The photopolymerization of multifunctional acrylates leads to the formation of a complex and insoluble network due to cross-linking. This characteristic is a useful property for stereolithography applications, where solid parts of the desired shape are cured using a pre-determined energy exposure profile. Traditionally, the required energy exposure is determined using a critical energy--depth of penetration, or Ec--Dp, model. The parameters Ec and Dp, are usually fit to experimental data at a specific resin composition and cure intensity. As a result, since the Ec--Dp model does not explicitly incorporate cure kinetics, it cannot be used for a different set of process conditions without first obtaining experimental data at the new conditions. Thus, the Ec--Dp model does not provide any insight when a new process needs to be developed, and the best processing conditions are unknown. The kinetic model for multifunctional acrylate photopolymerization presented here is based on a set of ordinary differential equations (ODE), which can be used to predict part height versus exposure condition across varying resin compositions. Kinetic parameter information used in the model is obtained by fitting the model to double bond conversion data from Fourier Transform Infrared Spectroscopy (FTIR) measurements. An additional parameter, the critical conversion value, is necessary for determining the formation of a solid part of the desired height. The initial rate of initiation, Ri, combines all the factors that impact part height, and therefore, it is an important quantity that is required in order to find the critical conversion value. The critical conversion value is estimated using the Ri and Tgel value from microrheology measurements. Information about network connectivity, which can be used to get properties such as molecular weight, cannot be derived from models using traditional mass-action kinetics for the cross-linking system. Therefore, in addition to modeling the reaction using the ODE based model, the results from a statistical model based on Kinetic Monte Carlo (KMC) principles are also shown here. The KMC model is applicable in situations where the impact of chain length on the kinetics or molecular weight evolution is of interest. For the present project, the detailed information from network connectivity was not required to make part height predictions, and the conversion information from the ODE model was sufficient. The final results show that the kinetic ODE model presented here, based on the critical conversion value, captures the impact of process parameters such as initiator concentration, light intensity, and exposure time, on the final part height of the object. In addition, for the case of blanket cure samples, the part height predictions from the ODE model make comparable predictions to the Ec--Dp model. Thus, the ODE model presented here is a versatile tool that can be used to determine optimum operating conditions during process development.

To enable fast and reliable processors, advances must be made in the interconnections on the printed circuit board and in the interconnections from the chip to the printed circuit board. Processing techniques have been demonstrated to fabricate a copper-clad encapsulated air dielectric layer to enable low loss off-chip electrical signal lines using sacrificial polymers and the three dimensional patterning capabilities of imprint lithography. The inclusion of an air gap can eliminate the dielectric loss allowing the signal to propagate over longer lengths. Additionally, the low dielectric constant of air lowers the loss contributions from the conductor and increases the signal propagation velocity reducing delay. The metal shielding could minimize the crosstalk noise and radiation losses that are significant at high frequencies. The three dimensional patterning capabilities of imprint lithography fabricated curved structures and rounded terminations which can reduce reflections at discontinuities. Furthermore, imprint lithography also created planarized surfaces which simplified the buildup process. Since imprint lithography, only uses temperature and pressure to make a pattern it is an inexpensive and simple process advancement. The metal-clad encapsulated air dielectric structures were fabricated in a comparable number of registration steps to traditional transmission lines. Implementation of all copper chip to substrate interconnects would provide high conductivity electrical connections, resistance to electromigration while avoiding formation of brittle intermetallics. High aspect ratio polymer molds for copper electroplating interconnects could enable improved integrated circuit electrical performance. The properties of a new aqueous base develop, negative-tone photosensitive polynorbornene polymer have been characterized to develop mechanically compliant all copper connections between the chip and printed circuit board. High aspect ratio features of 7:1 (height:width) were produced in 70 ìm thick films in a single coat with straight side-wall profiles and high fidelity. The polymer films studied had a contrast of 11.6 and a low absorption coefficient. To evaluate the polymer's suitability to microelectronics applications, epoxy cross-linking reactions were studied as a function of processing condition through Fourier transform infrared spectroscopy, nano-indentation, and dielectric measurements. The fully cross-linked films had an elastic modulus of 2.9 GPa and hardness of 0.18 GPa which can improve the mechanical compliance of the copper interconnections. A photo-imprint lithography process was developed to improve the photo-patterning of the polynorbornene polymer for high aspect ratio hollow structures. A shallow photo-imprint stamp was developed to physically displace material in the polymer core. Since the imprint stamp displaces material in the area of the feature, the effective film thickness is reduced compared to the bulk film. The reduction in film height reduced the effects of scattering in the core and also facilitated transport of developer within the core. The photo-imprint lithography process resulted in high aspect ratio hollow core pillars that exceeded optical resolution capabilities for comparable feature sizes.

Polymers play an integral part in the semiconductor electronic industry. Due to the expanding diversity of a polymer s structural design and the resulting properties, different polymers serve as different components in the makeup and fabrication of the electronic package. The limiting factor in computer processing speed shifts from the transistors gate delay to the interconnect delay below a circuit line width of 1.8 μm for interlayer dielectrics. Silicon dioxide has been used as the insulating layer between metal lines for many computer chip generations. Low dielectric constant polymers will need to supplant silicon dioxide as interlayer dielectrics in order to develop reliable circuits for future generations. Along with serving as interlayer dielectrics, low dielectric constant polymers are also incorporated in first and second level electronic packaging. Deposition and patterning of these polymers can be significantly reduced by using photodefinable polymers. Most photodefinable polymers are in a precursor form for exposure and development in order to dissolve in industrial developers. Once developed, the polymer precursors are cured to produce the final polymer structure. This temperature is as high as 350 oC for many polymers. Thermal curing sets limitations on the use of the polymer in the electronics industry because of either the unwanted stress produced or the incompatibility of other electronic components that do not survive the thermal cure. In addition to a low dielectric constant and photodefinability, many other properties are needed for successful implementation. Polymers must be soluble in organic solvents in order to spin coat films. Water absorption increases the dielectric constant of the patterned films and can lead to various adhesion problems and cause delamination of the film. Mismatches between the coefficients of thermal expansion in adjacent layers can produce residual film stresses which leads to warping of the substrate or interfacial delamination. The glass transition temperature must be high because the thermal expansion is greatly increased when the glass transition temperature is exceeded. A high Young s modulus is also required to withstand external forces from thermal, electrical, and packaging stresses. The goal of this research was to develop novel, low dielectric, photodefinable polymers that can be processed at low temperatures. All polymers discussed will contain one of two monomers with hexafluoroalcohol (HFA) functional groups. Fluorine provides many properties that are advantageous for low dielectric applications whereas alcohols absorb water and increase the dielectric constant. Characterization of the polymers show the effect the fluorine has on the alcohol s high water absorption. All polymers will be synthesized by condensation polymerization of a diamine with a dianhydride or diacid chloride. All other polymers will contain a novel HFA diamine. A new thermoplastic polymer structure based on the cyclization of an HFA situated ortho to an amide linkage produces a benzoxazine ring in the polymer backbone. Cyclization to form polybenzoxazines occurs at temperatures considerably lower than that needed to form polyimides. The lowest processing temperatures are achieved with protection of the HFA that can be cleaved with a photoacid generator.

Thesis (PhD) -- University of Western Sydney, 2002. / "A candidate for the degree of Doctor of Philosophy." "A thesis submitted in the School of Science, Food and Horticulture, University of Western Sydney." "June 2002" Bibliography: leaves 303 - 305.

Thesis (Ph.D.)--University of Western Sydney, 2008. / Thesis submitted to the University of Western Sydney, College of Health and Science, School of Natural Sciences, in fulfilment of the requirements for admission to the Doctor of Philosophy. Includes bibliography.

Disponibiliza??o do conte?do parcial, conforme Termo de Autoriza??o no trabalho. / Submitted by Jos? Henrique Henrique (jose.neves@ufvjm.edu.br) on 2017-02-07T17:34:06Z No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) larissa_almeida_alves_parcial.pdf: 127946 bytes, checksum: d9a934a0580a850c74fd0e5efc19ebe6 (MD5) / Approved for entry into archive by Rodrigo Martins Cruz (rodrigo.cruz@ufvjm.edu.br) on 2017-03-06T11:41:19Z (GMT) No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) larissa_almeida_alves_parcial.pdf: 127946 bytes, checksum: d9a934a0580a850c74fd0e5efc19ebe6 (MD5) / Made available in DSpace on 2017-03-06T11:41:19Z (GMT). No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) larissa_almeida_alves_parcial.pdf: 127946 bytes, checksum: d9a934a0580a850c74fd0e5efc19ebe6 (MD5) Previous issue date: 2016 / Carbon Dots (CDs) sol?veis em ?gua preparados a partir da desidrata??o ?cida da celulose foram utilizados como fotossensibilizadores na polimeriza??o da acrilamida na presen?a do co-iniciador trietanolamina. Os materiais preparados foram caracterizados por diferentes t?cnicas, incluindo MET, IVFT, espectroscopia UV-Vis e fotoluminesc?ncia, voltametria c?clica, TG-MS, titula??o potenciom?trica, entre outras. Os Carbon Dots preparados apresentaram tamanho de part?culas de aproximadamente 2,7 ?0,5nm, com uma superf?cie altamente funcionalizada com grupos funcionais oxigenados (carbox?licos, fen?licos, pironas, etc.) dos quais 65% s?o carbox?licos. Uma vez que estes grupos apresentam pKa ao redor de 4, potenciais zeta negativos foram observados em pHs ?cidos maiores que 4. Por outro lado, as caracteriza??es das suas propriedades ?pticas mostraram que os Carbon Dots apresentam uma absortividade molar (?) de 20,1 Lg-1cm-1 em ?= 254nm e 7,6 Lg-1cm-1 em ?= 360 com fotoluminesc?ncia dependente do comprimento de onda de excita??o e rendimento qu?ntico de 0,6%. Devido ?s suas propriedades, os Carbon Dots foram usados como fotossensibilizadores na polimeriza??o da acrilamida. A cin?tica da rea??o de polimeriza??o foi realizada em pHs 3, 6, 8 e 10, sendo que em pH 8 foi verificada uma maior taxa de convers?o. Neste pH as nanoestruturas possuem um pequeno excesso de carga negativa e a estrutura da trietanolamina est? predominantemente desprotonada (pKa = 7,86) o que facilita a intera??o das duas esp?cies promovendo a forma??o de radicais iniciadores da rea??o. O material fotopolimerizado foi caracterizado e os resultados obtidos s?o t?picos de poliacrilamida. Em adi??o, o material polim?rico obtido foi sol?vel em ?gua sugerindo que o pol?mero seja linear (n?o apresenta reticula??es) com uma massa molar viscosim?trica de at? 3,1x106 Da. A partir dos resultados experimentais obtidos e c?lculos te?ricos da estrutura de ambos, fotossensibilizador e co-iniciador, foi sugerido que devido ? capacidade dos Carbon Dots em receber el?trons em sua estrutura de bandas, sua alta absortividade molar e fotoestabilidade, as nanoestruturas quando excitadas foram capazes de gerar radicais amino, respons?veis pela inicia??o da polimeriza??o, devido ao acoplamento entre seus orbitais de fronteira com os orbitais HOMO-LUMO da trietanolamina. Por fim, os resultados apresentados demonstram uma nova e promissora aplica??o para estas nanopart?culas, com um grande potencial para o desenvolvimento futuro das tecnologias relacionadas ? fotopolimeriza??o. / Disserta??o (Mestrado) ? Programa de P?s-Gradua??o em Qu?mica, Universidade Federal dos Vales do Jequitinhonha e Mucuri, 2016. / Water soluble Carbon Dots (CDs) prepared from the acid dehydration of cellulose were used as photosensitizers in the polymerization of the acrylamide in the presence of co-initiator triethanolamine. The prepared materials were characterized by different techniques, including TEM, FTIR, UV-Vis spectroscopy and photoluminescence, cyclic voltammetry, TG-MS, potentiometric titration, among others. The Carbon Dots prepared showed the particle size of approximately 2.7 ? 0.5nm and a highly functionalized surface with oxygenated functional groups (carboxylic, phenolic, pyrones, etc.) 65% of them carboxylic. Since these groups have pKa around 4, negative zeta potentials were observed uawes of pH hifher than 4. Furthermore, the characterization of their optical properties showed that Carbon Dots exhibit a molar absorptivity (?) de 20.1 Lg-1cm-1 in ?= 254nm e 7.6 Lg-1cm-1 in ?= 360 with photoluminescence dependent of the excitation wavelength and quantum efficiency of 0.6%. Because their properties, the carbon dots were used as photosensitizers in the polymerization of the acrylamide. The kinetics of the polymerization reaction was carried out at pH 3,6,8 and 10, whereas at pH 8 was observed a higher conversion rate. At this pH the nanostructures have a small excess of negative charge and the structure of triethanolamine are predominantly deprotonated ( pKa = 7.86) that facilitates the interaction of the two species promoting the formation of radical reaction initiators. The polymeric material was characterized and the obtained results are typical of polyacrylamide. In addition, the polymerized material was water soluble and suggests that the polymer is linear (no presents crosslinks) and has a molecular weight of approximately 3.1x106 Da. The experimental results and theoretical calculations of the band structure of both, photosensitizer and co-initiator, suggest that due to the ability of Carbon Dots to receive electrons in its band structure, their high molar absorptivity and photostability, these nanostructures when excited were able to generate amine radicals, responsible for initiating polymerization, due to the coupling between their frontier orbitals with the HOMO-LUMO of triethanolamine. Finally, the results show a promising new application for carbon nanostructures in all areas related to photopolymerization.

Les gels de fibrine présentent un fort intérêt en médecine régénérative, puisqu’ils miment la matrice temporaire créée lors de la cicatrisation. Cependant, quand préparés à concentration physiologique, ils ne sont pas manipulables, ni conservables à sec. Pour contrer ces désavantages, ils peuvent être associés à un autre réseau de polymères, dans une architecture de Réseaux Interpénétrés de Polymères (RIP). Cette approche a été utilisée pour associer à un réseau de fibrine, un coréseau semi-synthétique d’albumine de sérum bovin (BSA) et de poly(oxyde d’éthylène) (POE), obtenu par photopolymérisation de BSA et PEG modifiés avec des fonctions méthacrylate (BSAm, PEGDM).Il a été démontré par des tests ex vivo et in vitro que ces matériaux ont de multiples applications potentielles, puisqu’ils supportent à leur surface, la croissance de nombreux types cellulaires. De plus, il a été observé que ces matériaux peuvent servir comme vecteurs pour la délivrance de molécules d’intérêt thérapeutique.La technologie a d’ailleurs été optimisée, en utilisant non plus des précurseurs modifiés avec des fonctions méthacrylate, mais acrylate. Cette modification a permis de réduire la toxicité du procédé de synthèse, tout en conservant les performances des matériaux. Il a également été démontré que divers matériaux optimisés ont des mécanismes de dégradation différents, et contrôlables par leur formulation initiale.Enfin, deux nouvelles familles de RIPs à base de fibrine ont été développées, en associant à un réseau de fibrine, un autre réseau de protéine, la fibroïne de soie. Des RIPs parfaitement manipulables ont été obtenus, supportant à leur surface la culture de fibroblastes. Ces matériaux sont donc prometteurs pour l’ingénierie tissulaire de la peau et d’autres applications. / Fibrin gels are of interest in regenerative medicine, as they mimic the provisory matrix synthesized during wound healing process. However, when prepared at physiologic concentration, these gels cannot be handled, nor stocked in dry state. To face these drawbacks, they can be associated with another polymer network, in an Interpenetrating Polymer Network (IPN). This strategy was used to associate to a fibrin network, a semi-synthetic conetwork composed of bovine serum albumin (BSA) and poly(ethylene oxide) (PEO), obtained by photopolymerization of methacrylate-modified BSA and PEG.It was demonstrated through ex vivo and in in vitro experiments that these materials have numerous potential applications, as they support on their surface, the culture of numerous cell types. Moreover, it was observed that they may be used as drug carrier for drug release applications.Moreover, the technology was optimized by modifying the methacrylate functions on the precursors for acrylate functions. This modification allowed to reduce the toxicity of the process, while preserving materials performances. It was also demonstrated that these optimized materials have different degradation mechanisms, which are controllable by their initial formulation.Finally, 2 new groups of fibrin-based IPNs were developed, by associating to a fibrin network, another protein network, the silk fibroin. Perfectly handable IPNs were obtained, which support on their surface the culture of fibroblasts. These materials are then very promising for skin tissue engineering, and most likely other applications.

Orientador: José Roberto Lovadino / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Odontologia de Piracicaba / Made available in DSpace on 2018-08-17T18:06:02Z (GMT). No. of bitstreams: 1 Miranda_DiogodeAzevedo_M.pdf: 1344077 bytes, checksum: 4e28fd76c33592cec253d42d20416b38 (MD5) Previous issue date: 2011 / Resumo: O objetivo neste estudo foi avaliar o efeito de três distâncias de fotoativação (0mm, 3mm e 6mm) e quatro meios de imersão (saliva artifical, Plax FreshMint, Plax Sem álcool e Plax Whitening) sobre a sorção e solubilidade de um compósito nanoparticulado. Os espécimes foram confeccionados em uma matriz de teflon de 6mm de diâmetro por 1mm de profundidade, e o compósito Filtek¿ Z350 (3M ESPE) foi inserido em incremento único e fotoativado por 20 segundos. Para controlar as distâncias de fotoativação, foi utilizado um dispositivo acoplado a um paquímetro digital. Inicialmente foram confeccionadas 15 amostras (n=5) e, em seguida, realizado o teste de Grau de Conversão (GC%). O GC% dos espécimes foi mensurado antes e após fotoativação, através do espectrômetro de raios infravermelhos transformado de Fourier (FTIR). O GC% foi calculado através da razão entre os espectros não-polimerizados e polimerizados do compósito. Para os testes de sorção e solubilidade foram confeccionados 60 espécimes (n=5), de acordo com as variáveis distâncias de fotoativação e meios de imersão. As amostras foram armazenadas em um dissecador com sílica em gel até a obtenção de uma massa inicial estável (m1). Após estabilização da massa inicial, o diâmetro e a espessura foram aferidos em quatro pontos eqüidistantes utilizando um paquímetro digital e, em seguida, calculado o volume individual (V) de cada amostra. Em seguida, as amostras foram imersas duas vezes ao dia, durante dois minutos nos enxaguatórios por 30 dias. Durante o intervalo de 12 horas, as amostras permaneciam imersas em saliva artificial. Por fim, as amostras foram retiradas das soluções, pesadas (m2) e, em seguida, colocadas no dessecador até a obtenção de uma massa final estável (m3). A sorção (Sp) e solubilidade (SI) foram calculadas através das seguintes fórmulas: Sl = m1-m3/V e Sp= m2-m3/V. Os dados de CG% foram analisados por meio de análise de variância (ANOVA) em esquema de parcelas subdivididas e as comparações múltiplas foram feitas pelo teste de Tukey, considerando o nível de significância de 5%. Os resultados mostraram que independente da distância de fotoativação, a superfície base teve os menores valores de GC% e, que somente quando fotoativado a 6mm de distância, os valores de GC% foram estatisticamente inferiores quando comparados as demais distâncias. Para sorção, os dados foram analisados por ANOVA two way e teste de Tukey, considerando o nível de significância de 5%. Quando fotoativado a 3mm de distância, o Plax Whitening diferiu dos demais enxaguatórios. Durante a fotoativação a 6mm de distância, observou-se diferença estatística em relação as demais distâncias, entretanto não ocorreu diferença estatística entre os enxaguatórios. Os dados de solubilidade foram analisados pelos testes não paramétricos de Kruskal Wallis e Dunn, com nível de significância de 5%. Para todas as distâncias e soluções, os valores foram negativos. Pode-se concluir que o GC% e a sorção do compósito foram influenciados quando fotoativados a 6mm, entretanto, não houve diferença estatística entre os enxaguatórios. Quanto a solubilidade, os valores negativos sugerem que o fenômeno foi mascarado pela sorção / Abstract: The aim of this study was to evaluate the effects of three curing tip distances (0mm, 3mm and 6mm) and four immersion media (artificial saliva, Plax FreshMint, Plax Alcohol-Free and Plax Whitening) on the sorption and solubility of nanofilled composite.The specimens were prepared in a Teflon matrix of 6mm Ø and 1mm height, and Filtek ¿ Z350 (3M ESPE) was inserted in one increment and light cured for 20 seconds. To control the curing tip distances, we used a device coupled to a digital caliper. Initially 15 samples were prepared (n = 5) and then performed the test degree of conversion (DC%). The DC% of the specimens was measured before and after curing, by ray spectrometer, Fourier transform infrared (FTIR). The GC% was calculated as the ratio of the spectra non-polymerized and polymerized composite. For the sorption and solubility tests were prepared 60 specimens (n = 5), according to the variable distances polymerization and immersion media. The samples were stored in a desiccator with silica gel to obtain a stable initial mass (m1). After stabilization of the initial mass, diameter and thickness were measured at four equidistant points by using a digital caliper and then calculated the individual volume (V) of each sample. Then the samples were immersed twice a day for two minutes in mouthrinses for 30 days. During the 12 hours, the samples were immersed in artificial saliva. Finally, samples were taken from the solutions, weighed (m2) and then placed in a desiccator until obtaining a stable final mass (m3). Sorption (Sp) and solubility (SI) were calculated by the following formula: Sl=m1-m3/V and Sp=m3-m2/V. Data from GC% were analyzed by analysis of variance (ANOVA) in split plots and multiple comparisons were made by Tukey test, considering the significance level of 5%. The results showed that regardless of the distance of curing, the bottom surface has the lowest GC%, and that cured only when the distance of 6mm, GC% values were significantly lower when compared with the other distances. For sorption, the data were analyzed by two-way ANOVA and Tukey test, considering the significance level of 5%. When photoactivated to 3mm away, Plax Whitening differed from the others mouthrinses. During polymerization the 6mm away, there was statistical difference from the other distances, but no statistical difference between the mouthrinses. The solubility data were analyzed by nonparametric Kruskal Wallis and Dunn, with a significance level of 5%. For all distances and solutions, the values were negative. It can be concluded that the GC% and sorption properties were influenced when photoactivated to 6mm, however, there was no statistical difference between rinses. As the solubility negative values suggest that the phenomenon was masked by sorption / Mestrado / Dentística / Mestre em Clínica Odontológica

Orientador: Edison Bittencourt / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-06T05:15:57Z (GMT). No. of bitstreams: 1 Fregolente_PatriciaBogalhosLucente_M.pdf: 761293 bytes, checksum: da2a8c420bdda1b10fb1d7888911e1b9 (MD5) Previous issue date: 2006 / Resumo: Atualmente, o mercado procura materiais com qualidades ópticas que satisfaçam as exigências dos usuários e que possuam facilidades de processamento. De forma geral, para um polímero apresentar boas propriedades ópticas, este necessita ter boas características como alto índice de refração, alta transmitância da luz, baixo peso específico, resistência ao impacto, estabilidade dimensional pós cura e estabilidade por exposição à luz e ao calor. Industrialmente, utiliza-se para a fabricação de lentes oftálmicas, a técnica de polimerização térmica, ou cura térmica. Dessa maneira, necessita-se de um tempo de cura muito longo (cerca de 20 horas) para evitar defeitos nas lentes. Entretanto, a cura através de irradiação de luz ultra-violeta (UV) permite obter os mesmos tipos de materiais e com características semelhantes com um tempo de processo reduzido em até poucos minutos. No presente trabalho, para confecção das lentes foram estudados os seguintes monômeros e oligômeros: metacrilato de metila (MAM), 1,6-Hexanediol diacrilato (HDODA), diacrilato uretano alifático tetrafuncional (Ebecryl 284) e diacrilato epóxi bisfenol-A (Ebecryl 3700) e para cada formulação o fotoiniciador 2- hidroxi-2-metil-1-fenilpropanona (Darocure 1173). O tempo de fotocura da mistura dura entre 4 a 7 minutos, de acordo com a espessura do molde. As lentes obtidas foram caracterizadas por medidas de dureza Shore D, transmitância nas regiões visível, UVA e UVB, índice de refração, análises térmicas para determinação da temperatura de transição vítrea. As lentes foram recobertas por uma resina multifuncional através do método de deposição por spin-coating e curada por UV. A caracterização dessa camada foi realizada por testes de dureza superficial utilizando graduações de grafites além de um planejamento experimental para observar as variáveis do processo de spin-coating que mais interferem na formação do recobrimento. As lentes produzidas apresentam ótimas qualidades ópticas e mecânicas e esta tecnologia de fotocura apresenta grande potencial para ser aplicada e produzir lentes em escala industrial / Abstract: The materials used for ophthalmic lenses need to present some optical qualities and to satisfy the requirements of the users. Various characteristics are required for the transparent synthetic resins as optical material. A polymer, to have good optical properties, needs to be colorless and tranparent, present good characteristics as high refractive index, high light transmittance, low specific weight, impact resistance, and stability to the exposition to the light and the heat. Industrially, for the manufacture of opthalmic lenses is used the technique of thermal polymerization, or thermal cure. This way, it is needed a long time of cure (about 20 hours) to prevent defects in the lenses. The monomers and monofunctional and multi-functional oligomers that have been studied for production of the lenses are methyl methacrylate (MAM), 1,6-hexanediol diacrylate (HDODA), aliphatic uretane diacrylate and bisphenol A epoxy diacrylate. The photoinitiator 2-hydroxi-2-methyl-1-fenilpropanone was added to each mixture, varying its concentration of 1 to 3%. The cure through ultraviolet irradiation (UV) allows to get the same kind of materials than thermal cure with similar characteristics but with a time of processing of the order of few minutes. In the present work, characteristics as refractive index (n), heat resistance, light transmittance and hardness of the produced lenses were studied from mixtures of acrylates and multi-functional methacrylates through photopolymerization with UV lamp at room temperature. The pencil hardness test was used for characterize the surface coating by spin-coating method, beyond an experimental design to observe the variables of the process that influence the formation of the coating / Mestrado / Ciencia e Tecnologia de Materiais / Mestre em Engenharia Química

Orientador: Lourenço Correr Sobrinho / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Odontologia de Piracicaba / Made available in DSpace on 2018-08-12T15:55:48Z (GMT). No. of bitstreams: 1 Valentino_ThiagoAssuncao_D.pdf: 2265512 bytes, checksum: 25b3c165573480a2614fbef0d4bcee79 (MD5) Previous issue date: 2008 / Resumo: A durabilidade de uma restauração cerâmica depende de fatores como grau de conversão do agente de cimentação e interação deste agente de cimentação com a superfície interna da cerâmica. Estes estudos in vitro avaliaram: (1) a influência de diferentes cerâmicas e o efeito de diferentes modos de ativação na microdureza Knoop (KHN) de um agente de cimentação resinoso dual, imediatamente e 24 horas após a polimerização e (2) a resistência de união de um novo tratamento de superfície à base de glaze na união entre a cerâmica à base de zirconia e um agente de cimentação resinoso dual, em associação com os tratamentos: jateamento com partículas de óxido de alumínio com 50 e 110µm, condicionamento com ácido fluorídrico a 10% e silanização. Para avaliação da atenuação da luz e dos modos de ativação, 10 discos do cimento resinoso Panavia F 2.0 foram confeccionados para cada grupo e ativados por fotoativação direta, ativação química ou através de discos de diferentes cerâmicas com 1.2mm de espessura. Os valores de KHN foram obtidos imediatamente e após 24 horas de armazenagem a 37 oC. Para a análise da resistência de união à cerâmica à base de zircônia, 80 discos de cerâmica à base de zirconia tetragonal estabilizada por ítrio foram confeccionados e receberam 8 tratamentos de superfície: Grupo I- jateamento com partículas de óxido de alumínio com 110µm, Grupo II- jateamento com partículas de óxido de alumínio com 110µm e silanização, Grupo III - jateamento com partículas de óxido de alumínio com 50µm, Grupo IV- jateamento com partículas de óxido de alumínio com 50µm e silanização, Grupo V- glaze e condicionamento com ácido fluorídrico 10%, Grupo VI- glaze, condicionamento com ácido fluorídrico 10% e silanização, Grupo VII- glaze e jateamento com partículas de óxido de alumínio com 50µm e Grupo VIII- glaze, jateamento com partículas de óxido de alumínio com 50µm e silanização. Após os tratamentos, o cimento resinoso dual Enforce foi inserido em microtúbulos Tygon em contato com a superfície das cerâmicas e fotoativado por 40s. A resistência de união foi obtida por ensaio de microcisalhamento. Os dados foram submetidos à Análise de Variância e ao teste de Tukey (5%) e mostraram que o agente de cimentação fotoativado através das cerâmicas à base de vidro e di-silicato apresentaram KHN superiores aos fotoativados através das cerâmicas à base de alumina e zircônia, imediatamente e após 24 horas. A fotoativação direta levou a valores de KHN superiores aos grupos que foram ativados através das cerâmicas e ativação química, para o tempo imediato e 24 horas. A resistência de união à cerâmica zircônia foi afetada pelos diferentes tratamentos de superfície e a associação entre o glaze e o ácido fluorídrico apresentou os melhores resultados, independentemente do processo de silanização. Dessa forma, pode-se concluir que a fotoativação através das cerâmicas promove atenuação da luz e KHN superior para o tempo de armazenagem de 24 horas, exceto para o modo de ativação direto. O tratamento com glaze promove significante aumento nos valores de resistência de união. / Abstract: The durability of ceramic restoration depends of factors like the conversion degree of a luting agent and the interaction of this luting agent with the ceramic internal surface. These in vitro studies evaluate: (1) the influence of different ceramics and the effect of different activation modes on Knoop Hardness Number (KHN) of a dual agent luting, immediately and 24 hours after polymerization and (2) the bond strength of a novel surface treatment that use a glaze for promotes a bond between zirconia-based ceramic and a dual resin luting agent, in association with the treatments: 50 e 110µm air particle abrasion, 10% hydrofluoric acid etching and silanization. For the light attenuation and activated modes evaluation, 10 discs of Panavia F 2.0 resin cement were fabricated for each group and activated by directly photoactivation, chemical and activation through different ceramic discs of 1.2 mm thickness. KHN was obtained using microhardness immediately and after storage at 37oC for 24 hours. For the bond strength analysis to zirconia-based ceramic, 80 ceramic discs based on Yttrium-stabilized tetragonal Zirconia were fabricated and received 8 different surface treatments: Group I- 110µm aluminum oxide particle abrasion, Group II- 110µm aluminum oxide particle abrasion and silanization, Group III- 50µm aluminum oxide particle abrasion, Group IV- 50µm aluminum oxide particle abrasion and silanization, Group V- glaze and hydrofluoric acid conditioning, Group VIglaze, hydrofluoric acid conditioning and silanization, Group VII- glaze and 50µm aluminum oxide particle abrasion, and Group VIII- glaze, 50µm aluminum oxide particle abrasion and silanization. After the treatments, Enforce resin cement was placed into micro bore Tygon tubing in contact with the ceramic surfaces and photoactivated for 40s. The bond strength was obtained by the microshear bond test. The data were submitted to Analysis of Variance and Tukey's test (5%) and showed that the glass and di-silicate based ceramics presented higher KHN than alumina and zirconia based ceramics, immediately and after 24 hours. The direct photoactivation showed higher KHN than the activated through the ceramics groups and chemical activation for immediate and 24 hours. The bond strength to zirconia was affected by different treatments and the association between glaze and fluoric acid showed the best results, independent of the silanization process. Of this form, it can be concluded that the photoactivation through the ceramics promotes light attenuation and an improvement of KHN was found after 24 hours storage except for directly activated mode. The treatment with glaze promoted a significant increase of bond strength values. / Doutorado / Dentística / Doutor em Clínica Odontológica