Size-Dependent Melting Behavior of Colloidal In, Sn, and Bi Nanocrystals

128507-Thumbnail Image.png
Description

Colloidal nanocrystals are a technologically important class of nanostructures whose phase change properties have been largely unexplored. Here we report on the melting behavior of In, Sn, and Bi nanocrystals dispersed in a polymer matrix. This polymer matrix prevents the

Colloidal nanocrystals are a technologically important class of nanostructures whose phase change properties have been largely unexplored. Here we report on the melting behavior of In, Sn, and Bi nanocrystals dispersed in a polymer matrix. This polymer matrix prevents the nanocrystals from coalescing with one another and enables previously unaccessed observations on the melting behavior of colloidal nanocrystals. We measure the melting temperature, melting enthalpy, and melting entropy of colloidal nanocrystals with diameters of approximately 10 to 20 nm. All of these properties decrease as nanocrystal size decreases, although the depression rate for melting temperature is comparatively slower than that of melting enthalpy and melting entropy. We also observe an elevated melting temperature during the initial melt-freeze cycle that we attribute to surface stabilization from the organic ligands on the nanocrystal surface. Broad endothermic melting valleys and very large supercoolings in our calorimetry data suggest that colloidal nanocrystals exhibit a significant amount of surface pre-melting and low heterogeneous nucleation probabilities during freezing.

Date Created
2015-11-17
Agent

Thermal storage and transport in colloidal nanocrystal-based materials

154184-Thumbnail Image.png
Description
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,

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.
Date Created
2015
Agent

Metal Matrix-Metal Nanoparticle Composites With Tunable Melting Temperature and High Thermal Conductivity for Phase-Change Thermal Storage

Description

Phase-change materials (PCMs) are of broad interest for thermal storage and management applications. For energy-dense storage with fast thermal charging/discharging rates, a PCM should have a suitable melting temperature, large enthalpy of fusion, and high thermal conductivity. To simultaneously accomplish

Phase-change materials (PCMs) are of broad interest for thermal storage and management applications. For energy-dense storage with fast thermal charging/discharging rates, a PCM should have a suitable melting temperature, large enthalpy of fusion, and high thermal conductivity. To simultaneously accomplish these traits, we custom design nanocomposites consisting of phase-change Bi nanoparticles embedded in an Ag matrix. We precisely control nanoparticle size, shape, and volume fraction in the composite by separating the nanoparticle synthesis and nanocomposite formation steps. We demonstrate a 50–100% thermal energy density improvement relative to common organic PCMs with equivalent volume fraction. We also tune the melting temperature from 236–252 °C by varying nanoparticle diameter from 8.1–14.9 nm. Importantly, the silver matrix successfully prevents nanoparticle coalescence, and no melting changes are observed during 100 melt–freeze cycles. The nanocomposite’s Ag matrix also leads to very high thermal conductivities. For example, the thermal conductivity of a composite with a 10% volume fraction of 13 nm Bi nanoparticles is 128 ± 23 W/m-K, which is several orders of magnitude higher than typical thermal storage materials. We complement these measurements with calculations using a modified effective medium approximation for nanoscale thermal transport. These calculations predict that the thermal conductivity of composites with 13 nm Bi nanoparticles varies from 142 to 47 W/m-K as the nanoparticle volume fraction changes from 10 to 35%. Larger nanoparticle diameters and/or smaller nanoparticle volume fractions lead to larger thermal conductivities.

Date Created
2015-02-01
Agent