Foram confeccionados 50 corpos de prova, divididos em 30 próteses totais superiores e 20 bases de provas permanentes, padronizados, para se avaliar a alteração dimensional da base de prova permanente, com dupla polimerização, processada em forno de microondas convencional; base de prova permanente com dupla polimerização, processada no método convencional; e a prótese total em uma única polimerização. Para essa análise, essas próteses foram divididas em 5 grupos: grupo I – prótese total convencional – banho de água (controle); grupo II – base de prova permanente processada convencionalmente; grupo III – base de prova permanente processada em forno de microondas convencional; grupo IV – prótese total superior padronizada com base de prova permanente processada convencionalmente, com as bases do grupo II; grupo V – prótese total superior com base de prova permanente, processada no forno de microondas convencional, com as bases de prova do grupo III. Para avaliar essa alteração foi usado o recurso do scaneamento da região posterior das próteses, “Post-dam", desses corpos de prova. Após esse processo, a imagem capturada foi levada para o programa Photoshop 8.0 determinando a região de avaliação. Após essa seleção, a imagem é acessada no CorelTrace 11 para ser transformada em preto e branco e vetorizada, sendo, então, levada para o CorelDraw 11 para ser feita a medição do espaço da região posterior, entre o modelo e a base de prova/prótese total, para permitir a análise dos valores da alteração dimensional dos corpos de prova em questão, após o processamento. Os resultados mostram que: 1) a diferença da variação média para os lados esquerdo, centro e direito, respectivamente, na ordem de décimos ou centésimos de milímetros, para o grupo IV e I (0,07; 0,08 e 0,09); para o grupo V e I (0,10; 0,32 e 0,25) e para o grupo V e IV (0,17; 0,24 e 0,16) não pode ser considerada relevante clinicamente para afetar o ajuste da prótese na boca e promover a ocorrência de maiores transtornos clínicos; 2) A alteração média das áreas do lado esquerdo e direito para o grupo I, II e IV obtiveram uma homogeneidade na alteração, diferindo os Grupos III e V em relação aos outros, não existindo porém, diferença significante a nível de 5% entre as áreas desses segmentos; 3) A análise da variância do índice da área dos cinco (5) grupos não apresentou resultado significante que desabonasse a utilização de qualquer um dos métodos para a confecção da prótese total. No entanto, mais estudos devem ser realizados com o intuito de se aprimorar o uso do forno de microondas para o processamentos da prótese. / The 50 samples of pattern maxillary complete denture were processed, divided in 30 maxillary complete denture and 20 permanent proof base, to evaluated of dimensional changes in the permanent proof base with twice polymerization, process in microwave oven, to compare with the others two groups, the complete denture with conventional process and the complete denture with permanent proof base with twice polymerization in a conventional process. To evaluated this complete dentures they were divided in 5 groups: group I – conventional complete denture; group II – proof base conventional process; group III – proof base in microwave process; group IV – complete denture using the proof base of the group, with the conventional process and the group; group V – complete denture using the proof base of the group III, microwave process. To evaluated this alteration used the scanner in the “Post-dam", in this samples. After this proceding the image was putting in the Adobe Photoshop 8.0 program to determinate what region was evaluated. After this selection, the image access in the CorelTrace 11 program and transformed in black and white, and after to access in the CorelDraw 11 that was measured the region between the cast and the complete/permanent proof base, to allow the analysis of the values the dimensional alteration of the proof body, after the process. The results show: 1) The linear dimensional alteration the difference mean variation for the left, center and right sides, respectively, it was in decimal order or centesimal of millimeters, for the group IV and I (0,07; 0,08 and 0,09); and for the group V and I were (0,10; 0,32 and 0,25) and for the group V and IV (0,17; 0,24 and 0,16) and it cannot be considered clinically relevant to affect the prosthesis adjustment in the mouth, and promote the occurrence of more clinical disruptions; 2) The dimensional alterations in the areas (left and right side) of the proof bodies of the three groups I, II and IV were uniform, and the groups III and V weren’t homogeneous, but there is not a statically significant difference, about 5%, between the segment left and right areas; 3) The variation of the area index about five groups there is not a statically significant that couldn’t use of the both method to build the complete denture. Although, more studies are important to realize with the objective to improve the use the microwave over to process the denture.

Restauração provisória é uma importante fase da reabilitação bucal com prótese parcial fixa, deve fornecer proteção pulpar e periodontal, apresentar integridade marginal e estética, ter durabilidade suficiente para resistir às forças mastigatórias. Pacientes com bruxismo ou aqueles cujo tratamento requer períodos longos de uso das restaurações provisórias necessitam de material com melhores propriedades mecânicas. Vários métodos têm sido empregados para reforçar próteses fixas provisórias, como fios metálicos, reforço metálico e incorporação de diferentes tipos de fibras, como carbono, polietileno e vidro, nas resinas para restaurações provisórias. O objetivo desse estudo foi avaliar alteração de cor e propriedades mecânicas de resistência flexural, módulo de elasticidade e carga de ruptura em resinas acrílicas com incorporação de fibras de vidro silanizadas. Para avaliação de cor foram confeccionados quarenta corpos-de-prova circulares (15 x 3mm) de cada marca comercial de resina acrílica quimicamente ativada, usada para confecção de restaurações provisórias, Dencor (Clássico Ltda., São Paulo-SP, Brasil), Duralay (Reliance, Worth-IL, EUA) e Trim Plus II (Bosworth Company, Skokie-IL, EUA), sendo vinte corpos-de-prova controles, e vinte experimentais, com adição de 10% em peso de fibras de vidro moídas (Reforplás S/A, São Paulo, SP, Brasil). Após a realização do acabamento superficial dos corpos-de-prova com lixas de carborundum e feltros era realizada a avaliação dos componentes de cor (L*, a*, b*) em espectrocolorímetro portátil (BYK-Gardner GmbH, Gerestried, Alemanha), com três mensurações em cada corpo-de-prova. Para os ensaios de resistência flexural, módulo de elasticidade e carga de ruptura foram confeccionados 40 corpos-de-prova retangulares (10mm de comprimento, 65mm de largura e 3mm de espessura) de cada marca de resina, sendo vinte do grupo controle e vinte do experimental (com fibras). Os corpos-de-prova foram testados em uma máquina de ensaios universal (Emic DL 2000®, Emic, São José dos Pinhais, PR, Brasil), usando três, com velocidade de 5mm/min. Os dados foram analisados estatisticamente, usando testes paramétricos e não paramétricos, de acordo com a distribuição da amostra. Todos os componentes de cor (L*, a* e b*) foram alterados após a incorporação de fibras de vidro, com exceção do componente b* da resina Duralay. Para o ensaio de resistência flexural, a análise de variância evidenciou significância estatística (p<0,01) apenas para o fator resinas (Duralay: 85,748 N/mm2 (± 8,04) ,Trim Plus: 86,860 N/mm2 (± 7,73) e Dencor: 97,400 N/mm2 (± 8,18)).Na avaliação do módulo de elasticidade, a análise de variância mostrou significância estatística (p<0,01) para o fator tratamentos, sem fibra: 2572,138 MPa (± 290,92) e com fibras: 3446,691 MPa (± 411,13), e para a interação, evidenciando que a incorporação de fibras aumentou o módulo de elasticidade das três resinas avaliadas.Na carga de ruptura, a análise de Variância evidenciou significância estatística (p<0,01) para os fatores tratamentos, sem fibras: 482,607 N (± 53,18322) e com fibras: 557,53 N (± 59,49652), resinas Duralay: 494,06 N (± 86,63), Trim Plus: 525,177 N (± 42,85) e Dencor: 540,971 N (± 58,40). Conclui-se que a incorporação de fibras provocou alterações nos componentes de cor e aumentou ambos, módulo de elasticidade e carga de ruptura, contudo não alterou a resistência flexural. / Provisional restoration is an important rehabilitation phase in fixed prosthodontic therapy, it should provide pulpal and periodontal protection, showing marginal integrity and esthetics, should also have enough durability in order to resist to the forces of mastication. Patients with bruxism or those, whose treatment require long-term use of provisional restorations, need material with better mechanical properties. Several methods have been applied to reinforce fixed partial dentures, as well as metal wires, metal reinforcement and the application of different types of fibers, such as carbon, polyethylene and glass in the resins for temporary restorations. The aim of this study was to evaluate the color change as well as the mechanical properties of flexural strength, elastic modulus and load rupture in acrylic resin with silanized glass fibers. In order to evaluate the color, it was fabricated forty circular specimens (15 x 3mm) of each commercial brand of the resins chemically activated, used to make provisional restorations, Dencor (Clássico Ltda., São Paulo-SP, Brasil), Duralay (Reliance, Worth-IL, EUA) e Trim Plus II (Bosworth Company, Skokie-IL, EUA). Twenty specimens were control and the other twenty were experimental with an addition of 10% in glass fiber weights (Reforplás S/A, São Paulo, SP, Brasil). After the superficial finishing of the specimens with silicon carbide paper and rag wheel, it was done an evaluation of the color parameters (L*, a*, b*) with a portable spectrocolorimeter (BYK-Gardner GmbH, Gerestried, Alemanha), in three measures in each specimens. For the flexural strength, elastic modulus and load rupture, forty rectangular specimens were fabricated (10mm in length, 65mm wide and 3mm of thickness) of each resin brand and twenty were experimental with fibers. The specimens were tested on an universal machine (Emic DL 2000®, Emic, São José dos Pinhais, PR, Brasil), using a 3- point bending testing device at a crosshead speed of 5 mm/mim. The data was statistically analyzed using parametric and non-parametric tests, according to the sample distribution. All the color parameter (L*, a* e b*) were altered after putting glass fibers, except the parameter b* from resin Duralay. For flexural resistance, the variance analyzes showed significance statistic (p<0,01) just for the resins ( Duralay: 85,748 N/mm2 (± 8,04) ,Trim Plus: 86,860 N/mm2 (± 7,73) and Dencor: 97,400 N/mm2 (± 8,18)). In the elastic modulus evaluation, the variance analyses showed significance statistic (p<0,01) for the treatment factors, without fibers (2572,138 MPa (± 290,92)) and with fibers (3446,691 (± 411,13)). Regarding the interaction, it showed that the incorporation of the fibers increased the elastic modulus in the three resins analyzed. Regarding the load rupture, the variance analyzed showed significance statistic of (p<0,01) for the treatment factors with fibers: 482,607 N (± 53,18322) and without fibers: 557,53 N (± 59,49652), resins (Duralay: 494,06 N (± 86,63), Trim Plus:525,177 N(± 42,85) e Dencor: 540,971 N (± 58,40)). The results of this study indicated that the incorporation of the fibers caused alterations in the color components and increased both elastic modulus and load rupture; therefore, it didnt increase the flexural resistance.

In the present work, a super water-absorbent poly(acrylic acid) was synthetized by inverse suspension polymerization, using Span60 as the dispersant, toluene as the dispersing organic phase, trimethylolpropane triacrylate as the crosslinking agent, and sodium persulfate as the initiator. The synthesis was conducted in a small-scale glass reactor operated in semi-batch mode. The following reaction conditions were evaluated: effects of initiator concentration, temperature, percentage of multifunctional cross-linker agent and monomer concentration. Also, two important properties were determined, conversion and gel fraction. A kinetic model including a population balance was employed to simulate the process. The proposed model uses the numerical fractionation technique and is capable of predicting the pre-gel and post-gel properties, the effect of the crosslinking agent level on the polymer properties and the dynamic of gelation. The model was compared with the experimental results and showed a satisfactory representation of the system after parameter adjusting. / No presente trabalho, o poli (ácido acrílico) super-absorvente foi sintetizado por polimerização em suspensão inversa, usando Span 60 como o dispersante, tolueno como fase orgânica, trimetilolpropano triacrilato como agente de reticulação e persulfato de sódio como iniciador. A síntese foi conduzida num reator de vidro em escala de bancada, operado em modo semi-batelada-batelada. As seguintes condições da reação foram avaliadas: os efeitos da concentração de iniciador, a temperatura, a porcentagem de agente de reticulação multifuncional e a concentração de monómero. Além disso, foram determinadas propriedades importantes, como a conversão e a fração de gel. Da mesma forma, foi desenvolvido um modelo de balanço populacional para simular o processo em conjunto com a técnica de fracionamento numérico, que é capaz de prever as propriedades pré-gel e pós-gel, o efeito do nível do agente de reticulação no polímero e as propriedades da dinâmica de gelificação. O modelo foi comparado com os resultados experimentais e mostrou uma representação satisfatória do sistema após o ajuste dos parâmetros.

Restauração provisória é uma importante fase da reabilitação bucal com prótese parcial fixa, deve fornecer proteção pulpar e periodontal, apresentar integridade marginal e estética, ter durabilidade suficiente para resistir às forças mastigatórias. Pacientes com bruxismo ou aqueles cujo tratamento requer períodos longos de uso das restaurações provisórias necessitam de material com melhores propriedades mecânicas. Vários métodos têm sido empregados para reforçar próteses fixas provisórias, como fios metálicos, reforço metálico e incorporação de diferentes tipos de fibras, como carbono, polietileno e vidro, nas resinas para restaurações provisórias. O objetivo desse estudo foi avaliar alteração de cor e propriedades mecânicas de resistência flexural, módulo de elasticidade e carga de ruptura em resinas acrílicas com incorporação de fibras de vidro silanizadas. Para avaliação de cor foram confeccionados quarenta corpos-de-prova circulares (15 x 3mm) de cada marca comercial de resina acrílica quimicamente ativada, usada para confecção de restaurações provisórias, Dencor (Clássico Ltda., São Paulo-SP, Brasil), Duralay (Reliance, Worth-IL, EUA) e Trim Plus II (Bosworth Company, Skokie-IL, EUA), sendo vinte corpos-de-prova controles, e vinte experimentais, com adição de 10% em peso de fibras de vidro moídas (Reforplás S/A, São Paulo, SP, Brasil). Após a realização do acabamento superficial dos corpos-de-prova com lixas de carborundum e feltros era realizada a avaliação dos componentes de cor (L*, a*, b*) em espectrocolorímetro portátil (BYK-Gardner GmbH, Gerestried, Alemanha), com três mensurações em cada corpo-de-prova. Para os ensaios de resistência flexural, módulo de elasticidade e carga de ruptura foram confeccionados 40 corpos-de-prova retangulares (10mm de comprimento, 65mm de largura e 3mm de espessura) de cada marca de resina, sendo vinte do grupo controle e vinte do experimental (com fibras). Os corpos-de-prova foram testados em uma máquina de ensaios universal (Emic DL 2000®, Emic, São José dos Pinhais, PR, Brasil), usando três, com velocidade de 5mm/min. Os dados foram analisados estatisticamente, usando testes paramétricos e não paramétricos, de acordo com a distribuição da amostra. Todos os componentes de cor (L*, a* e b*) foram alterados após a incorporação de fibras de vidro, com exceção do componente b* da resina Duralay. Para o ensaio de resistência flexural, a análise de variância evidenciou significância estatística (p<0,01) apenas para o fator resinas (Duralay: 85,748 N/mm2 (± 8,04) ,Trim Plus: 86,860 N/mm2 (± 7,73) e Dencor: 97,400 N/mm2 (± 8,18)).Na avaliação do módulo de elasticidade, a análise de variância mostrou significância estatística (p<0,01) para o fator tratamentos, sem fibra: 2572,138 MPa (± 290,92) e com fibras: 3446,691 MPa (± 411,13), e para a interação, evidenciando que a incorporação de fibras aumentou o módulo de elasticidade das três resinas avaliadas.Na carga de ruptura, a análise de Variância evidenciou significância estatística (p<0,01) para os fatores tratamentos, sem fibras: 482,607 N (± 53,18322) e com fibras: 557,53 N (± 59,49652), resinas Duralay: 494,06 N (± 86,63), Trim Plus: 525,177 N (± 42,85) e Dencor: 540,971 N (± 58,40). Conclui-se que a incorporação de fibras provocou alterações nos componentes de cor e aumentou ambos, módulo de elasticidade e carga de ruptura, contudo não alterou a resistência flexural. / Provisional restoration is an important rehabilitation phase in fixed prosthodontic therapy, it should provide pulpal and periodontal protection, showing marginal integrity and esthetics, should also have enough durability in order to resist to the forces of mastication. Patients with bruxism or those, whose treatment require long-term use of provisional restorations, need material with better mechanical properties. Several methods have been applied to reinforce fixed partial dentures, as well as metal wires, metal reinforcement and the application of different types of fibers, such as carbon, polyethylene and glass in the resins for temporary restorations. The aim of this study was to evaluate the color change as well as the mechanical properties of flexural strength, elastic modulus and load rupture in acrylic resin with silanized glass fibers. In order to evaluate the color, it was fabricated forty circular specimens (15 x 3mm) of each commercial brand of the resins chemically activated, used to make provisional restorations, Dencor (Clássico Ltda., São Paulo-SP, Brasil), Duralay (Reliance, Worth-IL, EUA) e Trim Plus II (Bosworth Company, Skokie-IL, EUA). Twenty specimens were control and the other twenty were experimental with an addition of 10% in glass fiber weights (Reforplás S/A, São Paulo, SP, Brasil). After the superficial finishing of the specimens with silicon carbide paper and rag wheel, it was done an evaluation of the color parameters (L*, a*, b*) with a portable spectrocolorimeter (BYK-Gardner GmbH, Gerestried, Alemanha), in three measures in each specimens. For the flexural strength, elastic modulus and load rupture, forty rectangular specimens were fabricated (10mm in length, 65mm wide and 3mm of thickness) of each resin brand and twenty were experimental with fibers. The specimens were tested on an universal machine (Emic DL 2000®, Emic, São José dos Pinhais, PR, Brasil), using a 3- point bending testing device at a crosshead speed of 5 mm/mim. The data was statistically analyzed using parametric and non-parametric tests, according to the sample distribution. All the color parameter (L*, a* e b*) were altered after putting glass fibers, except the parameter b* from resin Duralay. For flexural resistance, the variance analyzes showed significance statistic (p<0,01) just for the resins ( Duralay: 85,748 N/mm2 (± 8,04) ,Trim Plus: 86,860 N/mm2 (± 7,73) and Dencor: 97,400 N/mm2 (± 8,18)). In the elastic modulus evaluation, the variance analyses showed significance statistic (p<0,01) for the treatment factors, without fibers (2572,138 MPa (± 290,92)) and with fibers (3446,691 (± 411,13)). Regarding the interaction, it showed that the incorporation of the fibers increased the elastic modulus in the three resins analyzed. Regarding the load rupture, the variance analyzed showed significance statistic of (p<0,01) for the treatment factors with fibers: 482,607 N (± 53,18322) and without fibers: 557,53 N (± 59,49652), resins (Duralay: 494,06 N (± 86,63), Trim Plus:525,177 N(± 42,85) e Dencor: 540,971 N (± 58,40)). The results of this study indicated that the incorporation of the fibers caused alterations in the color components and increased both elastic modulus and load rupture; therefore, it didnt increase the flexural resistance.

As restaurações provisórias no tratamento reabilitador oral são de suma importância. Por isso é preocupante que os materiais utilizados para a execução das mesmas sejam críticos com relação à sua resistência e longevidade, principalmente, quando estas são executadas em tratamentos prolongados e/ou em espaços desdentados extensos. O objetivo deste trabalho foi avaliar em 4 grupos reforçados, compostos por 9 espécimes cada um, a resistência e o modo de fratura, de uma resina acrílica poli(metilmetacrilato) auto-polimerizável (Dencor® - Clássico®, São Paulo, SP, Brasil) utilizada para restaurações provisórias quando reforçada com fibras de vidro (Fibrante® e Interlig® - Angelus®, Londrina, PR, Brasil), fibras de aramida (Kevlar® - Du Pont®, USA) y fio ortodôntico &#x2205; 0, 7mm. E um grupo controle sem nenhum tipo de reforço, com a mesma quantidade de corpos de prova. A análise dos resultados (ANOVA, p < 0,05), para o teste de resistência, mostrou haver diferença estatística entre os grupos. O teste de Tukey encontrou que os grupos reforçados, aqueles que alcançaram maior média de resistência à fratura foram os que utilizaram a fibra de vidro trançada pré-impregnada com resina composta foto-polimerizável, Interlig® (1083 N); a fibra de vidro unidirecional préimpregnada com dimetacrilato de glicol, Fibrante® (1022 N) e a fibra de poli(aramida) unidirecional sem pré-impregnação, Kevlar® 29, aumentando em 26%, 22% e 17%, respectivamente, esta resistência em relação ao grupo controle (800 N), não havendo diferença estatística significante entre eles. O grupo reforçado com fio de aço com &#x2205; 0,7 mm (871 N) apareceu em seguida com uma resistência somente 8% maior e semelhante àquela apresentada pelo grupo controle sem reforço. A análise das fraturas concorreu com a elaboração de um novo sistema de classificação dividindo-as em quatro tipos: Ausente, Parcial, Total Não Separada e Total Separada. As fraturas dos espécimes reforçados foram consideradas mais favoráveis ocorrendo, predominantemente, os tipos Ausente e Parcial. / Provisional restorations are of ultimate importance in the oral rehabilitation treatment. Thus, clinicians have to bear in mind that materials used for their fabrication are critical due to its longevity and strength, when these are done for longterm therapy and/or large edentulous spaces. The aim of this work was to evaluate the flexural resistance and fracture mode of an auto-cure polymethylmetacrilate resin (Dencor® - Classico® , Sao Paulo, SP, Brasil) used for provisional restorations and reinforced with four materials. Samples were divided in four groups of nine each, as the following: glass fiber (Fibrante® and Interlig® Angelus®, Londrina, PR, Brasil), aramide fibers (Kevlar® Du Pont®, USA), and orthodontic wire &#x2205; 0,7mm. one group whitout reinforcement served as control. Data was submitted to statistical analysis with one-way ANOVA (p<.05) test. Results showed statistically significant difference among the groups. Tukeys test showed that glass-fiber Interlig® exhibited the greatest value of flexural strength (1083 N); followed by unidirectional glycol dimetacrylate glass-fiber Fibrante® (1022 N) and aramid fiber Kevlar® (966 N). These values represent 26%, 22% and 17% in relation to the control group (800 N), being non statistically significant difference observed among them. The group with &#x2205; 0,7mm orthodontic wire (871 N) had a resistance only 8% higher and similar of that of control group without reinforcement. Fracture analysis was conducted by the following scale: absence, partial, complete without separation, and complete with separation. Fracture modes observed on reinforced samples were considered more favorable, with types absent and partial seeing more frequently.

Materiais odontológicos inovadores que apresentem propriedades antimicrobianas são altamente desejáveis na cavidade oral. O objetivo deste estudo foi avaliar a atividade antimicrobiana do vanadato de prata nanoestruturado (&beta;-AgVO3) incorporado em duas resinas acrílicas frente a Candida albicans, Streptococcus mutans, Staphylococcus aureus e Pseudomonas aeruginosa, além de examinar as propriedades mecânicas e o padrão de incorporação do nanomaterial nas resinas. O nanomaterial foi caracterizado por difração de raios X (DRX), espectroscopia no infravermelho por transformada de Fourier (FTIV), análise elementar por energia dispersiva (EDS) e microscopia eletrônica de varredura (MEV). As propriedades antimicrobianas das resinas acrílicas incorporadas com diferentes porcentagens de &beta;-AgVO3 foram investigadas pelo método de redução do XTT, unidades formadoras de colônias (UFC) e microscopia confocal à laser e o comportamento mecânico por meio de ensaios de dureza e rugosidade superficial, resistência à flexão, à compressão e ao impacto. O padrão de incorporação do &beta;-AgVO3 nas resinas foi analisado por microscopia eletrônica de varredura (MEV) e análise elementar por energia dispersiva (EDS). Os dados foram analisados por ANOVA, Tukey e pelo teste Generalized Linear Models (&alpha;=0,05). Para ambas as resinas, em relação ao grupo controle, a incorporação de 5% e 10% de &beta;-AgVO3 reduziram significantemente a atividade metabólica de C. albicans e P. aeruginosa (p<0,05), enquanto que para S. mutans houve redução significante apenas com a incorporação de 10% (p<0,05). Não houve diferença na atividade metabólica pelo método do XTT frente a S. aureus (p> 0,05). Para ambas as resinas, observou-se uma redução significativa no número de UFC/mL de C. albicans para o grupo incorporado com 10% de &beta;-AgVO3 e de S. mutans para os grupos com 2,5%, 5% e 10% do nanomaterial (p<0,05). Para S. aureus e P. aeruginosa, houve redução significante com a incorporação de 5% e 10% (p<0,05). A dureza superficial da resina termopolimerizável permaneceu inalterada pela incorporação do nanomaterial (p>0,05) e da autopolimerizável aumentou com 0,5% (p<0,05). Concentrações maiores que 1% promoveram redução na resistência flexural das resinas (p<0,05) enquanto que a rugosidade superficial permaneceu inalterada (p>0,05). A resistência à compressão da resina autopolimerizável permaneceu inalterada (p>0,05) e da termopolimerizável reduziu com a incorporação de 0,5% e 10% (p<0,05). As concentrações de 5% e 10% promoveram redução significante na resistência ao impacto das resinas, em relação ao controle (p<0,05). A caracterização das resinas quanto a dispersão da carga utilizada mostrou a presença de domínios de &beta;-AgVO3 ao longo da matriz polimérica seguindo um padrão circular. Conclui-se que o método proposto foi capaz de promover atividade antimicrobiana às resinas acrílicas frente aos micro-organismos avaliados, sendo a mesma dependente da concentração do nanomaterial. Porém, alterações na dispersão do &beta;-AgVO3 na matriz dos polímeros são necessárias para não sacrificar as propriedades mecânicas e para potencializar o efeito antimicrobiano / Innovative dental materials that have antimicrobial properties are highly desirable in the oral cavity. The aim of this study was to evaluate the antimicrobial activity of nanostructured silver vanadate (&beta;-AgVO3) incorporated into two acrylic resins against Candida albicans, Streptococcus mutans, Staphylococcus aureus and Pseudomonas aeruginosa, while examining the mechanical properties and the pattern of nanomaterial incorporation into resins. The nanomaterial was characterized by X-ray diffraction (XRD), infrared spectroscopy Fourier transform (FTIR), elemental analysis by energy dispersive (EDS) and scanning electron microscopy (SEM). The antimicrobial properties of acrylic resins incorporated with different percentages of &beta;-AgVO3 were investigated by the reduction of XTT method, colony forming units (CFU) and confocal laser microscopy and the mechanical behavior through hardness, surface roughness, flexural, compression and impact tests. The pattern of incorporation of &beta;-AgVO3 resins was analyzed by scanning electron microscopy (SEM) and elemental analysis by energy dispersive (EDS). Data were analyzed by ANOVA, Tukey test and the Generalized Linear Models (&alpha; = 0.05). For both resins, compared to the control group, the incorporation of 5% and 10% &beta;-AgVO3 caused a significantly reduced in the metabolic activity of C. albicans and P. aeruginosa (p <0.05), while for S. mutans significant reduction was observed only with the incorporation of 10% (p <0.05). There was no difference in metabolic activity by XTT method against S. aureus (p> 0.05). For both resins, there was a significant reduction in the number of CFU / mL for C. albicans incorporated group with 10% &beta;-AgVO3 and S. mutans in groups with 2.5%, 5% and 10% of nanomaterial (p <0.05). For P. aeruginosa and S. aureus, there was a significant decrease with the incorporation of 5% to 10% (p <0.05). The surface hardness of the heat-cured resin was unchanged by the incorporation of the nanomaterial (p <0.05) and increased self-cured with 0.5% (p <0.05). Concentrations above 1% promote the reduction in flexural strength of the resins (p <0.05) while the surface roughness remained unchanged (P> 0.05). The compressive strength of the self-cured resin remained unchanged (P> 0.05) and heat-cured reduced with the incorporation of 0.5% and 10% (p <0.05). Concentrations of 5% and 10% caused a significant reduction in impact strength of resins, compared to control (p <0.05). The characterization of the resins as the dispersion of the filler used showed the presence of &beta;-AgVO3 domains along the polymer matrix following a circular pattern. It was concluded that the proposed method was able to promote antimicrobial activity to acrylic resins against microorganisms evaluated, with the same concentration dependent of the nanomaterial. However, changes in the &beta;-AgVO3 dispersion in the polymer matrix are necessary to do not sacrifice the mechanical properties and to enhance the antimicrobial effect

In recent years, electrochemical capacitors have emerged as devices with the potential to enable major advances in electrical energy storage. Electrochemical capacitors (ECs) are akin to conventional capacitors but employ higher surface-area electrodes and thinner dielectrics to achieve larger capacitances. This helps ECs to attain energy densities greater than those of conventional capacitors and power densities greater than those of batteries. Akin to conventional capacitors, ECs also have high cycle-lives and can be charged and discharged rapidly. But ECs are yet to match the energy densities of mid to high-end batteries and fuel cells. On the basis of mechanism involved in the charge-storage process, ECs are classified as electrical double-layer capacitors (EDLCs) or pseudocapacitors. Charge storage in EDLCs and pseudocapacitors is brought about by non-faradaic and faradaic processes, respectively. Faradaic process, such as an oxidation-reduction reaction, involves the transfer of charge between electrode and electrolyte. By contrast, a non-faradaic process does not use a chemical mechanism and charges are distributed on surfaces by physical processes that do not involve any chemical reaction. ECs employ both aqueous and non-aqueous electrolytes in either liquid or solid form, the latter providing the advantages of freedom from leakage of any liquid component, compactness, reliability and large operating potential-window. In the literature, polymer electrolytes are the most widely studied solid electrolytes. Complexation of functional-groups of certain polymers with cations results in the formation of polymer-cation complexes commonly referred to as solid-polymer electrolytes (SPEs). Mixing a polymer with an alkali metal salt dissolved in an organic solvent result in the formation of a polymer gel electrolyte. Organic solvents with low molecular-weights, such as ethylene carbonate and propylene carbonate, employed in polymer gel electrolytes are commonly referred to as plasticizers. When water is used as a plasticizer, the polymer electrolyte is called a polymer hydrogel electrolyte. Part I of the thesis is directed to studies pertaining to Polymer Hydrogel Electrolytes for Electrochemical Capacitors and comprises four sections. After a brief survey of literature on polymer hydrogel electrolytes employed in ECs in Section I.1, Section I.2 of Part I describes the studies on electrochemical capacitors employing cross-linked poly (vinyl alcohol) hydrogel membrane electrolytes with varying perchloric acid dopant concentration. Acidic poly (vinyl alcohol) hydrogel membrane electrolytes (PHMEs) with different perchloric acid concentrations are prepared by cross-linking poly (vinyl alcohol) with glutaraldehyde in the presence of a protonic acid acting as a catalyst under ambient conditions. PHMEs are characterized by scanning electron microscopy and temperature-modulated differential scanning calorimetry in conjunction with relevant electrochemical techniques. An optimised electrochemical capacitor assembled employing PHME in conjunction with black pearl carbon (BPC) electrodes yields a maximum specific capacitance value of about 96 F g-1, phase angle value of about 79o and a discharge capacitance value of about 88 F g-1. Section I.3 of Part I describes the studies on cross-linked poly (vinyl alcohol)/ploy (acrylic acid) blend hydrogel electrolytes for electrochemical capacitors. Acidic poly (vinyl alcohol)/poly (acrylic acid) blend hydrogel electrolytes (BHEs) have been prepared by cross-linking poly (vinyl alcohol)/poly (acrylic acid) blend with glutaraldehyde in presence of perchloric acid. These acidic BHEs have been treated suitably to realize alkaline and neutral BHEs. Thermal characteristics and glass-transition behavior of BHEs have been followed by differential scanning calorimetry. Ionic conduction in acidic BHEs has been found to take place by Grötthus-type mechanism while polymer segmental motion mechanism is predominantly responsible for ion motion in alkaline and neutral BHEs. Ionic conductivity of BHEs has been found to range between 10-3 and 10-2 S cm-1 at 298 K. Electrochemical capacitors assembled with acidic PVA hydrogel electrolyte yield a maximum specific capacitance of about 60 and 1000 F g-1 with BPC and RuOx.xH2O/C electrodes, respectively. Section I.4 of Part I describes the studies on gelatin hydrogel electrolytes and their application to electrochemical capacitors. Gelatin hydrogel electrolytes (GHEs) with varying NaCl concentrations have been prepared by cross-linking an aqueous solution of gelatin with aqueous glutaraldehyde under ambient conditions, and characterized by scanning electron microscopy, temperature-modulated differential scanning calorimetry, cyclic voltammetry, electrochemical impedance spectroscopy and galvanostatic chronopotentiometry. Glass transition temperatures for GHEs range between 340 and 377 K depending on the dopant concentration. Ionic conductivity behavior of GHEs is studied with varying concentrations of gelatin, glutaraldehyde and NaCl, and conductivity values are found to vary between 10-3 and 10-1 S cm-1 under ambient conditions. GHEs have a potential window of about 1 V with BPC electrodes. The ionic conductivity of pristine and 0.25 N NaCl-doped GHEs follows Arrhenius behavior with activation energy values of 1.9×10-4 and 1.8×10-4 eV, respectively. Electrochemical capacitors employing GHEs in conjunction with black pearl carbon electrodes are assembled and studied. Optimal values for capacitance, phase angle, and relaxation time constant of about 81 F g-1, 75o, and 0.03 s are obtained for 3 M NaCl-doped GHE, respectively. EC with pristine GHE exhibits continuous cycle life for about 4.3 h as against 4.7 h for the electrochemical capacitor with 3 M NaCl-doped GHE. Unlike electrochemical capacitors, fuel cells do not store the charge internally but instead use a continuous supply of fuel from an external storage tank. Thus, fuel cells have the potential to solve the most challenging problem associated with the electrochemical capacitors, namely their limited energy-density. A fuel cell is an electrochemical power source with advantages of both the combustion engine and the battery. Like a combustion engine, a fuel cell will run as long as it is provided with fuel; and like a battery, fuel cells convert chemical energy directly to electrical energy. As an electrochemical power source, fuel cells are not subjected to the Carnot limitations of combustion (heat) engines. A fuel cell operates quietly and efficiently and, when hydrogen is used as a fuel, it generates only power and potable water. Thus, a fuel cell is a so called ‘zero-emission engine’. In the past, several fuel cell concepts have been tested in various laboratories but the systems that are being potentially considered for commercial developments are: (i) Alkaline Fuel Cells (AFCs), (ii) Phosphoric Acid Fuel Cells (PAFCs), (iii) Polymer Electrolyte Fuel Cells (PEFCs), (iv) Solid-Polymer-Electrolyte-Direct Methanol Fuel Cells (SPE-DMFCs), (v) Molten Carbonate Fuel Cells (MCFCs) and (vi) Solid Oxide Fuel Cells (SOFCs). Among the aforesaid systems, PEFCs that employ hydrogen as fuel are considered attractive power systems for quick start-up and ambient-temperature operations. Ironically, however, hydrogen as fuel is not available freely in the nature. Accordingly, it has to be generated from a readily available hydrogen carrying fuel such as natural gas, which needs to be reformed. But, such a process leads to generation of hydrogen with some content of carbon monoxide, which even at minuscule level is detrimental to the fuel cell performance. Pure hydrogen can be generated through water electrolysis but hydrogen thus generated needs to be stored as compressed / liquefied gas, which is cost-intensive. Therefore, certain hydrogen carrying organic fuels such as methanol, ethanol, propanol, ethylene glycol, and diethyl ether have been considered for fuelling PEFCs directly. Among these, methanol with a hydrogen content of about 13 wt. % (specific energy = 6.1 kWh kg-1) is the most attractive organic liquid. PEFCs using methanol directly as fuel are referred to as SPE-DMFCs. But SPE-DMFCs suffer from methanol crossover across the polymer electrolyte membrane, which affects the cathode performance and hence the cell performance during its operation. SPE-DMFCs also have inherent limitations of low open-circuit-potential and low electrochemical-activity. An obvious solution to the aforesaid problems is to explore other promising hydrogen carrying fuels such as sodium borohydride, which has a hydrogen content of about 11 wt. %. Such fuel cells are called direct borohydride fuel cells (DBFCs). Part II of the thesis includes studies on direct borohydride fuel cells and comprises three sections. After a brief introduction to DBFCs in section II.1, Section II.2 describes studies on an alkaline direct borohydride fuel cell with hydrogen peroxide as oxidant. A peak power density of about 150 mW cm-2 at a cell voltage of 540 mV could be achieved from the optimized DBFC operating at 70oC. Section II.3 describes studies on poly (vinyl alcohol) hydrogel membrane as electrolyte for direct borohydride fuel cells. This DBFC employs a poly (vinyl alcohol) hydrogel membrane as electrolyte, an AB5 Misch metal alloy as anode, and a gold-plated stainless steel mesh as cathode in conjunction with aqueous alkaline solution of sodium borohydride as fuel and aqueous acidified solution of hydrogen peroxide as oxidant. The performance of the PHME-based DBFC in respect of peak power outputs, ex-situ cross-over of oxidant, fuel, anolyte and catholyte across the membrane electrolytes, utilization efficiencies of fuel and oxidant as also cell performance durability under ambient conditions are compared with a similar DBFC employing a Nafion®-117 membrane electrolyte (NME). Peak power densities of about 30 and 40 mW cm-2 are observed for the DBFCs with PHME and NME, respectively. The PHME and NME-based DBFCs exhibit cell potentials of about 1.2 and 1.4 V, respectively, at a load current density of 10 mA cm-2 for 100 h. Publications of Nurul Alam Choudhury 1. Gelatin hydrogel electrolytes and their application to electrochemical supercapacitors, N. A. Choudhury, S. Sampath, and A. K. Shukla, J. Electrochem. Soc., 155 (2008) A74. 2. Cross-linked polymer hydrogel electrolytes for electrochemical capacitors, N. A. Choudhury, A. K. Shukla, S. Sampath, and S. Pitchumani, J. Electrochem. Soc., 153 (2006) A614. 3. Hydrogel-polymer electrolytes for electrochemical capacitors: an overview, N. A. Choudhury, S. Sampath, and A. K. Shukla, Energy and Environmental Science (In Press). 4. Cross-linked poly (vinyl alcohol) hydrogel membrane electrolytes with varying perchloric acid dopant concentration and their application to electrochemical capacitors, N. A. Choudhury, S. Sampath, and A. K. Shukla, J. Chem. Sc. (Submitted) 5. An alkaline direct borohydride fuel cell with hydrogen peroxide as oxidant, N. A. Choudhury, R. K. Raman, S. Sampath, and A. K. Shukla, J. Power Sources, 143 (2005) 1. 6. Poly (vinyl alcohol) hydrogel membrane as electrolyte for direct borohydride fuel cells, N. A. Choudhury, S. K. Prashant, S. Pitchumani, P. Sridhar, and A. K. Shukla, J. Chem. Sc. (Submitted). 7. A phenyl-sulfonic acid anchored carbon-supported platinum catalyst for polymer electrolyte fuel cell electrodes, G. Selvarani, A. K. Sahu, N. A. Choudhury, P. Sridhar, S. Pitchumani, and A. K. Shukla, Electrochim. Acta, 52 (2007) 4871. 8. A high-output voltage direct borohydride fuel cell, R. K. Raman, N. A. Choudhury, and A. K. Shukla, Electrochem. Solid-State Lett., 7 (2004) A 488. 9. Carbon-supported Pt-Fe alloy as a methanol-resistant oxygen-reduction catalyst for direct methanol fuel cells, A. K. Shukla, R. K. Raman, N. A. Choudhury, K. R. Priolkar, P. R. Sarode, S. Emura, and R. Kumashiro, J. Electroanal. Chem., 563 (2004) 181.

Die vorliegende Arbeit befasst sich mit der kontinuumsmechanischen Formulierung des Aushärteverhaltens polymerer Werkstoffe sowie der Implementierung und Simulation von Aushärtestoffgesetzen im Rahmen der Finite-Elemente-Methode. Auf Basis eines allgemeinen Modellierungsrahmens wird ein konkretisiertes Stoffgesetz für die Nachbildung von Aushärteprozessen eines acrylischen Knochenzements entwickelt. Darüber hinaus werden verschiedene Finite-Elemente-Simulationen zum klinischen Verfahren der Vertebroplastie präsentiert. / This work deals with the continuum mechanical formulation of curing phenomena in polymers as well as the implementation and simulation of curing models within the finite element method. Based on a general modelling framework, a specified material model for the simulation of curing processes in an acrylic bone cement is developed. Moreover, different finite element simulations regarding the clinical procedure of vertebroplasty are presented.

Cette thèse rapporte le greffage chimique de brosses de polymères neutres de poly(acrylate de tert-butyle) (PtBA) et de brosses chargées d’acide polyacrylique (PAA) sur des substrats de mica afin d’étudier leur conformation en fonction de la densité de greffage, du pH et de la force ionique. Le greffage est réalisé par polymérisation contrôlée par transfert d’atome (ATRP) initiée depuis la surface de mica afin de contrôler la croissance du polymère et sa densité de greffage. L’étude de la conformation des brosses de PtBA et de PAA a été menée avec la technique AFM en mesurant les épaisseurs des films à sec et gonflés sous différentes conditions de solvant, de pH et de force ionique. Une monocouche d’amorceurs est tout d’abord greffée sur du mica porteur de groupes hydroxyles créés par plasma (Ar/H2O). Cette couche a été caractérisée par des mesures d’angle de contact et par la technique TOF-SIMS. L’amorceur greffé a ensuite permis d’initier l’ATRP directement depuis la surface pour former des brosses neutres de PtBA liés de façon covalente au mica. La croissance linéaire de l’épaisseur du film avec la masse molaire du polymère en solution et le taux de conversion montre que la polymérisation est contrôlée. De plus, la ré-initiation des chaînes greffées atteste du caractère vivant de la polymérisation. L’hydrolyse des brosses de PtBA, confirmée par des mesures d’angle de contact, d’épaisseur et par FT-IR, conduit à des brosses de PAA. Les différentes couches greffées sont stables à l’air, en milieu organique et en milieu aqueux et leur gonflement est réversible. Le degreffage de la couche de PAA est observé suite à une longue exposition à pH basique. Cette étude représente le premier exemple de brosses greffées chimiquement sur du mica par polymérisation initiée depuis la surface. La variation des paramètres de la réaction de greffage de l’amorceur, tels que la concentration et la durée de réaction, a permis de contrôler le taux de recouvrement de l’amorceur et la densité de greffage du polymère. Une grande gamme de taux de recouvrement de l’amorceur est accessible et se traduit par un intervalle de densités de greffage allant de faibles à élevées (e.g. 0,04 chaîne/nm2 à 0,5 chaîne/nm2). L’étude de la conformation des chaînes de PtBA dans le DMF montre que cet intervalle de densités recouvre le régime crêpe au régime brosse. Le gonflement de brosses de PAA et la variation de la hauteur de la brosse L ont été étudiés en fonction de la densité de greffage, du pH et du sel ajouté cs (NaCl). Une transition brusque de collapsée à étirée est observée avec l’augmentation du pH, indépendamment de la densité de greffage. A pH neutre, les brosses sont collapsées et se comportent comme des brosses neutres en mauvais solvant. A pH basique, les brosses sont gonflées et chargées et se trouvent dans un régime de Pincus caractéristique des polyélectrolytes forts. En présence de sel, les charges sont partiellement écrantées et les répulsions électrostatiques dominent toujours dans la brosse. Cette étude contribue à une meilleure compréhension du comportement complexe des brosses de polyélectrolytes faibles et apporte un soutien expérimental à la théorie sur le comportement de ces brosses. / Neutral polymer brushes of poly(tert-butyl acrylate) (PtBA) and polyelectrolyte brushes of poly(acrylic acid) (PAA) were chemically grafted on mica in order to study their conformation as a function of grafting density, pH and ionic strength. The brushes were prepared via surface-initiated atom-transfer radical polymerization (SI-ATRP). This approach allows the control of the polymer growth and of the polymer grafting density. The study of brush conformation was investigated by measuring the dry and the swollen film thicknesses by Atomic Force microscopy (AFM) under various environmental conditions. Mica substrates were activated by a plasma method leading to OH-functionalized surfaces to which a radical initiator was covalently bound using standard siloxane protocols. The initiator grafting on the mica substrate was confirmed by water contact angle measurements and time-of-flight secondary ion mass spectrometry (TOF-SIMS). The covalently immobilized initiator successfully underwent SI-ATRP with tert-butyl acrylate, yielding end-grafted PtBA brushes that are covalently linked to mica. A linear relationship of the polymer thickness with respect to the molecular weight of the free polymer and with respect to the monomer conversion is obtained confirming that SI-ATRP is well controlled. The PtBA brushes were then hydrolyzed to PAA as confirmed by water contact angle measurements, polymer thickness measurements and FT-IR. The grafted layers show a good stability in air, organic solvent and aqueous solution and a reversible swelling. Film cleavage is observed for long exposure time in basic solution. This study represents the first example of chemically grafted brushes on mica via SI-ATRP. The polymer grafting density of poly(tert-butyl acrylate) was controlled by tuning the initiator surface coverage. By adjusting parameters such as the immobilization reaction time and concentration of the initiator, a wide range of initiator surface coverages and hence polymer densities on mica were possible ranging from 0.04 chain/nm2 to 0.5 chain/nm2). The swelling behavior of PAA brushes was investigated as a function of the polymer grafting density, pH and ionic strength cs (NaCl). A sharp transition from collapsed to stretched conformation was found with increasing pH. At neutral pH, the brushes are collapsed and behave like neutral brushes in poor solvent. At high pH, the brushes are swollen and charged and belong to the Pincus regime. In the presence of salt, the Coulombic repulsions are screened. The observed behavior of PAA brushes resembles the one of strong polyelectrolyte brushes. This study contributes to a better understanding of the complex behaviour of weak polyelectrolyte brushes and brings experimental support to theoretical studies.

The self-assembly of polystyrene-stabilized cadmium sulfide nanoparticles (PS-CdS) with amphiphilic stabilizing chains of polystyrene-block-poly(acrylic acid) (PS-b-PAA) into colloidal quantum dot compound micelles (QDCMs) is studied on two-phase gas-liquid segmented microfluidic reactors. The resulting particle sizes are found to arise from the interplay of shear-induced coalescence and particle breakup, depending on a combination of chemical and flow conditions. Variation of water content, gas-to-liquid ratio, and total flow rate, enable control of QDCM sizes in the range of 140 – 40 nm. The flow-variable shear effect on similar microfluidic reactors is then applied to direct the solution self-assembly of a PS-b-PAA block copolymer into various micelle morphologies. The difference between off-chip and on-chip morphologies under identical chemical conditions is explained by a mechanism of shear-induced coalescence enabled by strong and localized on-chip shear fields, followed by intraparticle chain rearrangements to minimize local free energies. Time-dependent studies of these nanostructures reveal that on-chip kinetic structures will relax to global equilibrium given sufficient time off-chip. Further investigations into the effect of chemical variables on on-chip shear-induced morphologies reveal a combination of thermodynamic and kinetic effects, opening avenues for morphology control via combined chemical (bottom-up) and shear (top-down) forces. An equilibrium phase diagram of off-chip micelle morphologies is constructed and used in conjunction with kinetic considerations to rationalize on-chip mechanisms and morphologies, including cylinders and vesicles, under different chemical conditions. Finally, we extend our strategy of two-phase microfluidic self-assembly of PS-b-PAA to the loading of fluorescent hydrophobic probes (pyrene and naphthalene) with different affinities for the PS core. The on-chip loading approach provides a fast alternate to the slow off-chip method, with implications for the potential development for point-of-care devices for drug loading. On-chip loading results indicate that loading efficiencies are dependent on water content and, to a lesser extent, on flow rate; the results also suggest that the on-chip morphologies of the PS-b-PAA micelles are an important factor in the loading efficiencies. / Graduate