Methods to stabilize aqueous supercooling identified by use of an isochoric nucleation detection (INDe) device.

Stable aqueous supercooling has shown significant potential as a technique for human tissue preservation, food cold storage, conservation biology, and beyond, but its stochastic nature has made its translation outside the laboratory difficult. In this work, we present an isochoric nucleation detection (INDe) platform for automated, high-throughput characterization of aqueous supercooling at >1 mL volumes, which enables statistically-powerful determination of the temperatures and time periods for which supercooling in a given aqueous system will remain stable. We employ the INDe to investigate the effects of thermodynamic, surface, and chemical parameters on aqueous supercooling, and demonstrate that various simple system modifications can significantly enhance supercooling stability, including isochoric (constant-volume) confinement, hydrophobic container walls, and the addition of even mild concentrations of solute. Finally, in order to enable informed design of stable supercooled biopreservation protocols, we apply a statistical model to estimate stable supercooling durations as a function of temperature and solution chemistry, producing proof-of-concept supercooling stability maps for four common cryoprotective solutes.

Hollow Atomic Force Microscopy Cantilevers with Nanoscale Wall Thicknesses.

In atomic force microscopy, the cantilever probe is a critical component whose properties determine the resolution and speed at which images with nanoscale resolution can be obtained. Traditional cantilevers, which have moderate resonant frequencies and high quality factors, have relatively long response times and low bandwidths. In addition, cantilevers can be easily damaged by excessive deformation, and tips can be damaged by wear, requiring them to be replaced frequently. To address these issues, new cantilever probes that have hollow cross-sections and walls of nanoscale thicknesses made of alumina deposited by atomic layer deposition are introduced. It is demonstrated that the probes exhibit spring constants up to ≈100 times lower and bandwidths up to ≈50 times higher in air than their typical solid counterparts, allowing them to react to topography changes more quickly. Moreover, it is shown that the enhanced robustness of the hollow cantilevers enables them to withstand large bending displacements more readily and to be more resistant to tip wear.

Ionocaloric refrigeration cycle.

Developing high-efficiency cooling with safe, low-global warming potential refrigerants is a grand challenge for tackling climate change. Caloric effect-based cooling technologies, such as magneto- or electrocaloric refrigeration, are promising but often require large applied fields for a relatively low coefficient of performance and adiabatic temperature change. We propose using the ionocaloric effect and the accompanying thermodynamic cycle as a caloric-based, all-condensed-phase cooling technology. Theoretical and experimental results show higher adiabatic temperature change and entropy change per unit mass and volume compared with other caloric effects under low applied field strengths. We demonstrated the viability of a practical system using an ionocaloric Stirling refrigeration cycle. Our experimental results show a coefficient of performance of 30% relative to Carnot and a temperature lift as high as 25°C using a voltage strength of ~0.22 volts.

Thermal fluids with high specific heat capacity through reversible Diels-Alder reactions.

Thermal fluids are used as heat transfer fluids and thermal energy storage media in many energy technologies ranging from solar thermal heating to battery thermal management. The heat capacity of state-of-the-art thermal fluids remains ∼50% of that of water (which suffers from a limited operation range between 0°C and 100°C), and their viscosities are typically more than one order of magnitude higher than that of water. Our results demonstrate that the heat capacity of the proposed thermochemical fluid is significantly higher than that of state-of-the-art thermal fluids over a broad temperature range and is also higher than that of water between 60°C and 90°C. The viscosity of our liquid is only 3 times higher than that of water, and the operating temperature range is between -90°C and 135°C. Furthermore, a model was developed allowing for novel design of thermochemical thermal fluids in the future with even higher heat capacity.

Micron-gap spacers with ultrahigh thermal resistance and mechanical robustness for direct energy conversion.

In thermionic energy converters, the absolute efficiency can be increased up to 40% if space-charge losses are eliminated by using a sub-10-µm gap between the electrodes. One practical way to achieve such small gaps over large device areas is to use a stiff and thermally insulating spacer between the two electrodes. We report on the design, fabrication and characterization of thin-film alumina-based spacers that provided robust 3-8 µm gaps between planar substrates and had effective thermal conductivities less than those of aerogels. The spacers were fabricated on silicon molds and, after release, could be manually transferred onto any substrate. In large-scale compression testing, they sustained compressive stresses of 0.4-4 MPa without fracture. Experimentally, the thermal conductance was 10-30 mWcm-2K-1 and, surprisingly, independent of film thickness (100-800 nm) and spacer height. To explain this independence, we developed a model that includes the pressure-dependent conductance of locally distributed asperities and sparse contact points throughout the spacer structure, indicating that only 0.1-0.5% of the spacer-electrode interface was conducting heat. Our spacers show remarkable functionality over multiple length scales, providing insulating micrometer gaps over centimeter areas using nanoscale films. These innovations can be applied to other technologies requiring high thermal resistance in small spaces, such as thermophotovoltaic converters, insulation for spacecraft and cryogenic devices.

Nanocardboard as a nanoscale analog of hollow sandwich plates.

Corrugated paper cardboard provides an everyday example of a lightweight, yet rigid, sandwich structure. Here we present nanocardboard, a monolithic plate mechanical metamaterial composed of nanometer-thickness (25-400 nm) face sheets that are connected by micrometer-height tubular webbing. We fabricate nanocardboard plates of up to 1 centimeter-square size, which exhibit an enhanced bending stiffness at ultralow mass of ~1 g m-2. The nanoscale thickness allows the plates to completely recover their shape after sharp bending even when the radius of curvature is comparable to the plate height. Optimally chosen geometry enhances the bending stiffness and spring constant by more than four orders of magnitude in comparison to solid plates with the same mass, far exceeding the enhancement factors previously demonstrated at both the macroscale and nanoscale. Nanocardboard may find applications as a structural component for wings of microflyers or interstellar lightsails, scanning probe cantilevers, and other microscopic and macroscopic systems.

Ultralight shape-recovering plate mechanical metamaterials.

Unusual mechanical properties of mechanical metamaterials are determined by their carefully designed and tightly controlled geometry at the macro- or nanoscale. We introduce a class of nanoscale mechanical metamaterials created by forming continuous corrugated plates out of ultrathin films. Using a periodic three-dimensional architecture characteristic of mechanical metamaterials, we fabricate free-standing plates up to 2 cm in size out of aluminium oxide films as thin as 25 nm. The plates are formed by atomic layer deposition of ultrathin alumina films on a lithographically patterned silicon wafer, followed by complete removal of the silicon substrate. Unlike unpatterned ultrathin films, which tend to warp or even roll up because of residual stress gradients, our plate metamaterials can be engineered to be extremely flat. They weigh as little as 0.1 g cm(-2) and have the ability to 'pop-back' to their original shape without damage even after undergoing multiple sharp bends of more than 90°.