abstract: Silicone compounds have a very low surface energy due to highly flexible Si-O-Si backbone and large number of –CH3 groups, but these compounds are extremely hydrophobic and thus have limited applications in aqueous formulations. Modification of such silicone compounds by grafting hydrophilic chains provides a wide range of silicone products called "Silicone Surfactants". Silicone surfactants are surface active agents which get adsorbed at the air-water interface thereby, reducing the interfacial tension. Some of the larger applications of silicone surfactant are in the manufacture of plastic foams, in personal care products and as spreading and wetting agents (Hill, R.M, 2002). In this thesis, a series of silicone surfactant graft copolymers were synthesized via hydrosilylation reaction. Poly(ethylene glycol) (PEG) of different chain length was grafted to a hydrophobic Poly(methylhydrosiloxane) (PMHS) backbone to improve the final hydrophilicity. Also, a positively charged quaternary ammonium salt (allyltriethylammonium bromide) was grafted to the PMHS backbone. The objective of this thesis was to synthesize polymers in predefined ratios of the above mentioned side groups and utilize these polymers to- 1) Study the effect of PEG chain length and its composition on the hydrophilicity of the polymer. 2) Study the effect of PEG: ammonium salt ratio on the surface tension of aqueous systems. Analysis of FT-IR and 1H NMR spectra of the polymers confirmed the predicted structure. The absence of characteristic Si-H absorbance peak at 2160 cm-1 in FT-IR spectra indicates consumption of silane groups along the polymer backbone. The actual moles of the side chain grafted on the backbone are calculated by 1H NMR peak integration. The results of contact angle studies indicated an increase in hydrophilicity with an increase in the composition of PEG in molecule. A 2*2 factorial DOE analysis reported that the fraction of Si-H bonds converted to PEG grafts was the critical factor towards increasing the hydrophilicity (p value of 0.015). Surface tension studies report that the air-water interfacial tension of the synthesized polymers is between 28mN/m – 45mN/m. The amount of Si-H was concluded to be the deciding factor in lowering the surface tension. / Dissertation/Thesis / Masters Thesis Chemical Engineering 2016

Orientador: Eduardo Piza Pellizzer / Banca: Milton Carlos Gonçalves Salvador / Banca: Humberto Gennari Filho / Banca: Eduardo Piza Pellizzer / Resumo: A relação existente entre os métodos de processamento das resinas acrílicas e a espessura de resina das bases de dentaduras, bem como a associação com o tamanho e forma do arco maxilar, tem sido um assunto bastante discutido no que diz respeito à possíveis alterações no posicionamento dos dentes e selamento posterior de próteses totais maxilares. Sendo assim, o propósito desse trabalho foi avaliar a movimentação dentária que ocorre durante o processamento de próteses totais maxilares com três diferentes espessuras de base, frente a dois métodos de inclusão e submetidas à polimerização por microondas. Quarenta e duas (42) amostras foram aleatoriamente divididas em 6 grupos de 7 amostras cada, respeitando, evidentemente, a espessura da base (1,25 mm - 2,50 mm - 3,75 mm) e o tipo de revestimento em mufla (silicone e gesso pedra). Pontos foram demarcados sobre os dentes artificiais para permitir a mensuração das R ee ssum o amostras através do software AutoCad. A diferença das médias dos segmentos entre o modelo encerado e demuflado de cada grupo foi submetida à analise de variância (ANOVA) e teste de Tukey. De acordo com os resultados obtidos pode-se concluir que: todas as técnicas de processamento juntamente com as diferentes espessuras de base de prótese total avaliadas apresentaram alteração na posição dos dentes artificiais após o processamento. A técnica de inclusão com barreira de silicone foi a que apresentou as maiores alterações dimensionais, independentemente da espessura. Na análise dos segmentos, houve uma maior alteração dos segmentos A/B/C (Triângulo maior) com relação aos segmentos D/E/F (Triângulo menor). Independente do tipo de inclusão, não houve diferença estatística entre as espessuras das bases (p<0,059), entretanto, analisando o comportamento de alteração, as prótese totais com bases mais finas apresentaram maior... (Resumo completo, clicar acesso eletrônico abaixo). / Abstract: The existent relationship between the methods of processing of the acrylic resins and the thickness of dentures bases resin, as well as the association with the size and form of the maxillary arch, it has been a subject quite discussed with regard to possible alterations in the teeth positioning and maxillary complete denture postdamming. So that, the aim of the study was to evaluate the dental movement that it happens during the processing of maxillary complete dentures with three base thickness different, front of two inclusion methods and submitted to the microwaves polymerization. Forty two (42) samples were randomly divided in 6 groups of 7 samples each, respecting, evidently, the base thickness (1,25 mm - 2,50 mm - 3,75 mm) and the type in flask investment (silicone and plaster stone). Points were demarcated on the artificial teeth to allow the measurement of the samples through the AutoCad software. The averages difference of the segments between the Ab ss tt rr a cc tt waxed model and deflasked of each group was submitted to it analysis of variance (ANOVA – á=0,05) and Tukey test. In agreement with the obtained results it can be conclusion that: all the processing techniques together with the different thickness of complete denture base evaluated, presented alteration in the artificial teeth positionig after the processing. The silicone flasking technique was that presented the largest dimensional alterations, independently of the thickness. In the segments analysis, there was a larger alteration of the segments A/B/C (larger Triangle) regarding the segments D/E/F (smaller Triangle). Independent of the flasking type, there was not difference statistics among the thickness of the bases (p <0,059), however, analyzing the alteration behavior, thinner bases presented larger movement in the position of the artificial teeth than thicken base that complete denture them. The completed... (Complete abstract, click electronic address below). / Mestre

Orientador: Marcelo Coelho Goiato / Banca: Stefan Fiúza de Carvalho Dekon / Banca: Ricardo Coelho Okida / Banca: Aimeé Maria Guiotti / Banca: Fellippo Ramos Verri / Resumo: O presente estudo teve por objetivo avaliar a influência de dois pigmentos (pó de cerâmica e tinta a óleo) e um opacificador (sulfato de barium) sobre as propriedades físicas de estabilidade de cor, dureza, absorção e solubilidade do silicone facial MDX4-4210, submetido ao envelhecimento acelerado. Para a confecção das amostras, foram utilizadas 2 matrizes metálicas em alumínio, contendo em seu interior 10 compartimentos circulares com 45mm de diâmetro apresentando estes, em uma matriz, uma espessura de 2mm para os testes de estabilidade de cor e dureza e, na outra, 1mm para os ensaios de absorção e solubilidade. Foram confeccionadas 120 amostras, metade para os ensaios de análise cromática e dureza e, a outra metade, para o teste de absorção e solubilidade. As amostras destinadas para cada teste foram distribuídas em seis grupos, incolor (G1), incolor com opacificador (G2), cerâmica (G3), cerâmica com opacificador (G4), óleo (G5), óleo com opacificador (G6). Após a obtenção das amostras, a análise cromática inicial foi verificada por meio da análise visual e da espectrofotometria de reflexão. Os ensaios de dureza foram realizados com auxílio de um durômetro Shore A. Os testes de absorção e solubilidade foram realizados por meio de um dessecador no qual as amostras permaneceram neste ambiente em estufa à temperatura de 37±2°C, sendo pesadas diariamente até obtenção de massa constante (W1); posteriormente as amostras foram submetidas ao envelhecimento seguido de nova pesagem (W2), e nova dessecação com pesagem final (W3). As amostras foram submetidas ao envelhecimento acelerado por 1008 horas, sendo os ensaios realizados nos períodos correspondentes a 252, 504 e 1008 horas. Os dados obtidos foram submetidos à ANOVA e Tukey, com significância de 5%. Pode-se observar pela análise espectrofotométrica que os grupos com opacificador apresentaram melhor... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The aim of this study was to evaluate the influence of two pigments (ceramic powder and oil paint) and one opacifier (barium sulfate) on physical properties of color stability, hardness, absorption and solubility of the facial silicone MDX4-4210 submitted to artificial aging. The replicas were fabricated in two metallic matrixes in aluminum containing 10 circular compartments with 45mm in diameter. One matrix generated specimens with 2mm in thickness for color stability and hardness evaluations while the other matrix, specimens with 1mm in thickness for absorption and solubility tests. The replicas were divided into six groups: colorless (G1), colorless with opacifier (G2), ceramic (G3), ceramic with opacifier (G4), oil (G5) and oil with opacifier (G6). Initial chromatic evaluation was performed by visual analysis and reflection spectrophotometry. The hardness tests were carried out by a Shore A durometer. The evaluations of absorption and solubility were performed through a desiccator to maintain the replicas in a stove at 37±2°C. The specimens were weighed daily until obtaining a constant mass, (W1). Then, the replicas were submitted to aging followed by a new weighing (W2) and drying with final weighing (W3). The replicas were submitted to accelerated aging during 1008 hours with evaluation after 252, 504 and 1008 hours. Data were submitted to statistical analysis by ANOVA and Tukey's test at 5% level of significance. According to spectrophotometry, the groups with opacifier presented statistically significant better chromatic stability than the other groups. The accelerated aging generated significant chromatic alterations in all groups, except for colorless and oil groups both with opacifier. There was no statistically significant difference among the groups after aging regarding hardness, absorption and solubility. According to the results, it may be concluded that... (Complete abstract, click electronic access below) / Doutor

Orientador: Altair Antoninha Del Bel Cury / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Odontologia de Piracicaba / Made available in DSpace on 2018-07-27T06:49:07Z (GMT). No. of bitstreams: 1 Rached_RodrigoNunes_D.pdf: 4205811 bytes, checksum: 1ed41d341da9732e487d8fd07df025a9 (MD5) Previous issue date: 2000 / Resumo: Este estudo avaliou a eficiência de uma técnica de reparo para próteses totais utilizando resina acrílica para microondas e silicone extra-duro como material de revestimento. Avaliou-se a resistência ao impacto Izod (IZ), penetração (PR) e recuperação Rockwell (RR), sorção (SO) e solubilidade em água (SL), e estabilidade de cor (EC) de resinas polimerizadas pelas técnicas L (Lucitone 199, L199, 8 h./74°C, molde de gesso ), A (Acron MC, AMC, 3 mÍn./500 W, molde de gesso), AR (Acron MC/R, GC Int., 2 bares/45°C/15 min.) e ASI (ídem à técnica A, porém molde de silicone). As amostras de IZ foram confeccionadas com e sem entalho, e as de EC envelhecidas artificialmente. Adicionalmente, 40 próteses totais superiores (PT) (metade em L199 ou AMC) foram fraturadas na linha média e reparadas com L, A, AR ou AS, e tiveram os parâmetros adaptação (AD) e alterações horizontal (AR) e vertical (AV) do plano oclusal avaliadas antes e após o reparo. Testes de resistência à flexão (RF) foram conduzidos em 84 espécimes retangulares. Destes, 24 foram confeccionados com L, A, AR e ASI e mantidos intactos. Os 60 restantes foram confeccionados com L ou A, tiveram a parte central removida (10 mm) e foram reparados com L, A, AR, AS (ídem à ASl, porém ciclo de 2 min./500 W - 1 min./O W - 2 mÍn./500 W) ou ASI. Os resultados mostraram que apenas L diferiu e foi superior às Ldemais técnicas para IZ. O entalho reduziu IZ nas técnicas. Os resultados de PR para A, ASI, AR e L foram, respectivamente, 71,1-70,5-104-88,5 um; A e ASI não diferiram entre si, e diferiram de AR e L, os quais diferiram entre si. AR apresentou a menor (75,1%) RR, e os demais grupos (L=83,1%; A=86,9% e ASl=86,8%) não diferiram entre si. Para a SO, houve diferença entre os pares L-A e AR-AS! (29,6-28,3-20,9 e 21,7 J.lglmm3). Nenhum grupo diferiu para SL. Para EC, A e AS não diferiram, sendo que os demais grupos diferiram entre si; o envelhecimento acelerado afetou EC de todos os grupos. Os grupos intactos de RF diferiram entre si (L=70,8 A=80,6 AR=65,3 ASl=75,4 MPa). Nos espécimes confeccionados com L, AS (49,6 MPa) foi inferior a AS! (65,7 MPa). AS diferiu das demais técnicas e AS! não; as demais técnicas de reparo (L=70,7 A=69,2 AR=63,5 MPa) não diferiram entre si. Nos espécimes confeccionados com AMC, AS (51,2 MPa) e AS!(44 MPa) diferiram dos demais, e estes não diferiram entre si; as demais técnicas (L=70,6 A=67,2 AR=65 MPa) não diferiram entre si. O reparo com AS! apresentou maior RF em espécimes confeccionados com L199 comparado com aqueles confeccionados com Acron MC. Falhas coesivas foram mais frequentes para L e A. Já AR, AS e ASl mostraram falhas adesivas com maior frequência. Houve influência do fator "reparo" para AD, sendo que AR apresentou a melhor adaptação (0,5%); as demais técnicas não diferiram entre si (L=27,2 A=28,9 AS=21,2%). Na avaliação da AR, houve diferença entre AR e as demais técnicas para 16-26, 11-26 e 21-16, entre AR e AS para 11-21, e entre A e AS para 16-26. Quanto a AV, não houve diferenças entre os grupos. As conclusões são: 1) O molde de silicone afetou apenas a SO de AMC; 2) A interação "material da base-reparo" não influenciou AD; 3) AR forneceu a melhor AD; 4) A interação "material da base-reparo" não afetou AH; 5) O fator "reparo" alterou AH; 5) Nenhum fator alterou AV / Abstract: This study evaluated the efficacy of a new repair technique of removable prosthodontics using microwave acrylic resin and very-hard silicone as the investment material. The first part evaluated Izod impact test (IZ), Rockwell penetration (RP) and recovery (RR), water sorption (WS) and solubility (SO), and color stability (CS) of acrylic resin samples processed by the following techniques: L (Lucitone 199, L199, 8 h./74°C, gypsum mold), A (Acron MC, AMC, 3 min./500 W, gypsum mold), AR (Acron MC/R, GC Int., 2 bars/45°C/15 min.) and AS1 (similar as A, but silicone mold was used). Notched and unnotched samples were tested for IZ. EC samples were artificially aged. In the second part, forty upper dentures were equally made of L199 or AMC. These dentures were sagittally ITagmented in the middle line and repaired by L, A, AR or AS. Adaptation (AD), horizontal: (HC) and vertical changes (VC) in the occlusal plane were assayed by comparing measurements taken before and after the repair procedure. Eighty four rectangular specimens were tested for flexural strength (RF). Twenty-four intact ones were made with L, A, AR and AS1. The 60 remained ones were made ofL199 or AMC and had the middle part removed (10 mm). Then, they were repaired with L, A, AR, AS (similar to AS1, but a different cyc1e was used: 2 min./500 W - 1 mÍn./O W - 2 min./500 W) or AS1. The results showed that L was superiorly different than the other techniques for IZ; additionally, unnotched samples were stronger than notched ones. Considering RP, A and AS1 (71,1-70,5 um) were not different, whilst AR and L (104-88,5 um) differed ITom each other as well as ITom A and AS1. AR showed the lowest value (75,1%) for RR and differed ITom the other groups (L=83,1%; A=86,9% and AS1=86,8%), which did not differ among each other. For WS, the pairs L-A and AR-ASI (29,6-28,3-20,9 e 21,7 _glmm3) were statistically different. No differences were detected for SO tests. EC results did not differ for A and AS; the other groups differed among each other, and artificial aging affected EC of alI groups. RF intact groups were all different (L=70,8 A=80,6 AR=65,3 ASl=75,4 MPa). For specimens made ofL199, AS (49,6 MPa) was weaker than ASI (65,7 MPa); AS differed from the other techniques, and ASI did not; the other techniques were not different (L=70,7 A=69,2 AR=63,5 MPa). ASI showed higher RF values when performed in samples made of L199, compared to those made of AMC. Cohesive failures were more common in L and A, while adhesive ones were in AR, AS e ASI. The technique AR showed the best AD (0,5%), while the other techniques were not different (L=27,2 A=28,9 AS=21,2%). There was a statistical difference between AR and the other techniques for the HC measurements between teeth 16-26, 11-26 e 21-16; AR and AS were different for 11-21 measurement, as well as A and AS for 16-26. Differences were not detected for VC variable. The conclusions were: 1) Silicon mold technique affected WS of AMC; 2) AD was not affected by the interaction "base material-repair procedure"; 3) AR technique generated the best AD results; 4) "Base material-repair procedure" interaction did not affect HC; 5) HC was affected by the "Repair" variable; 6) Differences were not detected for VC assessments / Doutorado / Protese Dental / Doutor em Clínica Odontológica

Orientador: Marcelo Ferraz Mesquita / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Odontologia de Piracicaba / Made available in DSpace on 2018-08-15T15:52:10Z (GMT). No. of bitstreams: 1 Silva_JoaquimAlbertoda_D.pdf: 1108935 bytes, checksum: 15a0a956cee4dcf34973383fda778eb8 (MD5) Previous issue date: 2010 / Resumo: O objetivo neste estudo foi comparar o efeito de dois métodos de envelhecimento acelerado (termociclagem e simulação do intemperismo natural) sobre a propriedade de deformação permanente de dois reembasadores resilientes permanentes usados como forradores de próteses removíveis, um à base de silicone (UP) e outro à base resina acrílica (DF), submetidos ou não à aplicação de selante de superfície. Foram confeccionados 120 corpos-de-prova (12,7 mm de diâmetro, e 19 mm de comprimento), distribuídos aleatoriamente em doze grupos (n=10) e submetidos a envelhecimento acelerado (2.000 ciclos) por meio da termociclagem, ou simulação do intemperismo natural (67 ciclos). Para o ensaio, foi utilizado um aparelho mecânico descrito na especificação no18 da A.D.A., com aplicação de carga compressiva (750 gf) durante 30 segundos. Para comparações do mesmo material com e sem selante e entre os materiais no mesmo intervalo de envelhecimento, foi realizada a análise estatística pelo teste de Mann-Whitney (p=0,05). Os testes de Kruskal-Wallis associado ao método de Dunn foram utilizados para comparação do efeito das técnicas de envelhecimento em cada material (p=0,05). O reembasador à base de silicone apresentou menor deformação permanente que o à base de resina, independente do método de envelhecimento (P<0,05). Foi observado que a aplicação do selante de superfície teve efeito sobre a deformação permanente apenas no grupo do material à base de silicone submetido à termociclagem, e que o envelhecimento acelerado promoveu aumento na deformação permanente apenas para o material à base de resina acrílica. / Abstract: This study was performed in order to compare the effects of two different accelerated aging methods on the property of permanent deformation of two permanent softliners. The softliners selected were an auto-polymerizing acrylic resin based and an auto-polymerizing silicone based. The use of surface sealer was also evaluated on both relining materials. For the permanent deformation test specimens were manufactured with 12.7 mm of diameter and 19 mm length, according to A.D.A. specification number 18. A total of 120 specimens were manufactured, sixty of each relining material. All specimens were randomly distributed into twelve groups (n=10) and later submitted to one of the accelerated aging processes (2000 thermocycling cycles or 67 cycles in an EQUV chamber). The permanent deformation test was performed with a mechanical device described in the specification number 18 of A.D.A. with a compressive load of 750 gf applied during 30 seconds. All data was submitted to statistical analysis. MannWhitney test was performed in order to compare the effect of the surface sealer on each material and to compare the permanent deformation of the materials in the same aging group (p=0.05). Kruskal-Wallis and Dunn tests were performed to compare all aging groups of each material (p=0.05). After analysis of the results it was observed that the silicone based reliner presented lower permanent deformation than the acrylic resin based reliner, regardless of the aging procedure. The surface sealer coating was effective only for the thermocycled silicone group and the accelerated aging processes affected only the permanent deformation of the acrylic resin based material. / Doutorado / Protese Dental / Doutor em Clínica Odontológica

Orientador: Teresa Dib Zambon Atvars / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-24T04:00:22Z (GMT). No. of bitstreams: 1 Quites_FernandoJunior_D.pdf: 4476724 bytes, checksum: ad6fd1bd74a45cdc5e9333e1f66da8c0 (MD5) Previous issue date: 2013 / Resumo: Nesta Tese as propriedades foto e eletroluminescentes de diferentes polímeros conjugados foram abordadas: poli[(9,9-dioctilfluoreno-2,7-diil)-alt-co-(9,9-di-{5 f-pentanil}-fluoreno-2,7-diil)] (PFP) emissor na região do azul, poli[(9,9-dihexilfluoreno-2,7-diil)-alt-co-(bitiofeno)] (F6T2) emissor na região do verde e poli[2-metóxi-5(3 f,7 f-dimetiloctilóxi)1-,4-fenilenovinileno] (MDMO-PPV) emissor na região do vermelho. Primeiramente foram preparados materiais híbridos orgânico-inorgânico baseados em PFP e siliconas (polímeros de silício). Devido à presença de grupos vinílicos laterais na cadeia do PFP, estes foram ligados quimicamente às siliconas através da reação de hidrossililação produzindo dois tipos de siliconas: uma com menor grau (PDHS-PDVS-l-PFP-X) e outra com maior (PDHSS-PDVS-h-PFP-X) grau de reticulação. As propriedades fotofísicas destes materiais híbridos foram comparadas com o polímero PFP na forma de filme e em soluçõoes de THF e de diferentes polissiloxanos usados na reação de hidrossililação. Através de medidas de fotoluminescência no estado estacionário e medidas dinâmicas verificou-se que as cadeias de PFP estão desordenadas em solução e no filme fino e nas siliconas com menor grau de reticulação (PDHS-PDVS-l-PFP-X) independente da quantidade de PFP usada. Entretanto, nas siliconas híbridas com maior grau de reticulação (PDHSS-PDVS-h-PFP-X) uma fase cristalina, conhecida como fase a, foi formada. Além disso, nestes híbridos foram observados agregados emitindo em regiões de mais baixa energia quando a quantidade de PFP foi aumentada (PDHSS-PDVS-h-PFP-X, com X = 2 e 3). Portanto, a força dirigente para a formação da fase cristalina a pode ser pensada como uma combinação de interações p -p entre a cadeia principal planar do polímero e interações hidrofóbicas dos grupos laterais no ambiente mais confinado causado pelas cadeias das siliconas com maior grau de reticulação (PDHSS-PDVS-h-PFP-X). Após o estudo detalhado das propriedades fotofísicas do PFP tanto em solução como no estado sólido, blendas poliméricas baseadas neste polímero e no copolímero F6T2 foram preparadas. As investigações fotofísicas mostraram que há uma eficiente transferência de energia do doador PFP para o receptor F6T2 nestas blendas (PFP/F6T2). A transferência de energia se dá pelos processos não radiativo (mecanismo do tipo Förster) e radiativo. Foram também preparados diodos eletroluminescentes usando as blendas poliméricas de PFP/F6T2 como camada ativa (configuração do diodo ITO/PEDOT:PSS/blenda polimérica/Ca/Al) com a intenção de produzir dispositivos poliméricos emissores de luz branca (WPLEDs). Nestes dispositivos foi observada uma transferência de energia do PFP para o F6T2 e uma eficiente recombinação de cargas sendo favorecida nos domínios do copolímero F6T2, impossibilitando a preparação de WPLEDs empregando este dois componentes na mesma camada ativa. Como a preparação de WPLEDs foi comprometida usando blendas de PFP e F6T2, devido a eficiente recombinação de cargas nos domínios do F6T2, foi proposta uma metodologia empregando dois materiais poliméricos com propriedades de emissão de luz diferentes: um composto eletroluminescente, neste caso foi usado o PFP e outro composto fotoluminescentes (para isto foi escolhido o MDMO-PPV). Nesta metodologia foi construido um diodo EL baseado no polímero PFP (ITO/PEDOT/PSS:PFP/Ca/Al) que emitiu luz azul-esverdeada. Na face oposta deste dispositivo (onde há a saída de luz, substrato de quartzo/ITO) foi colocado um filme fino (depositado sobre um substrato de quartzo) do polímero MDMO-PPV. Este filme absorve na região da eletroemissão esverdeada do PFP, ou seja, a luz emitida pelo PFP e capaz de excitar as moléculas de MDMO-PPV, e ambos os componente emitem fazendo surgir uma emissão de luz branca. A cor branca foi confirmada pela coordenada de cromaticidade CIE (x = 0.35 e y = 0.31). / Abstract: In this work the photo and electroluminescent properties of the different conjugated polymers were investigated: poly[(9,9-dioctylfluorene-2,7-diyl)-alt-(9,9-di(pent-4-en-1-yl)fluorene-2,7-diyl)]) (PFP) blue emitter, poly [(9,9-dihexilfluoreno-2 ,7-diyl)-alt-co-(bithiophene)] (F6T2) green emitter and poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylenevinylene] ( MDMO -PPV ) red emitter. Firstly, we prepared organic-inorganic hybrid materials based on silicones and PFP polymer. The presence of vinyl moieties in the side chain of PFP react with Si-H groups of the silicone by the hydrosilylation producing two types of silicones: with lower (PDHS-PDVS-l-PFP-X) and higher (PDHSS-PDVS-PFP-h-X) crosslinking degree. The photophysical properties of these hybrid materials were compared with PFP polymer in film form and in the solutions of THF and of the different polysiloxanes used in the hydrosilylation reaction. Based on the steady-state and dynamic photoluminescence data, PFP chains are disordered in solutions, in the film and in the silicones with a lower degree of crosslinking (PDHS-PDVS-l-PFP-X) independent of the amount of PFP used. Nevertheless, in the hybrids with a higher degree of crosslinking (PDHSS-PDVS-PFP-h-X) the crystalline a-phase of the polyfluorene was formed. Aggregates emitting in longer wavelengths are only formed when other crystalline phases are present in PDHSS-PDVS-h-PFP-X (X = 2 and 3) silicones. The driving force for this formation is probably a combination of p - p interaction between the planar backbone and the hydrophobic interactions of the lateral groups in the poor solvent in a more confined environment such as brittle PDHSS-PDVS-h-PFP. After detailed study of the photophysical properties of PFP both in solution and in the solid state, polymer blends based on this polymer and in the F6T2 copolymer were prepared. The photophysical investigations showed that there is an efficient energy transfer from the donor (PFP) to the acceptor (F6T2) in these blends (PFP/F6T2). The energy transfer occurs by non-radiative process (Förster-type mechanism) and radiative. Electroluminescent diodes were also studied using polymer blends of PFP/F6T2 as active layer (device configuration: ITO/PEDOT:PSS/polymer blend/Ca/Al) with the intention of produce white polymer light-emitting diodes (WPLEDs). In these diodes was also observed an efficient energy transfer from the PFP to F6T2, and the charge recombination was favored in the dominions of the F6T2 copolymer. The higher transfer energy from donor to acceptor in these diodes compromised the blue light and the withe light using this polymer in the same active layer do not produced. Thus, white-emitting electroluminescent diode was obtained with a single layer of an electro-active greenish component (PFP) and an external photoluminescent (PL) red-emitting material (MDMO-PPV), in a diode configuration of ITO/PEDOT-PPS/PFP/Ca/Al//MDMO-PPV. A thin film of this PL component was deposited onto a glass plate and mounted on the opposite face of a glass/ITO substrate. The MDMO-PPV polymer electronic absorption matches the greenish electroemission of the PFP. The white color, based on the CIE color coordinates (x = 0.35 e y = 0.31), was obtained by the red emission of the external MDMO-PPV film and the blue-greenish EL emission from the formed PFP diode. White emission was produced by adjusting the absorbance of the layer thickness and the blue-greenish component until it reached the CIE white coordinates. / Doutorado / Quimica Inorganica / Doutor em Quimica

The synthetic studies include the synthesis of the cyclic siloxydiyne, 3,3,5,5,8,8,10,10-octamethyl-4,9-dioxa-3,5,8,10-tetrasilacyclodeca-1,6- diyne [VI] and its novel iron carbonyl complex. In the preparation of [VI] by HBr promoted condensation of bis (methoxydimethylsilyl) acetylene, a minor product, a cyclic trimer was always formed along with the major product [VI]. No evidence of an equilibrium between the trimerization product and the dimerization product was found. Compound [VI] can react with iron carbonyl reagents to produce a novel binuclear iron complex of trimethylenemethane [VII] in very low yield either in a thermal or photo-reaction. The key step proposed by us in the formation of [VII] is a I,2-silyl shift in a complexed bis (silyl) acetylene to form a vinylidene intermediate. Experiments aimed at isolating this intermediate were not successful.

Orientadores: Maria Leticia Cintra, Cassio Menezes Raposo do Amaral / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Ciencias Medicas / Made available in DSpace on 2018-07-20T00:27:27Z (GMT). No. of bitstreams: 1 Tiziani_Valdenize_D.pdf: 3584406 bytes, checksum: 71b81f0a408df6231f33acf1b7882c6b (MD5) Previous issue date: 1995 / Resumo: O gel dos implantes de silicona pode entrar em contacto direto com o organismo em decorrência do vazamento através da membrana elastomérica do implante ou devido à rotura desta membrana. Estudou-se os efeitos da silicona gellivre injetada no tecido subcutâneo de ratos. Analisou-se as características morfológicas dos gânglios linfáticos axilares e inguinais. Foram injetados 3 cm3 de silicona gel no tecido subcutâneo de 96 ratos Wistar. Os animais do grupo controle (96 ratos Wistar) receberam injeção subcutânea de água destilada. Oito animais tratados e oito animais controle foram sacrificados decorridos 1, 3, 7, 9, 15, 30, 60, 90, 120, 180, 270 e 365 dias da injeção. Não foram observadas alterações morfológicas nos gânglios linfáticos sugestivas de migração ou de resposta reacional à silicona gel. Pequenas quantidades não detectáveis de silicona poderiam migrar para os gânglios linfáticos e provocar hiperplasia daquelas estruturas. Para avaliar esta possibilidade fêz-se um estudo morfométrico auxiliado por computador, onde comparou-se a área dos cortes dos gânglios linfáticos dos animais tratados com os do grupo controle. A análise estatística não mostrou diferenças significativas entre o grupo tratado e o controle. Se ocorreu migração de silicona, não provocou manifestação morfológica de hiperplasia dos gânglios linfáticos / Abstract: The gel of the silicone gel implants may bleed through the elastomeric envelope or may enter in contact with the organism due to a rupture of the implant. It was studied the effects of free silicone gel injected into the subcutaneous tis sue of rats. It was analysed the morphologic features of the axilar and inguinallymph nodes. Ninety six Wistar rats were injected in their subcutaneous space with 3 cm3 of silicone gel. The animaIs of control group, ninety six Wistar rats, were injected in their subcutaneous space with distilled water. The animaIs were sacrificed on days: 1, 3, 7, 9, 15, 30, 60, 90, 120, 180, 270 and 365 after the injection. There was no detectable silicone and no damage to the lymph nodes based on routine histopathological analysis. Little amounts of silicone that could migrate to lymph nodes could result in hyperplasia. In order to evaluate this possibility, a morphometric study based on a computer aided system compared the area of lymph node sections between treated and contraI animais. The statistical analysis didn't show any difference between treated and control groups. If silicone migration ocurred it did not provoke morphologic manifestation or hyperplasia of the lymph nodes / Doutorado / Anatomia Patologica / Doutor em Ciências Médicas

The dissertation thesis is focused of the method of testing the building sealnats. This is a summary of the research focused on the evaluation of sealants in interaction with the underlying materials. Attention is focused on the official test methods contained in European technical standards, the benefits of individual methods, their advantages and disadvantages are discussed. Also included are the overall findings of the practical application of the test procedures applied to 10 commercially available industrial sealants on 8 different substrates, including facade lining boards used for lightweight envelope systems. The dissertation thesis contains general conclusions about individual test methods. The research also includes various ways of preparing and conditioning test specimens that simulate different environmental conditions and, in some cases, play a crucial role in the final evaluation of sealants.

At the beginning, this master thesis briefly describes the principle of semiconductors. It states their types, methods of operation, fields of use, and it interprets the manner of semiconductor devices’ passivation. Then it introduces silicones, their properties and usage. Later on, this thesis summerize air humidity theory and materiál moisturing including mathematical interpretation. Next chapter is devoted to basics of dielectric materials’ behavior. And finally, the last part of this thesis estimates charakteristics of passivation materiál, Dow Corning HIPEC Q1-9205 silicone rubber.