This thesis examines melting in superheated silicon films in contact with SiO₂ under pulsed laser irradiation. An excimer-laser pulse was employed to induce heating of the film by irradiating the film through the transparent fused-quartz substrate such that most of the beam energy was deposited near the bottom Si-SiO₂ interface. Melting dynamics were probed via in situ transient reflectance measurements. The temperature profile was estimated computationally by incorporating temperature- and phase-dependent physical parameters and the time-dependent intensity profile of the incident excimer-laser beam obtained from the experiments. The results indicate that a significant degree of superheating occurred in the subsurface region of the film. Surface-initiated melting was observed in spite of the internal heating scheme, which resulted in the film being substantially hotter at and near the bottom Si-SiO₂ interface. By considering that the surface melts at the equilibrium melting point, the solid-phase-only heat-flow analysis estimates that the bottom Si-SiO₂ interface can be superheated by at least 220K during excimer-laser irradiation. It was found that at higher laser fluences (i.e., at higher temperatures), melting can be triggered internally. At heating rates of 10¹⁰ K/s, melting was observed to initiate at or near the (100)-oriented Si-SiO₂ interface at temperatures estimated to be over 300K above the equilibrium melting point. Based on theoretical considerations, it was deduced that melting in the superheated solid initiated via a nucleation and growth process. Nucleation rates were estimated from the experimental data using Johnson-Mehl-Avrami-Kolmogorov (JMAK) analysis. Interpretation of the results using classical nucleation theory suggests that nucleation of the liquid phase occurred via the heterogeneous mechanism along the Si-SiO₂ interface.

OBJETIVO: Comparar os resultados de duas técnicas cirúrgicas guiadas pela análise de frente de onda, a ceratectomia fotorrefrativa (PRK) e a ceratomileusis in situ a laser (LASIK), para correção da miopia baixa a moderada, associada ou não ao astigmatismo. LOCAL: Setor de Cirurgia Refrativa da Clínica Oftalmológica do Hospital das Clínicas da Faculdade de Medicina da Universidade de São Paulo, São Paulo, Brasil. MÉTODOS: Estudo prospectivo randomizado envolvendo 70 olhos (35 pacientes) submetidos ao LASIK personalizado em um olho e PRK personalizado no olho contralateral para correção de miopia até 5 dioptrias (D) e astigmatismo até 1,5D. Avaliou-se acuidade visual não-corrigida (AVNC), melhor acuidade visual corrigida (MAVC), resultados refratométricos, aberrometria, sensibilidade ao contraste fotópico e mesópico, acuidade visual de baixo contraste (AVBC), qualidade da imagem retiniana (Função de Transferência Modular e Strehl ratio) e espalhamento intraocular de luz (EIL) no período pré-operatório e no 1o, 3o, 6o e 12o mês pós-operatório. RESULTADOS: O equivalente esférico (EE) médio pré-operatório foi -2,57 ± 0,95D no grupo LASIK e, no grupo PRK, -2,52 ± 0,90D (p = 0,722). No 12o mês pósoperatório (PO), EE foi -0,06 ± 0,33D e -0,12 ± 0,41D, respectivamente (p = 0,438). No grupo LASIK, 60,0% dos olhos apresentaram AVNC 20/16 e 96,7% 20/20, e no grupo PRK, 66,6% e 96,7%, respectivamente (p = 0,667). No período pré-operatório, o total das aberrações de alta ordem (HOAs) foi 0,37 ± 0,09 m no grupo LASIK e 0,36 ± 0,11m no grupo PRK (p = 0,752). No 12o mês PO, o total das HOAs foi 0,46 ± 0,21m no grupo LASIK e 0,42 ± 0,14m no grupo PRK (p = 0,438). Tanto o teste de sensibilidade ao contraste fotópico como o mesópico apresentaram resultados semelhantes entre as técnicas, exceto pela freqüência 1,5 ciclos por grau (cpg) do teste mesópico no 12o mês PO, a favor do grupo PRK. Os índices de qualidade da imagem retiniana mostraram comportamento similar entre as técnicas ao longo do seguimento. Não houve aumento significativo do espalhamento intraocular da luz em ambos os grupos, quatro olhos cursaram com aumento transitório. CONCLUSÃO: Dentro das condições deste estudo, ambas as técnicas apresentaram excelentes resultados refratométricos e função visual semelhante. Apesar do tratamento personalizado guiado pela análise de frentes de onda, houve indução das HOAs, de forma similar, tanto no LASIK como no PRK. / PURPOSE: To compare clinical results of two wavefront-guided treatments, photorefractive keratectomy (PRK) and laser in situ keratomileusis (LASIK), for low to moderate myopia correction, with or without astigmatism. SETTING: Refractive Surgery Service, General Hospital, University Of São Paulo, São Paulo, Brazil. METHODS: Prospective randomized study of 70 eyes (35 patients) submitted to custom LASIK and custom PRK (contralateral eye) for myopia up to 5D and astigmatism up to 1,5D. Uncorrected visual acuity (AVNC), best-corrected visual acuity (MAVC), refractive results, wavefront analysis, photopic and mesopic contrast sensitivity, low contrast visual acuity (AVBC), retinal image quality (Modulation Transfer Function and Strehl ratio) and intraocular straylight (EIL) were performed preoperatively and at one, three, six and twelve months postoperatively. RESULTS: The mean preoperative spherical equivalent (EE) was -2,57 ± 0,95D in the LASIK group and -2,52 ± 0,90D in the PRK group (p = 0,722). At twelve months postoperatively (PO), the mean EE was -0,06 ± 0,33D and -0,12 ± 0,41D, respectively (p = 0,438). In the LASIK group, 60,0% had AVNC 20/16 and 96,7% 20/20, and in the PRK group, 66,6% e 96,7%, respectively (p = 0,667). The mean pre-treatment total high-order aberrations (HOAs) was 0,37 ± 0,09 m in the LASIK group and 0,36 ± 0,11m in the PRK group (p = 0,752). At twelve months PO, the mean total HOAs was 0,46 ± 0,21m in the LASIK group and 0,42 ± 0,14 m in the PRK group (p = 0,438). No significant difference in photopic and mesopic contrast sensitivity between groups was noted, apart from the 1,5 cpg frequency of the mesopic test, favoring PRK, at the 12th month PO. Similar results were found for retinal image quality metrics during the follow-up. No significant increase of the intraocular straylight was found for both techniques, four eyes presented transitory elevations. CONCLUSION: In the conditions of this study, both techniques had excellent refractive results and similar visual function. In spite of the wavefront-guided treatments, HOAs were induced similarly after LASIK and PRK

abstract: White organic light emitting diodes (WOLEDs) are currently being developed as the next generation of solid state lighting sources. Although, there has been considerable improvements in device efficiency from the early days up until now, there are still major drawbacks for the implementation of WOLEDs to commercial markets. These drawbacks include short lifetimes associated with highly efficient and easier to fabricate device structures. Platinum (II) complexes are been explored as emitters for single emissive layer WOLEDs, due to their higher efficiencies and stability in device configurations. These properties have been attributed to their square planar nature. Tetradentate platinum (II) complexes in particular have been shown to be more rigid and thus more stable than their other multidentate counterparts. This thesis aims to explore the different pathways via molecular design of tetradentate platinum II complexes and in particular the percipient engineering of a highly efficient and stable device structure. Previous works have been able to obtain either highly efficient devices or stable devices in different device configurations. In this work, we demonstrate a device structure employing Pt2O2 as the emitter using mCBP as a host with EQE of above 20% and lifetime values (LT80) exceeding 6000hours at practical luminance of 100cd/m2. These results open up the pathway towards the commercialization of white organic light emitting diodes as a solid state lighting source. / Dissertation/Thesis / Masters Thesis Materials Science and Engineering 2016

OBJETIVO: Comparar os resultados de duas técnicas cirúrgicas guiadas pela análise de frente de onda, a ceratectomia fotorrefrativa (PRK) e a ceratomileusis in situ a laser (LASIK), para correção da miopia baixa a moderada, associada ou não ao astigmatismo. LOCAL: Setor de Cirurgia Refrativa da Clínica Oftalmológica do Hospital das Clínicas da Faculdade de Medicina da Universidade de São Paulo, São Paulo, Brasil. MÉTODOS: Estudo prospectivo randomizado envolvendo 70 olhos (35 pacientes) submetidos ao LASIK personalizado em um olho e PRK personalizado no olho contralateral para correção de miopia até 5 dioptrias (D) e astigmatismo até 1,5D. Avaliou-se acuidade visual não-corrigida (AVNC), melhor acuidade visual corrigida (MAVC), resultados refratométricos, aberrometria, sensibilidade ao contraste fotópico e mesópico, acuidade visual de baixo contraste (AVBC), qualidade da imagem retiniana (Função de Transferência Modular e Strehl ratio) e espalhamento intraocular de luz (EIL) no período pré-operatório e no 1o, 3o, 6o e 12o mês pós-operatório. RESULTADOS: O equivalente esférico (EE) médio pré-operatório foi -2,57 ± 0,95D no grupo LASIK e, no grupo PRK, -2,52 ± 0,90D (p = 0,722). No 12o mês pósoperatório (PO), EE foi -0,06 ± 0,33D e -0,12 ± 0,41D, respectivamente (p = 0,438). No grupo LASIK, 60,0% dos olhos apresentaram AVNC 20/16 e 96,7% 20/20, e no grupo PRK, 66,6% e 96,7%, respectivamente (p = 0,667). No período pré-operatório, o total das aberrações de alta ordem (HOAs) foi 0,37 ± 0,09 m no grupo LASIK e 0,36 ± 0,11m no grupo PRK (p = 0,752). No 12o mês PO, o total das HOAs foi 0,46 ± 0,21m no grupo LASIK e 0,42 ± 0,14m no grupo PRK (p = 0,438). Tanto o teste de sensibilidade ao contraste fotópico como o mesópico apresentaram resultados semelhantes entre as técnicas, exceto pela freqüência 1,5 ciclos por grau (cpg) do teste mesópico no 12o mês PO, a favor do grupo PRK. Os índices de qualidade da imagem retiniana mostraram comportamento similar entre as técnicas ao longo do seguimento. Não houve aumento significativo do espalhamento intraocular da luz em ambos os grupos, quatro olhos cursaram com aumento transitório. CONCLUSÃO: Dentro das condições deste estudo, ambas as técnicas apresentaram excelentes resultados refratométricos e função visual semelhante. Apesar do tratamento personalizado guiado pela análise de frentes de onda, houve indução das HOAs, de forma similar, tanto no LASIK como no PRK. / PURPOSE: To compare clinical results of two wavefront-guided treatments, photorefractive keratectomy (PRK) and laser in situ keratomileusis (LASIK), for low to moderate myopia correction, with or without astigmatism. SETTING: Refractive Surgery Service, General Hospital, University Of São Paulo, São Paulo, Brazil. METHODS: Prospective randomized study of 70 eyes (35 patients) submitted to custom LASIK and custom PRK (contralateral eye) for myopia up to 5D and astigmatism up to 1,5D. Uncorrected visual acuity (AVNC), best-corrected visual acuity (MAVC), refractive results, wavefront analysis, photopic and mesopic contrast sensitivity, low contrast visual acuity (AVBC), retinal image quality (Modulation Transfer Function and Strehl ratio) and intraocular straylight (EIL) were performed preoperatively and at one, three, six and twelve months postoperatively. RESULTS: The mean preoperative spherical equivalent (EE) was -2,57 ± 0,95D in the LASIK group and -2,52 ± 0,90D in the PRK group (p = 0,722). At twelve months postoperatively (PO), the mean EE was -0,06 ± 0,33D and -0,12 ± 0,41D, respectively (p = 0,438). In the LASIK group, 60,0% had AVNC 20/16 and 96,7% 20/20, and in the PRK group, 66,6% e 96,7%, respectively (p = 0,667). The mean pre-treatment total high-order aberrations (HOAs) was 0,37 ± 0,09 m in the LASIK group and 0,36 ± 0,11m in the PRK group (p = 0,752). At twelve months PO, the mean total HOAs was 0,46 ± 0,21m in the LASIK group and 0,42 ± 0,14 m in the PRK group (p = 0,438). No significant difference in photopic and mesopic contrast sensitivity between groups was noted, apart from the 1,5 cpg frequency of the mesopic test, favoring PRK, at the 12th month PO. Similar results were found for retinal image quality metrics during the follow-up. No significant increase of the intraocular straylight was found for both techniques, four eyes presented transitory elevations. CONCLUSION: In the conditions of this study, both techniques had excellent refractive results and similar visual function. In spite of the wavefront-guided treatments, HOAs were induced similarly after LASIK and PRK

Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(工学) / 甲第17595号 / 工博第3754号 / 新制||工||1572(附属図書館) / 30361 / 京都大学大学院工学研究科高分子化学専攻 / (主査)教授 伊藤 紳三郎, 教授 赤木 和夫, 教授 金谷 利治 / 学位規則第4条第1項該当

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The recent developments in Low Temperature Co-fired Ceramic (LTCC) as a substrate material enable it to be used in the micro and millimetre wave range providing low dissipation factors at high frequencies, good dielectric properties and a high degree of integration for further miniaturised devices. The most common metallisation method used in LTCC technology is screen printing with high cost noble metals such as silver and gold that are compatible with the high sintering temperatures (850°C). However, these techniques require high capital cost and maintenance cost. As the commercial world requires convenient and low cost process technologies for mass production, alternative metallisation methods should be considered. As a result, electroless copper plating of fired LTCC was mainly investigated in this research. The main goals of this project were to carry out electroless plating of fired LTCC with sufficient adhesion and to extend the process to metallise closed LTCC channel structures to manufacture Substrate Integrated Waveguide (SIW) components. The objectives were focused on electroless copper deposition on fired LTCC with improved adhesion. Electroless deposits on the Sn/Pd activated LTCC surface showed poor adhesion without any surface pre-treatments. Hence, chemical etching of fired LTCC was carried out using concentrated NaOH solution. NaOH pre-treatment of LTCC led to the formation of flake like structures on the LTCC surface. A number of surface and chemical analysis techniques and weight measurements were used to investigate the mechanism of the modification of the LTCC surface. The results showed that the flake like structures were dispersed in the LTCC material and a material model for the LTCC structure was proposed. SEM EDX elemental mapping showed that the flake like structure consisted of aluminium, calcium, boron and oxygen. Further experiments showed that both the concentration of NaOH and the immersion time affect the surface morphology and the roughness of fired LTCC. The measured Ra values were 0.6 μm for untreated LTCC and 1.1 μm for the LTCC sample treated with 4M NaOH for 270 minutes. Adhesion tests including peel test and scratch test were carried out to examine the adhesion strength of the deposited copper and both tests indicated that the NaOH pre-treatment led to an improvement, with the best results achieved for samples treated with 4M NaOH. A second aspect of the research focused on the selective metallisation of fired LTCC. Excimer laser machining was used to pattern a resist film laminated on the LTCC surface. This process also roughened the substrate and created channels that were characterised with respect to the laser operating parameters. After patterning the resist layer, samples were activated using Sn/Pd catalyst solution followed by the electroless copper deposition. Electroless copper was selectively deposited only on the patterned LTCC surface. Laser parameters clearly affected the copper plating rate. Even with a similar number of shots per area, the tracks machined with higher repetition rate showed relatively more machining depth as well as good plating conditions with low resistance values. The process was further implemented to realize a complete working circuit on fired LTCC. Passive components including a capacitor and an inductor were also fabricated on LTCC using the mask projection technique of the excimer laser system. This was successful for many designs, but when the separation between conductor lines dropped below 18 μm, electroless copper started to deposit on the areas between them. Finally, a method to deposit copper films on the internal walls of closed channel structures was developed. The method was first demonstrated by flowing electroless copper solutions through silane treated glass capillaries. A thin layer (approx. 60 nm) of electroless copper was deposited only on the internal walls of the glass capillaries. The flow rate of the electroless copper solution had to be maintained at a low level as the copper deposits tended to wash away with higher flow rates. The structures were tested for transmission losses and showed low (<10dB) transmission losses in the terahertz region of the electromagnetic spectrum. The process was further applied to deposit electroless copper on the internal walls of the LTCC closed channel structures to manufacture a LTCC Substrate Integrated Waveguide (SIW).

O objetivo do presente trabalho é a otimização experimental, modelagem matemática e simulação do processo de pré-polimerização fotoiniciada do metacrilato de metila (MMA), visando a produção de um pré-polímero com distribuição estreita de massas moleculares (MWD) e conversão de monômero definida. Os experimentos foram realizados em dois sistemas experimentais em batelada, compostos por reatores fotoquímicos anulares e tanques de recirculação. No primeiro sistema experimental empregou-se uma lâmpada de mercúrio de média pressão, Heraeus TQ 150W. No segundo uma fonte de radiação de excímeros de xenônio e cloro (XeCl) alimentada por um gerador de pulsos e operada em uma larga faixa de freqüências de pulsos (840Hz – 46,4 kHz) foi empregada. Avaliaram-se as evoluções experimentais da concentração de benzoína (iniciador fotoquímico), da concentração do monômero e da concentração e distribuição de massas moleculares do pré-polímero, em função do tempo de irradiação, para diferentes condições de freqüência de pulsos de excitação, de concentração inicial de iniciador e de vazão de circulação. Para tanto, empregaram-se técnicas de análise como espectrofotometria, actinometria química (ferrioxalato), medidas de cromatografia por exclusão de tamanho e em fase reversa. As otimizações foram realizadas segundo dois planejamentos experimentais baseados na matriz Doehlert. As variáveis do processo escolhidas afetam significativamente as características do produto final, devido as diferentes condições de taxa de produção de radicais primários que se mostrou como etapa chave no controle da MWD e conversão do monômero. A modelagem matemática baseou-se nos balanços de massa, quantidade de movimento e transporte de fótons. Os mecanismos de geração de di-radicais monoméricos e dos radicais primários a partir das reações fotoquímicas foram incluídos em um modelo baseado na cinética clássica de polimerização por radicais livres. Os balanços foram desenvolvidos de acordo com o método dos momentos da distribuição de tamanhos de cadeia. O modelo matemático proposto foi validado confrontando-se os dados experimentais com os resultados simulados por um programa de fluido dinâmica computacional (PHOENICS). / The aim of this work is the experimental optimization, the mathematical modeling and the simulation of the photochemically initiated pre-polymerization process of methyl methacrylate (MMA). According to the industrial interests a pre-polymer of narrow molecular weight distribution (MWD) and defined weight concentration was pointed as an optimum since it improves the production process and the characteristics of Plexiglas. The experiments were carried out employing two experimental set-ups, which consist of an annular photochemical reactor connected to reservoir. In the first experimental set-up a medium pressure mercury lamp, Heraeus TQ 150 W was employed. In the second a xenon and chlorine (XeCl) source of radiation was employed. The electricity was supplied by a pulse generator, which operates within a wide frequency range (840Hz – 46,4kHz). The experimental time-evolution of the initiator (benzoin) and the MMA concentration as well as the molecular weight distribution of the pre-polymer were evaluated for different pulse frequencies, initial initiator concentrations and recirculation flow rates conditions. Therefore, analytical techniques were employed as spectrophotometry, chemical actinometry, size exclusion chromatography and reverse phase chromatography. The experimental optimizations were carried out according to two optimal experimental designs based on the classical Doehlert matrix. The chosen variables affect significantly the characteristics of the final product. Mainly due to the different conditions of initial radical production rates, which have shown to be the key on controlling the MWD and the MMA conversion. The mathematical modeling was based on mass, momentum and photons balance equations. The kinetic mechanism of bi-radical and initial radical production from MMA and benzoin respectively, were included in the classical kinetic model of free radical polymerization. The reaction rate equations were developed according to method of the chain size distribution moment. The proposed mathematical model was validated comparing the simulation results obtained with a computational fluid dynamics program (PHOENICS) and the experimental results.

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Added 1 bitstream(s) on 2015-08-11T03:25:36Z : No. of bitstreams: 4 Publico-026a.pdf: 72550 bytes, checksum: afe0787528f227bc8c799cf1cd67fcc7 (MD5) Publico-026b.pdf: 2073659 bytes, checksum: b85cc4a971ac414e9e8aa01daa4ad8ed (MD5) Publico-026c.pdf: 2083167 bytes, checksum: 806646b87026c136bf8b329233fe315b (MD5) Publico-026d.pdf: 895113 bytes, checksum: 37de279e78fead2b9aa3c17fd44ab0f0 (MD5) / Objetivos: Comparar os resultados de acuidade visual, refração estática, aberrometria e sensibilidade ao contraste em olhos com miopia moderada submetidos à ceratectomia fotorrefrativa (PRK) com mitomicina C (MMC) ou à ceratomileuse assistida por excimer laser in situ (LASIK) em cirurgias guiadas por frente de onda durante acompanhamento de um ano. Avaliar o aspecto biomicroscópico nos dois grupos durante seguimento. Avaliar subjetivamente percepção de dor, queixas visuais e satisfação com resultado cirúrgico nos dois grupos durante acompanhamento. Analisar índices de microscopia especular nos dois grupos antes e seis meses após cirurgia. Comparar propriedades biomecânicas da córnea nos dois grupos um ano após o procedimento cirúrgico. Métodos: Quarenta e quatro pacientes (88 olhos) com miopia moderada e cálculo de consumo corneano maior que 50 μm na plataforma LADARWave 4000 (Alcon) em ambos os olhos foram selecionados para receber aleatoriamente LASIK em um olho e PRK com aplicação de MMC 0,002% durante um minuto no olho contralateral em cirurgias guiadas por frente de onda. Topografia corneana (EyeSys 2000, EyeSys e Orbscan II, Orbtek/Bausch & Lomb), acuidade visual sem correção (AVSC, tabela Early Treatment Diabetic Retinopaty Study), refração estática, acuidade visual com correção (AVCC), aberrometria (LADARWave 4000), paquimetria ultrassônica corneana central (Sonogage) e exame oftalmológico completo foram realizados no pré-operatório e no seguimento de um, três, seis e doze meses pós-operatório. Sensibilidade ao contraste fotópica e mesópica (Optec 6500, F.A.C.T.; Stereo Optical) com correção foram realizadas nos dois olhos antes da cirurgia e três, seis e doze meses após. Questionário subjetivo de dor foi aplicado no pós-operatório recente, e questionário de sintomas visuais e satisfação com o procedimento em cada olho foi aplicado nas visitas de acompanhamento com um, três, seis e doze meses de pós-operatório. Biomicroscopia de segmento anterior foi realizada no período pós-operatório recente e nas visitas de acompanhamento sempre como último exame do dia (examinador mascarado para procedimento cirúrgico). Microscopia especular (Topcon SP 2000p) foi realizada antes e seis meses após cirurgia. Avaliação biomecânica da córnea (ORA, Reichert) foi realizada um ano após o procedimento cirúrgico. Os testes ANOVA para medidas repetidas e t de student foram utilizados para análise estatística. Resultados: A média de idade dos pacientes do estudo foi de 31,7 anos (variou entre 21 e 54 anos). Não houve diferença significativa entre os grupos antes da cirurgia quanto a AVSC, AVCC, aberrometria, sensibilidade ao contraste ou microscopia especular. O equivalente esférico (EE) médio programado nos olhos que receberam LASIK foi de - 3,99±1,20 dioptrias (D) e de - 3,85±1,12 D nos olhos que receberam PRK com MMC (p>0,05). A profundidade de ablação média foi de 73,09±14,55 μm e 70,70±14,07 μm, no grupo LASIK e no grupo PRK com MMC, respectivamente (p>0,05). Quarenta e dois pacientes (95,5%) completaram um ano de acompanhamento. Os olhos que receberam PRK com MMC apresentaram média de AVSC significativamente superior aos olhos que receberam LASIK com três, seis e doze meses de pós-operatório. A média de AVCC também foi estatisticamente superior no grupo PRK com MMC na visita de um ano de pós-operatório (p<0,05). Não houve diferença estatística entre os grupos quanto ao EE ao longo do acompanhamento. Todos os olhos que receberam PRK com MMC completaram a reepitelização corneana em até cinco dias após o procedimento, e nenhum olho apresentou haze maior que grau 1 (escala de Fantes). Os olhos que receberam LASIK apresentaram valores de aberrações de baixa e alta ordem estatisticamente superiores aos olhos que receberam PRK com MMC durante todo o acompanhamento (p<0.05). Os olhos que receberam PRK com MMC obtiveram desempenho superior no teste de sensibilidade ao contraste em condições fotópicas e mesópicas quando comparados ao grupo LASIK durante seguimento (p<0,05). Até o quinto dia de pós-operatório, o grupo PRK com MMC apresentou índices de dor superiores ao grupo LASIK. O grupo PRK com MMC foi melhor avaliado no questionário subjetivo de queixas visuais e satisfação cirúrgica. Não houve diferença estatística entre os grupos quanto à microscopia especular (p>0,05). Na avaliação biomecânica da córnea, o grupo LASIK apresentou valores de fator de resistência corneana (CRF) e histerese (CH) significativamente superiores ao grupo PRK com MMC (p<0,05). Conclusões: Os olhos que receberam PRK com MMC apresentaram melhores valores de AVSC e AVCC, melhor correção de aberrações de baixa ordem e menores valores de aberrações de alta ordem em relação aos olhos que receberam LASIK. O grupo PRK com MMC também apresentou valores superiores de sensibilidade ao contraste e foi melhor avaliado em questionário subjetivo de satisfação cirúrgica. Não houve presença de haze clinicamente significativo no grupo PRK com MMC. O grupo PRK com MMC apresentou maiores índices de dor no período pósoperatório recente. Não houve diferença entre os índices de microscopia especular nos dois grupos. O grupo LASIK apresentou índices superiores de CRF e CH. / Purpose: To compare visual acuity results, cycloplegic refraction, aberrometry and contrast sensitivity in eyes that underwent photorefractive keratectomy (PRK) with mitomycin C (MMC) or laser in situ keratomileusis (LASIK) for wavefront-guided myopic corrections during one year follow-up. To evaluate slit-lamp microscopy in both groups during follow-up. To evaluate subjective pain, visual complains and satisfaction with visual results in the two groups during follow-up. To analyse specular microscopy values before and six months after surgeries in both groups. To compare biomechanical properties of the cornea in the two groups one year after surgeries. Methods: Forty-four patients (88 eyes) with moderate myopia and an estimated ablation depth greater than 50 μm using the LADARWave 4000 (Alcon Laboratories) platform in both eyes were randomized to receive LASIK in one eye and PRK with application of MMC 0.002% for one minute in the fellow eye in wavefront-guided surgeries. Corneal topography (EyeSys 2000, EyeSys and Orbscan II, Orbtek/Bausch & Lomb), uncorrected visual acuity (UCVA, Early Treatment Diabetic Retinopaty Study table), cycloplegic refraction, best spectacle-corrected visual acuity (BSCVA), aberrometry (LADARWave 4000), central ultrasound corneal pachymetry (Sonogage Inc) and a comprehensive ophthalmologic examination were performed before surgeries and at one, three, six and twelve months postoperative visits. Photopic and mesopic contrast sensitivity (Optec 6500, F.A.C.T.; Stereo Optical Co) with BSCVA was performed in both eyes before surgeries and at three, six and 12 months follow-up. A subjective pain questionnaire was applied at early postoperative visits and another visual complain and satisfaction questionnaire with surgery in each eye was applied one, three, six and twelve months after surgical procedures. Slit-lamp anterior segment microscopy was performed at early postoperative visits and at follow-up visits always as the last examination (blind examiner for surgical procedure). Specular microscopy (Topcon SP 2000p, Topcon) was performed before and six months after surgeries. Biomechanical properties of the cornea (ORA, Reichert) were evaluated one year after surgeries. The tests ANOVA for repeated measures and the student’s t test were used for statistical analyses. Results: The mean age was 31.7 years (range, 21-54 years). There was no statistically significant between-group difference in UCVA, BSCVA, aberrometry, contrast sensitivity or specular microscopy before surgeries. The mean attempted spherical equivalent (SE) was - 3.99±1.20 diopters (D) in LASIK eyes and - 3.85±1.12 D in PRK with MMC eyes (p>0.05). The mean ablation depth was 73.09±14.55 μm and 70.70±14.07 μm in LASIK and PRK with MMC eyes, respectively (p>0.05). Forty-two patients (95.5%) completed one year follow-up. The PRK with MMC eyes presented statistically significant better mean UCVA values than LASIK eyes at three, six and 12 months visits. The mean BSCVA was also statistically significant better in PRK with MMC eyes than in LASIK eyes one year after surgeries (p<0.05). There was no between-groups statistical difference in SE during one year follow-up. All PRK with MMC eyes reepithelialized within five days after surgical procedure and no eye presented more than grade 1 haze (Fantes scale). The LASIK eyes presented statistically significant higher lower and higher order aberrations values than PRK with MMC eyes during follow-up (p<0.05). The PRK with MMC group showed better results in photopic and mesopic contrast sensitivity than LASIK eyes during one year follow-up (p<0.05). Until the fifth postoperative day, PRK with MMC eyes presented higher pain scores than LASIK eyes. PRK with MMC eyes were better rated in terms of subjective visual symptoms and visual satisfaction. There were no statistical differences between the groups in specular microscopy (p>0.05). LASIK eyes showed statistically significant higher corneal resistance factor (CRF) and corneal hysteresis (CH) values than PRK with MMC eyes (p<0.05). Conclusions: The PRK with MMC eyes presented better UCVA, BSCVA, better correction of lower order aberrations and lower higher order aberration values than LASIK eyes. It also showed better contrast sensitivity results and was better rated in terms of visual satisfaction. There was no clinically significant haze in PRK with MMC eyes. The PRK with MMC eyes presented higher pain scores at early postoperative visits. There was no between groups differences in specular microscopy. LASIK eyes presented higher CRF and CH values one year after surgeries. / TEDE / BV UNIFESP: Teses e dissertações

O objetivo do presente trabalho é a otimização experimental, modelagem matemática e simulação do processo de pré-polimerização fotoiniciada do metacrilato de metila (MMA), visando a produção de um pré-polímero com distribuição estreita de massas moleculares (MWD) e conversão de monômero definida. Os experimentos foram realizados em dois sistemas experimentais em batelada, compostos por reatores fotoquímicos anulares e tanques de recirculação. No primeiro sistema experimental empregou-se uma lâmpada de mercúrio de média pressão, Heraeus TQ 150W. No segundo uma fonte de radiação de excímeros de xenônio e cloro (XeCl) alimentada por um gerador de pulsos e operada em uma larga faixa de freqüências de pulsos (840Hz – 46,4 kHz) foi empregada. Avaliaram-se as evoluções experimentais da concentração de benzoína (iniciador fotoquímico), da concentração do monômero e da concentração e distribuição de massas moleculares do pré-polímero, em função do tempo de irradiação, para diferentes condições de freqüência de pulsos de excitação, de concentração inicial de iniciador e de vazão de circulação. Para tanto, empregaram-se técnicas de análise como espectrofotometria, actinometria química (ferrioxalato), medidas de cromatografia por exclusão de tamanho e em fase reversa. As otimizações foram realizadas segundo dois planejamentos experimentais baseados na matriz Doehlert. As variáveis do processo escolhidas afetam significativamente as características do produto final, devido as diferentes condições de taxa de produção de radicais primários que se mostrou como etapa chave no controle da MWD e conversão do monômero. A modelagem matemática baseou-se nos balanços de massa, quantidade de movimento e transporte de fótons. Os mecanismos de geração de di-radicais monoméricos e dos radicais primários a partir das reações fotoquímicas foram incluídos em um modelo baseado na cinética clássica de polimerização por radicais livres. Os balanços foram desenvolvidos de acordo com o método dos momentos da distribuição de tamanhos de cadeia. O modelo matemático proposto foi validado confrontando-se os dados experimentais com os resultados simulados por um programa de fluido dinâmica computacional (PHOENICS). / The aim of this work is the experimental optimization, the mathematical modeling and the simulation of the photochemically initiated pre-polymerization process of methyl methacrylate (MMA). According to the industrial interests a pre-polymer of narrow molecular weight distribution (MWD) and defined weight concentration was pointed as an optimum since it improves the production process and the characteristics of Plexiglas. The experiments were carried out employing two experimental set-ups, which consist of an annular photochemical reactor connected to reservoir. In the first experimental set-up a medium pressure mercury lamp, Heraeus TQ 150 W was employed. In the second a xenon and chlorine (XeCl) source of radiation was employed. The electricity was supplied by a pulse generator, which operates within a wide frequency range (840Hz – 46,4kHz). The experimental time-evolution of the initiator (benzoin) and the MMA concentration as well as the molecular weight distribution of the pre-polymer were evaluated for different pulse frequencies, initial initiator concentrations and recirculation flow rates conditions. Therefore, analytical techniques were employed as spectrophotometry, chemical actinometry, size exclusion chromatography and reverse phase chromatography. The experimental optimizations were carried out according to two optimal experimental designs based on the classical Doehlert matrix. The chosen variables affect significantly the characteristics of the final product. Mainly due to the different conditions of initial radical production rates, which have shown to be the key on controlling the MWD and the MMA conversion. The mathematical modeling was based on mass, momentum and photons balance equations. The kinetic mechanism of bi-radical and initial radical production from MMA and benzoin respectively, were included in the classical kinetic model of free radical polymerization. The reaction rate equations were developed according to method of the chain size distribution moment. The proposed mathematical model was validated comparing the simulation results obtained with a computational fluid dynamics program (PHOENICS) and the experimental results.