Search for: All records

Predictive synthesis of aqueous organic solutions with desired liquid–solid phase equilibria could drive progress in industrial chemistry, cryopreservation, and beyond, but is limited by the predictive power of current solution thermodynamics models. In particular, few analytical models enable accurate liquidus and eutectic prediction based only on bulk thermodynamic properties of the pure components, requiring instead either direct measurement or costly simulation of solution properties. In this work, we demonstrate that a simple modification to the canonical ideal solution theory accounting for the entropic effects of dissimilar molecule sizes can transform its predictive power. Incorporating a Flory-style entropy of mixing term that includes both the mole and volume fractions of each component, we derive size-dependent equations for the ideal chemical potential and liquidus temperature, and use them to predict the binary phase diagrams of water and 10 organic solutes of varying sizes. We show that size-dependent prediction outperforms the ideal model in all cases, reducing average error in the predicted liquidus temperature by 59% (to 5.6 K), eutectic temperature by 45% (to 9.7 K), and eutectic composition by 43% (to 4.7 mol%), as compared to experimental data. Furthermore, by retaining the ideal assumption that the enthalpy of mixing is zero, we demonstrate that, for aqueous organic solutions, much of the deviation from ideality that is typically attributed to molecular interactions may in fact be explained by simple entropic size effects. These results suggest an underappreciated dominance of mixing entropy in these solutions, and provide a simple approach to predicting their phase equilibria. 

It is well established that near-field radiative heat transfer (NFRHT) can exceed Planck’s blackbody limit1 by orders of magnitude owing to the tunneling of evanescent electromagnetic frustrated and surface modes2-4, as has been demonstrated experimentally for NFRHT between two large parallel surfaces5-7 and between two subwavelength membranes8,9. However, while nanostructures can also sustain a much richer variety of localized electromagnetic modes at their corners and edges,10,11 the contributions of such additional modes to further enhancing NFRHT remain unexplored. Here, we demonstrate both theoretically and experimentally a new physical mechanism of NFRHT mediated by these corner and edge modes, and show it can dominate the NFRHT in the “dual nanoscale regime” in which both the thickness of the emitter and receiver, and their gap spacing, are much smaller than the thermal photon wavelengths. For two coplanar 20 nm thick SiC membranes separated by a 100 nm vacuum gap, the NFRHT coefficient at room temperature is both predicted and measured to be 830 W/m2K, which is 5.5 times larger than that for two infinite SiC surfaces separated by the same gap, and 1400 times larger than the corresponding blackbody limit accounting for the geometric view factor between two coplanar membranes. This enhancement is dominated by the electromagnetic corner and edge modes which account for 81% of the NFRHT between the SiC membranes. These findings are important for future NFRHT applications in thermal management and energy conversion. 

The need for efficient energy utilization is driving research into ways to harvest ubiquitous waste heat. Here, we explore pyroelectric energy conversion from low-grade thermal sources that exploits strong field- and temperature-induced polarization susceptibilities in the relaxor ferroelectric 0.68Pb(Mg1/3Nb2/3)O3–0.32PbTiO3. Electric-field-driven enhancement of the pyroelectric response (as large as − 550 μC m−2 K−1) and suppression of the dielectric response (by 72%) yield substantial figures of merit for pyroelectric energy conversion. Field- and temperature-dependent pyroelectric measurements highlight the role of polarization rotation and field-induced polarization in mediating these effects. Solid-state, thin-film devices that convert lowgrade heat into electrical energy are demonstrated using pyroelectric Ericsson cycles, and optimized to yield maximum energy density, power density and efficiency of 1.06 J cm−3, 526 W cm−3 and 19% of Carnot, respectively; the highest values reported to date and equivalent to the performance of a thermoelectric with an effective ZT ≈ 1.16 for a temperature change of 10 K. Our findings suggest that pyroelectric devices may be competitive with thermoelectric devices for low-grade thermal harvesting.