Recent increases in marijuana use and legalization without adequate knowledge of the risks necessitate the characterization of the billions of nanoparticles contained in each puff of smoke. Tobacco smoke offers a benchmark given that it has been extensively studied. Tobacco and marijuana smoke particles are quantitatively similar in volatility, shape, density and number concentration, albeit with differences in size, total mass and chemical composition. Particles from marijuana smoke are on average 29% larger in mobility diameter than particles from tobacco smoke and contain 3.4× more total mass. New measurements of semi-volatile fractions determine over 97% of the mass and volume of the particles from either smoke source are comprised of semi-volatile compounds. For tobacco and marijuana smoke, respectively, 4350 and 2575 different compounds are detected, of which, 670 and 536 (231 in common) are tentatively identified, and of these, 173 and 110 different compounds (69 in common) are known to cause negative health effects through carcinogenic, mutagenic, teratogenic, or other toxic mechanisms. This study demonstrates striking similarities between marijuana and tobacco smoke in terms of their physical and chemical properties.
The particulate matter (PM) emitted from a single-cylinder compression-ignition, natural-gas engine fitted with a HighPressure Direct-Injection (HPDI) system distinctly different from a duel fuel engine was investigated, and characterized by size distribution, morphology, mass-mobility exponent, effective density, volatility, mixing state, and primary particle size using transmission electron microscopy (TEM), and tandem measurements from differential mobility analyzers (DMA) and a centrifugal particle mass analyzer (CPMA). Six engine conditions were selected with varying load, speed, exhaust gas recirculation (EGR) fraction, and fuel delivery strategy. An increase in engine load increased both the number concentration and the geometric mean diameter of the particulate. The fraction of the number of purely volatile particles to total number of particles (number volatile fraction, NVF) was found to decrease as load increased, although at the lower speed, partially premixed mode, the lowest NVF. All size distributions were also found to be unimodal. The size-segregated ratio of the mass of internally mixed volatile material to total particle mass (mass volatile fraction, MVF) decreased with load and with particle mobility-equivalent diameter. A roughly constant amount of volatile material is likely produced at each engine mode, and the decrease in MVF is due to the increase in PM number with load. Effective density and massmobility exponent of the non-volatile soot at the different engine loads were the same or slightly higher than soot from traditional diesel engines. Denuded effective density trends were observed to collapse to approximately the same line, although engine modes with higher MVFs had slightly higher effective densities suggesting that the soot structures have collapsed into more dense shapes-a suspicion that is confirmed with TEM images. TEM results also indicated that primary particle size first decreases from low to medium load, then increases from medium to high load. An increase in EGR was also seen to increase primary particle size. Coefficients were determined for a relation that gives primary particle diameter as a function of projected area equivalent diameter. A decrease in load or speed results in a stronger correlation.
The properties and impacts of aggregated aerosol particles (i.e., soot, metal oxide fumes) depend on their morphology, as characterized by fractal dimension, prefactor, and primary particle diameter. The morphology may be measured directly by time-consuming ex situ microscopy or rapid but indirect in situ methods. Previously, it was found that particle mass and mobility measurements could be used for the estimation of the primary particle diameter of zirconia aggregates, using plausible assumptions related to the fractal structure (specifically, prefactor k a and exponent D a ). Since the formation and growth of zirconia aggregates are different from carbon soot, here we compare primary particle diameters measured directly from transmission electron microscopy analysis of soot particles with the diameters estimated from mass-mobility measurements. Performing extensive measurements on soot emissions from two reciprocating engines over a range of operating conditions, we found that there are no universal values of k a and D a that can be used for all conditions. However, new optimized values of k a and D a are estimated here for soot particles. The variation of the primary particle diameter with particle size is also taken into consideration and is shown to be essential to obtain physically realistic results. Using optimized values of k a and D a , the average primary particle sizing error is reduced for all soot types. This suggests that with some calibration, in situ sizing of the primary particle diameter, using mass and mobility measurements, can provide useful accuracy.
The agglomeration and self‐assembly of gas‐phase 1D materials in anthropogenic and natural systems dictate their resulting nanoscale morphology, multiscale hierarchy, and ultimate macroscale properties. Brownian motion induces collisions, upon which 1D materials often restructure to form bundles and can lead to aerogels. Herein, the first results of collision rates for 1D nanomaterials undergoing thermal transport are presented. The Langevin dynamic simulations of nanotube rotation and translation demonstrate that the collision kernels for rigid nanotubes or nanorods are ≈10 times greater than spherical systems. Resulting reduced order equations allow straightforward calculation of the physical parameters to determine the collision kernel for straight and curved 1D materials from 102 to 106 nm length. The collision kernels of curved 1D structures increase ≈1.3 times for long (>102 nm), and ≈5 times for short (≈102 nm) relative to rigid materials. Applications of collision frequencies allow the first kinetic analysis of aerogel self‐assembly from gas‐phase carbon nanotubes (CNTs). The timescales for CNT collision and bundle formation (0.3–42 s) agree with empirical residence times in CNT reactors (3–15 s). These results provide insights into the CNT length, number, and timescales required for aerogel formation, which bolsters our understanding of mass‐produced 1D aerogel materials.
The direct growth of single-walled carbon nanotubes (SWCNTs) with narrow chiral distribution remains elusive despite substantial benefits in properties and applications. Nanoparticle catalysts are vital for SWCNT and more generally nanomaterial synthesis, but understanding their effect is limited. Solid catalysts show promise in achieving chirality-controlled growth, but poor size control and synthesis efficiency hampers advancement. Here, we demonstrate the first synthesis of refractory metal nanoparticles (W, Mo, and Re) with near-monodisperse sizes. High concentrations (N = 105 to 107 cm−3) of nanoparticles (diameter 1 to 5 nm) are produced and reduced in a single process, enabling SWCNT synthesis with controlled chiral angles of 19° ± 5°, demonstrating abundance >93%. These results confirm the interface thermodynamics and kinetic growth theory mechanism, which has been extended here to include temporal dependence of fast-growing chiralities. The solid catalysts are further shown effective via floating catalyst growth, offering efficient production possibilities.
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