Дисертації з теми "Photoinitiator system"

Thesis (M.S.D.)--Indiana University School of Dentistry, 2009.
Title from PDF t. p. (viewed Feb. 9, 2010) Advisor(s): Jeffrey A. Platt, Chair of the Research Committee, Carl J. Andres, Suteena Hovijitra, David Brown, John A. Levon. Curriculum vitae. Includes abstract. Includes bibliographical references (leaves 56-59).

Orientador: Mário Alexandre Coelho Sinhoreti
Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Odontologia de Piracicaba
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Resumo: O objetivo neste estudo foi determinar a influência da concentração e proporção de canforoquinona (CQ) e etil-dimetilaminobenzoato (amina terciária - DABE) em propriedades de compósitos microhíbridos experimentais. Foram testados o Grau de Conversão (GC), Amarelamento (AM), Módulo de Elasticidade (ME), Resistência à Flexão (RF), Sorção de Água (SO) e Solubilidade (SL). Para tanto, 10 compósitos experimentais com a mesma composição monomérica (Bis-GMA, UDMA, BisEMA e TEGDMA) foram manipulados, variando-se apenas as concentrações e proporções de CQ/DABE (% em peso): 0,4/0,4 (C1); 0,4/0,8 (C2); 0,6/0,6 (C3); 0,6/1,2 (C4); 0,8/0,8 (C5); 0,8/1,6 (C6); 1/1 (C7); 1/2 (C8); 1,5/1,5 (C9) e 1,5/3 (C10). Para o ensaio de GC, 8 espécimes de cada material foram confeccionados, a partir de uma matriz de silicone em forma de barra (comprimento = 7 mm; largura = 2mm e espessura = 1mm), os quais foram fotoativados com um aparelho LED (Radii Cal, SDI, 800 mW/cm2), durante 20 segundos. Após 24 horas, o GC foi analisado por Espectroscopia de Infravermelho Transformada de Fourier (FTIR). Posteriormente, as mesmas amostras foram submetidas ao ensaio de flexão de 3 pontos em máquina de ensaio universal (Instron), e a RF e ME calculados. Para os testes de AM, SO e SL, foi utilizada uma matriz de silicone cilíndrica (diâmetro = 6 mm e espessura = 0,5 mm), e confeccionadas 5 amostras de cada material para cada teste. Todas as amostras foram armazenadas em estufa a 37º C, até que fossem submetidas aos seus respectivos testes. O AM foi mensurado após 24 horas de armazenamento em água, utilizando o espectrofotômetro Chroma Meter CR-400 (Konica Minolta). A análise se baseou no eixo b* (+b = amarelo; -b = azul). Para os testes de SO e SL, as amostras foram dissecadas por 1 semana e pesadas diariamente até que a variação máxima de massa fosse de 0,0001 g de um dia para o outro, obtendo m1. Para obter m2, as amostras foram armazenadas em água por 1 semana e pesadas novamente, uma única vez. Por último, m3 foram obtidas do mesmo modo em que m1, após recondicionamento das amostras. Para o cálculo foram utilizadas as fórmulas: SO = (m2-m3) / V e SL = (m1-m3) / V. Após os testes, os dados foram submetidos ao ANOVA one-way e teste Tukey (5%). As diferentes concentrações e proporções de CQ e DABE não alteraram significativamente as propriedades de RF e SO. Por outro lado, o GC foi influenciado positivamente, seguindo a ordem crescente da concentração CQ/DABE (C1 a C10). A SL foi inversamente proporcional à concentração do sistema CQ/DABE. Já relacionado ao ME, observou-se valores diretamente proporcionais à porcentagem em volume de CQ/DABE. Os compósitos 9 e 10, com maiores concentrações de CQ, apresentaram maior AM, comparados aos demais. Pode-se concluir que as altas concentrações de CQ/DABE levaram às melhores propriedades, porém ao maior AM. O aumento na proporção do co-iniciador (DABE) não influenciou nas propriedades de todas as formulações experimentais
Abstract: The aim of this study was to determine the influence of the concentration and ratio of camphorquinone (CQ) and ethyl-dimethylaminobenzoic (tertiary amine - DABE) on properties of microhybrids experimental composites. It was tested Degree of Conversion (DC), Yellowing (YL), Elastic Modulus (EM), Flexural Strength (FS), Water Sorption (WSP) and Solubility (SL). For this, 10 experimental composites with the same monomer composition (Bis-GMA, UDMA, BisEMA and TEGDMA) were manipulated by varying the concentration and ratio of CQ / DABE (wt%): 0.4 / 0.4 (C1); 0.4 / 0.8 (C2); 0.6 / 0.6 (C3); 0.6 / 1.2 (C4); 0.8 / 0.8 (C5); 0. 8 / 1. 6 (C6); 1 / 1 (C7); 1 / 2 (C8); 1.5 / 1.5 (C9); 1.5 / 3 (C10). For DC testing, 8 specimens of each material were prepared from a matrix of silicone-shaped bar (length = 7 mm, width = 2 mm and thickness = 1mm), which were photoactivated with one LED unit (Radii Cal, SDI, 800 mW/cm²) for 20 seconds . After 24 hours, the DC was analyzed by Infrared Fourier Transformed (FTIR). Subsequently, the same samples were subjected to bending test of three points on a universal testing machine (Instron), and the FS and EM calculated. For testing of YL, WSP and SL was used an array of cylindrical silicon (diameter = 6 mm and thickness = 0.5 mm), and made 5 samples of each material for each test. All samples were stored at 37 º C until they were subjected to their respective tests. The YL was measured after 24 hours of storage in water using the spectrophotometer Chroma Meter CR-400 (Konica Minolta). The analysis was based on the axis b * (+ b = yellow,-b = blue). For testing WSP and SL, the samples were dissected for 1 week and weighed daily until the maximum variation in weight was 0.0001 g of an overnight, obtaining m1. For m2, the samples were stored in water for 1 week and weighed once again. Finally, m3 were obtained in the same manner in which m1, after reconditioning of samples. For the calculation, were used: WSP = (m2-m3) / V and SL = (m1-m3) / V. After the tests, the data were subjected to one-way ANOVA and Tukey test (5%). The different concentration and ratio of CQ and DABE not significantly altered the properties of FS and WSP. Moreover, the DC was influenced positively in the order of increasing concentration of CQ / DABE (C1 to C10). The SL was inversely proportional to the concentration of the system CQ / DABE. Related to EM, was observed values directly proportional to the percentage by volume of CQ / DABE. The composites 9 and 10, with higher concentration of CQ showed higher YL, compared to the others. It can be concluded that high concentrations of CQ / DABE took the best properties, but the larger YL. The increase in the proportion of co-initiator (DABE) did not affect the properties of all experimental formulations
Mestrado
Materiais Dentarios
Mestre em Materiais Dentários

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The objective of this study was to evaluate the effectiveness of benzodioxole derivatives as co-initiators of radical polymerization of experimental self-etching adhesive systems. To compose the experimental self-etching adhesive systems a primer, containing methacrylate monomers and solvents, was developed. A monomer mixture, based on 50 wt % of Bisphenol A glicidyl dimethacrylate (Bis-GMA), 25 wt% of triethyleneglycol dimethacrylate (TEGDMA) and 25 wt% of 2-hydroxyethyl methacrylate(HEMA), was used as a model dental adhesive resin. Camphorquinone (CQ) 1 mol % was used as a photoinitiator to initiate polymerization. Different co-initiators (1,3- benzodioxole and piperonyl alcohol) and concentrations (0.25, 0.50, 1, 2, 4, 8, 16 mol %) were used in a model dental adhesive resin, to compose the experimental groups. Additionally, tertiary amine (EDAB) was used as co-initiator in the control group. The physical, chemical and mechanical properties and characteristics of the polymer obtained for the experimental adhesives (ABDO, APA, AEDAB) were evaluated using polymerization kinetics, sorption and solubility, flexural strength and elastic modulus. The microtensile bond strength (µTBS) to enamel and dentin, and fracture mode were investigated. Adicionalmente morphological analysis of the dentin bonding Interface were evaluated. The results indicated that the BDO and PA were effective co-initiators for the photoinitiator system based on CQ. Comparisons between the benzodioxole derivative co-initiators and traditionally used amine EDAB, showed similar performance in the kinetics of polymerization, flexural strength, water sorption and solubility of the model dental adhesive resin evaluated. In the microtensile bond strength dentin means were higher than enamel and mixed failures were predominant. APA showed higher bond strengths than AEDAB, while ABDO showed intermediate data. The hybrid layer for all groups was shown to be shallow (1-2 µm thick). No appreciable differences in homogeneity were detected along the bonded interface. BDO and PA were feasible alternatives to conventional amine as co-initiator of radical polymerization, moreover, as these benzodioxoles are found in the human diet, this characteristic made them more promising and advantageous to use in dental adhesive resin formulations than amine.
O objetivo deste estudo foi avaliar a efetividade de componentes derivados de benzodioxolas, como co-iniciadores da polimerização radicalar de um adesivo autocondicionante experimental. Para compor sistemas adesivos autocondicionantes experimentais foi desenvolvido um primer, composto por monômeros metacrilatos e solventes. O adesivo foi formulado utilizando uma resina adesiva modelo, composta por 50% de bisfenol A glicidil dimetacrilato (Bis-GMA), 25% de 2-hidroxietil metacrilato (HEMA) e 25% de trietilenoglicol dimetacrilato (TEGDMA), em massa. Canforoquinona (CQ) na concentração 1% molar foi utilizada como fotoiniciador da polimerização da resina modelo. Os grupos experimentais foram formulados com diferentes coiniciadores na resina adesiva: 1,3-benzodioxola (BDO) e álcool piperonílico (AP), em diferentes concentrações molares (0.25, 0.50, 1, 2, 4, 8, 16 %). Adicionalmente um grupo com amina terciária, etil,4-dimetilamino benzoato (EDAB) como co-iniciador, foi formulado como controle. Características e propriedades físicas, químicas e mecânicas do polímero obtido pelos adesivos experimentais foram avaliadas utilizando as metodologias de cinética de polimerização, sorção e solubilidade, resistência à flexão e módulo de elasticidade. A resistência de união à microtração (MPa) ao esmalte e à dentina, com a caracterização do tipo de fratura foi investigada. Adicionalmente, análise morfológica da interface adesiva em dentina foi avaliada. Os resultados indicaram que o BDO e PA foram co-iniciadores efetivos para sistemas fotoiniciadores à base de canforoquinona (CQ). Comparações entre os adesivos experimentais com co-iniciadores derivados de benzodioxolas (ABDO e AAP) e amina (AEDAB), mostraram performance similar na avaliação da cinética de polimerização, resistência à flexão, sorção e solubilidade da resina adesiva modelo avaliada. Na avaliação da resistência de união ao esmalte e à dentina, foi detectada diferença estatística e houve predominância de falhas mistas. APA apresentou maior resistência de união que AEDAB, enquanto ABDO mostrou resultados intermediários. A camada híbrida para todos os grupos apresentou uma espessura entre 1 e 2 Vm. Não foi observada diferença na homogeneidade da interface adesiva em dentina. BDO e PA se revelaram alternativas viáveis à amina como co-iniciadores para a polimerização radicalar. Ademais, estas benzodioxolas são mais promissoras e vantajosas que as aminas, por sua biocompatibilidade e presença na dieta humana

This master's thesis deals with a present problem of alternative dental fillings, which should replace amalgam fillings. Although there are health concerns about these alternative materials, especially resin composite fillings raise concerns, because they release potentionally harmful substances into the oral cavity. Accordingly even this medical device subjects various tests before releasing to the commercial market and one of these tests was carried out according to ČSN EN ISO 10993 and available scientific literature in the experimental part of this thesis. The amalgam controversy, substances used for manufacturing of resin dental fillings and analytical methods are described in the theoretical part of the thesis. In the experimental part of the thesis, 30 days long cumulative extraction experiments were carried out into various extraction mediums in order to assess suitability of new dental resin filling from ADM, a.s. by comparison with commercially available dental material from company GC EUROPE N.V. These samples were analysed by LC-MS and the amount of eluted substances from dental composites to extraction medium was quantified.

Les technologies de photopolymérisation en cuve émergent rapidement dans le domaine de la fabrication additive. Pour suivre cette expansion rapide du marché, des résines photosensibles très efficaces et abordables sont nécessaires. Dans ce travail, nous introduisons un nouveau système photoamorceur à trois composants (3K PIS) basé sur le colorant Safranine O (SFH+) qui a été identifié comme un composé très efficace dans plusieurs 3K PIS pour les processus de photopolymérisation.Le colorant est combiné avec un sel de tétraphénylborate (TPB) comme donneur d'électrons et un dérivé de la triazine (TA) comme accepteur d'électrons pour former un système photocyclique. Le mécanisme réactionnel est exploré par photolyse laser éclair (LFP) et la photopolymérisation est étudiée par spectroscopie infrarouge à transformée de Fourier en temps réel (RT-FTIR). Des expériences infrarouges avec plusieurs irradiances permettent de créer un modèle empirique prédisant la conversion en fonction du temps et de l'intensité lumineuse.Ensuite, des expériences de profondeur de polymérisation sont menées suivant l'équation de Jacobs, permettant d’obtenir les paramètres d'impression3D de la résine ; à savoir l'énergie critique (Ec) et la profondeur de pénétration (Dp). Ces paramètres sont reliés aux analyses RT-FTIR, ce qui permet de déterminer le temps critique (tc) et la conversion au point de gel.Enfin, des pièces complexes de haute résolution sont imprimées avec la résine dont la composition a été sélectionnée en fonction de nos résultats, démontrant la viabilité de cette formulation pour l'impression 3D DLP
Vat photopolymerization technologies are emerging quickly in the field of additive manufacturing. To follow this fast expansion of the market, highly efficient and affordable photosensitive resins are necessary. In this work, we introduce a new three-component phototiniating system (3K PIS) based on the Safranine O (SFH+) dye which has been identified as a very efficient initiator in several 3K PIS for photopolymerization processes.The dye is combined with a Tetraphenylborate salt (TPB) as electron donor and a Triazine derivative (TA) as electron acceptor to form a photochemical regenerating cycle. The photocycling mechanism is explored via laser flash photolysis (LFP) and the photopolymerization is investigated through Real-Time-Fourier Transform Infrared spectroscopy (RT-FTIR). Infrared experiments with several irradiances allow disclosure of an empirical model predicting conversion as a function of time and light intensity.Following this, cure depth experiments are conducted in agreement with Jacobs’ equation and the resin 3D printing parameters, i.e. critical energy (Ec) and penetration depth (Dp), are established. These parameters are linked to RT-FTIR data, resulting in the determination of the critical time (tc) and the conversion at gel point.Finally, high resolution complex pieces are printed with the resin which composition was tailored in accordance with our studies, demonstrating the viability of this formulation in DLP 3D printing

Current hydrophilic resin adhesives undergo hydrolytic degradation and show a decrease in bond strength over time. Nanoleakage and ultrastructure studies suggest that inadequately infiltrated collagen leads to enzymatic degradation and resin-dentin bond failure. Adequate degree of conversion (DC) of resin adhesives is also critical to resin-dentin bond strength and durability. The long-term goal of this dissertation is the realization of durable resin-dentin bond. It is hypothesized that ethanol-wet bonding technique (EW) may effectively facilitate the infiltration of hydrophobic monomers into hydrophilic acid-etched dentin by maintaining interfibrillar spacing, stiffening collagen matrix, and improving adhesive resin-demineralized dentin matrix miscibility. Chlorhexidine (CHX), Matrix Metalloproteinase-inhibitor (MMP-inhibitor), should further preserve collagen integrity and resin-dentin bond strength. Moreover, efficient photoinitiator systems that broaden light absorptivity and provide more reactive radicals may enhance polymerization. In this dissertation, a clinically-relevant EW protocol, 3×15s absolute ethanol rinsing, provided significantly higher microtensile bond strength (πTBS) of a hydrophobic resin (70%BisGMA/30%TEGDMA) to dentin as compared to water-wet bonding (WW). All groups showed no significant drop of πTBS after 1-year storage except EW without CHX application, showing marginally significant reduction in πTBS (p=0.0558) suggesting MMP-inhibition by CHX in EW. These results were consistent with subsequent experiments. EW maintained interfibrillar width and hybrid layer thickness for resin infiltration and retention. Monomer molar concentration across the hybrid layer was significantly higher in EW than WW. An application of 2% CHX diacetate further preserved collagen banding in EW. WW showed more generalized spotted nanoleakage, while EW presented localized reticular nanoleakage. The use of Irgacure 819 (BAPO) alone and in combination with benzoyl peroxide (BPO) or camphorquinone (CQ) increased DC of hydrophobic and hydrophilic resins over resins containing the CQ/amine (4E) control. Only BAPO and BAPO/BPO demonstrated significantly higher immediate shear bond strength than CQ/4E. Within the limitations of these studies, EW improved resin-dentin bond durability by maintaining collagen interfibrillar spaces for efficient infiltration of a hydrophobic BisGMA/TEGDMA resin resulting in significantly higher πTBS and monomer molar concentrations with less nanoleakage distribution within the hybrid layer than WW. CHX further maintained collagen integrity and πTBS in EW. BAPO is a potential alternative photoinitiator of dental resins.

Chemistry
Ph.D.
DNA provides the genetic code which is almost universal in all living organisms. When DNA is exposed to ultra-violet light it can cause cell degradation and mutation which are two of the major causes which lead to cancer. The nature of decay in DNA oligomers is a widely studied topic. Fluorescence and Transient Absorption (TA) experiments on polynucleotides which compare the behavior of the decay to the monomer bases have revealed the presence of longer-lived components in the multimeric systems. There has been heated debate over the character of the excited states responsible for the long-lived signals. Theoretical methods are well suited to compliment experiment by providing a description of processes and physical properties on the molecular level. We have studied π-stacked adenines in the gas-phase with Quantum Mechanical (QM) methods, but also in the helical environment using high-level ab initio methods, classical simulations and the combination of the two (QM/MM). Inclusion of the environmental interactions dramatically alters the shape of the potential energy surfaces due to steric interactions from the backbone and interactions with the surrounding bases and environment. This work examines the complete picture of photophysical processes occurring in adenine oligonucleotides within the helical environment after the absorption of a photon: the nature of initial absorption and the subsequent radiative and non-radiative decay pathways. It contributes key discoveries inherent to the mechanisms which govern photo-initiated processes in DNA, and also contributes to our fundamental knowledge of the photophysical behavior of π-stacked chromophores. The work reveals the effects of π-stacking interactions and the environment on photo-initiated processes in oligonucleotides. It reveals that excitonic coupling is responsible for the key differences in features in the absorption spectrum of adenine oligomers compared to the isolated bases, illustrates the role of charge transfer (CT) mixing in both absorption and decay processes, and the importance of bonded excimers in deactivation. The work also illustrates that CT excimers are responsible for the long-lived signals evidenced in Transient Absorption and Fluorescence experiments and that neutral excimers can exist within the DNA helical environment. It also adds to the discussion in the field on the nature of photodecay mechanisms occurring within the DNA helix.
Temple University--Theses

The present work was performed at Sherwin–Williams Sweden group AB with the objective of comparing short-wavelength light emitting diodes (UVB/UVC) with the conventional mercury arc lamp as a curing method of acrylate-based, UV-paint undergoing free-radical polymerization when exposed to UV-radiation. Due to environmental and health risks, mercury-doped radiation sources will be phased out in the near future, according to the United Nations Minamata convention, hence new alternatives are needed. Light-emitting diodes differ from the mercury arc lamp as they provide semi-discrete output intensity lines within the UV spectrum instead of a broad output distribution with several main intensity lines. The power output is also considerably lower compared to the conventional method which limits the irradiance and dose that are key parameters in activating and propagating free-radical polymerization of UV-paint. Seven different light-emitting diodes between 260–320 nm was examinedand compared to the conventional mercury arc lamp. Cured coatings were evaluated by measuring the relative extent of acrylate conversion with ATR-FTIR and micro-hardness indentation test. Both methods correlate to the relative cross-linking density and qualitatively describe the curing process for each radiant source at a specific irradiance and dose. Three different paint formulations with widely different properties were used in the experiments. All three paints were able to cure with one or several light emitting diodes at comparable doses and 10 to 20 times lower irradiance to the conventional mercury arc lamp, resulting in similar acrylate conversion and hardness.

La photopolymérisation est une technologie qui gagne de plus en plus d’importance de par ses nombreuses applications et ses énormes avantages par rapport à la polymérisation thermique tels que le respect de l’environnement, des coûts économiques maitrisés car la technologie est mise en œuvre à température ambiante et ne requiert qu’une faible consommation d'énergie. De plus, elle n'utilise pas ou très peu de solvants, d'où la réduction d’émission de produits polluants. Le processus de polymérisation photochimique présente également l’avantage d’être très rapide : en effet les réactions de photopolymérisation sont souvent rapides voire même quasi instantanées. De plus le procédé de polymérisation devient photolatent : la polymérisation impliquant les formulations actives seulement en présence de lumière, la réaction peut être déclenchée « quasi à la demande ». Ce processus chimique nécessite des composants nommés « photoamorceurs », lesquels absorbent la lumière et produisent le démarrage de la réaction de polymérisation. En particulier, le développement de systèmes photoamorceurs capables d’absorber de la lumière visible a un intérêt croissant pour différentes applications industrielles, notamment l’holographie. Dans la cadre de cette thèse, des diverses systèmes photoamorceurs contenant un colorant et un ou deux co-amorceurs, qui après réaction avec les états excités des colorants génèrent les radicaux actifs, ont été étudiés, depuis leurs propriétés photophysiques fondamentales et moléculaires, jusqu’aux applications et performances pour la polymérisation des résines acrylates. Cette thèse est articulée autour de six chapitres. Dans le premier chapitre une introduction et une étude bibliographique des différents systèmes photoamorceurs développés ces dernières années sont présentées et comparés. Les chapitres deux et trois sont consacrés à l’étude des propriétés photochimiques et photophysiques réalisés sur des photoamorceurs absorbant de la lumière ultraviolette et visible respectivement. Les techniques utilisés dans ces chapitres incluent, mais ne sont pas limités à, la spectroscopie d’absorption UV-Vis stationnaire, la fluorescence, la photolyse éclaire (LFP), la fluorescence résolue en temps par comptage de photon unique (TC-SPC), la spectroscopie ultrarapide nanoseconde et femtoseconde, la spectroscopie de résonance paramagnétique électronique (EPR), entre autres. Le chapitre deux porte sur l’étude de la photophysique d’un colorant de type cyanine : l’astrazone Orange R (AO R). La photophysique de ce colorant n’est pas connue et une étude exhaustive a été menée avec des spectroscopies ultra rapides (femtoseconde) ainsi que par modélisation moléculaire. Malgré sa photophysique compliquée ce colorant, fonctionne comme un photoamorceur très efficace dans la région bleue du spectre électromagnétique. Les chapitres suivants forment une deuxième partie de la thèse dédiée à l’étude des mécanismes d’amorçage de photopolymérisation, dont le chapitre quatre aborde le cas d’irradiation le plus « traditionnel », qui est l’irradiation en mode continu (ou CW). Est ensuite abordé l’étude de la polymérisation sous irradiation pulsée ultra-courte : dans cette partie la source d’irradiation continue classique est remplacée par un laser Nd :Yag qui produit des impulsions lumineuses d’une durée de quelques 9-10 nanosecondes. Cette polymérisation avec laser pulsé ou PLP est très originale et sera étudiée par spectroscopie infrarouge à transformée de Fourier résolue en temps (RT-FTIR). Dans le chapitre trois, donc, on retrouve les études réalisés avec différents types de systèmes photoamorceurs visibles. Ainsi, les propriétés des colorants capables d’absorber de la lumière visible à différentes longueurs d’onde ont été étudiées dans des systèmes photoamorceurs à deux et trois composants
Photopolymerization is a technology that is gaining more and more importance due to its numerous applications and its advantages compared to thermic polymerization. This chemical process requires compounds called photoinitiators, which absorb light and produce the initiation of the radical polymerization. The development of photoinitiating systems (PIS) which are able to absorb visible light have an increasing interest due to its industrial applications, such as holographic recording. During this thesis, many PIS were studied, from its photophysical properties to its application in acrylate polymerization. There are many different types of photoinitiators. The most classical ones are Type I PI, which are molecules that overcome homolytic cleavage from their excited state, generating initiating radicals immediately after photon absorption. Type II PI, in contrast, are composed by two molecules: one that absorbs the photon, and other that will react with the excited state of the first via electron transfer or hydrogen transfer, generating radicals that will be able to initiate polymerization. In last place, there are the most efficient Photocyclic Initiating Systems (PCIS) whose mechanism is more complicated and will be widely discussed within these pages. A state of the art of the PIS available up to date is made in the first chapter. Given the importance of the properties of the molecules involved in the photoinitiating process, the studies of the photophysical properties of a Photoinitiator, the Astrazone Orange (AO), are shown. It was found that this molecule suffers an isomerization process from its excited state, which then comes slowly back to the more stable conformer. This process being viscosity-dependent makes AO a suitable photoinitiator for polymerization with visible light in highly viscous media. The last three chapters of this thesis are devoted to the study of a novel technique called Pulsed Laser Polymerization (PLP). This technique consists in the irradiation of the samples with a short duration pulsed laser, which allows the separation of the initiation steps of the polymerization reaction from the steps of propagation and termination. A simple Type I PI was used as a model to study the properties of this technique of polymerization. The monomer conversion was registered by RT-FTIR and analyzed. To a better understanding of these results, a mathematical model was developed. Thanks to it, it was possible to collect valuable information about propagation and termination rate constants (kp and kt, respectively), the variation of viscosity with conversion and other aspects relatives to PLP mechanism. Furthermore, the efficiency of many visible light PIS was studied by PLP. Their performance was compared and studied and contrasted with the classical continuous irradiation mode (CW). The characteristics that a PIS must have in order to show efficient polymerization in PLP mode were found and discussed. Finally, the effect of formulation viscosity in PLP and CW was analyzed by diluting the sample with different amounts of DMSO. In PLP, it was seen that the highest conversion is found for the most concentrated samples, while the opposite effect is noticed in CW. This result is attributed to the different conditions given by the difference in irradiation methods

Photopolymerization has become the standard for many coating and printing applications that require rapid curing at room temperature due to its potential to reduce volatile organic compound (VOC) emissions while providing a means for efficient manufacturing processes. These advantages could be useful in a variety of emerging applications, such as anisotropic conductive films (ACF) if photopolymerization could extend into relatively narrow shadow regions which are not directly illuminated, and if visible wavelengths that are not absorbed by polyimide films could be used to trigger the reaction. The broad objectives of this research are i) to examine the factors that determine the attainable extent of shadow cure in free radical polymerizations, and ii) to develop initiator systems effective for polymerization using visible light and light emitting diode (LED) lamps. Project I: Shadow Cure in Free Radical Photopolymerizations In this project, the extent of shadow cure in visible-light-induced free radical photopolymerization is investigated. A number of effective methods such as adding additives, utilizing a reflective stage, and increasing the light intensity are introduced. In addition, the use of fluorescent dyes in multi-component photoinitiator systems proved to be very effective for shadow cure because the fluorescent light emitted from the dye could irradiate the shadow region. When considering practical resins, mixtures of oligomers and monomers, the viscosity is the major barrier that must be overcome in order to achieve high conversion in the shadow regions using visible-light-induced multi-component photoinitiator systems. Hence, instead of using multi-component systems, a commercial visible-light-induced single-component photoinitiator is investigated. As a result, a high conversion in shadow regions of the viscous oligomer containing resin is achieved. Project II: Experimental and Modeling Studies of Photoinitiator Systems for Effective Polymerizations with LEDs In this project, various LED photocuring systems are investigated and characterized. The light intensities of LEDs become weaker as their peak emission wavelengths decrease. Therefore, to design the practical process of LED curing, the effect of both the light intensity and the emission spectrum of the lamp must be considered. Photopolymerization for four representative UV photoinitiators with different LEDs are investigated experimentally and theoretically. The effective light source is dependent on the photoinitiators and several LEDs demonstrate high thin cure ability. The calculated results from a model display good qualitative correspondence with the experimental results. Various interesting suggestions are obtained using this model. For example, the commercialization of 355 nm LEDs might be able to superior photopolymerization compared to other currently available LED lamps.

Cationic photopolymerization of multifunctional epoxides is very useful for efficient cure at room temperature and has been widely used in coatings and adhesives. Despite excellent properties of the final cured polymers, cationic photopolymerizations of epoxides have seen limited application due to slow reactions (relative to acrylates) and brittleness associated with a highly crosslinked, rigid network. To address these issues, two reaction systems were studied in this thesis: photoinitiated cationic copolymerizations of a cycloaliphatic diepoxide with epoxidized elastomers and acrylate/epoxide hybrid photopolymerizations. Oligomer/monomer structures, viscosity, compositions, and photoinitiator system were hypothesized to play important roles in controlling photopolymerizations of the epoxide-based mixtures. A fundamental understanding of the interplay between these variables for the chosen systems will provide comprehensive guidelines for the future development of photopolymerization systems comparable to the epoxide-based mixtures in this research. For diepoxide/oligomer mixtures, the observed overall enhancement in polymerization rate and ultimate conversion of the cycloaliphatic diepoxide was attributed to the activated monomer mechanism associated with hydroxyl terminal groups in the epoxidized oligomers. This enhancement increased with increasing oligomer content. The mixture viscosity influenced the initial reactivity of the diepoxide for oligomer content above 50 wt.%. Real-time consumption of internal epoxides in the oligomers was successfully determined using Raman spectroscopy. Initial reactivity and ultimate conversion of the internal epoxides decreased with increasing the diepoxide content. This trend was more pronounced for the oligomer containing low internal epoxide content. These results indicate that the reactivity of the hydroxyl groups is higher toward cationic active centers of the diepoxide than those of the internal epoxides in the oligomers. These conclusions are consistent with physical property results. The enhanced fracture toughness and impact resistance were attributed to multimodal network chain-length distribution of copolymers containing the oligomer content between 70% and 80%. For acrylate/epoxide hybrid mixtures, diacrylate oligomers significantly suppressed reactivities of cycloaliphatic mono/diepoxides, which was attributed to high mixture viscosity and highly crosslinked acrylate network. In this case, the dual photoinitiator system did not favor the epoxide reaction. Depending on the monovinyl acrylate secondary functionalities, enhanced reactivity and ultimate conversion of the diepoxide were attributed to a combined effect of a reduced viscosity and the radical-promoted cationic polymerization associated with the dual photoinitiator. The retarded and inhibited diepoxide reactivities with ether and urethane secondary groups were attributed to solvation and nucleophilicity/basicity effects, respectively. The influence of the diepoxide on the acrylate reactivity was attributed to dilution and polarity effects. In this case, high concentration of the free-radical photoinitiator is required for the dual photoinitiator system. Physical properties of hybrid polymers also varied with acrylate structures and monomer composition. Dynamic modulation methods were proposed to enhance the diepoxide reactivity and final properties in the presence of urethane acrylates.

Ce travail de thèse aborde l’étude mécanistique de systèmes photoamorceurs complexes et la modélisation cinétique du processus de photopolymérisation. Dans un premier temps, le mécanisme photochimique d’un système combinant le [Ru(bpy)3]2+ et des agents RAFT pour l’amorçage et le contrôle d’un processus radicalaire a été étudié. Un transfert d’énergie a été clairement démontré, contredisant le mécanisme de transfert d’électron généralement proposé. Un système photoamorceur à 3 composants bicyclique dual ITX/IOD+/RSH a ensuite été considéré pour la synthèse de matériaux hybrides organiques-inorganiques. Sous excitation lumineuse, ce système produit simultanément des radicaux et des protons, permettant d’amorcer, respectivement, des processus de polymérisation radicalaire et sol-gel. Dans un second temps, l’interdépendance entre les cinétiques de photopolymérisation et l’évolution des propriétés du milieu réactionnel a été étudiée par le biais du développement d’un modèle cinétique permettant la simulation de l’intégralité du processus de photopolymérisation. Des systèmes photoamorceurs de complexité croissante ont été inclus afin d’étudier les spécificités de leurs cinétiques. Un système de type I a permis de mettre en évidence les modes de terminaison majoritaires et leur évolution au cours de la synthèse des polymères, tandis que le rôle non négligeable du transfert d’électron inverse a été mis en exergue pour des systèmes photoamorceurs de type II. La fonction d’agent de terminaison d’un photoproduit issu d’un colorant cationique, ainsi que certaines spécificités des systèmes photocycliques à 3 composants, ont été finalement étudiés grâce à la modélisation
This thesis deals with the mechanistic study of complex photoinitiating systems and the kinetic modeling of the photopolymerization process. In a first time, the photochemical mechanism of a system combining [Ru(bpy)3]2+ and RAFT agents for the initiation and control of a radical process has been studied. An energy transfer has been clearly demonstrated, contradicting the electron transfer mechanism generally proposed. A dual bicyclic three-component photoinitiating system ITX/IOD+/RSH has been considered for the synthesis of organic-inorganic hybrid materials. Under light exposure, this system produces simultaneously radicals and protons, enabling the initiation of a radical polymerization and a sol-gel process, respectively. In a second time, interdependence between photopolymerization kinetics and evolution of the medium’s properties has been studied, through developing a kinetic model for the simulation of the whole photopolymerization process. Photoinitiating systems of growing complexity have been included in order to study specificities of their kinetics. A type-I system has shown major termination modes and their evolution during the polymer synthesis, while the non-negligible role of back electron transfer has been highlighted for type-II photoinitiating systems. Role of terminating agent of a photoproduct based on a cationic dye, as well as some specificities of photocyclic three-component systems, have been finally studied with the model

Indiana University-Purdue University Indianapolis (IUPUI)
Objectives: A new technology has been introduced into the field of dental resin composites that professes to enhance light-curing efficiency. Rapid amplified photopolymerization (RAP) initiator technology has not yet been fully compared with resin composites with conventional initiators such as camphorquinone (CQ). The purpose of this study was to compare and contrast the effects of this novel technology (RAP) on properties of two light-cured resin composites. Flowable (EFQ) and microfilled (ESQ) experimental composites were fabricated and supplied from Tokuyama Dental with (w/RAP) and without RAP (w/o RAP). The flexural strength (MPa) and flexural modulus (MPa) were obtained using a three-point bending apparatus (Sintech Renew 1123, Instron Engineering Corp., Canton, MA). Polymerization stress curves were created using a tensometer (American Dental Association Health Foundation, NIST, Gaithersburg, MD) which were then used to calculate the maximum stress rate. Finally, the degree of conversion was measured using infrared spectroscopy (Jassco FT-IR spectrometer, Model: 4100, Jasco Corporation, Tokyo, Japan). When evaluating the flexural strength, the peak stress for EFQ w/RAP was significantly higher than EFQ w/o RAP (p = 0.0001). This was statistically not significant for the ESQ group, even though ESQ w/RAP did have a higher peak stress then ESQ w/o RAP (p = 0.28). The interaction between resin type and RAP was not significant when evaluating the flexural modulus (p = 0.21). Formulations with RAP had a significantly higher flexural modulus then w/o RAP (p = 0.0001). Experimental resins with RAP had significantly higher maximum stress rates than those w/o RAP when evaluating polymerization stress (p = 0.0001). Finally, groups w/ RAP appeared to have a higher degree of conversion than groups without (p = 0.0057). This study showed that the experimental composites with RAP had greater mechanical properties than those without. Unfortunately, the increase in polymerization stress causes concern clinically due to the chance of leakage at the restoration/tooth interface. One of the main potential disadvantages of this new RAP technology is an increase in the polymerization stress. Deciding if this amount of polymerization stress is clinically acceptable is yet to be accomplished.

碩士
國立臺灣科技大學
化學工程系
104
The effect of costabilizer concentration on the Ostwald ripening rate in styrene (ST) miniemulsion systems stabilized by various type of photoinitiator either commercial as darocur 1173 (PI_1173), darocur TPO (PI_TPO), modified photoinitiators as PI_C8, PI_C12, PI_C18 and PI_C20 or mixed HD and PI_1173 was investigated. The miniemulsions were prepared by dispersing ST in water with surfactant (SDS) to homogenize using ultrasonic homogenizer. The phenomenon of creaming is no apparent correlation between the creaming rates with differently of photoinitiator but trended to decrease with increasing volume fraction of HD in mixed costabilizer in ST miniemulsion systems. The Ostwald ripening rates of ST miniemulsions with PI_1173 as a costabilizer was determined at costabilizer volume fraction (φ_C) in the range 0.05-0.35 and 0.01-0.04 for PI_C8, PI_C12, PI_C18 and PI_TPO, which showed in the same feature to decrease with increasing content of costabilizer. The general validity of the semi empirical model 1/R_O=1/R_(O,m) (1+K_1 φ_c+K_2 〖φ_c〗^2) was proposed to adequately predict the Ostwald ripening rate data then based on LSW theory the water solubility of these photoinitiator could be estimated and showed to decreasing in order is: PI_1173 > PI_TPO > PI_C8 > PI_C12 > PI_C18 > PI_C20. Furthermore, the Ostwald ripening behavior approach with thermodynamic was investigated from the developed modified Kabalnov equation 1/R_O=1/R_(O,m)+φ_c/R_(O,c)+(∁/R_(O,c))φ_c^2 in ST miniemulsion systems. The reciprocal of Ostwald ripening rate as a function of φ_c for miniemulsion stabilized these series of photoinitiatos as a costabilizers upon aging at 25 °C indicated with high values of coefficient of determination (R2). As expected, R_O decreases with increasing φ_c and at a constant of φ_c, R_O increases with increasing number of carbon in photoinitiators as costabilizers. The negative value of ∆H_mix illustrates that formation of regular solution of ST miniemulsions stabilized by these series of photoinitiator is exothermic. The value of σ were estimated and shown to decreases with increasing the number of carbon in modified of photoinitiators as a costabilizer in this ST miniemulsion systems. On the other hand, the hydrophobicity of photoinitiator trend to increases with increasing molecular weight of photoinitiators as a costabilizers. Regarding to the Ostwald ripening rates of mixed costabilizers HD:PI_1173 showed in the same feature with creaming rate, the average monomer droplets diameter and water solubility, which trended to be decrease with increasing of HD content. On the other hand HD is dominant in retarding the Ostwald ripening rate in ST miniemulsions stabilized by mixed costabilizer of HD and PI_1173.

In the present era where MEMS (Micro Electro-Mechanical Systems) technology is in¬evitable from the perspective of applications in non-silicon based micro-devices (such as biosensors, microfluidics, microvalves etc.), it is imperative to develop different micro¬fabrication technologies which are simple in operation, have low operational cost and high versatility in terms of incorporating different materials. The microfabrication tech¬nologies (e.g: bulk micromachining, surface micromachining, X-ray LIGA (lithoqraphie galvanoformung abformung) etc.), which exist commercially are mostly limited to sili¬con based technologies. They are either constrained in fabricating complex geometry in micro dimension or have high operational cost. Microstereolithography (MSL) is one such rapid prototyping technique, which can satisfy the above requirements to a larger extent. MSL h8B evolved in the l8Bt decade from conventional stereolithographic (SLA) technique, which involves the free-form microfabrication of a UV sensitive liquid resin layer by layer photo-polymerization process, when it is exposed to UV irradiation accord¬ing to the predefined CAD (Computer Aided Design). However, this technique is not limited to polymer microfabrication and it h8B an immense potential to fabricate com¬plex 3D structures of ceramics in micro dimension. In this thesis, the primary focus is on developing an in house built scanning b8Bed MSL system indigenously and to explore the possibility of micro fabrication of different materials (from polymer to ceramics involving different routes. In addition, polymer micro cantilever h8B been fabricated using this technique and its application to surface stress me8Burement h8B been demonstrated. The thesis comprises of eight chapters. The following section describes the summary of the individual chapters. Chapter 1 describes the introduction and background literature of this technol¬ogy. A brief review on MSL technology developed by various research groups and their achievements h8B been listed. Since photopolymerizable resin is the primary material to fabricate micro dimensional structures, the rate of photopolymerization is an impor¬tant phenomena which requires an attention before choosing the photopolymerizable resin. Further, this chapter also describes the photoinitiation principles and the type of photo initiators (PI) which help to photopolymerize the resin in order to fabricate micro dimensional polymer structures. In addition, this chapter also gives a glimpse of applications of this technology in fabrication of micro cantilever b8Bed sensors. The later part of the chapter focused on the microfabrication of ceramic from colloidal and met¬alorganic routes in brief. In Chapter 2, the design of the in house built MSL system and its working princi¬ples including various optical issues have been addressed. Several research groups have attempted to optimize photopolymerization parameters to incre8Be the throughput of the scanning b8Bed MSL systems through modified beam scanning techniques. Efforts in reducing the curing line width in order to get low feature size have been implemented through high numerical aperture (NA) optical setups. However, the intensity contour symmetry and the depth of field of focus have led to grossly non-vertical and non-uniform curing profiles. The focus of the work h8B been to exploit the rich potential of photoreactor scanning system in achieving desired fabrication modalities (minimum curing width, uniform depth profile, and vertical curing profile) even with a reduced NA optical setup and a single movable stage. The present study tries to manipulate to its advantage the effect of optimized lower photoinitiator (PI) concentration ([c]) in reduc¬ing the minimum curing width to 10-15 jJm, even with the higher spot size (21.4 jJm) rv through a judiciously chosen gmonomer UPIi' system. In this chapter, two different cl8BS of multifunctional acrylates (1,6 Hexane diol diacrylate (HDDA) and Trimethylol propanetriacrylate (TMPTA)) and one monofunctional methacrylate (methyl mathacry¬late (MMA)) have been chosen to explore their fabricability in micro dimensions using this MSL technology, by varying the various operational parameters including the type and the concentration of the PI. Chapter 3 deals with the application of this technology in micro cantilever based sensors. Microcantilever based sensors have been explored for several decades for their application in bio-molecular or explosive detection, chemical sensing etc. Due to the adsorption of molecular species on the cantilever surface, differential surface stress gen¬erates between the top and bottom surface of the cantilever. Depending on the type of stress (tensile or compressive) generated, the cantilever bends accordingly. The, novel diffraction based deflection method has been proposed in order to measure the deflection profile accurately for low dimensional structures. To prove this method, a dual mi¬crocantilever structure with sufficiently low gap (100 f.lm) has been fabricated using the developed MSL set up, such that diffraction occurs during transillumination by spherical wavefronts. Among the two micro cantilevers one was fabricated bent with a specific di¬mension with respect to the other. The cantilever material was chosen as poly HDDA for its low elastic modulus in order to achieve high sensitivity. From the obtained diffraction pattern, the bent profile of the each cross section of one cantilever corresponding to the other has been measured. This proposition will enable to measure surface stress at each cross section of the cantilever depending on the adsorbed analyte molecule adsorption. In Chapter 4, an effort has been made to improve the thermal, thermo mechanical and mechanical properties of the cantilever material (poly HDDA). The sensitivity of a micro cantilever depends precisely on fabrication and material aspects. The former de¬pends on the aspect ratio of the structure and can be controlled by fabrication parameters whereas the latter is inherently limited by the choice of the material. The properties of the material which impact the applicability are elastic modulus, Poisson's ratio, thermal expansion and thermal stability. Hence, these properties are studied for poly HDDA. However, the properties are not completely satisfactory for only poly HDDA (PHDDA) since, PHDDA will fail for high surface stress measurement (>275 mN/m). Hence, it h8B been copolymerized with MMA with an intention to improve the above mentioned properties and to determine the best composition for the micro cantilever application. It is observed by Finite Element Analysis (FEM) that Phpm5050 (HDDA:MMA(50:50)) composition shows optimum sensitivity when reliability is concerned for me8Buring high surface stress (275 mN/m). Chapter 5 bridges Chapter 2 and Chapter 6. Chapter 2 highlights the polymer mi¬crofabrication where8B, Chapter 6 deals with the microfabrication of ceramics. In order to fabricate ceramic micro objects by MSL, ceramic particles need to be blended with a photopolymerizable monomer followed by l8Ber induced photopolymerization . Under l8Ber irradiation, the monomer gets cured and traps the ceramic particles. Thus near net shape of green ceramic structures are 0 btained. After achieving the near net shape, it is important to remove the polymer, which acts 8B the binder for the green ceramic body. This debinding should be diffusion controlled so 8B to achieve defect free micro ceramics. Here two multifunctional monomers (HDDA and TMPTA) have been chosen 8B a b8Be monomer for fabricating ceramics. Therefore it is essential to understand the debinding mechanism of these polymers. However, (HDDA) h8B high shrinkage upon polymeriza¬tion with low rate of polymerization kinetics and low viscosity where8B the properties of (TMPTA) are exactly opposite. Hence, in order to optimize these properties, copoly¬merization of HDDA and TMPTA h8B been carried out for different compositions and their thermal properties have been investigated to understand the degradation mech¬anism. This chapter deals with the mechanism of thermal degradation by model free kinetic methods with an intention to determine the optimum composition of HDDA and TMPTA copolymer, to used 8B the b8Be monomer material for ceramic microfabrication. Besides, the debinding strategy is also discussed b8Bed on the degradation profile of the optimum composition. TH20S0(TMPTA: HDDA(20:S0)) is found to be the ideal com¬position to fabricate ceramic micro-component by MSL since its degradation is diffusion controlled in N 2 atmosphere. Chapter 6 describes the methodology of microfabrication of ceramics by the de-veloped MSL technique. A colloidal approach has been adopted to fabricate ceramics in micro-dimensions. Two different ceramics have been chosen, which have potential applications in structural (alumina) and functional (Lead Iron Niobate (PFN))aspects. Before fabricating ceramic micro-objects, ceramic particles need to be blended in the monomer suspension in the presence of dispersant at an optimum solids loading. Opti¬mization of solids loading is important in view of low dimensional shrinkage after sin¬tering. However, lower loading leads to higher shrinkage whereas higher loading would increase the viscosity of the suspension and make the suspension inconvenient to deal with. Hence, rheological studies have been carried out to optimize the solids loading and dispersant concentration. 40 vol% alumina and 35 vol% PFN are found to be the highest achievable solids loading for the chosen monomer (TH2080) composition. This chapter also describes the limitation involved in ceramic microfabrication depending on their scattering factors during laser irradiation. The chapter demonstrates the fabrica¬tion methodology of several complex ceramic(alumina and PFN) micro-objects by the in house built MSL instrument. Chapter 7 investigates the possibility of microfabrication of ceramics from metalor¬ganic precursor. In this route, titanium metal-organic (Ti-n butoxide) precursor has been chosen which is stabilized by the addition of chelating monomer (2-( methacryloyloxy) ethyl acetoacetate). Following this, the crosslinker and photoinitiators have been added to form Ti photoresist which is coated on top of the bare silicon substrate by spin coating to achieve specific thickness. The coated silicon wafer by the above photoresist has been patterned by selectively exposure in the MSL setup. The cured patterns are washed and heat treated at high temperature in order to 0 btain the net shape of the Ti02 pattern of polycrystalline rutile phase. It is observed this route is advantageous in terms of reduc¬ing curing dimension (curing width 14 f.lm) than the colloidal route (curing width more than 80 f.lm ) of fabrication of ceramics where the scattering factor greatly influences the dimensions of the feature size. The key findings and future aspects are summarized in the Chapter 8. The work reported in this thesis has been carried out by the candidate as part of the Ph.D. programme. He hopes that this would constitute a worthwhile contribution towards developing an MSL technique and its aspects in micro fabrication of polymer and ceramic structures of any complex shape and its possible applications in microdevices.