Scott N. Schiffres

Tunable electrical and thermal transport in ice-templated multilayer graphene nanocomposites through freezing rate control.

We demonstrate tunable electrical and thermal conductivities through freezing rate control in solution-based nanocomposites. For a prototypical suspension of 1 vol % multilayer graphene suspended in hexadecane, the solid-liquid electrical conductivity contrast ratio can be tuned from 1 to 4.5 orders of magnitude for freezing rates between 10(2) and 10(-3) °C/min. We hypothesize that this dramatic variation stems from ice-templating, whereby crystal growth drives nanoparticles into concentrated intercrystal regions, increasing the percolation pathways and reducing the internanoparticle electrical resistance. Optical microscopy supports the ice-templating hypothesis, as these dramatic property changes coincide with changing crystal size. Under the same range of freezing rates, the nanocomposite solid-liquid thermal conductivity contrast ratio varies between 2.3 and 3.0, while pure hexadecanes varies between 2.1 and 2.6. The nanocomposites thermal conductivity contrast ratios and solid phase enhancements are greater than effective medium theory predictions. We suggest this is due to ice-templating, consistent with our electrical measurements, as well as nanoparticle-induced molecular alignment of alkanes.

Vibrational Mismatch of Metal Leads Controls Thermal Conductance of Self-Assembled Monolayer Junctions

We present measurements of the thermal conductance of self-assembled monolayer (SAM) junctions formed between metal leads (Au, Ag, Pt, and Pd) with mismatched phonon spectra. The thermal conductance obtained from frequency domain thermoreflectance experiments is 65 ± 7 MW/m(2) K for matched Au-alkanedithiol-Au junctions, while the mismatched Au-alkanedithiol-Pd junctions yield a thermal conductance of 36 ± 3 MW/m(2) K. The experimental observation that junction thermal conductance (per molecule) decreases as the mismatch between the lead vibrational spectra increases, paired with results from molecular dynamics (MD) simulations, suggest that phonons scatter elastically at the metal-SAM interfaces. Furthermore, we resolve a known discrepancy between measurements and MD predictions of SAM thermal conductance by using a contact mechanics model to predict 54 ± 15% areal contact in the Au-alkanedithiol-Au experimental junction. This incomplete contact obscures the actual junction thermal conductance of 115 ± 22 MW/m(2) K, which is comparable to that of metal-dielectric interfaces.

Improved 3-omega measurement of thermal conductivity in liquid, gases, and powders using a metal-coated optical fiber

A novel 3ω thermal conductivity measurement technique called metal-coated 3ω is introduced for use with liquids, gases, powders, and aerogels. This technique employs a micron-scale metal-coated glass fiber as a heater/thermometer that is suspended within the sample. Metal-coated 3ω exceeds alternate 3ω based fluid sensing techniques in a number of key metrics enabling rapid measurements of small samples of materials with very low thermal effusivity (gases), using smaller temperature oscillations with lower parasitic conduction losses. Its advantages relative to existing fluid measurement techniques, including transient hot-wire, steady-state methods, and solid-wire 3ω are discussed. A generalized n-layer concentric cylindrical periodic heating solution that accounts for thermal boundary resistance is presented. Improved sensitivity to boundary conductance is recognized through this model. Metal-coated 3ω was successfully validated through a benchmark study of gases and liquids spanning two-orders of magnitude in thermal conductivity.

Large Thermal Conductivity Differences between the Crystalline and Vitrified States of DMSO with Applications to Cryopreservation.

Thermal conductivity of dimethyl-sulfoxide (DMSO) solution is measured in this study using a transient hot wire technique, where DMSO is a key ingredient in many cryoprotective agent (CPA) cocktails. Characterization of thermal properties of cryoprotective agents is essential to the analysis of cryopreservation processes, either when evaluating experimental data or for the design of new protocols. Also presented are reference measurements of thermal conductivity for pure water ice and glycerol. The thermal conductivity measurement setup is integrated into the experimentation stage of a scanning cryomacroscope apparatus, which facilitates the correlation of measured data with visualization of physical events. Thermal conductivity measurements were conducted for a DMSO concentration range of 2M and 10M, in a temperature range of -180°C and 25°C. Vitrified samples showed decreased thermal conductivity with decreasing temperature, while crystalline samples showed increased thermal conductivity with decreasing temperature. These different behaviors result in up to a tenfold difference in thermal conductivity at -180°C. Such dramatic differences can drastically impact heat transfer during cryopreservation and their quantification is therefore critical to cryobiology.

A New Device and Technique for Thermal Conductivity Measurements of Glass-Forming Materials With Application to Cryopreservation

The current study is aimed at developing a device and technique to measure the thermal conductivity of materials relevant to cryopreservation — the preservation of biomaterials at very low temperatures. It is well established that ice formation is the cornerstone of low-temperature injury [1]. In an effort to improve the outcome of cryopreservation, ice crystallization can be controlled by the addition of cryoprotective agents (CPAs), such as dimethyl sulfoxide (DMSO). CPA solutions are characterized by exponentially increasing viscosity with the decreasing temperature. If cooled rapidly enough, the crystalline phase can be completely suppressed and the material is trapped in a solid-like state known as vitrification (vitreous in Latin means glassy). While correlating the quality of the cryopreserved product with the thermal history may be straightforward to obtain in small specimens, characterized by close-to-uniform temperature distribution, analysis of larger specimens requires integration of mathematical tools to estimate the spatial temperature distribution at any instant along the cryogenic protocol. The data developed in the current study is aimed at enabling the corresponding thermal analysis, while exploring the variation in thermal conductivity between the crystalline and glassy states.Copyright

Thermal Conductivity of Carbon Nanotube Aerogels With Different Filling Gases

We report on measurements of thermal conductivity in single-walled carbon nanotube (SWCNT) aerogels in vacuum, and as infiltrated by different gases. The remarkable thermal, mechanical and electrical properties of single CNTs have led to great interest in bulk carbon nanotube materials, including the CNT aerogels. Carbon nanotube aerogels are light-weight (7–8kg/m3) and porous, which means that heat will be conducted in parallel through the SWCNT matrix and the filling gas. The overall thermal conductivity of the aerogel was measured with helium, and argon filling gases, using a modified 3ω method designed to interrogate low thermal effusivity materials. Measurements of thermal conductivity at vacuum are 0.023 W/m-K and at atmospheric pressure infiltrated SWCNT aerogels have thermal conductivities in helium of 0.19 W/m-K and in argon of 0.039 W/m-K. Our vacuum measurement suggests that transport within the aerogel is limited by the thermal interface resistance between SWCNTs, rather than by phonon transport within the SWCNT itself. We have also extracted the mean distance traveled by gas molecules between collisions with SWCNT aerogel by fitting the gas contribution to thermal conductivity using a kinetic theory based model.Copyright

A Modified 3-Omega Technique to Measure Thermal Conductivity in Liquids, Gases, and Powders

A novel modified 3ω thermal conductivity measurement technique called metal coated 3ω is introduced for use with liquids, gases, and powders. This technique employs a micron-scale metal coated glass fiber. Metal coated 3ω exceeds alternate 3ω based fluid sensing techniques in a number of key metrics including fraction of heat generated entering fluid, signal strength per temperature oscillation intensity and thermal boundary sensitivity. The advantages of this technique to Transient Hot-Wire (THW) and steady-state techniques are also discussed. A generalized n-layer concentric cylindrical periodic heating solution that accounts for thermal boundary resistance is presented. The technique is validated through a benchmark study of gases and liquids.Copyright