering of nanomembranes and nanoporous materials. Solution self–assembly in selective solvents, including pH and temperature sensitivity, can be tuned to match the needs of different biomedical applications, such as drug encapsulation/delivery, tissue engineering, etc. In this context, block copolymers of L–lactide (LLA) and 2–dimethylaminoethyl methacrylate (DMAEMA) are of great interest. Since the control over self–assembly of block copolymer systems is enabled on a molecular level, it is of great importance to prepare well–defined block copolymers with predictable block lengths and low polydispersity. Thus, a major part of the research in this study was devoted to developing optimal synthetic procedures with detailed characterization of linear di– and triblock copolymers of LLA and PDMAEMA. A simple tool to determine homo–PLLA impurity was developed, which helped to determine and explain several undesired routes. The latter includes possible involvement of the bifunctional initiator used, and an alternative bifunctional initiator/catalyst system was proposed. Racemization of LLA by (P)DMAEMA moieties was observed during LLA polymerization thus limiting the utilization of PDMAEMA–first approach for the preparation of PLLA–b–PDMAEMA. Thermal and crystallization studies, including on quaternized block copolymers, revealed a significant retardation effect of the PDMAEMA block on the crystallization kinetics. The blocks were found to be miscible in the melt at low molecular weights, and maintained partial miscibility after quaternization. Depending on the length and the quaternization degree of PDMAEMA, PLLA crystallization was studied in a templated, soft or hard confinement environment. Crystalline lamellae twisting observed in certain diblock copolymers was facilitated in triblock copolymers, where the formation of banded spherulites was observed in all thermal conditions used.
189

MOCVD and electrochemical polymeric thin films : elaboration, characterization, properties ans applications / FIlms minces polymères par CVD et électrodeposition : élaboration, caractérisation, propriétes et applications

Manole, Claudiu Constantin 07 December 2012 (has links)
Ce mémoire traite de deux types de polymères en films minces: le poly (méthacrylate de méthyle) (PMMA) et le polypyrrole (PPy). Ces films minces ont été déposés par voie sèche et par voie humide. La voie sèche consiste à faire croitre les films polymères par un procédé original de dépôt chimique en phase vapeur assisté par photons (Chemical Vapor Deposition, CVD). La croissance implique l'activation UV des espèces monomères dans la phase gazeuse. Les deux polymères PMMA et PPy ont été obtenus pour la première fois par ce procédé de photo-CVD. La caractérisation des propriétés a mis en évidence des applications possibles en microélectronique, micro-optique et les dispositifs générant de la chaleur. La voie humide mise en œuvre pour déposer des films minces de polymères et d’hybrides organiques/inorganiques est une méthode électrochimique. Des films de PPy (organique) et de TiO2 nanostructuré (inorganique) ont été obtenus et caractérisés par différentes techniques électrochimiques. Des aspects supplémentaires de la croissance de PPy ont été mis en évidence par la résonance des plasmons de surface. / The thesis deals with two types of polymeric thin films: poly (methyl methacrylate) (PMMA) and polypyrrole (PPy). The thin films were grown by a dry and a wet route. The dry route involved the growth of the polymeric films by an original process of Chemical Vapor Deposition, namely Photo-CVD. The growth involves the UV activation of the monomer species in the gas phase. Both PMMA and PPy were obtained for the first time by this Photo-CVD. The characterization highlighted properties with possible applications in microelectronics, micro-optics and as heat generating devices. The wet route involved the growth of polymeric and hybrid organic/inorganic thin films by an electrochemical approach. Organic PPy and inorganic TiO2 nanostructures were obtained and characterized by various electrochemical techniques. The growth aspects of PPy were supplementary highlighted by the Surface Plasmon Resonance.
190

Étude de l'élaboration de nano-particules élastomères et application de celles-ci en tant qu'agents renforçants pour le poly(acide lactique) / Study of the development of elastomer nanoparticles and their application as reinforcing agents for poly(lactic acid)

Fang, Yuan 07 December 2012 (has links)
Le poly (acide lactique) (PLA), est un polymère synthétisé à partir de ressources renouvelables, qui est l'objet de beaucoup d'études à l'heure actuelle mais qui souffre d'une faible résistance au choc. Le but de ce travail est de rechercher des pistes permettant la préparation d'un matériau à base de PLA avec une résistance au choc améliorée tout en minimisant la perte de résistance à la traction. Les travaux présentés ici ont étudié le rôle de nanoparticules élastomères de poly (acrylate de butyle) (PBA) chargées de laponite (LRD) (PBA-LRD) ainsi que de nanocomposites coeur-écorce (PBA-LRD)/poly(méthacrylate de méthyle) (PMMA) en tant qu'agents de renforcement d'une matrice de PLA. Ces nanoparticules ont été dispersées dans la matrice PLA à l'état fondu. La synthèse de ces nanoparticules a été effectuée par polymérisation en émulsion ou miniémulsion. La laponite a été incorporée dans les nanoparticules afin de minimiser la perte de la rigidité tout en améliorant la résistance au choc de PLA. Trois types de tensioactifs et des modifications de surface de la laponite ont été testées pour améliorer l'adhérence entre les particules de PBA et la matrice de PLA. Enfin une écorce de PMMA a été utilisée pour assurer la bonne adhérence entre les particules de PBA et de matrice PLA. Nous avons montré que les particules coeur-écorce ont permis d'augmenter la résistance au choc au 3 fois du PLA tout en réduisant la diminution du module d'Young et la perte de résistance à la traction (~25%). Les propriétés de les particules synthétiques et les propriétés des mélange du PLA avec les particules PBA ou particules coeur-écorce ont été étudiées par diverses techniques de caractérisation (DLS, FTIR, ATG, MET, MEB, RMN 1H, DSC, DMTA...) / Poly (lactic acid) (PLA), come from renewable resources, one of the most important biopolymers, suffers from weak impact resistance. The aim of this work is to develop a process that will allow preparing a PLA with improved impact resistance while minimizing loss in tensile strength. The work presented here examined in detail the synthesis of poly(butyl acrylate) (PBA) nanoparticles charged with laponite (LRD) (PBA-LRD) and (PBA-LRD) / poly(methyl methacrylate) (PMMA) core-shell nanocomposites. They were dispersed phase in PLA matrix and were synthesized by emulsion or miniemulsion polymerization. The clay such as laponite was included in these nanoparticles to minimize the loss of rigidity while improving the impact resistance of PLA. Note that three types of surfactants and some modify agents for LRD have been tried to improve the adhesion between the PBA particles and matrix PLA, PMMA was finally used to ensure a good adhesion between the PBA particles and the matrix. To this end, we explored successively the PLA blend, using PBA nanocomposites and the PBA/PMMA core-shell nanoparticles as reinforcing agents, with improved impact resistance, showing that core-shell particles allowed increasing of 3 times of impact strength of the PLA with a minimum amount of loss (~25%) in Young?s modulus and tensile strength. The properties of the synthetic particles and the properties of PLA blends have been demonstrated by various characterization techniques (DLS, FTIR, TGA, TEM, SEM, 1H-NMR, DSC, DMTA ...)

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