Efflorescence of Ammonium Sulfate and Coated Ammonium Sulfate Particles: Evidence for Surface Nucleation

Using optical microscopy, we investigated the efflorescence of ammonium sulfate (AS) in aqueous AS and in aqueous 1:1 and 8:1 (by dry weight) poly(ethylene glycol)-400 (PEG-400)/AS particles deposited on a hydrophobically coated slide. Aqueous PEG-400/AS particles exposed to decreasing relative humidity (RH) exhibit a liquid−liquid phase separation below 90% RH with the PEG-400-rich phase surrounding the aqueous AS inner phase. Pure aqueous AS particles effloresced in the RH range from 36.3% to 43.7%, in agreement with literature data (31−48% RH). In contrast, aqueous 1:1 (by dry weight) PEG-400/AS particles with diameters of the AS phase from 7.2 to 19.2 μm effloresced between 26.8% and 33.9% RH and aqueous 8:1 (by dry weight) PEG-400/AS particles with diameters of the AS phase from 1.8 to 7.3 μm between 24.3% and 29.3% RH. Such low efflorescence relative humidity (ERH) values have never been reached before for AS particles of this size range. We show that these unprecedented low ERHs of AS in PEG-400/AS particles could not possibly be explained by the presence of low amounts of PEG-400 in the aqueous AS phase, by a potential inhibition of water evaporation via anomalously slow diffusion through the PEG coating, or by different time scales between various experimental techniques. High-speed photography of the efflorescence process allowed the development of the AS crystallization fronts within the particles to be monitored with millisecond time resolution. The nucleation sites were inferred from the initial crystal growth sites. Analysis of the probability distribution of initial sites of 31 and 19 efflorescence events for pure AS and 1:1 (by dry weight) PEG-400/AS particles, respectively, showed that the particle volume can be excluded as the preferred nucleation site in the case of pure AS particles. For aqueous 1:1 (by dry weight) PEG-400/AS particles preferential AS nucleation in the PEG phase and at the PEG/AS/substrate contact line can be excluded. On the basis of this probability analysis of efflorescence events together with the AS ERH values of pure aqueous AS and aqueous PEG-400/AS particles aforementioned, we suggest that in pure aqueous AS particles nucleation starts at the surface of the particles and attribute the lower ERH values observed for aqueous PEG-400/AS particles to the suppression of the surface-induced nucleation process. Our results suggest that surface-induced nucleation is likely to also occur during the efflorescence of atmospheric AS aerosol particles, possibly constituting the dominating nucleation pathway

Electron-vibration interaction in single-molecule junctions: from contact to tunneling regime

Point contact spectroscopy on a H2O molecule bridging Pt electrodes reveals a clear crossover between enhancement and reduction of the conductance due to electron-vibration interaction. As single channel models predict such a crossover at transmission probability of t=0.5, we used shot noise measurements to analyze the transmission and observed at least two channels across the junction where the dominant channel has t=0.51+/-0.01 transmission probability at the crossover conductance, which is consistent with the predictions for single-channel models.Comment: 4 pages, 1 table, 4 figure

The design and evaluation of grazing incidence relay optics

X-ray astronomy, both solar and celestial, has many needs for high spatial resolution observations which have to be performed with electronic detectors. If the resolution is not to be detector limited, plate scales in excess of 25 microns arc/sec, corresponding to focal lengths greater than 5 m, are required. In situations where the physical size is restricted, the problem can be solved by the use of grazing incidence relay optics. A system was developed which employs externally polished hyperboloid-hyperboloid surfaces to be used in conjunction with a Wolter-Schwarzschild primary. The secondary is located in front of the primary focus and provides a magnification of 4, while the system has a plate scale of 28 microns arc/sec and a length of 1.9 m. The design, tolerance specification, fabrication and performance at visible and X-ray wavelengths of this optical system are described

Liquid-liquid phase separation and morphology of internally mixed dicarboxylic acids/ammonium sulfate/water particles

Knowledge of the physical state and morphology of internally mixed organic/inorganic aerosol particles is still largely uncertain. To obtain more detailed information on liquid-liquid phase separation (LLPS) and morphology of the particles, we investigated complex mixtures of atmospherically relevant dicarboxylic acids containing 5, 6, and 7 carbon atoms (C5, C6 and C7) having oxygen-to-carbon atomic ratios (O:C) of 0.80, 0.67, and 0.57, respectively, mixed with ammonium sulfate (AS). With micrometer-sized particles of C5/AS/H_2O, C6/AS/H_2O and C7/AS/H_2O as model systems deposited on a hydrophobically coated substrate, laboratory experiments were conducted for various organic-to-inorganic dry mass ratios (OIR) using optical microscopy and Raman spectroscopy. When exposed to cycles of relative humidity (RH), each system showed significantly different phase transitions. While the C5/AS/H_2O particles showed no LLPS with OIR = 2:1, 1:1 and 1:4 down to 20% RH, the C6/AS/H_2O and C7/AS/H_2O particles exhibit LLPS upon drying at RH 50 to 85% and ~90%, respectively, via spinodal decomposition, growth of a second phase from the particle surface or nucleation-and-growth mechanisms depending on the OIR. This suggests that LLPS commonly occurs within the range of O:C < 0.7 in tropospheric organic/inorganic aerosols. To support the comparison and interpretation of the experimentally observed phase transitions, thermodynamic equilibrium calculations were performed with the AIOMFAC model. For the C7/AS/H_2O and C6/AS/H_2O systems, the calculated phase diagrams agree well with the observations while for the C5/AS/H_2O system LLPS is predicted by the model at RH below 60% and higher AS concentration, but was not observed in the experiments. Both core-shell structures and partially engulfed structures were observed for the investigated particles, suggesting that such morphologies might also exist in tropospheric aerosols

Experimental evidence for excess entropy discontinuities in glass-forming solutions

Glass transition temperatures T_g are investigated in aqueous binary and multi-component solutions consisting of citric acid, calcium nitrate (Ca(NO_3)_2), malonic acid, raffinose, and ammonium bisulfate (NH_4HSO_4) using a differential scanning calorimeter. Based on measured glass transition temperatures of binary aqueous mixtures and fitted binary coefficients, the T_g of multi-component systems can be predicted using mixing rules. However, the experimentally observed T_g in multi-component solutions show considerable deviations from two theoretical approaches considered. The deviations from these predictions are explained in terms of the molar excess mixing entropy difference between the supercooled liquid and glassy state at T_g. The multi-component mixtures involve contributions to these excess mixing entropies that the mixing rules do not take into account

Nondispersive solutions to the L2-critical half-wave equation

We consider the focusing $L^2$-critical half-wave equation in one space dimension $$i \partial_t u = D u - |u|^2 u,$$ where $D$ denotes the first-order fractional derivative. Standard arguments show that there is a critical threshold $M_* > 0$ such that all $H^{1/2}$ solutions with $\| u \|_{L^2} < M_*$ extend globally in time, while solutions with $\| u \|_{L^2} \geq M_*$ may develop singularities in finite time. In this paper, we first prove the existence of a family of traveling waves with subcritical arbitrarily small mass. We then give a second example of nondispersive dynamics and show the existence of finite-time blowup solutions with minimal mass $\| u_0 \|_{L^2} = M_*$. More precisely, we construct a family of minimal mass blowup solutions that are parametrized by the energy $E_0 >0$ and the linear momentum $P_0 \in \R$. In particular, our main result (and its proof) can be seen as a model scenario of minimal mass blowup for $L^2$-critical nonlinear PDE with nonlocal dispersion.Comment: 51 page