A microchannel heat exchanger was designed for diesel waste heat recovery and its performance was evaluated. The 21x15x8 cm unit was constructed from diffusion brazed stainless steel lamina and weighed 11 kg. Operating from a 13.4 kW generator with an exhaust temperature of 500 °C the unit delivered 11.1 kW of thermal energy at the design point with an effectiveness of 0.87. If coupled with an organic Rankine bottoming cycle this has the potential of boosting system power output by 35%. Performance was found to be insensitive to cold side flow conditions. Soot accumulation was found to be problematic, which caused a steady exhaust pressure rise at the device but did not affect the thermal performance. / Graduation date: 2012

O escopo deste trabalho foi o desenvolvimento de microrreatores em tecnologia LTCC para produção de biodiesel, com foco na otimização de uma geometria de micromisturador. Esta proposta é resultado das oportunidades identificadas em três áreas do conhecimento: Microtecnologia, Intensificação de processos e Biocombustíveis. A principal ferramenta de desenvolvimento desta proposta é a fluidodinâmica computacional. Os microcanais baseados em geometrias com sucessivos cotovelos foram os escolhidos, para a investigação computacional e experimental. A metodologia computacional desenvolvida para alcançar os objetivos propostos envolve as etapas de: definição de um padrão de comparação, projeto das distâncias entre cotovelos, escolha de uma geometria com base na comparação entre diversas geometrias baseadas em sucessivos cotovelos e a otimização da geometria em função dos parâmetros fluidodinâmicos. Paralelamente, ensaios para a produção de biodiesel foram realizados, bem como, a investigação da produção de emulsões para avaliar como uma etapa do processo de produção do biodiesel. A geometria escolhida e otimizada foi a serpentina 3D, o que permitiu a otimização do módulo de tempo de residência e o projeto do microrreator. Finalizando, um microrreator foi projetado com parâmetros ótimos, obtendo assim a intensificação de processo por meio de conceitos de microtecnologia, para aplicação na produção de biocombustíveis. / The scope of this work was the development of microreactors in LTCC technology for biodiesel production, with a focus on the optimization of a micromixer geometry. This proposal is resulted from the opportunities identified in three areas of knowledge: Microtechnology, processes intensification and Biofuels. The main tool for development of this proposal is the computational fluid dynamics (CFD). The microchannels geometry with successive elbows were chosen for computational and experimental research. The computational methodology developed to achieve the proposed goals involves the following steps: defining a standard of comparison, a project of the distances between elbows, a choice of geometry based on the comparison between different geometries based on successive elbows and geometry optimization for the parameters hydrodynamic. In addition, tests for the production of biodiesel were being made and the investigations of production of emulsions to evaluate a step in the producing of biodiesel process. The geometry was chosen and optimized serpentine 3D, allowing the optimization of residence time module and the design of the microreactor. Finally, a microreactor was designed with optimal parameters, thus obtaining the intensification process through microtechnology concepts for application in the biofuels production.

In the first part of this work, magnetized nanoporous silica based microparticles (MMPs) are used for horseradish peroxidase (HRP) immobilization and applied in amperometric peroxidase-based biosensors. A homemade magnetized carbon paste electrode permits the MMPs attraction close to the electrode surface. The resulting original biosensor is applied to the investigation of enzymatic oxidation of model drug compounds namely, clozapine (CLZ) and acetaminophen (APAP) by HRP in the presence of hydrogen peroxide. The biosensor operates at a low applied potential and the signal corresponds to the electro-reduction of electroactive species enzymatically generated. The biosensor allows performing the quantitation of the two drug compounds in the micromolar concentration range. It allows also the study of thiol compounds based on the inhibition of the biosensor response. Interestingly, distinct inhibition results are observed for HRP entrapped in the silica microparticles compared to the soluble HRP.<p>We expect that this type of biosensors holds high promise in quantitative analysis and in biotransformation studies of drug compounds.<p><p>In the second part of this thesis work, HRP immobilized magnetic nanoparticles are injected on-line and magnetically retained, as a microreactor, in the capillary of a CE setup. The purpose of such a configuration is to develop an analytical tool for studying “in vitro” drug biotransformation. The advantages expected are (i) minimum sample (drug compound) and biocomponent (enzyme) consumption, (ii) high analysis throughput, (iii) selectivity and sensitivity. In order to illustrate the potential of such an instrumental configuration, it has been applied to study acetaminophen as model drug compound. The mechanistic information obtained by the HRP/H2O2 system is in agreement with literature data on acetaminophen metabolization. Horseradish peroxidase kinetic studies are realized by this setup and the apparent Michaelis constant is determined. Capillary electrophoresis permitted the identification of APAP off-line biotransformed products such as N-acetyl-p-benzoquinone imine (NAPQI), the APAP dimer and APAP polymers as inferred from literature data. The formation of the APAP dimer was further confirmed by electrospray ionization mass spectrometry.<p> / Doctorat en Sciences biomédicales et pharmaceutiques / info:eu-repo/semantics/nonPublished

The performance of a combined vapor-compression cycle/ORC is evaluated using waste-heat from a diesel generator. A flat plate microchannel heat exchanger is employed to provide energy exchange between the diesel exhaust stream and an oil loop, which provides energy to a boiler. This study finds an increased diesel duty corresponds with an increased cooling capacity, for a maximum of 5 kW of cooling (with 13.5 kWe diesel load). System COP is reduced with a higher input power due to limitations in the cooling cycle. A number of solutions are identified to increase the COP and cooling capacity. A new microchannel heat exchanger to recovery heat is designed to increase performance compared to the previous version. / Graduation date: 2012

Microchannel process technology (MPT) offers several advantages to the field of nanomanufacturing: 1) improved process control over very short time intervals owing to shorter diffusional distances; and 2) reduced reactor size due to high surface area to volume ratios and enhanced heat and mass transfer. The objective of this thesis was to consider how nanomaterials, produced in part using MPT, could be used to solve problems associated with the fabrication of MPT devices. Specifically, many MPT devices are produced using transient liquid-phase brazing involving an electroplated interlayer consisting of a brazing alloy designed for melting temperature suppression. Unfortunately, these alloys can form brittle secondary phases which significantly reduce bond strength. In contrast, prior efforts have shown that it is possible to leverage the size-dependent properties of nanomaterials to suppress brazing temperatures. In this prior work, thin films of off-the-shelf elemental nanoparticles were used as interlayers yielding joints with improved mechanical properties. In the present investigation, efforts have been made to characterize the synthesis and deposition of various elemental nanoparticle suspensions for use in the transient liquid-phase brazing of aluminum and stainless steel. Advances were used to demonstrate the nanoparticle-assisted diffusion brazing of a microchannel array. In the first section, a silver nanoparticle (AgNP) interlayer was produced for the diffusion brazing of heat exchanger aluminum. Efforts are made to examine the effect of braze filler particle size (~5 nm and ~50 nm) and processing parameters (heating rate: 5ºC/min and 25ºC/min; brazing temperature: 550ºC and 570ºC) on thin coupons of diffusion-brazed 3003 Al. A tensile strength of 69.7 MPa was achieved for a sample brazed at 570°C for 30 min under 1 MPa with an interlayer thickness of approximately 7 μm. Further suppression of the brazing temperature to 500ºC was achieved by sputtering a 1 µm thick layer of Cu before depositing a 5 nm thick film of AgNPs resulting in a lap shear strength of 45.3±0.2 MPa. In the middle section of this thesis, several techniques are investigated for the synthesis of sub 10 nm diameter nickel nanoparticles (NiNPs) to be used in the diffusion brazing of 316L stainless steel. The average NiNP size was varied from 9.2 nm to 3.9 nm based on the synthesis technique, solvent and reducing agent used. Conventional wet-chemical synthesis using NiCl₂.6H₂O in ethylene glycol (solvent) and N₂H₄.H₂O (reducing agent) resulted in the formation of 5.4 ± 0.9 nm NiNPs. Continuous flow synthesis using a microchannel T-mixer (barrel diameter of 521µm) and a 10 second residence time of reactants in a bath temperature of 130ºC resulted in a particle size of with 5.3 ± 1 nm. To make the synthesis safer and less energy intense, microwave heating was used along with less toxic Ni(CH₃CO₂)₂·4H₂O (nickel salt), propylene glycol (solvent) and NaPH₂O₂ (reducing agent) yielding 3.9 ± 0.8 nm diameter NiNPs. For the final section, nickel nanoparticles were synthesized using NiCl₂.6H₂O (nickel salt), de-ionized water (solvent), NaBH₄ (co-reducing agent), N₂H₄.H₂O (reducing agent) and polyvinylpyrolidone (capping agent) yielding 4.2 ± 0.6 nm NiNP. Several deposition techniques were investigated for controlling film thickness and uniformity in the diffusion brazing of 316L stainless steel (SS). Using in-house prepared NiNP and automated dispensing, a hermetic joint up to 70 psi (tested pressure) was obtained in 316L SS substrates under brazing conditions of 800ºC, 2 MPa and 30 min. Throughout the course of this thesis, techniques used for characterizing nanoparticles, films and joints included FT-IR, XRD, SEM, TEM, HRTEM, EDS, EPMA, DSC, mass spectrometry, and lap-shear testing. / Graduation date: 2012

Hydrogen has been shown to be a promising replacement for fossil fuels for use in light duty vehicles because it is a clean, renewable and plentiful resource with a high gravimetric energy density. However, in order to obtain an acceptable volumetric energy density, densification of the hydrogen is required. Adsorptive materials have been shown in the literature to increase volumetric and gravimetric storage densities. A major issue with adsorptive storage is that the adsorption process generates heat and optimal storage conditions are at temperatures below 100 K at pressures up to 50 atm. There is a need to develop heat exchanging architecture that enables adsorbents to be a viable method for hydrogen storage by managing the thermal environment of the storage tank. Based on previous modeling efforts to determine an acceptable bed module height for removal of heat via microchannel cooling plates, a thermal management system has been designed and tested capable of removing the heat of adsorption within adsorbent-filled hydrogen storage tanks. The system uses liquid nitrogen cooling to maintain tank temperatures of below 80 K at 50 atm. System studies show that the microchannel architecture offers a high cooling capacity with about a 6% displacement volume. Simulations and experiments have been conducted to evaluate the design for the cooling capacity, pressure drop, and flow distribution between and across the cooling plates, stress due to the pressurized environment, and thermal stress. Cost models have been developed to demonstrate that the system can be manufactured for a reasonable cost at high production volumes. Experimental results show that the modular system offers an acceptable cooling capacity and pressure drop with good flow distribution while adequately managing thermal stresses during operation. / Graduation date: 2013

The marked increase in surface-to-volume ratio associated with microscale devices for hemodialysis leads to problems with hemocompatibility and blood flow distribution that are more challenging to manage than those encountered at the conventional scale. In this work, stable surface modifications with pendant polyethylene oxide (PEO) chains were produced on polycarbonate microchannel and polyacrylonitrile membrane materials used in construction of microchannel hemodialyzer test articles. These coatings were evaluated in relation to protein repulsion, impact on urea permeability through the membrane, and impact on bubble retention through single-channel test articles. PEO layers were prepared by radiolytic grafting of PEO-PBD-PEO (PBD = polybutadiene) triblock copolymers to microchannel and membrane materials. Protein adsorption was detected by measurement of surface-bound enzyme activity following contact of uncoated and PEO-coated surfaces with ��-galactosidase. Protein adsorption was decreased on PEO-coated polycarbonate and polydimethyl siloxane (PDMS) materials by 80% when compared to the level recorded on uncoated materials. Protein adsorption on membrane materials was not decreased with PEO-PBD-PEO treatment; a PEI (polyethylene imide) layer exists on the AN69 ST membrane which is intended to trap heparin during membrane pre-treatment. It is still unclear how this PEI layer interacts with PEO-PBD-PEO. Neither the PEO-PBD-PEO triblocks nor the irradiation process was observed to have any effect on polyacrylonitrile membrane permeability to urea, nor did the presence of additional fibrinogen and bovine serum albumin (BSA) in the urea filtrate. The PEO-PBD-PEO treatment was not able to visibly reduce bubble retention during flow through single-channel polycarbonate test articles, however, the rough surfaces of the laser-etched polycarbonate microchannels may be causing this bubble retention. This surface treatment holds promise as a means for imparting safe, efficacious coatings to blood processing equipment that ensure good hemocompatibility and blood flow distribution, with no adverse effects on mass transfer. / Graduation date: 2013

Metal oxide nanocrystals have attracted significant interests due to their unique chemical, physical, and electrical properties which depend on their size and structure. In this study, a continuous flow microreactor system was employed to synthesize metal oxide nanocrystals in aqueous solution. Assembly of nanocrystals is considered one of the most promising approaches to design nano-, microstructures, and complex mesoscopic architectures. A variety of strategies to induce nanocrystal assembly have been reported, including directed assembly methods that apply external forces to fabricate assembled structures. In this study ZnO nanocrystals were synthesized in an aqueous solution using a continuous flow microreactor. The growth mechanism and stability of ZnO nanocrystals were studied by varying the pH and flow conditions of the aqueous solution. It was found that convective fluid flow from Dean vortices in a winding microcapillary tube could be used for the assembly of ZnO nanocrystals. The ZnO nanocrystal assemblies formed three-dimensional mesoporous structures of different shapes including a tactoid, a retangle and a sphere. The assembly results from a competing interaction between electrostatic forces caused by surface charge of nanocrystals and collision of nanocrystals associated with Dean vortices. The as synthesized colloidal ZnO nanocrystals or assembly were directly deposited onto a substrate to fabricate ZnO nanostructured surfaces. The rectangular assembly led to flower-like ZnO nanostructured films, while the spherical assembly resulted in amorphous ZnO thin film and vertical ZnO nanowire (NW) arrays. In contrast to the formation of flower structure or amorphous thin film, only colloidal ZnO nanocrystals were used as the building blocks for forming vertical ZnO NW arrays. This study demonstrates the versatility of the microreactor-assisted nanomaterial synthesis and deposition process for the production of nanostrucuturesres with various morphologies by tuning the physical parameters while using the same chemical precursors for the synthesis. ZnO flower structure was coated on a microwick structure to improve the capillary flow. The coated microwick structure showed an enhanced capillary rise, which was attributed to the hydrophilic property and geometrical modification of ZnO nanostructure. Two-phase boiling heat transfer was performed using ZnO nanostructured surfaces. ZnO nanocoating altered the important characteristics including surface roughness and wettability. Hydrophilic nature of the ZnO nanocoating generally enhanced the boiling heat transfer performance, resulting in higher heat transfer coefficient (HTC), higher critical heat flux (CHF), and lower surface superheat comparing to the bare surface. Octahedral SnO and porous NiO films, fabricated by a continuous flow microreactor system, were suggested as potential boiling surfaces for the high porosity and irregularity of their structures. / Graduation date: 2013

This thesis described the development of new strategies for the preparation of micro- and nano-structured polymer materials. In particular, this thesis focused on: i) the synthesis of polymer particles in microreactors, and ii) the self-assembly of inorganic nanorods. First, this thesis presented the synthesis of polymer particles and capsules with pre-determined sizes and narrow size distributions (CV<2%) in continuous microfluidic reactors. The method includes (i) the emulsification of monomers in a microfluidic flow-focusing device and (ii) in-situ solidification of droplets via photopolymerization. This microfluidic synthesis provides a novel strategy for the control over the shapes, compositions, and morphologies of polymer particles. In particular, we demonstrated the control over particle shapes by producing polymer ellipsoids, disks, rods, hemispheres, plates, and bowls. We produced polymer particles loaded with dyes, liquid crystals, quantum dots, and magnetic nanoparticles. We generated core-shell particles, microcapsules, Janus and three-phasic polymer particles. Control over the number of cores per droplet was achieved by manipulating the flow rates of liquids in the microchannels. We further investigated the hydrodynamic mechanism underlying the emulsification of droplets, which helps in guiding scientists and engineers to utilize this technique. Second, we described the self-assembly of inorganic nanorods by using a striking analogy between amphiphilic ABA triblock copolymers and the hydrophilic nanorods tethered with hydrophobic polystyrene chains at both ends. We organized metal nanorods in structures with various geometries such as nanorings, nanochains, bundles, bundled nanochains, and nanospheres by tuning solely the quality of solvents. The self-assembly was tunable and reversible. This approach paved the way for the organization of anisotropic nanoparticles by using the strategies that are well-established for the self-assembly of block copolymers. We further described a systematic study of the self-assembly of polymer-tethered gold nanorods as a function of solvent composition in the system and the molecular weight of the polystyrene blocks. We found that the structure of the polymer pom-poms played an important role on the organization of polymer-tethered gold NRs. The 'supramolecular' assembly was governed by the competition between the end-to-end and side-by-side association of NRs and resulted in the controlled variation of the plasmonic properties of NRs, reflected in a 3-D plasmonic graph.

This thesis described the development of new strategies for the preparation of micro- and nano-structured polymer materials. In particular, this thesis focused on: i) the synthesis of polymer particles in microreactors, and ii) the self-assembly of inorganic nanorods. First, this thesis presented the synthesis of polymer particles and capsules with pre-determined sizes and narrow size distributions (CV<2%) in continuous microfluidic reactors. The method includes (i) the emulsification of monomers in a microfluidic flow-focusing device and (ii) in-situ solidification of droplets via photopolymerization. This microfluidic synthesis provides a novel strategy for the control over the shapes, compositions, and morphologies of polymer particles. In particular, we demonstrated the control over particle shapes by producing polymer ellipsoids, disks, rods, hemispheres, plates, and bowls. We produced polymer particles loaded with dyes, liquid crystals, quantum dots, and magnetic nanoparticles. We generated core-shell particles, microcapsules, Janus and three-phasic polymer particles. Control over the number of cores per droplet was achieved by manipulating the flow rates of liquids in the microchannels. We further investigated the hydrodynamic mechanism underlying the emulsification of droplets, which helps in guiding scientists and engineers to utilize this technique. Second, we described the self-assembly of inorganic nanorods by using a striking analogy between amphiphilic ABA triblock copolymers and the hydrophilic nanorods tethered with hydrophobic polystyrene chains at both ends. We organized metal nanorods in structures with various geometries such as nanorings, nanochains, bundles, bundled nanochains, and nanospheres by tuning solely the quality of solvents. The self-assembly was tunable and reversible. This approach paved the way for the organization of anisotropic nanoparticles by using the strategies that are well-established for the self-assembly of block copolymers. We further described a systematic study of the self-assembly of polymer-tethered gold nanorods as a function of solvent composition in the system and the molecular weight of the polystyrene blocks. We found that the structure of the polymer pom-poms played an important role on the organization of polymer-tethered gold NRs. The 'supramolecular' assembly was governed by the competition between the end-to-end and side-by-side association of NRs and resulted in the controlled variation of the plasmonic properties of NRs, reflected in a 3-D plasmonic graph.