A cinética de fotopolimerização do monômero metacrilato de metila (MMA) foi investigada usando o fotoiniciador tioxantona (TX) e o co-iniciador trietilamina (TEA), a fim de elucidar o mecanismo de fotopolimerização. A dilatometria foi usada como técnica para a determinação das cinéticas de polimerização. Determinaram-se os rendimentos quânticos de polimerização. Os estados excitados foram estudados por fluorescência estática para determinar as constantes de supressão de fluorescência pela amina e pelo monômero. Medidas de fotólise por pulso de laser permitiram obter o espectro de absorção triplete-triplete da tioxantona, bem como a constante de supressão do estado triplete. Os resultados mostraram que a supressão ocorre por um processo colisional no estado singlete e que os radicais eficientes na fotoiniciação são originados da amina TEA. A massa molecular média dos polímeros obtidos foi determinada por medidas de cromatografia de permeação em gel (GPC). Em uma segunda etapa, foi investigada a polimerização fotoiniciada por fotoiniciadores usados em resinas dentárias, canforquinona (CQ), 1,2-fenilpropanodiona (PPD), Lucirin e Irgacure. A velocidade de polimerização foi acompanhada por dilatometria usando excitação acima de 348 nm. Obteve-se os rendimentos quânticos de polimerização e os polímeros foram caracterizados por GPC. A maior constante de velocidade de polimerização obtida foi para o Irgacure e o maior rendimento quântico de polimerização obtido foi para o Lucirin. As diferenças na eficiência da polimerização são atribuídas à formação de radicais e à capacidade de gerar radicais a partir da absorção da luz incidente. Por fim, investigou-se os espectros de absorção triplete-triplete (TTA) da TX em diferentes solventes usando a técnica de fotólise por pulso de laser. Observou-se a formação de três bandas, duas referentes ao triplete da TX (uma em 300 nm e outra em 600 nm) e em 400 nm, observou-se a formação do radical cetila da TX. A abstração de hidrogênio do solvente pela TX pode ocorrer em 340 nm em solventes com constante de abstração de hidrogênio (kabstr) alto. Esse fator pode ser observado nos solventes 2-propanol e etanol. O substituinte na TX mostrou, através do parâmetro de Hammett do substituinte que com o aumento da eletronegatividade há um deslocamento do máximo de absorção do transiente para comprimentos de onda menores. / The photopolymerization of the monomer methyl methacrylate (MMA) using thioxanthone (TX) as photoinitiator and triethylamine (TEA) as co-initiator, was investigated in order to explain the photopolymerization mechanism. Dilatometry was used to determine the kinetics of polymerization. The polymerization quantum yields were determined. The excited states were studied using static fluorescence in order to determine the fluorescence rate quenching by the amine and the monomer. The triplet-triplet absorption (TTA) spectrum of thioxanthone and the rate constant of quenching of the triplet state were obtained using flash photolysis technique. The results showed that the singlet state quenching occurs by a colisional process and the efficient radicals in the photoinitiation process are originated from the amine TEA. The molar mass of the obtained polymers was determined by gel permeation chromatography (GPC). The polymerization photoinitiated by the photoinitiators used in dental resins, Camphorquinone (CQ), 1,2- Phenylpropanodione (PPD), Lucirine and Irgacure was investigated in a second step. The rate of polymerization was studied by dilatometry with excitation above 348 nm. The polymerization quantum yields were obtained and the polymers were characterized by GPC. The larger rate constant of polymerization was found for Irgacure and the larger polymerization quantum yield was obtained for Lucirine. The differences in polymerization efficiencies can be tracked to the formation of radicals and the capability to produce the radicals after incident light absorption. Finally, the TTA of TX was studied in different solvents using the flash photolysis technique. The spectrum presented three bands, two due to the transient of TX (at 300 and 600 nm), and one at 400 nm assigned to the cetyl radical. The abstraction of a solvent hydrogen by TX is observed at 340 nm in solvents with high hydrogen abstraction constant (kabstr). This fact can be observed in 2-propanol and ethanol. An increase in the solvent polarity stabilizes the electronic pp* states and unstabilizes the np* states. The substitution in the TX molecule produced a shift to lower wavelength in the maximum absorption of transient with the increase of the electronegativity, as indicated by the dependence of the Hammett parameter.

Este estudo in vitro teve como objetivo avaliar comparativamente a microdureza superficial e o desgaste de uma resina composta, FiltekTM Z-250 (3M/ESPE), sob influência de diferentes fontes de luz (LED Ultrablue IS - DMC, LED Ultralume 5 - Ultradent e halógena VIP - BISCO), com variação das densidades de potência (300, 600 e acima de 800mW/cm2) e energia (6, >8, 12, >16, 24, >32 J/cm2). Espécimes retangulares (15 x 5 x 4 mm) foram polimerizados, conforme os fatores de variação, totalizando 15 grupos (n=6). Em seguida receberam acabamento e polimento com lixas de abrasividade decrescente (300, 600, 1200 e 2000), sendo armazenados em água deionizada a 37º C por sete dias. As mensurações da microdureza Knoop foram realizadas com auxílio do Microdurômetro Shimadzu HMV-2, com carga estática de 100g por 5s nas superfícies de topo e lateral (50µm da superfície). Posteriormente os espécimes foram levados à máquina de ensaios para simulação de desgaste por escovação, utilizando-se escovas dentais macias (Oral B 30 Indicator) e creme dental (Colgate) diluído em água deionizada na proporção de 1:2 em peso. Ao final de 100.000 ciclos, a dureza da superfície lateral foi novamente mensurada e o desgaste da área escovada foi determinado por meio de perfilometria (Hommel Tester T 1000 basic - Hommelwerke). Os dados de microdureza e desgaste superficial obtidos foram submetidos à análise de variância (ANOVA) e teste de Tukey (p<0,05). Os resultados evidenciaram que a microdureza superficial da resina composta avaliada foi significantemente menor quando da fotoativação com VIP-300 mW/cm2, sendo que os maiores valores foram observados com o aparelho Ultralume 5. O desgaste superficial foi significativamente influenciado quando da utilização de baixa densidade de potência (300 mW/cm2) e energia de 6 J/cm2, tanto com o VIP como Ultrablue IS, que demonstraram maior efetividade quando da utilização de densidade de energia acima de 12J/cm2. De forma geral, observou-se correlação negativa quando da interação dos testes de dureza e desgaste superficial, ou seja, quando os valores de dureza aumentaram os de desgaste diminuíram inferindo, entretanto, que isoladamente o valor de dureza não constitui em parâmetro para qualificar o desempenho da resina composta quanto à resistência ao desgaste. / This in vitro study evaluated comparatively, the superficial microhardness and wear of a resin composite, FiltekTM Z-250 (3M/ESPE) under the influence of different light sources (LED Ultrablue IS/DMC, LED Ultralume 5/Ultradent and halogen VIP/BISCO); with power (300, 600 and above 800mW/cm2) and energy density (6, >8, 12, >16, 24, >32J/cm2) variations. Rectangular specimens (15 x 5 x 4 mm) were polymerized, as the variation factors, totalizing 15 groups (n=6). After, they were ground flat with water-cooled carborundum discs in decreasing abrasive order (300, 600, 1200 and 2000) and stored for seven days, before the tests, in deionized water at 37º C. The Knoop microhardness measurements were carried out using a microhardness tester (Shimadzu HMV-2), with a 100g static load applied for 5s on specimens\' top and lateral surfaces (50µm under surface). In sequence the specimens were taken to a machine for brushing simulation, using soft nylon bristles (Oral B 30 Indicator) and dental paste (Colgate) diluted in deionized water in the ratio of 1:2 in weight. After 100,000 cycles, the hardness of the lateral surface was again measured and the wear profile of the brushed area was determined by a profilometer (Hommel Tester T 100 basic/Hommelwerke). The microhardness and superficial wear data were submitted to the analysis of variance (ANOVA) and Tukey test (p<0.05). The results showed that the superficial microhardness of the evaluated resin composite was significantly lower when photoactivated with VIP-300 mW/cm2, being the biggest values observed for the Ultralume 5 device. The superficial wear was significantly influenced by the low power density (300 mWcm2) and energy density of 6 J/cm2. This was for both, VIP and Ultrablue IS, which demonstrated greater effectiveness when a density of energy above 12J/cm2 was used. In general, a negative correlation was observed between the two tests (wear and microhardness). In other words, there was an increase of hardness with the decrease in wear values, which demonstrates that only microhardness values do not constitute a parameter to qualify resin composite wear resistance behavior.

Ultraviolet-Assisted Direct Ink Write (UV-DIW) is a material extrusion additive manufacturing (AM) technology in which a viscous ink, often at room temperature, is selectively extruded through a translating nozzle to selectively deposit material. The extruded ink is solidified via UV irradiation (photocuring) and three-dimensional parts are created by repeating the process in a layer-by-layer fashion. UV-DIW is an attractive AM technology due to its ability to (1) extrude highly viscous inks (i.e. >10,000 Pa·s if ink exhibits shearthinning behavior) (2) the promise of leveraging the broad photopolymer material library and chemistries established for other AM technologies capable of processing photopolymers and (3) the promise of processing a wide range of inks, which enables the fabrication of metal, ceramic, polymer, bio-based, and multi-material parts. Currently, the technology faces a few shortcomings including (1) limited material selection for UV-DIW due to requirement for inks to be photocurable and limited mechanical properties of photocurable materials (2) lack of feature resolution and topological complexity of printed parts and (3) lack of material screening models providing robust definition of the material requirements (e.g., viscosity, cure time, strength) for successful UV-DIW printing. To address these shortcomings, the goal of this work is to gain a fundamental understanding of the rheological and reactive properties required for successful Ultraviolet-Assisted Direct Ink Write (UV-DIW). The first approach to answering the fundamental research question is establishing the existing rheology experiments used to characterize DIW inks and the relationships between rheology and printability. An in-depth literature review of the techniques and relationships was compiled to better understand ink requirements for successful printing (Chapter 2). This broad survey is not limited to only UV-DIW, but includes all variations of DIW. The first part of the review provides a summary of the rheological experiments that have been used to characterize a wide variety of DIW inks. The second part of this review focuses on the connections between rheology and printability. This survey helps identify the required rheological properties for successful printing that is then used throughout the rest of this work. Additionally, this review identifies shortcomings in current work and proposes areas for future work. From this exhaustive literature review, a systematic roadmap was developed that investigators can follow to quickly characterize the printability of new inks, independent of that ink's specific attributes (Chapter 3). The roadmap simplifies the trends identified in literature into a brief and intuitive guide to the rheology experiments relevant to DIW printing and the relationship between those experiment and printing results. The roadmap was demonstrated by evaluating the printability of two inks: (1) a silicone ink with both yield-stress and reactive curing behavior and (2) urethane acrylate inks with photocuring behavior. Experimental printing studies were used to support the conclusions on printability made in the roadmap. The second main approach focuses on the development of three novel UV-DIW inks to address the current limited material selection for UV-DIW and help better understand the rheological and reactive properties required for successful printing. For the three novel UVDIW inks, the iterative process of ink synthesis, analysis of ink rheology, and printability evaluation was detailed. Data from the development process contributed to gaining a fundamental understanding of how rheology and reactivity affect printability. The three inks each had novel rheological properties that impacted their printing behavior: (1) photocuring (2) yield-stress behavior + photocuring and (3) photocuring + thermal curing. Additionally, each ink had unique properties that expands material selection for UV-DIW including (1) an all-aromatic polyimide possessing a storage modulus above 1 GP a up to 400 °C (Chapter 4), (2) a styrene butadiene rubber (SBR) nanocomposite with elongation at break exceeding 300 % (Chapter 5), and (3) a dual-cure ink enabling the printing of inks containing over 60 vol% highly opaque solids (Chapter 6). The third approach details the development of two UV-DIW process models to better understand the process physics of the UV-DIW process and give insight to the properties of a successful ink. The first process model uses data from photorheology experiments to model how a photocurable ink spreads upon deposition from the nozzle, accounting for transient UV curing behavior (Chapter 7). This model allows for the rapid evaluation of an ink's behavior during the solidification sub-function of UV-DIW solely based on its rheology, without the time-consuming process of trial-and-error printing or complex computer simulations. The second process model combines modeling with a novel experimental method that uses a UV photorheometer to accurately characterize the relationship between cure depth and UV exposure for a wide range of photopolymers (Chapter 8). This model helps understand an inks photocuring behavior and ensure a sufficient cure depth is produced to adhere to the previous layer in UV-DIW printing. Lastly, two UV-DIW process modifications are introduced to address research gaps of printing high resolution features and limited material selection. A hybrid DIW + Vat Photopolymerization system is presented to improve the feature size and topographical complexities of parts, while still retaining UV-DIW's ability to print with very high viscosity photoresins (Chapter 9). A high temperature Heated-DIW system is presented to heat inks to over 300 °C and ultimately enable printing of poly(phenylene sulfide) aerogels (Chapter 10). In enabling the DIW of poly(phenylene sulfide) aerogels, the production of ultra-lightweight thermally insulating components for applications in harsh environments is enabled. With the use of additive manufacturing, hierarchical porosity on the macroscale is enabled in addition to the meso-scale porosity inherent to the aerogels. / Doctor of Philosophy / Direct Ink Write (DIW) is a type of three-dimensional (3D) printing that is used to automatically produce a range of 3D geometries. Specifically, the DIW process selectively extrudes a viscous ink, similar in consistency to peanut butter or toothpaste, through a small moving nozzle to create the features of each layer. This process is like using a frosting bag to decorate a cake with icing. Three-dimensional parts are created by repeating this process and depositing layer on top of layer. While seemingly a straightforward process, it remains relatively unclear what properties an ink needs to produce quality parts. To produce quality parts, the ink first needs to be extruded from the nozzle to form homogenous beads with a constant width and free from breaks. Second, the extruded ink needs to retain the shape that it was deposited in. If the ink spreads excessively, the as-deposited features will be lost and a part resembling a blob will be produced. Lastly, the ink deposited on the first layers needs to have enough strength to support the weight of the part. Otherwise, the part will collapse akin to the Leaning Tower of Pisa. To achieve all three steps and produce a quality part, a successful ink needs to be able to flow through the nozzle and then solidify upon deposition. This work focuses on a specific process called Ultraviolet-Assisted Direct Ink Write (UV-DIW) where materials that solidify when exposed to UV light, called photopolymers, are printed. Currently, the properties of the inks, especially how they cure when exposed to UV light, that produce successful printing remains unclear. This work focuses on understanding how the properties of the photopolymer inks affect the printing behavior of the ink. The ultimate goal of this work is to develop guidelines for the properties of successful inks which will help others develop the next generation of materials printed via UV-DIW. Specifically, experiments are used study how inks behave when they flow through the nozzle (rheology) and then solidify when exposed to UV light (reactivity). This behavior is then connected to the inks printing behavior (printability). In working to better understand the connection between rheology, reactivity, and printability multiple approaches were used. These approaches include the development of new materials for printing via UV-DIW, development of a modified UV-DIW printing process that reduces the size of the printed features, and development of models to predict how inks will behave during printing. The new plastic materials that were developed and successfully printed via UV-DIW have outstanding properties including remaining strong up to 400 °C, being extremely flexible, and a plastic containing a large fraction of a solid filler. With each new material, the formulation was varied to change the inks rheological and reactive properties until successful UV-DIW was enabled. Each new formulation introduced material capabilities not previously available to DIW 3D printing. Then, A modified UV-DIW process was developed that takes advantage of the reactivity of the photopolymers to enable the printing of high-resolution features and shapes not previously possible via DIW 3D printing. In this novel process, a projector is used to project patterned UV light at the material and selectively cure small portions of the deposited material, instead of curing all the deposited material. After printing, the uncured ink is washed away resulting in features much smaller than what can be produced when directly extruding them. Finally, the developed process models use the relatively simple rheology and reactivity experiments, to predict how an ink behaves during the UV-DIW process. Using the results of these experiments and the developed models, the inks behavior during the printing process is predicted. These models allow for the properties of new inks to be quickly measured and their printing behavior predicted. New ink formulations can be quickly screened, and optimal process parameters predicted. Overall, this work produces guidelines for the rheological and reactive properties required of a photopolymer ink to produce successful UV-DIW printing. Future researchers can use these guidelines to develop the next generation of materials printed via UV-DIW more easily.

Foi estudado o processo de fotopolimerização iniciado através de misturas dos fotoiniciadores, acilfosfínicos (MAPO e BAPO), com canforquinona (CQ). Também foi investigada a existência de um possível efeito sinérgico durante a fotoiniciação. A eficiência de polimerização das duas misturas, MAPO/CQ e BAPO/CQ, foi determinada por actinometria. A fotodilatometria foi a técnica utilizada para o acompanhamento das cinéticas de polimerização. A adição do co-iniciador EDB não apresentou efeito nas velocidades de polimerização iniciadas pelos fotoiniciadores acilfosfínicos. Do ponto de vista do rendimento quântico de polimerização, um efeito antagonístico foi observado devido a transferência de energia a partir dos fotoiniciadores mais eficientes (MAPO ou BAPO) para o menos eficiente, canforquinona (CQ). / The photopolymerization processes involving two different photoinitiators: acylphosphine oxides (MAPO and BAPO) and camphorquinone (CQ) were studied in order to determine possible synergistic effects. The polymerization efficiency of the two mixtures, MAPO/CQ and BAPO/CQ, was studied using actinometry. The polymerization kinetics was followed by photodilatometry. The presence of the coinitiator EDB had no effect in the polymerization rate initiated by the acylphosphine oxides. From the point of view of photopolymerization quantum yields, an antagonistic effect is observed due to the energy transfer from the more efficient initiator (MAPO or BAPO) to the less efficient (CQ).

Microfluidic devices have long been considered an ideal tool for rapid and inexpensive chemical analysis and reactions in areas ranging from point-of-care health to national security applications. However, fabricating microfluidic devices is time consuming, difficult and above all expensive. In commercial applications many thousand units need to be sold before the development costs are recovered. The problem is compounded since most microfluidic devices do not have generalized architectures which means that each end use requires a specialized design. The microfluidics marketplace can therefore be seen as being composed of 1000’s of niche markets. To address development costs, there is clearly a need for a versatile technology that can be used for many different applications and that enables rapid testing and optimization of new designs. This work describes such a technology: Contact Liquid Photolithographic Polymerization (CLiPP). The thesis consists of two parts: polymerization kinetics and the fabrication of polymeric microfluidic devices via CLiPP. The photopolymerization kinetics is evaluated for a number of monomer types, and the results are used to assess their suitability in the CLiPP process. Vinyl ether/maleate photoinitiated copolymerization is examined in detail. It is shown that the polymerization kinetics is dramatically influenced by the availability of easily abstractable hydrogens The presence of α-hydrogens adjacent to the vinyl ether functional group reduces the polymerization rate and the dependence of the polymerization rate as a function of initiation rate. Also, photoinitiated acrylate and methacrylate polymerization kinetics are presented. The kinetics results in these three monomer types are used to explain the different patterning properties of the monomer functionalities used in the CLiPP process, in which acrylates show enhanced patterning properties compared to methacrylates. The polymerization kinetics is studied with traditional tools and methods: photo Differential Scanning Calorimetry (photo-DSC), photo Fourier Transform Real Time Infrared Spectroscopy (photo-RTIR), and photo Real Time Electron Paramagnetic Spectroscopy (ESR). The microfluidic fabrication is performed via both in-house fabricated and commercially available CLiPP-specific hardware. The patterning qualities of the structures are evaluated via Scanning Electron Microscopy (SEM) and Optical Microscopy. The finished devices are used in their intended environment and evaluated in suitable manners to assess their utility. In this thesis, the development and design of specialized CLiPP fabrication machines, fabrication techniques and resulting microfluidic device features are presented anddiscussed. It is shown that the CLiPP scheme enables features such as 3 dimensional (3D) capabilities for minimized device footprints, a very large number of polymeric materials for optimized device components as well as facile integration of prefabricated components. Also, covalent layer adhesion and permanent surface modifications via living radical processes are demonstrated. These capabilities are exemplified in a number of examples that range from a 3D fluidic channel maze with separated fluidic streams and a device with independently moveable parts to a device constructed from multiple polymeric materials and devices with permanently modified surfaces, Also, batch processing capabilities are shown through fabrication of 400 identical undercut microstructures. Rapid and inexpensive design evaluations, multiple materials capabilities and the ability to seamlessly incorporate prefabricated microstructures of the CLiPP process strongly encourages continued method development. The future work that remains to be addressed is divided into two parts. First, to enable novel research devices, new polymer materials with enhanced mechanical and surface properties must be developed. Also, integration of prefabricated microstructures such as sensors and actuators has to be incorporated in a reproducible and rational manner. Secondly, to enable device mass fabrication, new automated equipment is to be developed in order to utilize the full batch processing potential of CLiPP. / QC 20101019

<p>Microfluidic devices have long been considered an ideal tool for rapid and inexpensive chemical analysis and reactions in areas ranging from point-of-care health to national security applications. However, fabricating microfluidic devices is time consuming, difficult and above all expensive. In commercial applications many thousand units need to be sold before the development costs are recovered. The problem is compounded since most microfluidic devices do not have generalized architectures which means that each end use requires a specialized design. The microfluidics marketplace can therefore be seen as being composed of 1000’s of niche markets.</p><p>To address development costs, there is clearly a need for a versatile technology that can be used for many different applications and that enables rapid testing and optimization of new designs. This work describes such a technology: Contact Liquid Photolithographic Polymerization (CLiPP).</p><p>The thesis consists of two parts: polymerization kinetics and the fabrication of polymeric microfluidic devices via CLiPP.</p><p>The photopolymerization kinetics is evaluated for a number of monomer types, and the results are used to assess their suitability in the CLiPP process. Vinyl ether/maleate photoinitiated copolymerization is examined in detail. It is shown that the polymerization kinetics is dramatically influenced by the availability of easily abstractable hydrogens The presence of α-hydrogens adjacent to the vinyl ether functional group reduces the polymerization rate and the dependence of the polymerization rate as a function of initiation rate. Also, photoinitiated acrylate and methacrylate polymerization kinetics are presented. The kinetics results in these three monomer types are used to explain the different patterning properties of the monomer functionalities used in the CLiPP process, in which acrylates show enhanced patterning properties compared to methacrylates. The polymerization kinetics is studied with traditional tools and methods: photo Differential Scanning Calorimetry (photo-DSC), photo Fourier Transform Real Time Infrared Spectroscopy (photo-RTIR), and photo Real Time Electron Paramagnetic Spectroscopy (ESR).</p><p>The microfluidic fabrication is performed via both in-house fabricated and commercially available CLiPP-specific hardware. The patterning qualities of the structures are evaluated via Scanning Electron Microscopy (SEM) and Optical Microscopy. The finished devices are used in their intended environment and evaluated in suitable manners to assess their utility.</p><p>In this thesis, the development and design of specialized CLiPP fabrication machines, fabrication techniques and resulting microfluidic device features are presented anddiscussed. It is shown that the CLiPP scheme enables features such as 3 dimensional (3D) capabilities for minimized device footprints, a very large number of polymeric materials for optimized device components as well as facile integration of prefabricated components. Also, covalent layer adhesion and permanent surface modifications via living radical processes are demonstrated. These capabilities are exemplified in a number of examples that range from a 3D fluidic channel maze with separated fluidic streams and a device with independently moveable parts to a device constructed from multiple polymeric materials and devices with permanently modified surfaces, Also, batch processing capabilities are shown through fabrication of 400 identical undercut microstructures.</p><p>Rapid and inexpensive design evaluations, multiple materials capabilities and the ability to seamlessly incorporate prefabricated microstructures of the CLiPP process strongly encourages continued method development. The future work that remains to be addressed is divided into two parts. First, to enable novel research devices, new polymer materials with enhanced mechanical and surface properties must be developed. Also, integration of prefabricated microstructures such as sensors and actuators has to be incorporated in a reproducible and rational manner. Secondly, to enable device mass fabrication, new automated equipment is to be developed in order to utilize the full batch processing potential of CLiPP.</p>

Mask Projection micro Stereolithography (MPuSLA) is an additive manufacturing process used to build physical components out of a photopolymer resin. Existing MPuSLA technology cut the CAD model of part into slices by horizontal planes and the slices are stored as bitmaps. A layer corresponding to the shape of each bitmap gets cured. This layer is coated with a fresh layer of resin by lowering the Z-stage inside a vat holding the resin and the next layer is cured on top of it. In our Thick-film MPuSLA(TfMPuSLA) system, incident radiation, patterned by a dynamic mask, passes through a fixed transparent substrate to cure photopolymer resin. The existing MPuSLA fabrication models can work only for controlling the lateral dimension, without any control over the thickness of the cured part. The proposed process plan controls both the lateral dimensions and the thickness of profile of the cured part. In this thesis, a novel process planning for TfMPuSLA method is developed, to fabricate films on fixed flat substrate. The process of curing a part using this system is analytically modeled as the column cure model. It is different from the conventional process - layer cure model. Column means that a CAD model of part is discretized into vertical columns instead of being sliced into horizontal layers, and all columns get cured simultaneously till the desired heights. The process planning system is modularized into geometrical, chemical, optical, mathematical and physical modules and validated by curing test parts on our system. The thesis formulates a feasible process planning method, providing a strong basis for continued investigation of MPuSLA technology in microfabrication, such as micro lens fabrication.

Foi estudado o processo de fotopolimerização iniciado através de misturas dos fotoiniciadores, acilfosfínicos (MAPO e BAPO), com canforquinona (CQ). Também foi investigada a existência de um possível efeito sinérgico durante a fotoiniciação. A eficiência de polimerização das duas misturas, MAPO/CQ e BAPO/CQ, foi determinada por actinometria. A fotodilatometria foi a técnica utilizada para o acompanhamento das cinéticas de polimerização. A adição do co-iniciador EDB não apresentou efeito nas velocidades de polimerização iniciadas pelos fotoiniciadores acilfosfínicos. Do ponto de vista do rendimento quântico de polimerização, um efeito antagonístico foi observado devido a transferência de energia a partir dos fotoiniciadores mais eficientes (MAPO ou BAPO) para o menos eficiente, canforquinona (CQ). / The photopolymerization processes involving two different photoinitiators: acylphosphine oxides (MAPO and BAPO) and camphorquinone (CQ) were studied in order to determine possible synergistic effects. The polymerization efficiency of the two mixtures, MAPO/CQ and BAPO/CQ, was studied using actinometry. The polymerization kinetics was followed by photodilatometry. The presence of the coinitiator EDB had no effect in the polymerization rate initiated by the acylphosphine oxides. From the point of view of photopolymerization quantum yields, an antagonistic effect is observed due to the energy transfer from the more efficient initiator (MAPO or BAPO) to the less efficient (CQ).

Le développement d'un nouveau système photo-initiateur 1 photoinitiateur capable d'absorber fortement la lumière dans la région de la lumière visible et de travailler sous irradiation LED a fait des progrès gratifiants. Ici, notamment l'azurant fluorescent en tant que classe de dérivés fluorophores, a été confirmé comme un Pl efficace pour la photopolymérisation radicalaire (FRP), l'un des principaux avantages est qu'ils peuvent travailler efficacement sous l'air, même à faible intensité lumineuse. Lorsqu'ils sont incorporés dans des systèmes photoinitiateurs multicomposants (en présence de sel d'iodonium (et éventuellement N-vinylcarbazole ou amine)), les dérivés du naphtalène-benzoxazole, des triazinylstilbènes sulfonés, du stilbène-biphényl sulfoné et du coumarinme inhibent d'excellentes capacités photoamorcantes pour la FRP des acrylates sous air. De plus, ils sont particulièrement efficaces pour la formation d'un réseau de polymères interpénétrés à travers une photopolymérisation cationique 1 radicale concomitante d'un mélange époxydes 1 acrylates.De plus, la substitution d'une certaine teneur en monomère acrylate avec de l'eau augmente positivement la conversion finale des fonctions acrylate polymérisables, spécialement formulée avec les systèmes initiateurs à base d'azurants hydrophiles. En outre, une formulation aqueuse d'acrylate contenant des systèmes d'amorçage à base d'azurants a permis la synthèse d'hydrogels assistée par LED. Cette méthode de synthèse consomme moins d'énergie et les hydrogels produits ont généralement une teneur élevée en eau. Et, l'étude des photopolymérisations qui se déroulent dans les mélanges acrylate 1 eau élargit les perspectives pour le polymère vert et la chimie organique. / The development of a new photoinitiator/photoinitiatng system being capable of strongly absorbing light in the visible-light region and working under LED irradiation has made gratifying advance. Herein, notably the fluorescent brightener as one class of fluorophore derivetives, has been confirmed as an efficient Pl for free radical photopolymerization (FRP), one of the major advantages is thalthey could efficiently work under air even exposure to a low LED light intensity. When incorporated into multicomponent photoinitiating systems (in the presence of iodonium salt (and optionally N-vinyl carbazole or amine)), the derivatives of naphthalene­ benzoxazole, sulfonated triazinylstilbenes, sulfonated stilbene-biphenyl and coumarinmexhibit quite excellent photoinitiating abilities for FRP of acrylates under air. Moreover, they are particularly efficient for the formation of interpenetrated polymer network through a concomitant cationic/radical photopolymerization of epoxides/acrylates blend.Additionally, substitution of a certain content of acrylate monomer with water is found to positively increase the final conversion of polymerizable acrylate functions, especially formulated with the hydrophilic brighteners-based initiating systems. Besides, an aqueous acrylate formulation containing brighteners-based initiating systems enabled the LED-assisted synthesis of hydrogels. This synthetic method is less energy-intensive and the hydrogels produced are typically of high water content. And, the investigation of photopolymerizations thal proceed in acrvlate/water blends broadens the perspectives for qreen polvmer and organic chemistry.

De nos jours, la polymérisation par voie photochimique connaît un grand essor dans différents domaines académiques et industriels comme en témoigne son nombre croissant d’applications. Les photopolymères sont omniprésents dans plusieurs domaines tels que les revêtements, le domaine dentaire, les implants chirurgicaux, les encres, l’impression 3D… Cependant, les avancées réalisées par rapport à cette voie de synthèse de matériaux polymères restent limitées et nécessitent encore plus de recherches et de développements. Cette nouvelle génération de polymères synthétisée par voie photochimique présente l’avantage d’être beaucoup plus écologique que leurs équivalents thermiques. En effet, leur préparation implique moins d’énergie que les autres techniques de synthèse de matériaux polymères. L’élaboration de polymères par voie photochimique est également plus avantageuse en termes de temps nécessaire pour la polymérisation. Moins de composés organiques volatils sont émis car la formulation ne contient que très peu voire pas du tout de solvant. Seules les zones irradiées sont polymérisées ce qui permet d’avoir un bon contrôle spatial de la polymérisation.De nombreuses recherches ont déjà été menées dans ce domaine en utilisant principalement les rayons ultraviolets. Cependant, cette gamme de longueurs d’onde peut être nocive pour la santé. De surcroît, les sources de rayonnement UV sont très énergivores et potentiellement toxiques. Par conséquent, cette technique risque de ne plus aller de pair avec les exigences environnementales actuelles. En parallèle, peu de systèmes photoamorceurs ont montré leur efficacité dans le domaine des longueurs d’onde du visible car ils nécessitent souvent des énergies beaucoup plus élevées.C’est ainsi que l’on s’est intéressé dans le cadre de cette thèse au développement de nouveaux systèmes photoamorceurs plus respectueux de l’environnement et plus efficaces pour amorcer les réactions de polymérisations radicalaire ou cationique sous lumière visible (conditions douces).La lumière visible présente plusieurs avantages par rapport à la lumière ultra-violette. En effet, une faible nocivité a été constatée ainsi qu’une faible consommation énergétique. Plusieurs dispositifs d’irradiation dans le visible ont été utilisés : des lampes halogènes, des diodes électroluminescentes (LED) … Plus intéressant encore, l’utilisation des LED émettant dans la gamme du visible présente un grand intérêt. Elles sont caractérisées par une faible consommation énergétique, un faible coût, une longue durée de vie, une forme compacte …L’utilisation des LED nécessite clairement d’améliorer la performance des systèmes photoamorceurs. Ainsi, l’étude de l’efficacité de nouveaux systèmes photoamorceurs pour la polymérisation radicalaire et/ou cationique sous irradiation de lumière visible à l’aide des LED est au cœur de ce présent sujet de thèse. Notre projet de développement des nouveaux photoamorceurs visibles se base essentiellement sur les approches suivantes : • Une bonne absorption de la lumière visible par les photoamorceurs (avec des coefficients d’extinction molaires élevés)• Un bon recouvrement entre le spectre d’absorption du nouveau photoamorceur et celui d’émission de la source d’irradiation utilisée• Utilisation de sources d’irradiation à faibles intensités (LED)• Développer des photoamorceurs hydrosolubles et efficaces pour amorcer les polymérisations dans l’eauPour les travaux menés au cours de cette thèse, on s’est intéressé à différentes familles de photoamorceurs afin d’établir la relation entre la structure, la réactivité et l’efficacité d’amorçage de réactions de polymérisation radicalaire, cationique ou pour la formation de réseaux interpénétrés de polymères.Ces travaux se divisent en deux grandes parties: une première est à caractère académique tandis qu’une seconde partie porte sur une étude appliquée dans le domaine dentaire. [...] / Nowadays, the photopolymerization processes are omnipresent in various academic and industrial fields such as the dental domain, surgical implants, 3D printing … However, the advances realized for this new way of polymer synthesis remain limited and require more developments.The polymers synthesized by photochemical process have the advantage of being more ecological than the thermal equivalents. Indeed, their preparation involves less energy than the other techniques of polymer synthesis. The elaboration of polymers by photochemical way is also more advantageous in terms of time required for the polymerization and fewer volatile organic compounds are emitted in the atmosphere. Moreover, only the irradiated zones are polymerized which allows a better spatial control of the polymerization. Several searches were already led in this domain by using mainly ultraviolet rays. However, this range of wavelengths could be harmful for the health. Besides, the UV sources are energy consuming. Consequently, this technique is no longer in agreement with the current environmental requirements. In parallel, few photoinitiating systems showed good efficiency in the visible wavelength range.In this context, we have been interested in the development of new photoinitiating systems more environment-friendly and more efficient to initiate radical, cationic and anionic polymerization under visible light irradiation.The visible light presents several advantages compared to the ultraviolet light. Indeed, it is less harmful and lower energy consuming. Particularly, light emitting diodes (LED) are interesting because they are compact and therefore easy to use, long lasting, no mercury is involved for the manufacturing … Thus, the performances improvement of the photoinitiating systems efficient upon visible LED irradiation is clearly required In this regard, the study of new high performances photoinitiating systems for radical, cationic and anionic polymerization under visible LED irradiation is at the core of the current PhD project.Our development project was based essentially on the following approaches: • Good absorption properties of the developed photoinitiators • The best matching between the absorption spectrum of the photoinitiator and the emission spectrum of the irradiation device• Use of LEDs • Development of water soluble photoinitiators for photopolymerization processes in aqueous medium.We were interested in various chromophore families in order to establish the relationship between the structure, the reactivity and the efficiency of the developed photoinitiating systems.The results obtained could be divided into two big parts: the first one has an academic character whereas the second part concerns an applied study in the dental domain.For the first part, various families of visible chromophores were introduced as high performances photoinitiators for radical photopolymerization in the visible range: i) camphorquinone derivatives ii) acylsilanes iii) naphthalimides iv) diketopyrrolopyrroles. Cationic photopolymerization has been studied also through the development of a new iodonium salt and across the use of new photoredox catalysts upon visible LED irradiation. And finally, new photobase generators have been developed for anionic polymerization upon near UV and visible LED irradiation.In the second part, a new class of photoinitiators based on silylglyoxylate structure have been introduce as efficient systems for the radical photopolymerization initiation process upon blue light and applied for the dental field. [...]