Ideal Adsorption Isotherm Behavior for Cooling Applications.

Purely heat-driven refrigeration has the potential for high primary-energy efficiency, especially when powered by waste heat or solar thermal sources. This paper presents a novel expression for the ideal adsorption step location as a function of operating conditions. This methodology is then applied to a hypothetical stepwise material to evaluate its intrinsic efficiency. This analysis technique is then extended to allow facile efficiency comparisons for any adsorbent-refrigerant pair using an adsorbent's isotherm and heat of adsorption properties. This work focuses on limitations to efficiency due to the equilibrium thermodynamics. It is found that a stepwise adsorbent can have a single-effect intrinsic efficiency of as high as about 85% of Carnot, assuming typical adsorbent specific heats and uptake capacity. Using these tools, we analyze the maximum ratio of cooling to heat input (coefficient of performance) for two adsorption pairs, zeolite 13X-water and UiO-66-water, which are found to have maximum coefficients of performance of 0.52 and 0.88 for a cold-side temperature of 10 °C and an ambient temperature of 30 °C, respectively. Meanwhile, the maximum fraction of Carnot cooling is 37% for zeolite 13X-water and 67% for UiO-66-water. Moreover, these peak fractions of Carnot occur at much higher regeneration temperatures for 13X (196 °C) than for UiO-66 (60 °C). These two materials could be coupled in a two-stage cascading triple-effect adsorption cycle that operates with a combined coefficient of performance of 1.50 at a regeneration temperature of 196 °C, a cold-side temperature of 10 °C, and an ambient temperature of 30 °C.

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.

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.

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 hexadecane's varies between 2.1 and 2.6. The nanocomposite's 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.

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.