Distinguishing Gas-Phase and Nanoparticle Contributions to Small-Angle X-ray Scattering in Reacting Aerosol Flows.

We have developed a strategy for distinguishing between small-angle X-ray scattering (SAXS) from gas-phase species and newly formed nanoparticles in mixed gas- and particle-phase reacting flows. This methodology explicitly accounts for temperature-dependent scattering from gases. We measured SAXS in situ in a sooting linear laminar partially premixed co-flow ethylene/air diffusion flame. The scattering signal demonstrates a downward curvature as a function of the momentum transfer (q) at q values of 0.2-0.57 Å-1. The q-dependent curvature is consistent with the Debye equation and the independent-atom model for gas-phase scattering. This behavior can also be modeled using the Guinier approximation and could be characterized as a Guinier knee for gas-phase scattering. The Guinier functional form can be fit to the scattering signal in this q range without a priori knowledge of the gas-phase composition, enabling estimation of the gas-phase contribution to the scattering signal while accounting for changes in the gas-phase composition and temperature. We coupled the SAXS measurements with in situ temperature measurements using coherent anti-Stokes Raman spectroscopy. This approach to characterizing the gas-phase SAXS signal provides a physical basis for distinguishing among the contributions to the scattering signal from the instrument function, flame gases, and nanoparticles. The results are particularly important for the analysis of the SAXS signal in the q range associated with particles in the size range of 1-6 nm.

Multiscale Photonic Emissivity Engineering for Relativistic Lightsail Thermal Regulation.

The Breakthrough Starshot Initiative aims to send a gram-scale probe to our nearest extrasolar neighbors using a laser-accelerated lightsail traveling at relativistic speeds. Thermal management is a key lightsail design objective because of the intense laser powers required but has generally been considered secondary to accelerative performance. Here, we demonstrate nanophotonic photonic crystal slab reflectors composed of 2H-phase molybdenum disulfide and crystalline silicon nitride, highlight the inverse relationship between the thermal band extinction coefficient and the lightsail's maximum temperature, and examine the trade-off between minimizing acceleration distance and setting realistic sail thermal limits, ultimately realizing a thermally endurable acceleration minimum distance of 23.3 Gm. We additionally demonstrate multiscale photonic structures featuring thermal-wavelength-scale Mie resonant geometries and characterize their broadband Mie resonance-driven emissivity enhancement and acceleration distance reduction. More broadly, our results highlight new possibilities for simultaneously controlling optical and thermal response over broad wavelength ranges in ultralight nanophotonic structures.

Relativistic Light Sails Need to Billow.

We argue that light sails with nanometer-scale thicknesses that are rapidly accelerated to relativistic velocities by lasers must be significantly curved in order to reduce their intrafilm mechanical stresses and avoid tears. Using an integrated opto-thermo-mechanical model, we show that the diameter and radius of curvature of a circular light sail should be comparable in magnitude, both on the order of a few meters, in optimal designs for gram-scale payloads. Moreover, we demonstrate that, when sufficient laser power is available, a sail's acceleration length decreases as its curvature increases. Our findings provide critical guidance for emerging light sail design programs, which herald a new era of interstellar space exploration to destinations such as the Oort cloud, the Alpha Centauri system, and beyond.

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.

Progress Toward High Power Output in Thermionic Energy Converters.

Thermionic energy converters are solid-state heat engines that have the potential to produce electricity with efficiencies of over 30% and area-specific power densities of 100 Wcm-2. Despite this prospect, no prototypes reported in the literature have achieved true efficiencies close to this target, and many of the most recent investigations report power densities on the order of mWcm-2 or less. These discrepancies stem in part from the low-temperature (<1300 K) test conditions used to evaluate these devices, the large vacuum gap distances (25-100 µm) employed by these devices, and material challenges related to these devices' electrodes. This review will argue that, for feasible electrode work functions available today, efficient performance requires generating output power densities of >1 Wcm-2 and employing emitter temperatures of 1300 K or higher. With this result in mind, this review provides an overview of historical and current design architectures and comments on their capacity to realize the efficiency and power potential of thermionic energy converters. Also emphasized is the importance of using standardized efficiency metrics to report thermionic energy converter performance data.

Controlled levitation of nanostructured thin films for sun-powered near-space flight.

We report light-driven levitation of macroscopic polymer films with nanostructured surface as candidates for long-duration near-space flight. We levitated centimeter-scale disks made of commercial 0.5-micron-thick mylar film coated with carbon nanotubes on one side. When illuminated with light intensity comparable to natural sunlight, the polymer disk heats up and interacts with incident gas molecules differently on the top and bottom sides, producing a net recoil force. We observed the levitation of 6-mm-diameter disks in a vacuum chamber at pressures between 10 and 30 Pa. Moreover, we controlled the flight of the disks using a shaped light field that optically trapped the levitating disks. Our experimentally validated theoretical model predicts that the lift forces can be many times the weight of the films, allowing payloads of up to 10 milligrams for sunlight-powered low-cost microflyers at altitudes of 50 to 100 km.

Critical Assessment of Photoionization Efficiency Measurements for Characterization of Soot-Precursor Species.

We present a critical evaluation of photoionization efficiency (PIE) measurements coupled with aerosol mass spectrometry for the identification of condensed soot-precursor species extracted from a premixed atmospheric-pressure ethylene/oxygen/nitrogen flame. Definitive identification of isomers by any means is complicated by the large number of potential isomers at masses likely to comprise particles at flame temperatures. This problem is compounded using PIE measurements by the similarity in ionization energies and PIE-curve shapes among many of these isomers. Nevertheless, PIE analysis can provide important chemical information. For example, our PIE curves show that neither pyrene nor fluoranthene alone can describe the signal from C16H10 isomers and that coronene alone cannot describe the PIE signal from C24H12 species. A linear combination of the reference PIE curves for pyrene and fluoranthene yields good agreement with flame-PIE curves measured at 202 u, which is consistent with pyrene and fluoranthene being the two major C16H10 isomers in the flame samples, but does not provide definite proof. The suggested ratio between fluoranthene and pyrene depends on the sampling conditions. We calculated the values of the adiabatic-ionization energy (AIE) of 24 C16H10 isomers. Despite the small number of isomers considered, the calculations show that the differences in AIEs between several of the isomers can be smaller than the average thermal energy at room temperature. The calculations also show that PIE analysis can sometimes be used to separate hydrocarbon species into those that contain mainly aromatic rings and those that contain significant aliphatic content for species sizes investigated in this study. Our calculations suggest an inverse relationship between AIE and the number of aromatic rings. We have demonstrated that further characterization of precursors can be facilitated by measurements that test species volatility.

Photoionization Efficiencies of Five Polycyclic Aromatic Hydrocarbons.

We have measured photoionization-efficiency curves for pyrene, fluoranthene, chrysene, perylene, and coronene in the photon energy range of 7.5-10.2 eV and derived their photoionization cross-section curves in this energy range. All measurements were performed using tunable vacuum ultraviolet (VUV) radiation generated at the Advanced Light Source synchrotron at Lawrence Berkeley National Laboratory. The VUV radiation was used for photoionization, and detection was performed using a time-of-flight mass spectrometer. We measured the photoionization efficiency of 2,5-dimethylfuran simultaneously with those of pyrene, fluoranthene, chrysene, perylene, and coronene to obtain references of the photon flux during each measurement from the known photoionization cross-section curve of 2,5-dimethylfuran.

Formation and emission of large furans and oxygenated hydrocarbons from flames.

Many oxygenated hydrocarbon species formed during combustion, such as furans, are highly toxic and detrimental to human health and the environment. These species may also increase the hygroscopicity of soot and strongly influence the effects of soot on regional and global climate. However, large furans and associated oxygenated species have not previously been observed in flames, and their formation mechanism and interplay with polycyclic aromatic hydrocarbons (PAHs) are poorly understood. We report on a synergistic computational and experimental effort that elucidates the formation of oxygen-embedded compounds, such as furans and other oxygenated hydrocarbons, during the combustion of hydrocarbon fuels. We used ab initio and probabilistic computational techniques to identify low-barrier reaction mechanisms for the formation of large furans and other oxygenated hydrocarbons. We used vacuum-UV photoionization aerosol mass spectrometry and X-ray photoelectron spectroscopy to confirm these predictions. We show that furans are produced in the high-temperature regions of hydrocarbon flames, where they remarkably survive and become the main functional group of oxygenates that incorporate into incipient soot. In controlled flame studies, we discovered ∼100 oxygenated species previously unaccounted for. We found that large alcohols and enols act as precursors to furans, leading to incorporation of oxygen into the carbon skeletons of PAHs. Our results depart dramatically from the crude chemistry of carbon- and oxygen-containing molecules previously considered in hydrocarbon formation and oxidation models and spearhead the emerging understanding of the oxidation chemistry that is critical, for example, to control emissions of toxic and carcinogenic combustion by-products, which also greatly affect global warming.