Spelling suggestions: "subject:"ailane"" "subject:"2silane""
241 |
Nouvelles méthodes de génération de radicaux silylés : application à des processus radicalaires sans étainRouquet, Guy 13 December 2010 (has links)
Deux nouveaux concepts, visant à reproduire la chimie radicalaire des diétains à l’aide de radicaux centrés sur le silicium, sont présentés à travers ce manuscrit. Le premier concept introduit les “silaboranes”, des molécules constituées d’un motif de type silane et d’un atome de bore. Ceux-ci ont pour la première fois été exploités comme générateurs de radicaux triméthylsilyle via l’utilisation de la réaction de SHi sur le silicium (Substitution Homolytique Intramoléculaire) à partir de disilanes. Des études cinétiques et de modélisation moléculaires de la réaction de SHi ont, entre autres, permis de rationaliser les résultats. Le potentiel des “silaboranes” en tant que substituts des diétains a été entrevu à travers des réactions d’additions radicalaires d’halogénures sur des éthers d’oxime sulfonylés. Le concept des "silaboranes" a ensuite été étendu à des hydrures de silicium, grâce à une réaction de transfert d’hydrogène intramoléculaire, permettant de produire des radicaux triphénylsilyles. Le second concept a révélé la capacité des allyl tris(triméthylsilyl)silanes pour reproduire les réactions radicalaires des diétains via une réaction de beta-fragmentation du groupement tris(triméthylsilyle). Ces substrats, source de radicaux tris(triméthysilyle) et simples d’accès, se sont avérés d’intéressants candidats pour assister l’addition de dérivés bromés et iodés sur des substrats sulfonylés de type allyl, vinyl et éther d’oxime. / Two new concepts, aiming to substitute ditin radical chemistry by using silyl radicals, are developed throughout this manuscript. The first concept introduces “silaboranes”, molecules made up of a silane unit and a boron atom. For the first time, the ability of these precursors to generate trimethylsilyl radicals was demonstrated by using the SHi reaction at silicon (Intramolecular Homolytic Substitution) from disilanes. Besides, results are supported by kinetic and computationnal studies of the SHi reaction at silicon. Capacity of “silaboranes” to achieve tin-free radical processes was demonstrated thanks to radical addition of halogenated species on sulfonyl oxime ethers. “Silaboranes” concept was then extended to silicon hydrides using intramolecular hydrogen transfer as source of triphenylsilyl radicals. The second concept highlights the ability of allyl tris(trimethylsilyl)silanes to make possible tin-free radical reactions via beta-fragmentation of the tris(trimethylsilyl) group. These compounds, source of tris(trimethylsilyl) radicals and easily available, open very interesting perspectives in tin-free radical addition of bromides and iodides species on sulfonyl derivatives as allyl sulfones, vinyl sulfones or sulfonyl oxime ethers.
|
242 |
Génération de surface nanostructurées par le contrôle des interactions aux interfaces / Versatile nanostructured surfaces generated by controlling interfacial interactionsSouharce, Grégoire 17 July 2012 (has links)
La génération de surfaces présentant des nanostructurations de surface variées et modulables est l’objectif principal de ce travail. L’auto-assemblage de copolymères à bloc ou de nanoparticules d’or a été privilégié, et nécessite pour se faire de moduler finement les interactions aux interfaces substrat/ matériaux déposés. Dans une première partie, un dispositif expérimental de greffage de silane alkyle en voie vapeur est décrit. Cette technique de greffage permet d’aboutir à des surfaces fonctionnalisées soit de façon homogène, soit de façon graduelle et ce, avec un ou deux silanes (substrat respectivement mono ou bi-composant). La robustesse, la simplicité et la flexibilité de notre procédé ont été démontrés par des caractérisations physico-chimique (mesure des propriétés de mouillabilité), chimique (spectroscopie de photoélectrons X) ainsi que par analyse topographique (microscopie à force atomique). Dans une deuxième partie, l’influence des interactions aux interfaces substrat / film sur l’auto-assemblage de copolymères à bloc PS-b-PMMA a été mise en évidence par AFM. A partir des substrats de silicium homogènes en énergie de surface, il a été possible de moduler la nanostructuration sur différents échantillons et à partir des surfaces fonctionnalisées graduellement, cette variation de nanostructuration a pu être obtenue sur un même substrat. Par l’utilisation de copolymère à bloc PS-b-PI, il est par ailleurs possible de générer des films nanostructurés sans préfonctionnalisation du substrat, sans recuit et ce quelle que soit l’épaisseur du film. Dans une troisième partie, l’influence des interactions aux interfaces sur l’assemblage capillaire/convectif dirigé de nanoparticules d’or a été démontré par microscopie à champ sombre. La nature chimique et la densité de greffage des silanes ainsi que la dimension des échantillons ont été modulées pour mettre en évidence le rôle de ces paramètres sur l’assemblage de ces particules. Cette étude montre que les interactions aux interfaces contrôlent l’assemblage des entités chimiques organiques et inorganiques et donc la nanostructuration de surface qui en résulte. / The purpose of this work is to develop a methodology based on the control of interactions at substrate/deposited material interfaces in order to achieve well-defined structures at the nanoscale (nanostructuration). In particular, silane molecules were grafted onto planar substrates to adjust the physico-chemical interactions in order to consequently control block copolymers / gold nanoparticles self-assemblies. The first part describes the experimental set-up developed to graft alkyl silanes through vapor phase strategy. The modification can be finely tuned such that homogeneously or gradually functionalized surfaces with either one or two silanes (or- or two-component substrate, respectively) are obtained. The versatility and simplicity of our process were demonstrated by wettability measurements, X-ray photoelectron spectroscopy and microscopic analysis (AFM) performed on these different surfaces. The second part points out the influence of grafting density and polarity on block copolymers self-assembly. PS-b-PMMA films were first used. With using homogeneously-modified substrates, it has been demonstrated that block copolymers self-assembly depends on substrate surface chemistry, and different cases (dewetting, wetting, parallel or perpendicular orientation of nanodomains) were achieved as a function of the grafting density of silanes on the substrate. Using gradually-modified surface, these different nanostructures were obtained on one unique sample. Moreover, by using appropriate deposition conditions with another block copolymer (PS-b-PI), well-oriented nanostructured films were obtained without pre-functionalization or annealing, regardless of film thickness. In the third part influence of surface chemistry on gold nanoparticles deposited through capillary/convective assembly is investigated and characterized by dark field microscopy. The careful selection of silane in conjunction with appropriate grafting density are adjusted in order to emphasize the impact of these parameters on the assembly process and therefore on the surface nanostructures. This study demonstrates that the control of interfacial interactions dictates the self-assembly of organic or inorganic materials deposited on a planar substrate.
|
243 |
Mise au point d'additifs siliciés pour l'adhérisation d'élastomères silicone sur supports métalliques / Development of silicon additives for bonding silicone elastomers onto metal substratesPicard, Loïc 28 November 2014 (has links)
L’objectif de ces travaux de thèse était de développer un primaire d’adhésion stable, permettant l’adhérisation de tous types d’élastomères silicone sur une grande majorité de surfaces métalliques, et ce de façon reproductible. Dans un premier temps, une étude bibliographique détaillée des différentes formulations de primaire à base de silanes utilisées pour l’adhésion de tous types d’élastomères silicone (EVC, EVF et LSR) a été effectuée. Pour compléter la compréhension du système métal/primaire d’adhésion/élastomère silicone étudié, trois formulations de primaire, dont une formulation « maison », et trois élastomères silicone ont été analysés et leurs compositions, ainsi que leurs propriétés en adhésion, ont été déterminées. La caractérisation de différentes résines silicone composant la formulation « maison » de primaire a également été effectuée. Cette dernière a ensuite été optimisée en synthétisant de nouvelles résines silicone, en ajustant les taux de chaque composant et en changeant le type de catalyseur. Dans un second temps, la caractérisation physico-chimique des primaires d’adhésion enduits sur la surface d’un métal (aluminium) a été effectuée. La topologie des films de primaire (épaisseur, rugosité et uniformité) et leurs propriétés de mouillage ont été déterminées. Ces résultats ont été complétés par la caractérisation des faciès de rupture des pièces composites métal/primaire/élastomère silicone. À la suite de ces différentes analyses complémentaires, le paramètre gouvernant la sélectivité d’un primaire d’adhésion pour un grade d’EVC a été isolé. Une courbe modèle permettant la formulation d’un primaire polyvalent a été proposée et validée par la formulation d’un primaire d’adhésion pouvant adhérer les différents grades d’EVC sélectionnés pour cette étude. / This PhD work aimed at developing a stable primer of adhesion, allowing the bonding of all types of silicone elastomers onto a vast majority of metallic surfaces, in a reproducible way. In a first approach, a detailed bibliographic study was performed on the different primer based-silane formulations used for the adhesion of any types of silicone elastomers (HCR, RTV and LSR). To better understand the metal/primer/silicone elastomer system, three primer formulations, including a homemade formulation, and three silicone elastomers were analyzed and their compositions, and adhesive properties, were determined. The characterization of different silicone resins entering in the composition of the homemade primer formulation was also carried out. The latter was optimized by synthetizing new silicone resins, by adjusting the content of each component and by changing the type of catalyst. In a second step, the characterization of the physical chemistry of the primer formulations coated on a metal surface (aluminum) was performed. The topology of the primer films (thickness, roughness and uniformity) and their wettability were determined. These information were completed by the characterization of fracture profiles of the composite part metal/primer/silicone elastomer. Following these additional analyses, the parameter governing the selectivity of a primer formulation for a grade of HCR was isolated and a model curve for the formulation of a polyvalent primer was proposed. This curve was validated by the formulation of a primer which can bond the different grades of HCR selected for this study.
|
244 |
Mise au point d'une méthode de fonctionnalisation de microcomposants par vois photochimique.Dendane, Nabil 14 December 2007 (has links) (PDF)
Le travail ici exposé a pour finalité le développement d'une méthode efficace de fonctionnalisation et d'adressage de biomolécules sur support solide fermé tel que des microcanaux ou capillaires. La fonctionnalisation de la surface de verre ou de silicium est réalisée en utilisant la formation d'un lien covalent oxime entre la molécule et le support. L'adressage est réalisé en utilisant une déprotection photochimique de la fonction oxyamine protégée par un groupe photolabile (NPPOC). Nous avons démontré en format plan et en format capillaire que la surface oxyamine protégée par un groupe photolabile est efficace pour l'immobilisation de plusieurs oligonucléotides de façon localisée. La stratégie a été étendue pour l'immobilisation dans les capillaires d'autres molécules tels que les sucres, peptides ou molécules hydrophobes et hydrophiles. Les résultats montrent l'efficacité de notre stratégie pour l'immobilisation de ce type de molécules. Nous avons également montré que l'utilisation d'une surface hydrophile (PEG) améliore sensiblement le bruit de fond.
|
245 |
Beiträge zum Verständnis des sauren nasschemischen Ätzens von SiliciumLippold, Marcus 20 June 2014 (has links) (PDF)
Der Siliciumauflöseprozess in HF-HNO3-H2SO4/H2O-Lösungen unterscheidet sich vom Ätzprozess in HF-HNO3-H2O-Standardmischungen in Bezug auf die Reaktivität gegenüber Silicium, erzielte Oberflächenmorpholgien sowie die beim Ätzen entstehenden gelösten und gasförmigen Produkte. Durch die Behandlung in H2SO4-reichen HF-HNO3-H2SO4/H2O-Lösungen werden auf Siliciumwafern Texturen mit hoher Rauigkeit und geringer Reflexion erzeugt. mc-Si-Solarzellen texturiert durch eine H2SO4-reiche Ätzlösung weisen vergleichend zu Solarzellen mit Standardtexturen höhere Wirkungsgrade auf. In HF-HNO3-H2SO4/H2O-Lösungen mit hohen Schwefelsäurekonzentrationen (c(H2SO4) > c(H2O)) wirkt sowohl das Salpetersäuremolekül HNO3 als auch das Nitrylion NO2+ als Oxidationsmittel. Trifluorsilan HSiF3 und Hexafluordisiloxan F3SiOSiF3 wurden erstmalig als gasförmige Produkte des sauren nasschemischen Ätzens identifiziert. Anhand von Modellreaktionen zur Reaktivität von Nitrylionen wurde deren Reduktionssequenz im Siliciumätzprozess aufgeklärt.
|
246 |
Nouveaux procédés d'obtention d'oxynitrure de siliciumTemple Boyer, Pierre 12 May 1995 (has links) (PDF)
Les techniques d'élaboration du matériau SiN[x], par LPCVD à partir du mélange disilane/ammoniac et par RTCVD à partir du mélange silane/ammoniac, ont été étudiées. L'obtention de films de stoechiométrie SiN[x] quelconque, uniformes en épaisseur et en composition, a ainsi été démontrée et un nouveau matériau, le silicium dopé azote baptisé NIDOS a été mis en évidence. L'étude de l'oxydation thermique du NIDOS a montré un effet de ralentissement de l'oxydation dû à la teneur en azote du film. Nous avons mis en évidence l'interférence des diffusions des espèces oxydantes et des atomes d'azote au cours de l'oxydation. Nous en avons déduit deux méthodes d'obtention d'oxynitrure SiO[x]N[y]: soit par oxydation thermique du NIDOS, soit par recuit de NIDOS déposé sur une couche d'oxyde enterrée. Nous avons enfin étudié la compatibilité du NIDOS avec les impératifs de la technologie silicium (rugosité, résistivité, propriétés de barrière à la diffusion des dopants), puis nous avons démontré la faisabilité de structures métal/oxynitrure/semi-conducteur utilisant une couche isolante oxynitrurée obtenue par oxydation ou recuit de NIDOS. La caractérisation électrique de ces structures a montré d'excellentes qualités isolantes: des champs électriques de claquage de 20 MV/cm et des charges stockées au claquage de 150C/cm[2] ont été mis en évidence
|
247 |
RAFT-Polymerisation an Oberflächen / RAFT Polymerization from SurfacesNguyen, Duc Hung 03 July 2007 (has links)
No description available.
|
248 |
Modificação do LLDPE através de silanos viabilizando a aplicação em camadas plásticas de linhas flexíveis / Study of silane grafting reactions of low density polyethylene for pipe applicationsAlexandre Borges Pessanha 26 August 2009 (has links)
As linhas flexíveis, estruturas compostas por um determinado número de camadas plásticas e de aço, possibilitam o escoamento de fluidos em operações de exploração e produção de hidrocarbonetos entre plataformas marítimas de petróleo e o leito marinho e/ou a costa. E, atualmente, têm sido utilizadas na exploração de hidrocarbonetos em lâminas dágua cada vez
maiores. O presente estudo visa modificar quimicamente o LLDPE através de processos de extrusão reativa envolvendo a graftização de VTMS na presença de peróxidos orgânicos, e
posterior formação de ligações cruzadas promovida pela água. Visa analisar também o efeito da introdução de ligações cruzadas nas propriedades térmicas e mecânicas do LLDPE. De
forma a atingir os objetivos propostos, um planejamento experimental foi realizado para analisar o efeito de variáveis como velocidade de rotação do parafuso da extrusora, tipo e teor de peróxido nos índices de fluidez dos produtos da reação do LLDPE com peróxido de dicumila (DCP) e 2,5-dimetil-peróxi-hexano (Trigonox 101). Essa metodologia também foi utilizada para avaliar o efeito da concentração de silano, da velocidade de rotação do parafuso da extrusora e do procedimento de imersão nos índices de fluidez dos produtos da reação do
LLDPE com 0,02% p/p de DCP e concentrações variáveis de silano. As amostras foram caracterizadas através dos ensaios para determinação de índice de fluidez (MFI) e teor de gel,
ensaios convencionais de tração e técnicas de análise térmica, TGA e DSC. A técnica de FTIR foi utilizada para verificar a ocorrência das reações de graftização e formação de
ligações cruzadas no LLDPE. As amostras reagidas com teores de 0,07% de DCP e 1,0 e 1,5% de silano, respectivamente, apresentaram valores significativos para os teores de gel em
ambas as velocidades de rotação (10 e 50rpm). A amostra reagida com 0,07% de DCP e 1,5% de silano, a 10rpm, apresentou um teor de gel de 74,77%. A análise termogravimétrica (TGA) realizada evidenciou que houve um aumento da estabilidade térmica do polímero devido à
formação de ligações cruzadas. Não se observou um aumento significativo para o limite de resistência para o LLDPE modificado devido à heterogeneidade dos corpos de prova. As análises de FTIR mostraram que houve a graftização e a formação de ligações cruzadas no LLDPE. / The flexible lines are flexible structures manufactured through plastic and steel layers that allows its use in order to permit fluid flow in exploration and production of hydrocarbon
between offshore oil units and sea bed and/or coast. Nowadays these pipes are one of the main ways to permit the exploration of hydrocarbon in deepwater. The present study aims to
analyze the LLDPE (Low Density Polyethylene) chemical changing through a reactive extrusion process involving VTMS grafting in presence of organic peroxides. After a crosslinking due to water, an analysis will be carried out in order to assess the PEX (crosslinked polyethylene) application in flexible pipe structures. The crosslinking effect at thermal and mechanical properties will also be studied. An experimental planning was carried out in order to evaluate the effect of variable variations such as the rotational velocity of the single-screw extruder, type and concentration of peroxides at melt flow index of the products originated from the LLDPE-peroxides (DCP and Trigonox 101) reaction, and in order to analyze the silane concentration effect, rotational velocity and immersion procedure at melt flow index in products with LLDPE and contents with DCP variable concentrations of silane. The samples were characterized through tests such as MFI (Melt Flow Index), gel content determination, tensile testing and thermal analyses, DSC (Differential Scanning Calorimetry) and TGA (Thermal Gravimetric Analysis). The Fourier Transformed Infrared Spectroscopy (FTIR) was also used to characterize the samples. The samples content 0,07% of DCP and 1,0 and 1,5% of silane, respectively, showed considerable value for gel contents in both rotational velocities (10 and 50rpm). The sample with 0,07% of DCP and 1,5% of silane, at 10rpm, a value of 74,77% of gel content could be noticed. The thermal analyses carried out showed that an increase of thermal stability for the polymer due to crosslinking generation happened. After tensile testing, a considerable changing in mechanical proprieties of the changed LLDPE was not seen due to the specimens heterogeneity. However through FTIR, silane
linking was noticed demonstrating the LLDPE reticulation.
|
249 |
Processos de formação de ligações cruzadas de polietileno de alto peso molecular / High weight molecular polyethylene crosslinks formation processesLorena Rodrigues da Costa Moraes 02 March 2015 (has links)
No projeto desenvolvido, ligações cruzadas foram formadas no polietileno de alta densidade e alto peso molecular, grade HS5103, através dos processos reticulação por peróxidos e silanos, com o objetivo de se avaliar o efeito da introdução de ligações cruzadas nas propriedades térmicas e mecânicas deste PEAD. Misturas entre o HS5103 e os peróxidos orgânicos, 2,5-Dimetil-2,5-di(terc-butilperoxi)hexano (DHBP) e peróxido de dicumila (DCP), foram produzidas e analisadas para a avaliação do efeito dos tipos de peróxido na reticulação e propriedades do PEAD e para determinação da concentração e do tipo de peróxido a ser utilizado como agente iniciador de reticulação por silano. Ensaios de índice de fluidez (MFI), reometria capilar, extração de polímero por xileno (teor de gel), análise termogravimétrica (TGA), calorimetria diferencial de varredura (DSC) e tração foram realizados para caracterização das misturas com peróxidos. Os resultados indicaram aumento da viscosidade com o aumento da concentração de peróxido, sendo o DHBP o que apresentou maior índice de aumento; não houve mudanças relevantes nas propriedades mecânicas e, ocorreu aumento do grau de cristalinidade, sendo mais significativo nas amostras com DCP. Após avaliação dos resultados citados, para as amostras a serem reticuladas via silano, foi promovida a graftização de diferentes concentrações de viniltrimetóxisilano (VTMS) na presença de 0,01%p/p de DCP com a adição de 0,05%p/p de catalisador, posteriormente a reticulação foi promovida em água. As amostras produzidas foram caracterizadas por ensaios de teor de gel, análise dinâmico-mecânica (DMA), espectroscopia de absorção no infravermelho (FTIR), TGA, ensaios de desgaste por deslizamento e tração. Nas amostras com silano a formação de ligações cruzadas foi gradativa, apresentando de 8% de gel para amostra com 0,5%p/p de VTMS a 57 % para amostra com1,5% p/p de silano, maior concentração utilizada. A análise dinâmico-mecânica (DMA) realizada evidenciou que houve um aumento densidade de ligações cruzadas e do módulo de armazenamento após temperatura de fusão com o teor de silano, concordando com os resultados de teor de gel. As análises de FTIR mostraram que houve a graftização e a formação de ligações cruzadas no PEAD HS5103. Não se observou um aumento significativo para o limite de resistência para o PEAD modificado. E os testes de desgaste por deslizamento indicaram um aumento da resistência ao desgaste das amostras reagidas com VTMS. / In the project carried out, crosslinks were formed in high density and high molecular weight polyethylene, grade HS5103, through peroxide and silane reticulation processes, aiming to evaluate the effects of the introduction of crosslinks in thermal and mechanical properties of this PEAD. Mixtures between HS103 and organic peroxides, 2,5-Bis(t-butylperoxy)-2,5-dimethylhexane (DHBP) and dicumyl peroxide (DCP) have been produced and analyzed for the evaluation of the effect of types of peroxide in reticulation and PEAD properties and to determine both concentration and type of the peroxide to be used as silane reticulation initiation agent. Melt flow index (MFI), capillary rheometry, xylem polymer extraction (gel content), thermogravimetric analysis (TGA), differential canning calorimetry (DSC) and traction tests were carried out for peroxide mixtures characterization. The results indicated increase of viscosity with the increase of the concentration of peroxide, being DHBP the one with the highest increase level; there have been no relevant changes concerning mechanical properties and there has been an increase in the crystallinity levels, mostly in DCP samples. After the assessment of the former results, for the samples to be reticulated through silane, graphitization of different concentrations of Vinyltrimethoxysilane (VTMS) was carried out, together with 0.01%p/p of DCP, adding 0.05%p/p of a catalyst; later, reticulation was carried out in water. The samples produced were characterized by gel content tests, dynamic-mechanical analysis (DMA), Fourier transform infrared spectroscopy (FTIR), TGA, sliding and traction wear tests. In the silane samples, formation of crosslinks was gradual, showing 8% of gel to the sample with com 0.5%p/p of VTMS to 57 % to the sample with 1.5% p/p of silane, the highest concentration used. The dynamic-mechanical analysis (DMA) showed an increase of density in crosslinks and storing mode after fusion temperature with silane content, converging with gel content results. FTIR analysis showed there has been graphitization and crosslink formations in PEAD HS5103. A significant increase has not been observed concerning the limit of resistance for the modified PEAD. Besides, sliding wear tests indicated an increase of resistance to the wear of samples reacted to VTMS.
|
250 |
Influência do processamento no comportamento mecânico de nanocompósitos de poliamida 6 com nanosílica / Influence of processing on the mechanical behaviour of polyamide 6/nanosilica nanocompositesQueiroz, Breno Dutra de 06 October 2015 (has links)
Submitted by Aelson Maciera (aelsoncm@terra.com.br) on 2017-05-25T19:49:56Z
No. of bitstreams: 1
DissBDQ.pdf: 27222907 bytes, checksum: eb17b232bd0096bfa1e0fb1dd7f4bf74 (MD5) / Approved for entry into archive by Ronildo Prado (ronisp@ufscar.br) on 2017-05-30T13:44:57Z (GMT) No. of bitstreams: 1
DissBDQ.pdf: 27222907 bytes, checksum: eb17b232bd0096bfa1e0fb1dd7f4bf74 (MD5) / Approved for entry into archive by Ronildo Prado (ronisp@ufscar.br) on 2017-05-30T13:45:05Z (GMT) No. of bitstreams: 1
DissBDQ.pdf: 27222907 bytes, checksum: eb17b232bd0096bfa1e0fb1dd7f4bf74 (MD5) / Made available in DSpace on 2017-05-30T13:50:33Z (GMT). No. of bitstreams: 1
DissBDQ.pdf: 27222907 bytes, checksum: eb17b232bd0096bfa1e0fb1dd7f4bf74 (MD5)
Previous issue date: 2015-10-06 / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / In this study nanocomposites of polyamide-6 (PA-6) reinforced with silica
nanoparticles (SiO2) were prepared in order to promote improved mechanical
properties for engineering applications. The nanoparticles’ surfaces were
chemically modified with the silane agent 3-aminopropyltrimethoxysilane (3-
APTMS) to improve the chemical and physical interactions between them and
the PA-6 matrix. Nuclear magnetic resonance analysis (NMR) and Fourier
transform infrared absorption spectroscopy (FT-IR) showed that 3-APTMS
grafting on nanoparticles surface was accomplished. The nanocomposites
mixing process was studied in two forms: by torque rheometry, using a torque
rheometer internal mixer; and in a co-rotating and intermeshing twin-screw
extruder. A preliminary study of the influence of processing variables at the
torque rheometer on the degradation of polyamide-6 matrix was performed. The
results showed that the greater the filling volume of the mixture in the chamber
and the rotational speed of the rheometer’s rotors, the lower the degradation of
the polyamide-6. Based on this preliminary study, compositions with 1, 2, and 4
% weight of SiO2 nanoparticles, both unmodified and chemically modified with
3-APTMS were prepared in the torque rheometer. The nanocomposites were
compression molded and it was observed that nanocomposites reinforced with
1 wt.% SiO2, both unmodified and surface-modified, presented the best tensile
properties. For the nanocomposite samples processed in the twin-screw
extruder, the influence of relevant variables – nanoparticle content, chemical
surface modification, physical form of the fed PA-6 (granule and powder),
rotational speed of screws and extruder feed rate – on mechanical, thermal, and
dynamic-mechanical properties were studied. The samples were afterwards
injection molded and it was observed that the samples produced using 1 wt.%
surface-modified and 100% finely ground PA-6 showed the higher tensile
modulus and yield strength values. / Neste estudo foram preparados nanocompósitos de poliamida 6 (PA6)
reforçados com nanopartículas de sílica (SiO2), com o objetivo de promover
melhoria de propriedades mecânicas para aplicações de engenharia. A
superfície das nanopartículas foi modificada quimicamente com o agente silano
3-aminopropiltrimetoxisilano (3-APTMS) para melhorar as interações químicas
e físicas entre elas e a matriz de PA6. Análises de ressonância magnética
nuclear (RMN) e espectroscopia de absorção no infravermelho por
transformada de Fourier (FT-IR) mostraram que houve sucesso na
funcionalização das nanopartículas com o agente silano. O processo de
mistura dos nanocompósitos foi estudado de duas formas: por meio de
reometria de torque em um misturador interno; e em extrusora com rosca dupla
co-rotacional e interpenetrante. Um estudo preliminar da influência das
variáveis de processamento no reômetro de torque sobre a degradação da
poliamida 6, mostrou que quanto maior o volume de preenchimento da câmara
de mistura e a velocidade de rotação dos rotores do reômetro, menor foi a
degradação da poliamida 6. Com base neste estudo preliminar, foram
preparadas no reômetro de torque composições com 1, 2 e 4% em massa de
nanopartículas de SiO2 não modificadas e modificadas quimicamente com 3-
APTMS. Os nanocompósitos obtidos foram moldados por compressão, tendo
sido observado que os nanocompósitos reforçados com 1 %m. de SiO2 não
modificada apresentaram as melhores propriedades mecânicas de resistência
à tração e deformação na ruptura em ensaio de tração, enquanto os
nanocompósitos com 1 %m. de nanosílica modificada apresentaram as
melhores propriedades mecânicas de módulo elástico também no ensaio de
tração. Para as amostras de nanocompósitos processadas na extrusora de
rosca dupla, foram estudadas as influências do teor de nanopartículas, da
modificação química superficial, da forma física da PA6 alimentada (grânulo e
pó), da velocidade de rotação das roscas e da taxa de alimentação da
extrusora sobre as propriedades mecânicas, térmicas e dinâmico-mecânicas.
Posteriormente, os corpos de prova foram moldados por injeção e observou-se
que a amostra cuja composição polimérica foi de 100% de PA6 fina e reforçada
com 1 %m. de nanosílica modificada superficialmente pelo agente silano 3-
APTMS apresentou os maiores valores de módulo de elasticidade e de tensão
no escoamento no ensaio mecânico sob tração.
|
Page generated in 0.1585 seconds