Metal-Assisted Electrochemical Nanoimprinting: Delivering Resolution and Throughput via Engineered Stamps

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Description
Recent advancements in the field of light wavefront engineering rely on complex 3D metasurfaces composed of sub-wavelength structures which, for the near infrared range, are challenging to manufacture using contemporary scalable micro- and nanomachining solutions. To address this demand, a

Recent advancements in the field of light wavefront engineering rely on complex 3D metasurfaces composed of sub-wavelength structures which, for the near infrared range, are challenging to manufacture using contemporary scalable micro- and nanomachining solutions. To address this demand, a novel parallel micromachining method, called metal-assisted electrochemical nanoimprinting (Mac-Imprint) was developed. Mac-Imprint relies on the catalysis of silicon wet etching by a gold-coated stamp enabled by mass-transport of the reactants to achieve high pattern transfer fidelity. This was realized by (i) using nanoporous catalysts to promote etching solution diffusion and (ii) semiconductor substrate pre-patterning with millimeter-scale pillars to provide etching solution storage. However, both of these approaches obstruct scaling of the process in terms of (i) surface roughness and resolution, and (ii) areal footprint of the fabricated structures. To address the first limitation, this dissertation explores fundamental mechanisms underlying the resolution limit of Mac-Imprint and correlates it to the Debye length (~0.9 nm). By synthesizing nanoporous catalytic stamps with pore size less than 10 nm, the sidewall roughness of Mac-Imprinted patterns is reduced to levels comparable to plasma-based micromachining. This improvement allows for the implementation of Mac-Imprint to fabricate Si rib waveguides with limited levels of light scattering on its sidewall. To address the second limitation, this dissertation focuses on the management of the etching solution storage by developing engineered stamps composed of highly porous polymers coated in gold. In a plate-to-plate configuration, such stamps allow for the uniform patterning of chip-scale Si substrates with hierarchical 3D antireflective and antifouling patterns. The development of a Mac-Imprint system capable of conformal patterning onto non-flat substrates becomes possible due to the flexible and stretchable nature of gold-coated porous polymer stamps. Understanding of their mechanical behavior during conformal contact allows for the first implementation of Mac-Imprint to directly micromachine 3D hierarchical patterns onto plano-convex Si lenses, paving the way towards scalable fabrication of multifunctional 3D metasurfaces for applications in advanced optics.
Date Created
2022
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Liquid-Phase Thermochemical Reactions For Thermal Energy Transport and Storage

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Description
District heating plays an important role in improving energy efficiency and providing thermal heat to buildings. Instead of using water as an energy carrier to transport sensible heat, this dissertation explores the use of liquid-phase thermochemical reactions for district heating

District heating plays an important role in improving energy efficiency and providing thermal heat to buildings. Instead of using water as an energy carrier to transport sensible heat, this dissertation explores the use of liquid-phase thermochemical reactions for district heating as well as thermal storage. Chapters 2 and 3 present thermodynamic and design analyses for the proposed district heating system. Chapter 4 models the use of liquid-phase thermochemical reactions for on-site solar thermal storage. In brief, the proposed district heating system uses liquid-phase thermochemical reactions to transport thermal energy from a heat source to a heat sink. The separation ensures that the stored thermochemical heat can be stored indefinitely and/or transported long distances. The reactant molecules are then pumped over long distances to the heat sink, where they are combined in an exothermic reaction to provide heat. The product of the exothermic reaction is then pumped back to the heat source for re-use. The key evaluation parameter is the system efficiency. The results demonstrate that with heat recovery, the system efficiency can be up to 77% when the sink temperature equals 25 C. The results also indicate that the appropriate chemical reaction candidates should have large reaction enthalpy and small reaction entropy. Further, the design analyses of two district heating systems, Direct District Heating (DDH) system and Indirect District Heating (IDH) system using the solvated case shows that the critical distance is 106m. When the distance is shorter than 1000,000m, the factors related to the chemical reaction at the user side and factors related to the separation process are important for the DDH system. When the distance is longer than 106m, the factors related to the fluid mechanic become more important. Because the substation of the IDH system degrades the quality of the energy, when the distance is shorter than 106m, the efficiency of the substation is significant. Lastly, I create models for on-site solar thermal storage systems using liquid-phase thermochemical reactions and hot water. The analysis shows that the thermochemical reaction is more competitive for long-duration storage applications. However, the heat recovery added to the thermochemical thermal storage system cannot help improving solar radiation absorption with high inlet temperature of the solar panel.
Date Created
2022
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Compression-Activated Thermally Enhanced Liquid Metal Composites with Tunable Functional Properties

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Description
Thermal management of electronics is critical to meet the increasing demand for high power and performance. Thermal interface materials (TIMs) play a key role in dissipating heat away from the microelectronic chip and hence are a crucial component in electronics

Thermal management of electronics is critical to meet the increasing demand for high power and performance. Thermal interface materials (TIMs) play a key role in dissipating heat away from the microelectronic chip and hence are a crucial component in electronics cooling. Challenges persist with overcoming the interfacial boundary resistance and filler particle connectivity in TIMs to achieve thermal percolation while maintaining mechanical compliance. Gallium-based liquid metal (LM) capsules offer a unique set of thermal-mechanical characteristics that make them suitable candidates for high-performance TIM fillers. This dissertation research focuses on resolving the fundamental challenges posed by integration of LM fillers in polymer matrix. First, the rupture mechanics of LM capsules under pressure is identified as a key factor that dictates the thermal connectivity between LM-based fillers. This mechanism of oxide “popping” in LM particle beds independent of the matrix material provides insights in overcoming the particle-particle connectivity challenges. Second, the physical barrier introduced due to the polymer matrix needs to be overcome to achieve thermal percolation. Matrix fluid viscosity impacts thermal transport, with high viscosity uncured matrix inhibiting the thermal bridging of fillers. In addition, incorporation of solid metal co-fillers that react with LM fillers is adopted to facilitate popping of LM oxide in uncured polymer to overcome this matrix barrier. Solid silver metal additives are used to rupture the LM oxide, form inter-metallic alloy (IMC), and act as thermal anchors within the matrix. This results in the formation of numerous thermal percolation paths and hence enhances heat transport within the composite. Further, preserving this microstructure of interconnected multiphase filler system with thermally conductive percolation pathways in a cured polymer matrix is critical to designing high-performing TIM pads. Viscosity of the precursor polymer solution prior to curing plays a major role in the resulting thermal conductivity. A multipronged strategy is developed that synergistically combines reactive solid and liquid fillers, a polymer matrix with low pre-cure viscosity, and mechanical compression during thermal curing. The results of this dissertation aim to provide fundamental insights into the integration of LMs in polymer composites and give design knobs to develop high thermally conducting soft composites.
Date Created
2022
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Condensation Heat Transfer on Actuated Thermally Enhanced Hydrophobic Tubes

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Description
Dehumidifiers are ubiquitous and essential household appliances in many parts of the world. They are used extensively in tropical and sub-tropical environments to lower humidity in living spaces, where high ambient humidity can lead to numerous negative health effects from

Dehumidifiers are ubiquitous and essential household appliances in many parts of the world. They are used extensively in tropical and sub-tropical environments to lower humidity in living spaces, where high ambient humidity can lead to numerous negative health effects from mild physical discomfort to more serious conditions such as mold build up in structures and dangerous illnesses in humans. Most common dehumidifiers are based on conventional mechanical refrigeration cycles, where the effects of condensation heat transfer play a critical role in their effectiveness. In these devices, humid ambient air flows over a cold evaporator, which lowers the temperature of the humid ambient air below its dew point temperature and therefore decreases its water content by causing liquid water condensation on the evaporator surface. The rate at which humidity can be extracted from the ambient air is governed in part by how quickly the evaporator can shed the condensed droplets. Recent advances in soft, stretchable, thermally enhanced (through the addition of liquid metals) silicone tubing offer the potential to use these stretchable tubes in place of conventional copper pipe for applications such as dehumidification. Copper is a common material choice for dehumidifier evaporator tubing owing to its ubiquity and its high thermal conductivity, but it has several thermal downsides. Specifically, copper tubes remain static and typically rely on gravity alone to remove water droplets when they reach a sufficient mass. Additionally, copper’s naturally hydrophilic surface promotes film-wise condensation, which is substantially less effective than dropwise condensation. In contrast to copper, thermally enhanced soft stretchable tubes have naturally hydrophobic surfaces that promote the more effective dropwise condensation mode and a soft surface that offers higher nucleation density. However, soft surfaces also increase droplet pinning, which inhibits their departure. This work experimentally explores the effects of periodic axial stretching and retraction of soft tubing internally cooled with water on droplet condensation dynamics on its exterior surface. Results are discussed in terms of overall system thermal performance and real-time condensation imaging. An overall null result is discovered, and recommendations for future experiments are made.
Date Created
2022
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Potential of Data-driven Approaches for Modeling Heat and Mass Convection Processes

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Description
In convective heat transfer processes, heat transfer rate increases generally with a large fluid velocity, which leads to complex flow patterns. However, numerically analyzing the complex transport process and conjugated heat transfer requires extensive time and computing resources. Recently, data-driven

In convective heat transfer processes, heat transfer rate increases generally with a large fluid velocity, which leads to complex flow patterns. However, numerically analyzing the complex transport process and conjugated heat transfer requires extensive time and computing resources. Recently, data-driven approach has risen as an alternative method to solve physical problems in a computational efficient manner without necessitating the iterative computations of the governing physical equations. However, the research on data-driven approach for convective heat transfer is still in nascent stage. This study aims to introduce data-driven approaches for modeling heat and mass convection phenomena. As the first step, this research explores a deep learning approach for modeling the internal forced convection heat transfer problems. Conditional generative adversarial networks (cGAN) are trained to predict the solution based on a graphical input describing fluid channel geometries and initial flow conditions. A trained cGAN model rapidly approximates the flow temperature, Nusselt number (Nu) and friction factor (f) of a flow in a heated channel over Reynolds number (Re) ranging from 100 to 27750. The optimized cGAN model exhibited an accuracy up to 97.6% when predicting the local distributions of Nu and f. Next, this research introduces a deep learning based surrogate model for three-dimensional (3D) transient mixed convention in a horizontal channel with a heated bottom surface. Conditional generative adversarial networks (cGAN) are trained to approximate the temperature maps at arbitrary channel locations and time steps. The model is developed for a mixed convection occurring at the Re of 100, Rayleigh number of 3.9E6, and Richardson number of 88.8. The cGAN with the PatchGAN based classifier without the strided convolutions infers the temperature map with the best clarity and accuracy. Finally, this study investigates how machine learning analyzes the mass transfer in 3D printed fluidic devices. Random forests algorithm is hired to classify the flow images taken from semi-transparent 3D printed tubes. Particularly, this work focuses on laminar-turbulent transition process occurring in a 3D wavy tube and a straight tube visualized by dye injection. The machine learning model automatically classifies experimentally obtained flow images with an accuracy > 0.95.
Date Created
2022
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Multiphase Liquid Metal Composites for Soft Thermal Applications

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Description
Soft thermal interface materials (TIMs) are critical for improving the thermal management of advanced microelectronic devices. Despite containing high thermal conductivity filler materials, TIM performance is limited by thermal resistances between fillers, filler-matrix, and external contact resistance. Recently, room-temperature liquid

Soft thermal interface materials (TIMs) are critical for improving the thermal management of advanced microelectronic devices. Despite containing high thermal conductivity filler materials, TIM performance is limited by thermal resistances between fillers, filler-matrix, and external contact resistance. Recently, room-temperature liquid metals (LMs) started to be adapted as an alternative TIM for their low thermal resistance and fluidic nature. However, LM-based TIMs face challenges due to their low viscosity, non-wetting qualities, chemical reactivity, and corrosiveness towards aluminum.To address these concerns, this dissertation research investigates fundamental LM properties and assesses their utility for developing multiphase LM composites with strong thermal properties. Augmentation of LM with gallium oxide and air capsules lead to LM-base foams with improved spreading and patterning. Gallium oxides are responsible for stabilizing LM foam structures which is observed through electron microscopy, revealing a temporal evolution of air voids after shear mixing in air. The presence of air bubbles and oxide fragments in LM decreases thermal conductivity while increasing its viscosity as the shear mixing time is prolonged. An overall mechanism for foam generation in LM is presented in two stages: 1) oxide fragment accumulation and 2) air bubble entrapment and propagation. To avoid the low thermal conductivity air content, mixing of non-reactive particles of tungsten or silicon carbide (SiC) into LM forms paste-like LM-based mixtures that exhibit tunable high thermal conductivity 2-3 times beyond the matrix material. These filler materials remain chemically stable and do not react with LM over time while suspended. Gallium oxide-mediated wetting mechanisms for these non-wetting fillers are elucidated in oxygen rich and deficient environments. Three-phase composites consisting of LM and Ag-coated SiC fillers dispersed in a noncuring silicone oil matrix address LM-corrosion related issues. Ag-coated SiC particles enable improved wetting of the LM, and the results show that applied pressure is necessary for bridging of these LM-coated particles to improve filler thermal resistance. Compositional tuning between the fillers leads to thermal improvements in this multiphase composite. The results of this dissertation work aim to advance our current understanding of LMs and how to design LM-based composite materials for improved TIMs and other soft thermal applications.
Date Created
2021
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Simulated Thermal Resistance of Thermogalvanic Cells with Triply Periodic Minimal Surface Structures using ANSYS

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Description
Buildings release an abundance of waste heat that is left unused. Thermogalvaniccells (TGCs) can take advantage of waste heat to generate electricity with a low temperature gradient. In this dissertation, I simulated the thermal transport of TGCs containing different triply periodic minimal

Buildings release an abundance of waste heat that is left unused. Thermogalvaniccells (TGCs) can take advantage of waste heat to generate electricity with a low temperature gradient. In this dissertation, I simulated the thermal transport of TGCs containing different triply periodic minimal surface (TPMS) structures, compared it to measured values and conducted a mesh convergence study to examine the viability of the computational fluid dynamics (CFD) solutions. Natural convection effects are one of the driving forces in TGCs. Using the Bousinesq approximation, I was able to capture those effects in the CFD simulations as it accounts for the density variations of the fluid. Upon simulating the TGC using the Schwarz P TPMS geometry, the cathode temperature converged as I refined the mesh and approached the measured value. As for the IWP TPMS structure, the solution converged as I refined the mesh, despite having a deviation to the measured values. This was due to the abundance of sharp regions along the walls of the TPMS that ANSYS had difficulty to accurately model. Furthermore, I simulated the TGCs using different boundary condition (BC) approximations to observe the cathode and anode temperatures as well as their overall ∆T across the cell. For the TGC containing the Schwarz P geometry, Case C (constant anode temperature BC with TPMS conduction) was the most accurate while Case D (convection BC at anode with TPMS conduction) deviated from the measured values, had the most accurate ∆T and was well within the uncertainty bounds of the measured values. Larger temperature fluctuations were seen closer to the cathode while the effects steadily decrease as the fluid approaches the anode. Moreover, the TGC containing the IWP structures presented interesting results. The main deviation was from the cathode temperatures because a higher temperature readings meant that more cells in the fluid domain were prone to diverging, thereby resulting in a higher calculated cathode temperature. Simulating the TGC with the Schwarz P geometry produced satisfactory results while the TGC using the IWP geometry deviated due to the software limitations. Finally, the effects of natural convection and TPMS on TGCs were studied and it was found that the absence of natural convection lead to a higher ∆T while the absence of TPMS resulted in a more uniform temperature distribution throughout the domain
Date Created
2021
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Experimental Study of Water-Ice Phase Change Process Improvement Using Ultrasonic Energy

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Description
The phase change process of freezing water is an important application in several fields such as ice making, food freezing technologies, pharmaceuticals etc. Due to the widespread usage of ice-related products, process improvements in this technology can potentially lead to

The phase change process of freezing water is an important application in several fields such as ice making, food freezing technologies, pharmaceuticals etc. Due to the widespread usage of ice-related products, process improvements in this technology can potentially lead to substantial energy savings. After studying the freezing process of water, the supercooling phenomenon was found to occur which showed a negative effect. Therefore, ultrasound was proposed as a technique to reduce the supercooling effect and improve the heat transfer rate. An experimental study was conducted to analyze the energy expenditures in the freezing process with and without the application of ultrasound. After a set of preliminary experiments, an intermittent application of ultrasound at 10W & 3.5W power levels were found to be more effective than constant-power application, and were explored in further detail. The supercooling phenomenon was thoroughly studied through iterative experiments. It was also found that the application of ultrasound during the freezing process led to the formation of shard-like ice crystals. From the intermittent ultrasound experiments performed at 10W and 3.5W power levels, percentage energy enhancements relative to no ultrasound of 8.9% ± 12.4% and 11.9% ± 24.6% were observed, respectively.
Date Created
2021
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Fundamentals of Soft, Stretchable Heat Exchanger Design

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Description
Deformable heat exchangers could provide a multitude of previously untapped advantages ranging from adaptable performance via macroscale, dynamic shape change (akin to dilation/constriction seen in blood vessels) to enhanced heat transfer at thermal interfaces through microscale, surface deformations. So far,

Deformable heat exchangers could provide a multitude of previously untapped advantages ranging from adaptable performance via macroscale, dynamic shape change (akin to dilation/constriction seen in blood vessels) to enhanced heat transfer at thermal interfaces through microscale, surface deformations. So far, making deformable, ‘soft heat exchangers’ (SHXs) has been limited by the low thermal conductivity of materials with suitable mechanical properties. The recent introduction of liquid-metal embedded elastomers by Bartlett et al1 has addressed this need. Specifically, by remaining soft and stretchable despite the addition of filler, these thermally conductive composites provide an ideal material for the new class of “soft thermal systems”, which is introduced in this work. Understanding such thermal systems will be a key element in enabling technology that require high levels of stretchability, such as thermoregulatory garments, soft electronics, wearable electronics, and high-powered robotics. Shape change inherent to SHX operation has the potential to violate many conventional assumptions used in HX design and thus requires the development of new theoretical approaches to predict performance. To create a basis for understanding these devices, this work highlights two sequential studies. First, the effects of transitioning to a surface deformable, SHX under steady state static conditions in the setting of a liquid cooling device for thermoregulation, electronics and robotics applications was explored. In this study, a thermomechanical model was built and validated to predict the thermal performance and a system wide analysis to optimize such devices was carried out. Second, from a more fundamental perspective, the effects of SHXs undergoing transient shape deformation during operation was explored. A phase shift phenomenon in cooling performance dependent on stretch rate, stretch extent and thermal diffusivity was discovered and explained. With the use of a time scale analysis, the extent of quasi-static assumption viability in modeling such systems was quantified and multiple shape modulation regime limits were defined. Finally, nuance considerations and future work of using liquid metal-silicone composites in SHXs were discussed.
Date Created
2020
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Stimuli Responsive Barrier Materials for Breathable, Chemically-Protective Wearable Fabrics

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Description
As experiencing hot months and thermal stresses is becoming more common, chemically protective fabrics must adapt and provide protections while reducing the heat stress to the body. These concerns affect first responders, warfighters, and workers regularly surrounded by hazardous chemical

As experiencing hot months and thermal stresses is becoming more common, chemically protective fabrics must adapt and provide protections while reducing the heat stress to the body. These concerns affect first responders, warfighters, and workers regularly surrounded by hazardous chemical agents. While adapting traditional garments with cooling devices provides one route to mitigate this issue, these cooling methods add bulk, are time limited, and may not be applicable in locations without logistical support. Here I take inspiration from nature to guide the development of smart fabrics that have high breathability, but self-seal on exposure to target chemical(s), providing a better balance between cooling and protection.

Natural barrier materials were explored as a guide, focusing specifically on prickly pear cacti. These cacti have a natural waxy barrier that provides protection from dehydration and physically changes shape to modify surface wettability and water vapor transport. The results of this study provided a basis for a shape changing polymer to be used to respond directly to hazardous chemicals, swelling to contain the agent.

To create a stimuli responsive material, a novel superabsorbent polymer was synthesized, based on acrylamide chemistry. The polymer was tested for swelling properties in a wide range of organic liquids and found to highly swell in moderately polar organic liquids. To help predict swelling in untested liquids, the swelling of multiple test liquids were compared with their thermodynamic properties to observe trends. As the smart fabric needs to remain breathable to allow evaporative cooling, while retaining functionality when soaked with sweat, absorption of water, as well as that of an absorbing liquid in the presence of water were tested.

Micron sized particles of the developed polymer were deposited on a plastic mesh with pore size and open area similar to common clothing fabric to establish the proof of concept of using a breathable barrier to provide chemical protection. The polymer coated mesh showed minimal additional resistance to water vapor transport, relative to the mesh alone, but blocked more than 99% of a xylene aerosol from penetrating the barrier.
Date Created
2020
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