ure of merit (zT) due to quantum connement eects. Improving the eciency of
thermoelectric devices allows for the development of better, more economical waste
heat recovery systems. Such systems may be used as bottoming or co-generation
cycles in conjunction with conventional power cycles to recover some of the wasted
heat. Thermal conductivity measurement systems are an important part of the char-
acterization processes of thermoelectric materials. These systems must possess the
capability of accurately measuring the thermal conductivity of both bulk and thin-lm
samples at dierent ambient temperatures.
This paper discusses the construction, validation, and improvement of a thermal
conductivity measurement platform based on the 3-Omega technique. Room temperature
measurements of thermal conductivity done on control samples with known properties
such as undoped bulk silicon (Si), bulk gallium arsenide (GaAs), and silicon dioxide
(SiO2) thin lms yielded 150 W=m􀀀K, 50 W=m􀀀K, and 1:46 W=m􀀀K respectively.
These quantities were all within 8% of literature values. In addition, the thermal
conductivity of bulk SiO2 was measured as a function of temperature in a Helium-
4 cryostat from 75K to 250K. The results showed good agreement with literature
values that all fell within the error range of each measurement. The uncertainty in
the measurements ranged from 19% at 75K to 30% at 250K. Finally, the system
was used to measure the room temperature thermal conductivity of a nanocomposite
composed of cadmium selenide, CdSe, nanocrystals in an indium selenide, In2Se3,
matrix as a function of the concentration of In2Se3. The observed trend was in
qualitative agreement with the expected behavior.
i
The current method of measuring thermal conductivity requires flat plates. For most common civil engineering materials, creating or extracting such samples is difficult. A prototype thermal conductivity experiment had been developed at Arizona State University (ASU) to test cylindrical specimens but proved difficult for repeated testing. In this study, enhancements to both testing methods were made. Additionally, test results of cylindrical testing were correlated with the results from identical materials tested by the Guarded Hot&ndashPlate; method, which uses flat plate specimens. In validating the enhancements made to the Guarded Hot&ndashPlate; and Cylindrical Specimen methods, 23 tests were ran on five different materials. The percent difference shown for the Guarded Hot&ndashPlate; method was less than 1%. This gives strong evidence that the enhanced Guarded Hot-Plate apparatus in itself is now more accurate for measuring thermal conductivity. The correlation between the thermal conductivity values of the Guarded Hot&ndashPlate; to those of the enhanced Cylindrical Specimen method was excellent. The conventional concrete mixture, due to much higher thermal conductivity values compared to the other mixtures, yielded a P&ndashvalue; of 0.600 which provided confidence in the performance of the enhanced Cylindrical Specimen Apparatus. Several recommendations were made for the future implementation of both test methods. The work in this study fulfills the research community and industry desire for a more streamlined, cost effective, and inexpensive means to determine the thermal conductivity of various civil engineering materials.
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.
The interface between rigid fill particles is a point contact with very little interfacial area connecting them. Silver and gallium-based liquid metal (LM) coatings provide soft interfaces that, under pressure, increase the interfacial area between particles and decrease the particle-particle boundary resistance. These engineered contacts are investigated both in and out of the polymer matrix and with and without magnetic alignment of the fill. Magnetically aligned in the polymer matrix, 350nm- thick silver coatings on nickel particles produce a 1.8-fold increase in composite thermal conductivity over the aligned bare-nickel composites. The LM coatings provide similar enhancements, but require higher volumes of LM to do so. This is due to the rapid formation of gallium oxide, which introduces additional thermal boundaries and decreases the benefit of the LM coatings.
The oxide shell of LM droplets (LMDs) can be ruptured using pressure. The pressure needed to rupture LMDs matches closely to thin-walled pressure vessel theory. Furthermore, the addition of tungsten particles stabilizes the mixture for use at higher pressures. Finally, thiols and hydrochloric acid weaken the oxide shell and boost the thermal performance of the beds of LMDs by 50% at pressures much lower than 1 megapascal (MPa) to make them more suitable for use in TIMs.