This research forms part of a programme of work at the University of Canterbury investigating the production of liquid fuels from biomass. The drivers for this research are the plentiful supply of woody biomass in New Zealand as well as the necessity for a reduction in the use of fossil fuels. Fischer-Tropsch synthesis has been chosen as the base conversion method for syngas to liquid fuels. While Fischer-Tropsch plants are traditionally very large, the low geographical density of the biomass feedstock necessitates a shift from a traditional economies of scale approach. In this research a sawmill integrated polygeneration scenario is proposed that recognises the synergy between the heat and electrical requirements of a mill and the Fischer-Tropsch process that can supply both as well as liquid fuels. Techno-economic modelling of variations to this polygeneration arrangement were performed using a traditional Fischer-Tropsch slurry reactor as the basis. The breakeven price of syncrude produced in the process based on a 30 year plant life and 10% discount factor was as low as $US 167 per barrel. This arrangement is coupled with development of and experimentation with a microchannel reactor in a further attempt to overcome economies of scale disadvantages. The lab scale microchannel reactor consisted of a shim with 50 channels of 37mm length with 0.2mm height and 0.3mm width. The microchannel reactor was tested with shorter run periods to compare different catalyst washcoats consisting of neat cobalt, cobalt on titania and a combustion synthesis method over a temperature range of 210-240°C at 20 bar. Comparison was also made to a lab scale fixed bed reactor with a powdered cobalt on titania catalyst. The neat cobalt washcoat proved to have the best performance per unit mass of catalyst of the three washcoats. The performance of the microchannel reactor was 32-40 times better per unit catalyst mass than the fixed bed reactor. From data based on the shorter runs the neat cobalt washcoat and the cobalt on titania washcoat were selected for further analysis over longer runs at a range of pressures from 2-20 bar and temperatures from 210-240°C. These runs were each approximately 70 hours long and provided a better analysis of the narrowed catalyst choice. The productivity results of the catalysts were fitted to established kinetic equations from literature with an excellent correlation. More accurate Anderson-Schultz-Flory selectivity values were also obtained ranging between 0.72 to 0.82. This is certainly an area that would warrant further attention as a higher selectivity has a very positive affect on plant economics. Establishment of the kinetic equations for the catalyst performance allowed modelling of reactors with greater volume along with investigation of mass transfer limitations to assist in scale up of the technology. It was found that under 4-5mm hydraulic diameter channel dimensions the mass transfer limitation from the bulk gas phase to the catalyst interface is negligible. A scaled up microchannel reactor concept design is proposed utilising stainless steel mesh folded into 2mm channels to increase catalyst surface area compared to straight shim. A costing correlation was produced per unit of reactor volume to allow a full scale cost of the microchannel reactor to be estimated for inclusion into the techno-economic model. The revised techno-economic model was optimised through pressure variation to give a breakeven syncrude value of $US118 per barrel at Fischer-Tropsch reaction conditions of 10 bar and 240°C. This brings the value well within historical crude price trends.

The growth of energy demand in the world requires addressing the increasing power requirements of industrial and residential consumers. Optimizing the design of new and existing large power producing systems can efficiently increase energy supply to meet the growing demand. Hydrogen as an energy carrier is a promising sustainable way to meet the growing energy demand, while protecting the environment. This thesis investigates the efficient production of hydrogen from the electrolysis of copper chloride, by predicting entropy production as a result of diffusive mass transfer. Also, this thesis investigates the possibility of producing electrical energy from waste heat produced by industrial or other sources. The thermocapillary motion of fluid droplet in a closed rectangular microchannel is used to generate electrical energy from waste heat in a piezoelectric membrane by inducing mechanical deformation as a result of the droplet motion. Modeling, fabrication, and experimental measurement of a micro heat engine (MHE) are investigated in this study. Analytical and experimental results are reported for both circular and rectangular microchannels. A novel fabrication technique using lead zirconate titanate (PZT) as substrate in microfluidic application is presented in this study. This thesis develops a predictive model of the entropy production due to thermal and fluid irreversibilities in the microchannel. Thermocapillary pressure and friction forces are modelled within the droplet, as well as surface tension hysteresis during start-up of the droplet motion. A new analytical model is presented to predict the effect of transient velocity on the voltage production in the MHE. In order to predict the effect of the applied stress on voltage, the different layers of deposition are considered for thin film laminates. The highest efficiency of the system from simulated taking into iv account the electromechanical coupling factor is about 1.6% with a maximum voltage of 1.25mV for the range of displacement considered in this study. In addition, new experimental and analytical results are presented for evaporation and de-pinning of deionised water and toluene droplets in rectangular microchannels fabricated from Su-8 2025 and 2075. / UOIT

Experiments were performed to study forced convective heat transfer of de-ionized water (DI water) and aqueous nanofluids flowing in a microchannel. An array of temperature nanosensors, called “Thin Film Thermocouples (TFT)”, was utilized for performing the experimental measurements. TFT arrays were designed (which included design of photomask layout), microfabricated, packaged and assembled for testing with the experimental apparatus. Heat removal rates from the heated surface to the different testing fluids were measured by varying the coolant flow rates, wall temperatures, nanoparticle material, nanoparticle morphology (shape and nanoparticle size) as well as mass concentrations of nanoparticles in the coolants. Anomalous thermal behavior was observed in the forced convective heat transfer experiments. Precipitation of the nanoparticles on the heat exchanging surface was monitored using Scanning Electron Microscopy (SEM) and Energy Dispersive X-Ray spectroscopy (EDX). Isolated precipitation of nanoparticles is expected to cause formation of “nanofins” leading to enhancement of surface area and thus resulting in enhanced convective heat transfer to the nanofluid coolants. However, excessive precipitation (caused due to the agglomeration of the nanoparticles in the nanofluid coolant) causes scaling (fouling) of the heat exchanging surfaces and thus results in degradation of convective heat transfer. This study shows that the surface morphology plays a crucial role in determining the efficacy of convective heat transfer involving suspensions of nanoparticles in coolants (or nanofluids). Flow visualization and quantitative estimation of near-wall temperature profiles were performed using quantum dots and fluorescent dyes. This non-contact measurement technique for temperature and flow profiles in microchannels using quantum dots is expected to make pioneering contribution to the field of experimental flow visualization and to the study of micro/nano-scale heat transfer phenomena, particularly for forced convective heat transfer of various coolants, including nanofluids. Logical extensions of this study were explored and future directions were proposed. Preliminary experiments to demonstrate feasibility showed significant enhancement in the flow boiling heat flux values for nanofluids compared to that of pure solvent (DIW). Based on the novel phenomena observed in this study several other topics for future research were suggested, such as, using Surface Plasmon Resonance (SPR) platforms to monitor precipitation of nanoparticles on microchannel surfaces in real time (e.g., for generating surface isotherms).

Microfluidics refers to devices and methods for controlling and manipulating fluid flows at length scales less than a millimeter. Miniaturization of a laboratory to a small device, usually termed as lab-on-a-chip, is an advanced technology that integrates a microfluidic system including channels, mixers, reservoirs, pumps and valves on a micro scale chip and can manipulate very small sample volumes of fluids. While several flow control concepts for microfluidic devices have been developed to date, here flow control concepts based on thermally responsive polymer solutions are presented. In particular, flow control concepts base on the thermally triggered reversible phase change of aqueous solutions of the polymer Pluronic will be discussed. Selective heating of small regions of microfluidic channels, which leads to localized gel formation in these channels and reversible channel blockage, will be used to control a membrane valve that controls flow in a separate channel. This new technology will allow generating inexpensive portable bioanalysis tools where microvalve actuation occurs simply through heaters at a constant pressure source without a need for large external pressure control systems as is currently the case. Furthermore, a concept for controlled cross-channel transport of particles and potentially cells is presented that relies on the continuous regeneration of a gel wall at the diffusive interface of two co-streaming fluids in a microfluidic channel.

Microfluidics refers to devices and methods for controlling and manipulating fluid flows at length scales less than a millimeter. Miniaturization of a laboratory to a small device, usually termed as lab-on-a-chip, is an advanced technology that integrates a microfluidic system including channels, mixers, reservoirs, pumps and valves on a micro scale chip and can manipulate very small sample volumes of fluids. While several flow control concepts for microfluidic devices have been developed to date, here flow control concepts based on thermally responsive polymer solutions are presented. In particular, flow control concepts base on the thermally triggered reversible phase change of aqueous solutions of the polymer Pluronic will be discussed. Selective heating of small regions of microfluidic channels, which leads to localized gel formation in these channels and reversible channel blockage, will be used to control a membrane valve that controls flow in a separate channel. This new technology will allow generating inexpensive portable bioanalysis tools where microvalve actuation occurs simply through heaters at a constant pressure source without a need for large external pressure control systems as is currently the case. Furthermore, a concept for controlled cross-channel transport of particles and potentially cells is presented that relies on the continuous regeneration of a gel wall at the diffusive interface of two co-streaming fluids in a microfluidic channel.

Zeotropic mixtures exhibit a temperature glide between the dew and bubble points during condensation. This glide has the potential to increase system efficiency when matched to the thermal sink in power generation, chemical processing, and heating and cooling systems. To understand the coupled heat and mass transfer mechanisms during phase change of high-glide zeotropic mixtures, a comprehensive investigation of the condensation of ammonia and ammonia/water mixtures in small diameter channels was performed. Condensation heat transfer and pressure drop experiments were conducted with ammonia and ammonia/water mixtures. Experiments on ammonia were conducted for varying tube diameters (0.98 < D < 2.16 mm), mass fluxes (75 < G < 225 kg m⁻² s⁻¹) and saturation conditions (30 < Tsat < 60°C). Zeotropic ammonia/water experiments were conducted for multiple tube diameters (0.98 < D < 2.16 mm), mass fluxes (50 < G < 200 kgm⁻² s⁻¹) and bulk ammonia mass fraction (xbulk = 0.8, 0.9, and > 0.96). An experimental methodology and data analysis procedure for evaluating the local condensation heat duty (for incremental ∆q), condensation transfer coefficient (for pure ammonia), apparent heat transfer coefficient (for zeotropic ammonia/water mixtures), and frictional pressure gradient with low uncertainties was developed. A new heat transfer model for condensation of ammonia in mini/microchannels was developed. Using the insights derived from the pure ammonia work, an improved zeotropic condenser design method for high-temperature-glide mixtures in small diameter channels, based on the non-equilibrium film theory, was introduced. The key features of the improved model were the consideration of annular and non-annular flow effects on liquid film transport, including condensate and vapor sensible cooling contributions, and accounting for mini/microchannel effects through the new liquid film correlation. By understanding the behavior of these mixtures in microchannel geometries, highly efficient, compact thermal conversion devices can be developed.

abstract: The heat transfer enhancements available from expanding the cross-section of a boiling microchannel are explored analytically and experimentally. Evaluation of the literature on critical heat flux in flow boiling and associated pressure drop behavior is presented with predictive critical heat flux (CHF) and pressure drop correlations. An optimum channel configuration allowing maximum CHF while reducing pressure drop is sought. A perturbation of the channel diameter is employed to examine CHF and pressure drop relationships from the literature with the aim of identifying those adequately general and suitable for use in a scenario with an expanding channel. Several CHF criteria are identified which predict an optimizable channel expansion, though many do not. Pressure drop relationships admit improvement with expansion, and no optimum presents itself. The relevant physical phenomena surrounding flow boiling pressure drop are considered, and a balance of dimensionless numbers is presented that may be of qualitative use. The design, fabrication, inspection, and experimental evaluation of four copper microchannel arrays of different channel expansion rates with R-134a refrigerant is presented. Optimum rates of expansion which maximize the critical heat flux are considered at multiple flow rates, and experimental results are presented demonstrating optima. The effect of expansion on the boiling number is considered, and experiments demonstrate that expansion produces a notable increase in the boiling number in the region explored, though no optima are observed. Significant decrease in the pressure drop across the evaporator is observed with the expanding channels, and no optima appear. Discussion of the significance of this finding is presented, along with possible avenues for future work. / Dissertation/Thesis / Ph.D. Mechanical Engineering 2013

Microfluidics refers to devices and methods for controlling and manipulating fluid flows at length scales less than a millimeter. Miniaturization of a laboratory to a small device, usually termed as lab-on-a-chip, is an advanced technology that integrates a microfluidic system including channels, mixers, reservoirs, pumps and valves on a micro scale chip and can manipulate very small sample volumes of fluids. While several flow control concepts for microfluidic devices have been developed to date, here flow control concepts based on thermally responsive polymer solutions are presented. In particular, flow control concepts base on the thermally triggered reversible phase change of aqueous solutions of the polymer Pluronic will be discussed. Selective heating of small regions of microfluidic channels, which leads to localized gel formation in these channels and reversible channel blockage, will be used to control a membrane valve that controls flow in a separate channel. This new technology will allow generating inexpensive portable bioanalysis tools where microvalve actuation occurs simply through heaters at a constant pressure source without a need for large external pressure control systems as is currently the case. Furthermore, a concept for controlled cross-channel transport of particles and potentially cells is presented that relies on the continuous regeneration of a gel wall at the diffusive interface of two co-streaming fluids in a microfluidic channel. / Applied Science, Faculty of / Mechanical Engineering, Department of / Graduate

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