Les travaux portent sur la synthèse des (co)polyoléfines bis(trialcoxysilyle) téléchéliques, liquides à température ambiante, pour des applications adhésives. La première approche est consacrée à la combinaison de la polymérisation par ouverture de cycle par métathèse (ROMP) et de la métathèse croisée (CM) d'une cyclooléfine ou d'un mélange de cyclooléfines en présence d'une oléfine trialcoxysilyle monofonctionnelle ou difonctionnelle agissant comme agent de transfert (CTA) et d'un catalyseur à base de ruthénium. Il est montré que l'efficacité de la réaction et la sélectivité / fonctionnalité des polymères dépendent notamment de la nature du solvant, du CTA, du catalyseur, et de l'utilisation (ou pas) de benzoquinone comme additif inhibiteur de l'isomérisation. Une très grande productivité catalytique (turnover number, TON, jusque 100 000) a été obtenue avec les conditions optimisées. La viscosité du copolymère a été contrôlée par ajustement de la nature et du ratio des co-monomères. La deuxième approche est consacrée à la dépolymérisation du polybutadiène (PBD) liquide à haute teneur en 1,4-cis en présence d'un CTA et d'un catalyseur au ruthénium. L'efficacité et la sélectivité de la réaction ont été optimisées en variant la méthode de la purification du PBD commercial, la nature du catalyseur et le protocole opératoire. Cette approche est néanmoins moins efficace que la première. / The work presented focuses on the synthesis of liquid (at room temperature) bis(trialkoxysilyl) telechelic polyolefins for adhesive applications. The first approach relies on the combined ring-opening metathesis polymerization/cross metathesis (ROMP/CM) of a cycloolefin or a mixture of cycloolefins using a trialkoxysilyl mono- or difunctionalized alkene acting as a chain transfer agent (CTA) and a ruthenium-based catalyst. The efficiency of the reaction and selectivity of the polymer functionality were found to depend much on the nature of the CTA, the catalyst, the solvent and the use of benzoquinone additive as isomerization inhibitor. A high catalytic productivity with a turnover number (TON) up to 100 000 was obtained under optimized conditions. The viscosity of polymers was controlled by adjusting the nature and the ratio of comonomers. The second approach is dedicated to the depolymerization of liquid high 1,4-cis polybutadiene (PBD) in the presence of a CTA and a ruthenium catalyst. The catalytic productivity and selectivity were optimized by changing the method of purification of the commercial PBD, the nature of catalyst and the reaction protocol. This second approach remains, however, less efficient than the first one.

M.Phil. / Cataracts have been identified as one of the leading causes of blindness, especially in the developing world. The only presently known effective treatment for this growing problem is surgical removal of the opaque lens followed by replacement with an artificial intra ocular lens. Newer methods have brought greater success, and greater costs. For people in the developing world, these newer methods are not always an option. Together with the increased cost, there is a growing demand because of this worldwide problem. This increased need for surgery has lead to the development of waiting lists in the state funded hospitals. To qualify for a cataract extraction in most state funded hospitals, a best visual acuity of 6/60 is required, compared to the 6/12 to 6/24 levels required in the industrial countries and private practices. With these levels of visual impairment in the developing world, many patients are left functionally blind for long periods of time until cataract extraction can be performed. Older methods such as extra-capsular cataract extraction are still being used in the developing world. This is mostly due to the increased density of the cataracts at the time when the extraction can be performed because of the long waiting time leading to further maturation of the cataract. This method requires a large corneal incision, which is normally closed with nylon sutures. With this method of surgery meticulous wound closure is very important, and in many cases surgically induced astigmatism is one of the unwanted consequences. It was therefore decided, for the purpose of this study, to use autokeratometric data to explore the refractive effects of two different methods of corneal wound closure following planned extra-capsular cataract extraction (ECCE). Astigmatism is a major problem associated with extra capsular cataract extraction, especially when the wound is closed by means of sutures. Studies by Minassian et al. (2001), Jacobi (2003) and Dowler et al. (2000) all show that newer methods of cataract extraction making use of smaller incisions and therefore fewer sutures show faster recovery and less astigmatism. These methods are however mostly restricted to private practice, and therefore potentially unsuited for use in developing countries. The type of material used for wound closure is another very important factor. Depending on the method of suturing wound gape and wound compression can cause increased amounts of astigmatism. Using a method of wound closure that would cause less traction on the cornea could therefore cause less of a problem postoperatively. Tissue adhesives such as Tisseel® fibrin glue could be such an alternative. Studies by Henrick et al. (1987), Kim and Kharod (2007) and Bhatia (2006) show that fibrin glue forms a watertight, non irritating wound while promoting the healing process by the cross linking of collagen fibres.

Thorough understanding of interfaces requires an assessment of both the surface and bulk properties through the use of multiple techniques. In this thesis, infrared absorption, Raman scattering and sum frequency generation were used as vibrational probes of different features of interfacial systems including the ability to measure surface and bulk effects. Two-dimension correlation analysis was used to study the relationship between the spectral response of the different techniques. Attenuated total reflection absorption, bulk Raman scattering and sum frequency generation were used to study the adsorption of ethanol--water mixture on fused silica. With the use of two-dimension correlation analysis, interesting results were observed concerning the behavior of the surface in respect to the bulk. Surface concentration of ethanol were concluded to be higher than in the bulk indicative of competitive adsorption. Furthermore, at low concentration ethanol was shown to adsorb to the surface in dimers, to then form a bilayer of strongly oriented ethanol molecules at higher concentration. At highest concentration, this bilayer is disturbed, leaving only one layer at the surface of oriented ethanol molecules. The same spectroscopic techniques were applied to pressure sensitive adhesives of different composition while drying on a sapphire surface. The presence or absence of acrylic acid in the material was shown to alter the reorientation at the surface while drying. In the case where no acrylic acid is present, the orientation of the polymer at the surface was driven by the packing of the molecules at the surface. When acrylic acid was present in the pressure sensitive adhesive, reorientation occurred much faster and was caused by strong hydrogen bonding with the surface of the sapphire. An increase in acrylic acid composition, increased the rate of reorientation. An experimental set up was constructed to specifically study interfaces with a nonuniform distribution within the plane of the surface. This allows for concomitant measurement of polarized total internal reflection Raman scattering and sum frequency generation spectroscopy along with bright field imaging and cross polarized imaging. This set up was used to study the L-histidine crystal in situ adsorbed on fused silica. The polarized experiments along with calculations allowed for a more in-depth analysis of the crystal orientation effect on the birefringence, the Raman and the sum frequency generation. / Graduate

d-Limonene (Lim) was used in various polymer formulations to achieve a more sustainable polymerization. Lim is a renewable and essentially non-toxic compound, derived from citrus fruit peels, that may replace some of the many toxic and fossil-based chemicals used in polymer synthesis. Bulk free-radical polymerizations of n-butyl acrylate (BA) with Lim were performed to investigate Lim co-polymerization kinetics and estimate the monomer reactivity ratios, important parameters in the prediction of copolymer composition. Kinetic modeling of the BA/Lim copolymerization was performed with PREDICI simulation software. The model supports the presence of a significant degradative chain transfer reaction due to Lim. This reaction mechanism is due to the presence of allylic hydrogen in Lim. Nonetheless, relatively high molecular weight polymers were produced. It was concluded that Lim behaves more like a chain transfer agent than a co-monomer. Terpolymerizations of BA, butyl methacrylate (BMA) with Lim were then performed. In order to predict the terpolymer composition, the monomer reactivity ratios for BA/BMA were estimated. By applying the three pairs of co-monomer reactivity ratios to the integrated Mayo-Lewis equation, terpolymer compositions were ably predicted up to high monomer conversion levels. Lim was then used as a chain transfer agent to prepare core-shell latex-based pressure sensitive adhesives (PSA) comprising BA and styrene via seeded semi-batch emulsion polymerization. By varying the concentration of Lim and divinylbenzene crosslinker, the core polymer microstructure was modified to yield different molecular weights and degrees of crosslinking. The core latex was then used as a seed to prepare core-shell latexes. By changing the Lim concentration during the shell-stage polymerization, the molecular weight of shell polymer was also modified. The latexes were characterized for their microstructure and were cast as films for PSA performance evaluation. The PSA performance was shown to be highly related to the polymer microstructure. Tack and peel strength showed a decrease with increasing Lim concentration. Shear strength went through a maximum with a core Lim concentration increase from 0 to 5 phm.

Routine products are used and procedures are followed in order to prevent and minimize the bacterial contamination of the surgical wound, and thus reduce the risk of postoperative wound infections. The overall aim of this thesis was to investigate the effect of different preoperative skin preparation before cardiac surgery. In study I, 10 healthy volunteers were compared in time to recolonization of the skin and bacterial growth with or without plastic adhesive drape. Bacterial samples were taken as paired samples on both side of the sternum. Plastic drape on disinfected skin seems to hasten recolonization compared with bare skin. In study II, 135 cardiac surgery patients were comparing plastic adhesive drape versus bare skin on the chest regarding intra-operative bacterial growth. Plastic adhesive drape did not reduce the bacterial recolonization or wound contamination, P. acnes colonizes males more often than females and P. acnes is not affected by disinfection with 0.5% chlorhexidine in ethanol. Study III, compared the leg harvesting site with or without microbal skin sealant in 135 CABG patients regarding intraoperative bacterial growth and postoperative wound infection. Almost no bacterial growth was found during surgery regardless of the use of microbial skin sealant and bare skin. A high incidence of postoperative wound infections (16.8%) in 2 month follow up was present and SSI was largely caused by S. aureus, i.e. other bacterial species than observed intraoperative. Study IV, a descriptive study using phenotypic and genotypic methods investigate susceptibility to chlorhexidine among S. epidermidis indicating that S. epidermidis isolates following preoperative skin disinfection are sensitive tochlorhexidine.

Orientador: Mário Alexandre Coelho Sinhoreti / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Odontologia de Piracicaba / Made available in DSpace on 2018-08-24T07:19:06Z (GMT). No. of bitstreams: 1 Leme_ArieneArcasTopalPaes_D.pdf: 1762862 bytes, checksum: df60c904446c386b9834989fa6847207 (MD5) Previous issue date: 2013 / Resumo: Neste estudo avaliou-se o efeito: (1) da adição de resina de troca aniônica (AER) a um cimento experimental, para reduzir a incompatibilidade entre sistemas adesivos simplificados e cimento resinoso de polimerização dupla, quando ativado quimicamente; (2) da aplicação de uma camada extra de adesivo entre o sistema adesivo simplificado e o cimento resinoso, na resistência da união, propriedades nanomecânicas da camada de cimento e micropermeabilidade na interface adesiva. Discos de resina composta foram cimentados com os sistemas adesivos ACE ALL Bond TE ([ACE] Bisco Inc.) e Scotchbond Universal ([SCU] 3M ESPE) ... Observação: O resumo, na íntegra, poderá ser visualizado no texto completo da tese digital. / Abstract: This study evaluated the effect of: (1) adding anion exchange resin (AER) to an experimental resin cement aiming to reduce incompatibility between simplified-step adhesive systems and dual-cured resin cement when chemically activated; (2) the application of an extra adhesive resin layer between the simplified adhesive system and resin cement, on the microtensile bond strength, nanomechanical properties of the cement layer and micropermeability at the adhesive layer. Resin composite discs were luted with the adhesive systems ACE ALL Bond TE ([ACE] Bisco Inc.) and Scotchbond Universal ([SCU] 3M ESPE) ... Note: The complete abstract is available with the full electronic document / Doutorado / Materiais Dentarios / Doutora em Materiais Dentários

Orientador: Milton Carlos Kuga / Resumo: Os objetivos dos estudos foram avaliar os efeitos da cimentação provisória intrarradicular de um pino metálico com cimentos temporários, de composição química diferentes, e analisar a influência da irrigação com agitação ultrassônica passiva (PUI), sobre a resistência de união do cimento resinoso autoadesivo (Relyx U200) na dentina do espaço radicular preparado para pino de fibra de vidro. Noventa raízes unirradiculares de dentes humanos, foram padronizadas com o comprimento de 17,0 mm, a partir do ápice radicular. Os canais radiculares foram instrumentados até o instrumento F5, irrigados a cada troca de instrumento com 5 mL de hipoclorito de sódio a 2,5% e obturados com cimento contendo resina epóxi (AH Plus; Dentsply DeTrey GmbH, Konstanz, GER). Após 7 dias, foi preparado o espaço intrarradicular para pino de fibra de vidro, na extensão de 11mm, a partir da face cervical radicular, com brocas tipo Largo #1 e #2, e dada a conformação final com a broca #2 do sistema White Post DC (FGM, Joinville, SC, BR). No estudo 1, quarenta espécimes foram distribuídos em 4 grupos (n =10), de acordo com o tipo de protocolo de cimentação provisório do pino metálico: G1 (CO), sem a realização prévia da cimentação provisória do pino metálico intrarradicular; G2 (PR), cimentação provisória do pino metálico com o sistema Provy (Dentsply); G3 (RT) cimentação provisória do pino metálico com o sistema Relyx Temp NE (3M) e G4 (TB), cimentação provisória do pino metálico com o sistema Temp Bond NE (... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The aims of this study are to evaluate the effects of temporary intraradicular cementation of a metallic pin with temporary cements made from different chemical composition, and to analyze the influence of agitation with passive ultrasonic irrigation (PUI) on the bond strength of the self-adhesive resin cement (Relyx U200) in the root space dentin prepared for fiberglass pin. Ninety one-root human teeth were standardized with a length of 17.0 mm from the radicular apex. The root canals were instrumented up to instrument F5, irrigated at each instrument change with 5 mL of 2.5% sodium hypochlorite and filled with cement containing epoxy resin (AH Plus; Dentsply DeTrey GmbH, Konstanz, GER). After 7 days, the intraradicular space, 11mm in length, was prepared for the fiberglass pin, from the root cervical face with Largo # 1 and # 2 drills, and given the final conformation with the drill # 2 from White Post DC system (FGM, Joinville, SC, BR). In study 1, forty specimens were distributed into 4 groups (n = 10), according to the type of provisional cementation protocol of the metal pin: G1 (CO), without executing beforehand the provisional cementation of the intraradicular metallic pin; G2 (PR), provisional cementation of the metallic pin with Provy system (Dentsply); G3 (RT) temporary cementation of the metallic pin with Relyx Temp NE (3M) and G4 (TB) system, provisional cementing of the metallic pin with Temp Bond NE system (Sybron Kerr). In all groups, with exception of CO, met... (Complete abstract click electronic access below) / Mestre

Abstract  Aim: To determine the shear bond strength of two commercially available self-adhesive resin cements on four different materials and to analyse the degree of conversion (DC) of those resin cements.  Materials and Methods: A total of 45 embedded specimens made of four different materials were prepared for the notched-edge shear bond strength test. Ten specimens each of resin composite, glass-ionomer, zirconia and 15 of human dentine. Pillars of two different self-adhesive resin cements were luted onto these specimens. Five of the dentine specimens were treated with Katana Cleaner before being luted with Panavia. A single sample from each self-adhesive resin cement was used to determine the DC using ATR-FTIR Spectroscopy. The samples were measured uncured, right after being light cured and 10 min thereafter. Results: The highest shear bond strength values were seen for RelyX, irrespective of the material tested. This difference was statistically significant. No statistically significant difference was seen between the dentine specimens pre-treated with Katana Cleaner and luted with Panavia, compared to no pre-treatment. No statistically significant differences were found regarding DC between Panavia and RelyX.  Conclusion: The bond between the dental materials and the tooth structure is extremely important for the longevity of the restoration. The bond strength of RelyX for all materials tested were 2.1 to 37.5 times higher than that for Panavia and the differences were statistically significant. Panavia had virtually no bonding to the dentine in this study which might be due to the treatment of the dentine. The differences regarding the degree of conversion between the two resin cements were not statistically significant. However, the DC 10 min after curing was 1.3 times higher than directly after curing for both resins.

The selection of suitable materials for the renovation of sliding shafts requires a comparison of several criteria. The main criteria were selected size shear strength under tensile stress lap bonded assemblies, resistance to adhesive wear and economic criteria. From the results of all tests is selected the most suitable friction material to repair worn out places of shaft. The technological process of sealing the shaft was drawn up on the basis of the literature, recommendations supplier of sliding materials and their own experience.

In this project, different MUF resins were synthesized with varying melamine content, F/NH2 molar ratio, number of addition steps and with varying addition order of the reactants during synthesis. Further, it was investigated how these synthesis parameters influenced resin properties including storage stability and free formaldehyde content. Additionally, NMR spectroscopy was used in order to study the resulting chemical structure of the resins and their molecular size and molecular size distribution were examined by SEC and MALDI-TOF-MS. The curing kinetics of the resins were studied by Raman spectroscopy. From the resins, cured glue joints were prepared and the mechanical properties and water resistance of these were tested through tensile shear testing after different pretreatments of the glue joints. It was confirmed that synthesis under both alkaline and acidic conditions resulted in a higher amount of ether bridges in the resin in comparison to synthesis under acidic conditions. Furthermore, a high melamine content and fewer urea additions resulted in resins with a higher amount of methylol groups and less substituted functional groups. Comparatively, when the F/NH2 molar ratio was increased or when formalin was added in two steps, a resin with higher amount of substituted groups and structures of higher degree of condensation was obtained. From the synthesis procedure it was concluded that a long condensation time at alkaline conditions was the most efficient way to achieve a low free formaldehyde content, while a high F/NH2 molar ratio resulted in the highest amount of free formaldehyde. Furthermore, a high amount of flexible ether bridges, low amount of methylol groups, low melamine content, high F/NH2 molar ratio and a high degree of branched chains seem to be important structural parameters for achieving resins with a long shelf life. Additionally, from the SEC-analysis it was found that the resins had an average molecular weight (Mn) between 1000-1600 g/mol and a broad molecular weight distribution, which were further verified by MALDI-TOF-MS. The resins with a high melamine content had shorter chains, and the molecular weight distribution was most significantly increased when the number of addition steps were changed. Through analysis of the curing process it was found that a higher hardener-to-resin mixing ratio resulted in a faster curing process and a higher final degree of cross-linking. Additionally, it appeared as the reaction of methylol groups was less pH-dependent than the reactions of ether bridges and methylene bridges, which both were favored at lower pH. From the kinetic profiles it was observed that the resin with a higher amount of ether bridges and lower amount of methylol groups had a more prolonged curing process. Furthermore, the mechanical testing of the resulting cured glue joints showed no significant difference in tensile strength between the resins when tested in the dry state. However, a reduced tensile strength were observed for the resin with higher melamine content when tested in the wet state, hence indicating that the increased melamine content used in this project is not enough in order to significantly improve the mechanical properties or water resistance of the cured glue joint observable with the used method. / I detta arbete har MUF-hartser syntetiserats med varierande melaminhalt, F/NH2 molkvot och satsningsförfarande av reaktanter under syntes. Vidare undersöktes det hur dessa syntesparametrar påverkar hartsernas egenskaper så som lagringsstabilitet och fri formaldehyd innehåll. Dessutom tillämpades NMR spektroskopi för att studera hartsernas kemiska struktur medan SEC och MALDITOF-MS analyser utfördes för att få en uppfattning om hartsernas molekylvikt samt molekylviktsfördelning. Vidare analyserades hartsernas härdningskinetik med Raman spektroskopi. Från de syntetiserade hartserna förbereddes härdade limfogar vars mekaniska egenskaper och vattenbeständighet studerades genom dragprovstestning efter olika förbehandlingar av fogarna. Från hartsernas kemiska struktur kunde det bekräftas att då syntes utfördes under både basiska och sura betingelser erhölls en högre mängd eterbryggor i hartserna i jämförelse med syntes under endast sura betingelser. Vidare konstaterades det att hartserna med högre melaminhalt samt hartset som tillverkades med färre ureasatsningar bestod av en högre mängd metylolgrupper och en mindre andel substituerade grupper på melamin och urea. Jämförelsevis resulterade en högre F/NH2 molkvot samt två formalinsatsningar under syntes i en större mängd substituerade grupper och i en högre andel större molekylstrukturer. Från den erhållna mängden fri formaldehyd i hartsen kunde det konstateras att en lång kondensationstid under basiska betingelser var det mest effektiva sättet att sänka detta värde. Jämförelsevis hade hartserna med hög F/NH2 molkvot det högsta innehållet av fri formaldehyd. Då hartsernas lagringstabilitet undersöktes visade det sig att en hög andel flexibla eterbryggor, en låg andel metylolgrupper, en låg melaminhalt, en hög F/NH2 molkvot och en hög andel grenade kedjor resulterade i förbättrad lagringsbeständighet. Från SEC-analysen erhölls hartsernas molekylvikter (Mn) i området 1000-1600 g/mol samt en bred molekylviktsfördelning. Resultaten var vidare bekräftade med MALDI-TOF-MS. Det observerades att hartserna med högre melaminhalt hade lägre molekylvikt samt att hartserna tillverkade med olika antal satsningar hade högst dispersitet. Då hartsernas härdningsförlopp studerades kunde det konstateras att ett högre bladningsförhållande av härdare/harts resulterade i en snabbare härdningsprocess samt i en större andel tvärbindningar i systemet. Dessutom visade det sig att reaktionen med metylolgrupper är mindre pH-beroende än omlagringen av eterbryggor och bildandet av metylenbryggor. De två sistnämda reaktionerna gynnas vid lägre pH. Då de kinetiska profilerna av hartserna jämfördes noterades det att hartset med en högre mängd eterbryggor och en lägre andel metylolgrupper hade en långsammare härdningsprocess. Från resultaten av de mekaniska analyserna på de härdade limfogarna kunde det konstateras att ingen signifikant skillnad i dragstyrka fanns mellan de olika fogarna då de testades i torrt tillstånd. Däremot observerades en minskad dragstyrka för hartset med högre melaminhalt då fogarna undersöktes i vått tillstånd. Detta visar på att den ökade melaminhalten som används i hartserna i detta projekt inte är tillräcklig för att resultera i en, med den använda metoden observerbar, förbättrad dragstyrka eller vattenbeständighet hos den motsvarande härdade limfogen.