In frequency-domain photothermal radiometry (FD-PTR) a low-power intensity-modulated optical excitation generates thermal-wave field inside the sample and the subsequent infrared radiation from the sample is analyzed to detect material’s inhomogeneities. The non-contact nature of FD-PTR makes it very suitable for non-destructive evaluation of broad range of materials. Moreover, the methodology is based on intrinsic contrast of light absorption which can be used as a diagnostic tool for inspection of malignancy in biological tissues. Nevertheless, the bottom line is that the physics of heat diffusion allows for a highly damped and dispersive propagation of thermal-waves. As a result, the current FD-PTR modalities suffer from limited inspection depth and poor axial/depth resolution. The main objective of this thesis is to show that using alternative types of modulation schemes (such as linear frequency modulation and binary phase coding) and radar matched filter signal processing, one can obtain localized responses from inherently diffuse thermal wave fields. In this thesis, the photothermal responses of turbid, transparent, and opaque media to linear frequency modulated and binary phase coded excitations are analytically derived. Theoretical simulations suggest that matched-filtering in diffusion-wave field acts as constructive interferometry, localizing the energy of the long-duty excitation under a narrow peak and allowing one to construct depth resolved images. The developed technique is the diffusion equivalent of optical coherence tomography and is named thermal coherence tomography. It was found that the narrow-band binary phase coded matched filtering yields optimal depth resolution, while the broad-band linear frequency modulation can be used to quantify material properties through the multi-parameter fitting of the experimental data to the developed theory. Thermophotonic detection of early dental caries is discussed in detail as a potential diagnostic application of the proposed methodologies. The performance of the diagnostic system is verified through a controlled demineralization protocol as well as in teeth with natural caries.

In frequency-domain photothermal radiometry (FD-PTR) a low-power intensity-modulated optical excitation generates thermal-wave field inside the sample and the subsequent infrared radiation from the sample is analyzed to detect material’s inhomogeneities. The non-contact nature of FD-PTR makes it very suitable for non-destructive evaluation of broad range of materials. Moreover, the methodology is based on intrinsic contrast of light absorption which can be used as a diagnostic tool for inspection of malignancy in biological tissues. Nevertheless, the bottom line is that the physics of heat diffusion allows for a highly damped and dispersive propagation of thermal-waves. As a result, the current FD-PTR modalities suffer from limited inspection depth and poor axial/depth resolution. The main objective of this thesis is to show that using alternative types of modulation schemes (such as linear frequency modulation and binary phase coding) and radar matched filter signal processing, one can obtain localized responses from inherently diffuse thermal wave fields. In this thesis, the photothermal responses of turbid, transparent, and opaque media to linear frequency modulated and binary phase coded excitations are analytically derived. Theoretical simulations suggest that matched-filtering in diffusion-wave field acts as constructive interferometry, localizing the energy of the long-duty excitation under a narrow peak and allowing one to construct depth resolved images. The developed technique is the diffusion equivalent of optical coherence tomography and is named thermal coherence tomography. It was found that the narrow-band binary phase coded matched filtering yields optimal depth resolution, while the broad-band linear frequency modulation can be used to quantify material properties through the multi-parameter fitting of the experimental data to the developed theory. Thermophotonic detection of early dental caries is discussed in detail as a potential diagnostic application of the proposed methodologies. The performance of the diagnostic system is verified through a controlled demineralization protocol as well as in teeth with natural caries.

The objectives of this work are to measure phase equilibria in the carbon dioxide + pyrrole system and to correlate and predict the phase behavior of this system with a thermodynamic model. This binary system is of interest due to the growing applications of supercritical carbon dioxide as a solvent or reaction medium for pyrrole. Polypyrrole is an electrically conducting polymer of interest in a number of applications such as anti-static coatings. Pyrrole has also been used as a reactant in enzymatic reaction. Knowledge of the phase behavior of carbon dioxide + pyrrole system is therefore necessary for evaluating optimal conditions and feasibility of such applications. Phase equilibria in the carbon dioxide + pyrrole system were measured at 313 K, 323 K, and 333 K using a synthetic method. Liquid-vapor (LV) phase behavior and liquid-liquid (LL) phase behavior were observed. The pressure in the experiments ranged from 84 to 151.1 bar. The Patel-Teja equation of state and the Mathias-Klotz-Prausnitz mixing rule with two temperature independent parameters was able to correlate the phase equilibrium data satisfactorily and was used to predict the phase behavior at other temperatures. A pressure-temperature diagram was then constructed from these calculations and suggests that the carbon dioxide + pyrrole system exhibit type IV phase behavior in the classification of Scott and van Konynenburg.

<p>Increasing concern about energy consumption and thesimultaneous need for an acceptable thermal environment makesit necessary to estimate in advance what effect differentthermal factors will have on the occupants. Temperaturemeasurements alone do not account for all climate effects onthe human body and especially not for local effects ofconvection and radiation. People as well as thermal manikinscan detect heat loss changes on local body parts. This factmakes it appropriate to develop measurement methods andcomputer models with the corresponding working principles andlevels of resolution. One purpose of this thesis is to linktogether results from these various investigation techniqueswith the aim of assessing different effects of the thermalclimate on people. The results can be used to facilitatedetailed evaluations of thermal influences both in indoorenvironments in buildings and in different types ofvehicles.</p><p>This thesis presents a comprehensive and detaileddescription of the theories and methods behind full-scalemeasurements with thermal manikins. This is done with new,extended definitions of the concept of equivalent temperature,and new theories describing equivalent temperature as avector-valued function. One specific advantage is that thelocally measured or simulated results are presented with newlydeveloped "comfort zone diagrams". These diagrams provide newways of taking into consideration both seat zone qualities aswell as the influence of different clothing types on theclimate assessment with "clothing-independent" comfort zonediagrams.</p><p>Today, different types of computer programs such as CAD(Computer Aided Design) and CFD (Computational Fluid Dynamics)are used for product development, simulation and testing of,for instance, HVAC (Heating, Ventilation and Air Conditioning)systems, particularly in the building and vehicle industry.Three different climate evaluation methods are used andcompared in this thesis: human subjective measurements, manikinmeasurements and computer modelling. A detailed description ispresented of how developed simulation methods can be used toevaluate the influence of thermal climate in existing andplanned environments. In different climate situationssubjective human experiences are compared to heat lossmeasurements and simulations with thermal manikins. Thecalculation relationships developed in this research agree wellwith full-scale measurements and subject experiments indifferent thermal environments. The use of temperature and flowfield data from CFD calculations as input produces acceptableresults, especially in relatively homogeneous environments. Inmore heterogeneous environments the deviations are slightlylarger. Possible reasons for this are presented along withsuggestions for continued research, new relationships andcomputer codes.</p><p><b>Key-words:</b>equivalent temperature, subject, thermalmanikin, mannequin, thermal climate assessment, heat loss,office environment, cabin climate, ventilated seat, computermodel, CFD, clothing-independent, comfort zone diagram.</p>

The A2Mo3O12 family, where A3+ is a large trivalent cation, can show interesting thermal properties such as negative thermal expansion, also known as thermomiotic behavior, where the overall volume of the material contracts with increasing temperature. A selection of compounds in this family, namely HfMgMo3O12, In2Mo3O12, Y2Mo3O12, Al2Mo3O12, In(HfMg)0.5Mo3O12, and In1.5(HfMg)0.25Mo3O12, have been synthesized using solid-state and mechanical activation techniques as well as a simplified sol-gel approach (Al2Mo3O12). Coefficients of thermal expansion were found to range from large-negative to low-positive in the orthorhombic phase, including near-zero in In(HfMg)0.5Mo3O12 and In1.5(HfMg)0.25Mo3O12. This set of materials provided insight into the role of low-frequency phonon modes in open-framework materials. Low-temperature heat capacity and thermal conductivity measurements confirmed that low-frequency modes were active in thermomiotic materials, and also present to some extent in all members of the open-framework A2Mo3O12 family examined. A clear correlation exists between the magnitude and sign of the coefficient of thermal expansion in the orthorhombic phase and the contribution of low-energy modes to the low-temperature heat capacity, with negative thermal expansion materials having a larger contribution. The low-frequency phonon modes result in low thermal conductivity and reduced phonon mean free paths when compared to conventional ceramics and indicate that these low values are characteristic of open-framework materials in NTE families even if the materials in the families are not thermomiotic themselves.

<p>Low thermal conductivity is a primary limitation in the development of energy-efficient heat transfer fluids that are required in numerous industrial sectors. Recently submicron and high aspect ratio particles (nanoparticles and nanotubes) were introduced into the heat transfer fluids to enhance the thermal conductivity of the resulting nanofluids. The aim of this project was to investigate the physico-chemical properties of nanofluids synthesized using submicron and high aspect ratio particles suspended in heat transfer fluids .</p>

abstract: The rapid progress of solution-phase synthesis has led colloidal nanocrystals one of the most versatile nanoscale materials, provided opportunities to tailor material's properties, and boosted related technological innovations. Colloidal nanocrystal-based materials have been demonstrated success in a variety of applications, such as LEDs, electronics, solar cells and thermoelectrics. In each of these applications, the thermal transport property plays a big role. An undesirable temperature rise due to inefficient heat dissipation could lead to deleterious effects on devices' performance and lifetime. Hence, the first project is focused on investigating the thermal transport in colloidal nanocrystal solids. This study answers the question that how the molecular structure of nanocrystals affect the thermal transport, and provides insights for future device designs. In particular, PbS nanocrystals is used as a monitoring system, and the core diameter, ligand length and ligand binding group are systematically varied to study the corresponding effect on thermal transport. Next, a fundamental study is presented on the phase stability and solid-liquid transformation of metallic (In, Sn and Bi) colloidal nanocrystals. Although the phase change of nanoparticles has been a long-standing research topic, the melting behavior of colloidal nanocrytstals is largely unexplored. In addition, this study is of practical importance to nanocrystal-based applications that operate at elevated temperatures. Embedding colloidal nanocrystals into thermally-stable polymer matrices allows preserving nanocrystal size throughout melt-freeze cycles, and therefore enabling observation of stable melting features. Size-dependent melting temperature, melting enthalpy and melting entropy have all been measured and discussed. In the next two chapters, focus has been switched to developing colloidal nanocrystal-based phase change composites for thermal energy storage applications. In Chapter 4, a polymer matrix phase change nanocomposite has been created. In this composite, the melting temperature and energy density could be independently controlled by tuning nanocrystal diameter and volume fractions. In Chapter 5, a solution-phase synthesis on metal matrix-metal nanocrytal composite is presented. This approach enables excellent morphological control over nanocrystals and demonstrated a phase change composite with a thermal conductivity 2 - 3 orders of magnitude greater than typical phase change materials, such as organics and molten salts. / Dissertation/Thesis / Doctoral Dissertation Mechanical Engineering 2015

Additive manufacturing (AM) is a manufacturing technique that adds material, such as polymers, ceramics, and metals, in patterned layers to build three-dimensional parts for applications related to medicine, aviation, and energy. AM processes for metals like selective laser melting (SLM) hold the unique advantage of fabricating metal parts with complex architectures that cannot be produced by conventional manufacturing techniques. Thermal transport can be a focal point of unique AM products and is likewise important to metal AM processes. This dissertation investigates AM metal meshes with spatially varied thermal conductivities that can be used to maximize the charge and discharge rates for thermal energy storage and thermal management by phase change materials (PCMs). Further, manufacturing these meshes demands excellent thermal control in the metal powder bed for SLM processes. Since the thermal conductivities of metal powders specific to AM were previously unknown, we made pioneering measurements of such powders as a function of gas infiltration. In the past, thermal transport was improved in phase change materials for energy storage by adding spatially homogeneous metal foams or particles into PCMs to create composites with uniformly-enhanced (UE) thermal conductivity. Spatial variation can now be realized due to the emergence of metal AM processes whereby graded AM meshes are inserted into PCMs to create PCM composites with spatially-enhanced (SE) thermal conductivity. As yet, there have been no studies on what kind of spatial variation in thermal conductivity can further improve charge and discharge rates of the PCM. Making such mesh structures, which exhibit unsupported overhangs that limit heat dissipation pathways during SLM processes, demands understanding of heat diffusion within the surrounding powder bed. This inevitably relies on the precise knowledge of the thermal conductivity of AM metal powders. Currently, no measurements of thermal conductivity of AM powders have been made for the SLM process. In chapter 2 and 3, we pioneer and optimize the spatial variation of metal meshes to maximize charge and discharge rates in PCMs. Chapter 2 defines and analytically determines an enhancement ratio of charge rates using spatially-linear thermal conductivities in Cartesian and cylindrical coordinates with a focus on thermal energy storage. Chapter 3 further generalizes thermal conductivity as a polynomial function in space and numerically optimizes the enhancement ratio in spherical coordinates with a focus on thermal management of electronics. Both of our studies find that higher thermal conductivities of SE composites near to the heat source outperform those of UE composites. For selected spherical systems, the enhancement ratio reaches more than 800% relative to existing uniform foams. In chapter 4, the thermal conductivities of five metal powders for the SLM process were measured using the transient hot wire method. These measurements were conducted with three infiltrating gases (He, N2, and Ar) within a temperature range of 295-470 K and a gas pressure range of 1.4-101 kPa. Our measurements indicate that the pressure and the composition of the gas have a significant influence on the effective thermal conductivity of the powder. We find that infiltration with He provides more than 300% enhancement in powder thermal conductivity, relative to conventional infiltrating gases N2 and Ar. We anticipate that this use of He will result in better thermal control of the powder bed and thus will improve surface quality in overhanging structures.

As electronic packages and their thermal solutions become more complex the reliability margins in the thermal solutions diminish and become less tolerant to errors in reliability predictions. The current method of thermally stress testing thermal solutions can be over or under predicting end of life thermal performance. Benefits of accurate testing and modeling are improved silicon yield in manufacturing, improved performance, lower cost thermal solutions, and shortened test times. The current method of thermally stress testing is to place the entire unit in an elevated isothermal temperature and periodically measure thermal performance. Isothermally aging is not an accurate representation of how the unit will be used by the customer and does not capture the thermal gradients and mechanical stresses due to different coefficients of thermal expansion of the materials used in the thermal solution. A new testing system, CITRAM which is an acronym for Constant Interface Temperature Reliability Method, has been developed that uses an electronic test board. The approach captures the thermal and mechanical stresses accurately and improves test time by 20-30% as a result of automation. Through this study a difference in the two methods has been identified and the new CITRAM method should be adopted as current practice.

In order to enhance the performance of a large horizontal thermal energy storage, a numerical model was generated and validated using measurements obtained from Drake Landing Solar Community (DLSC). A total of nine different baffle configurations were tested in order to enhance the thermal stratification. The designs were tested for a total of six different cases of charging, discharging and simultaneous charging and discharging in an attempt to better identify key features that mix the tank under realistic conditions. Characterization of the tank performance was done by monitoring the tank outlet temperature and computing Huhn's efficiency Second Law characterization index). Results show that the current tanks at DLSC experience excessive mixing due to plume entrainment that occurs during the spreading of the inlet jet. The introduction of a baffle into the middle of the tank was found to have no impact on the level of stratification. In addition, most designs tested have a relatively high level of stratification during charging, discharging and simultaneous charging and discharging, but fail to sustain the level of stratification when a positive buoyant jet is introduced. It was demonstrated that the inlets and outlets should be moved to the top and bottom of the tank to eliminate stagnant fluid that is not easily discharged. Horizontal baffles are effective in allowing the inlet jet to spread horizontally but not vertically, thus reducing the mixing. Alternatively, a simple solution would be to increase the size of the inlet, which has a comparable performance to the best baffle configurations. / Thesis / Master of Applied Science (MASc)