Two new mechanisms of droplet splashing and breakup during impact have been identified and analyzed. One is the internal rupture of spreading droplet film through formation of holes, and the other is the splashing of droplet due to its freezing during spreading. The mechanism of film rupture was investigated by two different methods. In the first method, circular water films were produced by directing a 1 mm diameter water jet onto a flat, horizontal plate for 10 ms. In the second method, films were produced by making 0.6 mm water droplets impact a solid surface mounted on the rim of a rotating flywheel. Substrate wettability was varied over a wide range, including superhydrophobic. In both cases, the tendency to film rupture first increased and then decreased with contact angle. A thermodynamic stability analysis predicted this behavior by showing that films would be stable at very small or very large contact angle, but unstable in between. Film rupture was also found to be promoted by increasing surface roughness or decreasing film thickness. To study the effect of solidification, the impact of molten tin droplets (0.6 mm diameter) on solid surfaces was observed for a range of impact velocities (10 to 30 m/s), substrate temperatures (25 to 200°C) and substrate materials (stainless steel, aluminum and glass) using the rotating flywheel apparatus. Droplets splashed extensively on a cold surface but on a hot surface there was no splashing. Splashing could be completely suppressed by either increasing the substrate temperature or reducing its thermal diffusivity. An analytical model was developed to predict this splashing behavior. The above two theories of freezing-induced splashing and film rupture were combined to predict the morphology of splats typically observed in a thermal spray process. A dimensionless solidification parameter, which takes into account factors such as the droplet diameter and velocity, substrate temperature, splat and substrate thermophysical properties, and thermal contact resistance between the two, was developed. Predictions from the model were compared with a wide range of experimental data and found to agree well.

In this research, wafer-level flexible input/output interconnection technologies, Mechanically Flexible Interconnects (MFIs), have been developed. First, Au-NiW MFIs with 65 µm vertical elastic range of motion are designed and fabricated. The gold passivation layer is experimentally verified to not only lower the electrical resistance but also significantly extend the life-time of the MFIs. In addition, a photoresist spray-coating based fabrication process is developed to scale the in-line pitch of MFIs from 150 µm to 50 µm. By adding a contact-tip, Au-NiW MFI could realize a rematable assembly on a substrate with uniform pads and a robust assembly on a substrate with 45 µm surface variation. Last but not least, multi-pitch multi-height MFIs (MPMH MFIs) are formed using double-lithography and double-reflow processes, which can realize an MFI array containing MFIs with various heights and various pitches. Using these advanced MFIs, large scale heterogeneous systems which can provide high performance system-level interconnections are demonstrated. For example, the demonstrated 3D interposer stacking enabled by MPMH MFIs is promising to realize a low profile and cavity-free robust stacking system. Moreover, bridged multiinterposer system is developed to address the reticle and yield limitations of realizing a large scale system using current 2.5D integration technologies. The high-bandwidth interconnection available within interposer can be extended by using a silicon chip to bridge adjacent interposers. MFIs assisted thermal isolation is also developed to alleviate thermal coupling in a high-performance 3D stacking system.

abstract: Graphene oxide membranes have shown promising gas separation characteristics specially for hydrogen that make them of interest for industrial applications. However, the gas transport mechanism for these membranes is unclear due to inconsistent permeation and separation results reported in literature. Graphene oxide membranes made by filtration, the most common synthesis method, contain wrinkles affecting their gas separation characteristics and the method itself is difficult to scale up. Moreover, the production of graphene oxide membranes with fine-tuned interlayer spacing for improved molecular separation is still a challenge. These unsolved issues will affect their potential impact on industrial gas separation applications. In this study, high quality graphene oxide membranes are synthesized on polyester track etch substrates by different deposition methods and characterized by XRD, SEM, AFM as well as single gas permeation and binary (H2/CO2) separation experiments. Membranes are made from large graphene oxide sheets of different sizes (33 and 17 micron) using vacuum filtration to shed more light on their transport mechanism. Membranes are made from dilute graphene oxide suspension by easily scalable spray coating technique to minimize extrinsic wrinkle formation. Finally, Brodie’s derived graphene oxide sheets were used to prepare membranes with narrow interlayer spacing to improve their (H2/CO2) separation performance. An inter-sheet and inner-sheet two-pathway model is proposed to explain the permeation and separation results of graphene oxide membranes obtained in this study. At room temperature, large gas molecules (CH4, N2, and CO2) permeate through inter-sheet pathway of the membranes, exhibiting Knudsen like diffusion characteristics, with the permeance for the small sheet membrane about twice that for the large sheet membrane. The small gases (H2 and He) exhibit much higher permeance, showing significant flow through an inner-sheet pathway, in addition to the flow through the inter-sheet pathway. Membranes prepared by spray coating offer gas characteristics similar to those made by filtration, however using dilute graphene oxide suspension in spray coating will help reduce the formation of extrinsic wrinkles which result in reduction in the porosity of the inter-sheet pathway where the transport of large gas molecules dominates. Brodie’s derived graphene oxide membranes showed overall low permeability and significant improvement in in H2/CO2 selectivity compared to membranes made using Hummers’ derived sheets due to smaller interlayer space height of Brodie’s sheets (~3 Å). / Dissertation/Thesis / Doctoral Dissertation Chemical Engineering 2018

Neste trabalho, filmes planos de polipropileno (CPP) cobertos com nanopartículas de dióxido de titânio (TiO2) foram feitos a partir da metodologia spray coating, facilmente reproduzida para a imobilização das nanopartículas de titânia nos suportes de polipropileno (PP). O tratamento superficial dos filmes CPP com plasma de nitrogênio (N2) e oxigênio (O2) foi utilizado com sucesso para a produção de polipropileno revestido com TiO2 com excelente estabilidade mecânica do revestimento, assim como atividade fotocatalítica / de autolimpeza como evidenciado pelos testes com corante cristal violeta (CV). Microscopia eletrônica de varredura (MEV) e microscopia confocal à laser de varredura (MCLV) foi utilizada para observar a morfologia de superfície / das fibras e topografia. A presença do revestimento de titânia foi confirmada por espectroscopia de emissão de raios-x com detecção dispersiva de energia (EDX). Tanto o tratamento com plasma como o carregamento significativo de revestimento de titânia resultam em maior hidrofilicidade, como observado pelas medidas de ângulo de contato estático em água. Os filmes CPP revestidos foram testados quanto à sua atividade fotocatalítica contra o corante CV. Os espectros eletrônicos no UV-vis mostraram que a eficiência da atividade fotocatalítica das amostras foi afetada pela quantidade de titânia. A fotoestabilidade do PP revestido com titânia foi medida por ressonância paramagnética eletrônica (RPE), uma vez que esta técnica é capaz de detectar pequena quantidade de radicais livres formados durante a precoce etapa de oxidação do polipropileno. Observa-se a partir das medições de RPE que o polipropileno tratado com plasma gerou as mesmas espécies de radicais livres que foram produzidas durante a radiação UV do polipropileno revestido e não-revestido. Entretanto, aumentando o número de ciclos de deposição da titânia a quantidade relativa de radicais livres diminui, sem perda de atividade fotocatalítica. Portanto, a metodologia empregada se mostrou eficiente para produzir uma superfície fotoativa/autolimpante no polipropileno revestido com dióxido de titânio, levando à diferentes aplicações neste campo, como por exemplo sistemas de filtragem de ar/água, remoção de poluentes orgânicos, produtos termoplásticos com características antibacterianas para uso doméstico e hospitalar, dispositivos de autolimpeza, entre outros. / Cast polypropylene (CPP) films were coated with titanium dioxide (TiO2) nanoparticles by na easily scaled-up spray coating methodology. The O2 and N2 plasma surface treatment of polypropylene was successfully used to produce TiO2-coated polypropylene with outstanding mechanical stability of the coating, as well as photocatalytic/self-cleaning activity toward crystal violet dye. Scanning Electron Microscopy and Confocal Scanning Laser Microscopy were used to observe surface / fibers morphology and topography. The presence of titânia coating was confirmed by X-ray Emission Spectroscopy with Energy Dispersive Detection (EDX). Titania coating results on higher hydrophilicity, as observed by measurements of static water contact angle. The CPP films were tested for their photocatalytic activity against Crystal Violet dye (CV). The UV/Vis electronic spectra showed that the photocatalytic activity efficiency of TiO2-coated CPP film was affected by both the plasma treatment and the titânia amount. The photostability of the titania coated polypropylene was measured by Electron Paramagnetic Resonance (EPR) since this technique is capable to detect tiny amount of free radicals formed during the early oxidation step of the polypropylene. It was observed from EPR measurements that the plasma treated polypropylene generated the same free radicals species that were produced during UV irradiation of the uncoated and TiO2-coated polypropylene. However, by increasing the number of deposition cycles of the titania the relative amount of free radicals decreases without loss of the photocatalytic activity. Therefore, the essayed methodology has been proved efficient to produce photoactive/selfcleaning surface of titania coated polypropylene, leading to different applications in this field, as water/air filtration systems, organic pollutant removal, hospital and domestic thermoplastic goods with antibacterial features, self-cleaning devices and others.

京都大学 / 0048 / 新制・課程博士 / 博士(エネルギー科学) / 甲第18381号 / エネ博第293号 / 新制||エネ||61(附属図書館) / 31239 / 京都大学大学院エネルギー科学研究科エネルギー基礎科学専攻 / (主査)教授 佐川 尚, 教授 八尾 健, 教授 萩原 理加 / 学位規則第4条第1項該当 / Doctor of Energy Science / Kyoto University / DGAM

Liquid spray is essential to industries requiring processes such as spray coating, spray drying, spray pyrolysis, or spray cooling. This thesis reports the design, fabrication, and characterization of a thin film deposition system which utilizes a linear multiplexed electrospray (LINES) atomizer. First, a thorough review of the advantages and limitations of prior multiplexed electrospray systems leads to discussion of the design rationale for this work. Next, the line of charge model was extended to prescribe the operating conditions for the experiments and to estimate the spray profile. The spray profile was then simulated using a Lagrangian model and solved using a desktop supercomputer based on Graphics Processing Units (GPUs). The simulation was extended to estimate the droplet number density flux during deposition. Pure ethanol was electrosprayed in the cone-jet mode from a 51-nozzle aluminum LINES atomizer with less than 3% relative standard deviation in the D10 average droplet diameter as characterized using Phase Doppler Interferometry (PDI). Finally a 25-nozzle LINES was integrated into a thin film deposition system with a heated, motion controlled stage, to deposit TiO2 thin films onto silicon wafers from an ethanol based nanoparticle suspension. The resulting deposition pattern was analyzed using SEM, optical profilometry, and macro photography and compared with the numerical simulation results. The LINES tool developed here is a step forward to enabling the power of electrospray for industrial manufacturing applications in clean energy, health care, and electronics

This research investigates the efficacy of liquid-precursor thermal spray coating (TSC) as a facile wood modification technique to bring hydrophobicity and UV durability to a wooden surface. The technique was successful in depositing Cu and TiO2 particles onto southern yellow pine (SYP) veneers by using copper azole, copper quaternary, and titanium tetraisopropoxide as the precursor solutions. Using optimized settings, the average coating surface coverage of > 90% and an average coating thickness of > 5 μm were obtained. The coatings displayed up to 4H rating in the film hardness scale and up to 3B rating in adhesion strength scale, suggesting reasonable mechanical durability under mild mechanical abrasion. TSC-modified wood with TiO2 created a water repellent layer, yielding a significant increase in hydrophobicity that changed the water contact angle from 57° to 126°. Accelerated weathering test results showed that the TSC-modified wood was more resistant to discoloration compared to unmodified wood.

Esta tese tem por objetivo o desenvolvimento de metodologias eficientes e de baixo custo para ajustar as propriedades elétricas de OFETs de canal p e de canal n, a fim de possibilitar a fabricação do circuito complementar orgânico, semelhante a uma estrutura CMOS. O desempenho do circuito complementar fabricado foi otimizado, e também foi confeccionado por impressão um OFETs de canal operando em baixas tensões. Para a fabricação do CMOS orgânico foi proposto um método baseado na seleção adequada do solvente da camada dielétrica para ajustar o desempenho elétrico dos OFETs de canal p e de canal n. Os solventes, MEK, nBA e DMSO foram selecionados para a dissolução do PMMA por apresentarem diferenças nos valores de momento de dipolo, de ponto de ebulição e de graus de ortogonalidade em relação as camadas semicondutoras de P3HT e de P(NDI2OD-T2) dos OFETs. A análise dos resultados dos OFETs de canal p e de canal n demonstrou que a metodologia proposta é adequada tanto para o ajuste das propriedades elétricas destes dispositivos quanto para a otimização do desempenho dos mesmos. Os melhores desempenhos elétricos para os OFETs de canal p e de canal n foram obtidos quando utilizados o DMSO e o MEK como solventes do PMMA, respectivamente, devido à perfeita ortogonalidade destes solventes em relação às camadas semicondutoras. Os OFETs de canal p que utilizaram o DMSO e os OFETs de canal n que utilizaram o nBA foram os que apresentaram desempenhos elétricos semelhantes, sendo portanto aplicados na fabricação do CMOS. Valores de ganho entre 6,8 e 7,8 e de margem de ruído entre 28,3 V e 34,5 V foram obtidos para inversores complementares fabricados nesta etapa do trabalho. OFETs de canal p utilizando uma blenda de PTAA: diF TES ADT como camada semicondutora, o PEDOT:PSS como eletrodos dreno/fonte e o P(VDF-TrFE-CFE) como camada dielétrica também foram fabricados neste trabalho. A técnica de blade-coating foi utilizada para a deposição dos eletrodos dreno/fonte e da camada semicondutora, ao passo que a técnica de spray-coating foi utilizada para a deposição da camada dielétrica. Da análise dos resultados foi possível inferir que a utilização de um dielétrico com elevada constante dielétrica (K), como o P(VDF-TrFE-CFE), possibilita o funcionamento dos transistores a baixas tensões (≤ 8 V), porém com valores de mobilidade reduzidos devido à elevada desordem dipolar na interface provocada por este dielétrico. Para minimizar esses efeitos, uma fina camada de um polímero fluorado foi depositada entre a camada semicondutora e a dielétrica pela técnica de blade-coating, constituindo assim uma bicamada dielétrica nos OFETs. Dos resultados das medidas elétricas dos OFETs constituídos pela bicamada dielétrica foi observada permanência do funcionamento destes dispositivos a tensões inferiores a 8 V com desempenho elétricos superiores a resultados já publicados na literatura. Por fim, inversores lógicos unipolares com transistores de carga foram fabricados com os OFETs que utilizaram a bicamada dielétrica, sendo obtidos valores de ganho entre 1,2 e 1,6 e de margem de ruído entre 56% e 68,5% de ½ VDD. / This thesis aimed to develop an efficient and low cost method to adjust the electrical properties of p- and n-channel OFETs to allow us to build an organic CMOS and the optimization of printed p-channel OFETs to work at low voltages. We proposed a method to fabricate the organic CMOS, based on the careful selection of dielectric solvent, which was adjusted to obtain the best performance of p- and n-channel OFETs. The dielectric solvents as MEK, nBA and DMSO were selected to dissolve the PMMA dielectric polymer due their different physical properties as dipole moment and boiling point and because they showed slightly different degrees of orthogonality to the P3HT and P(NDI2OD-T2) semiconductor layers of the OFETs. The results showed that the careful selection of the dielectric solvent not only allows to tune the electrical characteristics of the p- and n-channel OFETs, but also to improve the performance of these devices. The best performances were achieved when DMSO and MEK were used as dielectric solvents of the p and n-channel OFETs, respectively, as result of the perfectly orthogonality of these solvents to the semiconductor layers. P-channel OFETs using DMSO and n-channel OFETs using nBA showed similar electrical characteristics and thus, they were used to construct the organic CMOS. The organic complementary inverters showed high gain and noise margin values in the range of 6,8 to 7,8 and 28,3 V to 34,5 V, respectively. Printed p-channel OFETs were also fabricated, in which the blend PTAA:diF TES ADT was used as semiconductor channel, PEDOT:PSS as the drain/source electrodes and P(VDF-TrFE-CFE) as the dielectric layer. The blade-coating technique was used to deposit the source/drain electrodes and the semiconductor layer, while the spray-coating technique was used to deposit the dielectric layer. It was observed that using high-k dielectric as P(VDF-TrFE-CFE) enable to reduce the operating voltage of the OFETs (≤8 V), however, this high-k dielectric also reduced the field effect mobility due the dipolar disorder at the semiconductor/dielectric interface. To minimize the dipolar issue at the interface, we inserted a thin fluoropolymer dielectric layer by blade-coating between the semiconductor and the high-k dielectric layers, thus constituting a dielectric bilayer on the OFETs. From the electrical measurements of the OFETs with the dielectric bilayer, it was observed that the devices were still working at 8 V and they also showed better performance in comparison to results already published. Finally, organic unipolar inverters with load transistors were fabricated using the p-channel OFETs with the dielectric bilayer and they showed reasonable performance, with gain and noise margin in the range of 1,2 to 1,6 and 56% e 68,5% of ½ VDD, respectively.

Esta tese tem por objetivo o desenvolvimento de metodologias eficientes e de baixo custo para ajustar as propriedades elétricas de OFETs de canal p e de canal n, a fim de possibilitar a fabricação do circuito complementar orgânico, semelhante a uma estrutura CMOS. O desempenho do circuito complementar fabricado foi otimizado, e também foi confeccionado por impressão um OFETs de canal operando em baixas tensões. Para a fabricação do CMOS orgânico foi proposto um método baseado na seleção adequada do solvente da camada dielétrica para ajustar o desempenho elétrico dos OFETs de canal p e de canal n. Os solventes, MEK, nBA e DMSO foram selecionados para a dissolução do PMMA por apresentarem diferenças nos valores de momento de dipolo, de ponto de ebulição e de graus de ortogonalidade em relação as camadas semicondutoras de P3HT e de P(NDI2OD-T2) dos OFETs. A análise dos resultados dos OFETs de canal p e de canal n demonstrou que a metodologia proposta é adequada tanto para o ajuste das propriedades elétricas destes dispositivos quanto para a otimização do desempenho dos mesmos. Os melhores desempenhos elétricos para os OFETs de canal p e de canal n foram obtidos quando utilizados o DMSO e o MEK como solventes do PMMA, respectivamente, devido à perfeita ortogonalidade destes solventes em relação às camadas semicondutoras. Os OFETs de canal p que utilizaram o DMSO e os OFETs de canal n que utilizaram o nBA foram os que apresentaram desempenhos elétricos semelhantes, sendo portanto aplicados na fabricação do CMOS. Valores de ganho entre 6,8 e 7,8 e de margem de ruído entre 28,3 V e 34,5 V foram obtidos para inversores complementares fabricados nesta etapa do trabalho. OFETs de canal p utilizando uma blenda de PTAA: diF TES ADT como camada semicondutora, o PEDOT:PSS como eletrodos dreno/fonte e o P(VDF-TrFE-CFE) como camada dielétrica também foram fabricados neste trabalho. A técnica de blade-coating foi utilizada para a deposição dos eletrodos dreno/fonte e da camada semicondutora, ao passo que a técnica de spray-coating foi utilizada para a deposição da camada dielétrica. Da análise dos resultados foi possível inferir que a utilização de um dielétrico com elevada constante dielétrica (K), como o P(VDF-TrFE-CFE), possibilita o funcionamento dos transistores a baixas tensões (≤ 8 V), porém com valores de mobilidade reduzidos devido à elevada desordem dipolar na interface provocada por este dielétrico. Para minimizar esses efeitos, uma fina camada de um polímero fluorado foi depositada entre a camada semicondutora e a dielétrica pela técnica de blade-coating, constituindo assim uma bicamada dielétrica nos OFETs. Dos resultados das medidas elétricas dos OFETs constituídos pela bicamada dielétrica foi observada permanência do funcionamento destes dispositivos a tensões inferiores a 8 V com desempenho elétricos superiores a resultados já publicados na literatura. Por fim, inversores lógicos unipolares com transistores de carga foram fabricados com os OFETs que utilizaram a bicamada dielétrica, sendo obtidos valores de ganho entre 1,2 e 1,6 e de margem de ruído entre 56% e 68,5% de ½ VDD. / This thesis aimed to develop an efficient and low cost method to adjust the electrical properties of p- and n-channel OFETs to allow us to build an organic CMOS and the optimization of printed p-channel OFETs to work at low voltages. We proposed a method to fabricate the organic CMOS, based on the careful selection of dielectric solvent, which was adjusted to obtain the best performance of p- and n-channel OFETs. The dielectric solvents as MEK, nBA and DMSO were selected to dissolve the PMMA dielectric polymer due their different physical properties as dipole moment and boiling point and because they showed slightly different degrees of orthogonality to the P3HT and P(NDI2OD-T2) semiconductor layers of the OFETs. The results showed that the careful selection of the dielectric solvent not only allows to tune the electrical characteristics of the p- and n-channel OFETs, but also to improve the performance of these devices. The best performances were achieved when DMSO and MEK were used as dielectric solvents of the p and n-channel OFETs, respectively, as result of the perfectly orthogonality of these solvents to the semiconductor layers. P-channel OFETs using DMSO and n-channel OFETs using nBA showed similar electrical characteristics and thus, they were used to construct the organic CMOS. The organic complementary inverters showed high gain and noise margin values in the range of 6,8 to 7,8 and 28,3 V to 34,5 V, respectively. Printed p-channel OFETs were also fabricated, in which the blend PTAA:diF TES ADT was used as semiconductor channel, PEDOT:PSS as the drain/source electrodes and P(VDF-TrFE-CFE) as the dielectric layer. The blade-coating technique was used to deposit the source/drain electrodes and the semiconductor layer, while the spray-coating technique was used to deposit the dielectric layer. It was observed that using high-k dielectric as P(VDF-TrFE-CFE) enable to reduce the operating voltage of the OFETs (≤8 V), however, this high-k dielectric also reduced the field effect mobility due the dipolar disorder at the semiconductor/dielectric interface. To minimize the dipolar issue at the interface, we inserted a thin fluoropolymer dielectric layer by blade-coating between the semiconductor and the high-k dielectric layers, thus constituting a dielectric bilayer on the OFETs. From the electrical measurements of the OFETs with the dielectric bilayer, it was observed that the devices were still working at 8 V and they also showed better performance in comparison to results already published. Finally, organic unipolar inverters with load transistors were fabricated using the p-channel OFETs with the dielectric bilayer and they showed reasonable performance, with gain and noise margin in the range of 1,2 to 1,6 and 56% e 68,5% of ½ VDD, respectively.

A novel multilayer membrane electrode assembly (MEA) for polymer electrolyte membrane fuel cells (PEMFCs) is fabricated in this work, within a single spray-coating device. For the first time, direct membrane deposition is used to fabricate a PEMFC by spraying the short-side-chain ionomer Aquivion directly onto the gas diffusion electrodes. The fully sprayed MEA, with an Aquivion membrane 10 μm in thickness, achieved a high power density of 1.6 W/cm2 for H2/air operation at 300 kPaabs. This is one of the highest reported values for thin composite membranes operated in H2/air atmosphere. By the means of confocal laser scanning microscopy, individual carbon fibers from the gas diffusion layer are identified to penetrate through the micro porous layer (MPL), likely causing a low electrical cell resistance in the range of 150 Ω cm2 through the thin sprayed membranes. By spraying a 200 nm graphene oxide/cerium oxide (GO/CeO2) interlayer between two layers of Aquivion ionomer, the impact of the electrical short is eliminated and the hydrogen crossover current density is reduced to about 1 mA/cm2. The peak power density of the interlayer-containing MEA drops only by 10% compared to a pure Aquivion membrane of similar thickness.