Why Are Alkali Halide Solid Surfaces Not Wetted By Their Own Melt?

Alkali halide (100) crystal surfaces are anomalous, being very poorly wetted by their own melt at the triple point. We present extensive simulations for NaCl, followed by calculations of the solid-vapor, solid-liquid, and liquid-vapor free energies showing that solid NaCl(100) is a nonmelting surface, and that its full behavior can quantitatively be accounted for within a simple Born-Meyer-Huggins-Fumi-Tosi model potential. The incomplete wetting is traced to the conspiracy of three factors: surface anharmonicities stabilizing the solid surface; a large density jump causing bad liquid-solid adhesion; incipient NaCl molecular correlations destabilizing the liquid surface. The latter is pursued in detail, and it is shown that surface short-range charge order acts to raise the surface tension because incipient NaCl molecular formation anomalously reduces the surface entropy of liquid NaCl much below that of solid NaCl(100).Comment: 4 pages, 3 figure

Density changes of aerosol particles as a result of chemical reaction

International audienceThis paper introduces the capability to study simultaneously changes in the density, the chemical composition, the mobility diameter, the aerodynamic diameter, and the layer thickness of multi-layered aerosol particles as they are being altered by heterogeneous chemical reactions. A vaporization-condensation method is used to generate aerosol particles composed of oleic acid outer layers of 2 to 30 nm on 101-nm polystyrene latex cores. The layer density is modified by reaction of oleic acid with ozone for variable exposure times. For increasing ozone exposure, the mobility diameter decreases while the vacuum aerodynamic diameter increases, which, for spherical particles, implies that particle density increases. The aerosol particles are confirmed as spherical based upon the small divergence of the particle beam in the aerosol mass spectrometer. The particle and layer densities are calculated by two independent methods, namely one based on the measured aerodynamic and mobility diameters and the other based on the measured mobility diameter and particle mass. The uncertainty estimates for density calculated by the second method are two to three times greater than those of the first method. Both methods indicate that the layer density increases from 0.89 to 1.12 g·cm?3 with increasing ozone exposure. Aerosol mass spectrometry shows that, concomitant with the increase in the layer density, the oxygen content of the reacted layer increases. Even after all of the oleic acid has reacted, the layer density and the oxygen content continue to increase slowly with prolonged ozone exposure, a finding which indicates continued chemical reactions of the organic products either with ozone or with themselves. The results of this paper provide new insights into the complex changes occurring for atmospheric particles during the aging processes caused by gas-phase oxidants

CCN activation experiments with adipic acid: effect of particle phase and adipic acid coatings on soluble and insoluble particles

Slightly soluble atmospherically relevant organic compounds may influence particle CCN activity and therefore cloud formation. Adipic acid is a frequently employed surrogate for such slightly soluble organic materials. The 11 published experimental studies on the CCN activity of adipic acid particles are not consistent with each other nor do they, in most cases, agree with the Köhler theory. The CCN activity of adipic acid aerosol particles was studied over a significantly wider range of conditions than in any previous single study. The work spans the conditions of the previous studies and also provides alternate methods for producing "wet" (deliquesced solution droplets) and dry adipic acid particles without the need to produce them by atomization of aqueous solutions. The experiments suggest that the scatter in the previously published CCN measurements is most likely due to the difficulty of producing uncontaminated adipic acid particles by atomization of solutions and possibly also due to uncertainties in the calibration of the instruments. The CCN activation of the small (<i>d</i><sub><i>m</i></sub><150 nm) initially dry particles is subject to a deliquescence barrier, while for the larger particles the activation follows the Köhler curve. Wet adipic acid particles follow the Köhler curve over the full range of particle diameters studied. In addition, the effect of adipic acid coatings on the CCN activity of both soluble and insoluble particles has also been studied. When a water-soluble core is coated by adipic acid, the CCN-hindering effect of particle phase is eliminated. An adipic acid coating on hydrophobic soot yields a CCN active particle. If the soot particle is relatively small (<i>d</i><sub>core</sub>≤102 nm), the CCN activity of the coated particles approaches the deliquescence line of adipic acid, suggesting that the total size of the particle determines CCN activation and the soot core acts as a scaffold

Kinetics of submicron oleic acid aerosols with ozone: A novel aerosol mass spectrometric technique

The reaction kinetics of submicron oleic (9-octadecanoic (Z)-) acid aerosols with ozone was studied using a novel aerosol mass spectrometric technique. In the apparatus a flow of size-selected aerosols is introduced into a flow reactor where the particles are exposed to a known density of ozone for a controlled period of time. The aerosol flow is then directed into an aerosol mass spectrometer for particle size and composition analyses. Data from these studies were used to: (a) quantitatively model the size-dependent kinetics process, (b) determine the aerosol size change due to uptake of ozone, (c) assess reaction stoichiometry, and (d) obtain qualitative information about the volatility of the reaction products. The reactive uptake probability for ozone on oleic acid particles obtained from modeling is 1.6 (±0.2) × 10^(−3) with an upper limit for the reacto-diffusive length of ∼10 nm. Atmospheric implications of the results are discussed

Effect of oxidant concentration, exposure time, and seed particles on secondary organic aerosol chemical composition and yield

We performed a systematic intercomparison study of the chemistry and yields of secondary organic aerosol (SOA) generated from OH oxidation of a common set of gas-phase precursors in a Potential Aerosol Mass (PAM) continuous flow reactor and several environmental chambers. In the flow reactor, SOA precursors were oxidized using OH concentrations ranging from 2.0 × 10[superscript 8] to 2.2 × 10[superscript 10] molec cm[superscript −3] over exposure times of 100 s. In the environmental chambers, precursors were oxidized using OH concentrations ranging from 2 × 10[superscript 6] to 2 × 10[superscript 7] molec cm[superscript −3] over exposure times of several hours. The OH concentration in the chamber experiments is close to that found in the atmosphere, but the integrated OH exposure in the flow reactor can simulate atmospheric exposure times of multiple days compared to chamber exposure times of only a day or so. In most cases, for a specific SOA type the most-oxidized chamber SOA and the least-oxidized flow reactor SOA have similar mass spectra, oxygen-to-carbon and hydrogen-to-carbon ratios, and carbon oxidation states at integrated OH exposures between approximately 1 × 10[superscript 11] and 2 × 10[superscript 11] molec cm[superscript −3] s, or about 1–2 days of equivalent atmospheric oxidation. This observation suggests that in the range of available OH exposure overlap for the flow reactor and chambers, SOA elemental composition as measured by an aerosol mass spectrometer is similar whether the precursor is exposed to low OH concentrations over long exposure times or high OH concentrations over short exposure times. This similarity in turn suggests that both in the flow reactor and in chambers, SOA chemical composition at low OH exposure is governed primarily by gas-phase OH oxidation of the precursors rather than heterogeneous oxidation of the condensed particles. In general, SOA yields measured in the flow reactor are lower than measured in chambers for the range of equivalent OH exposures that can be measured in both the flow reactor and chambers. The influence of sulfate seed particles on isoprene SOA yield measurements was examined in the flow reactor. The studies show that seed particles increase the yield of SOA produced in flow reactors by a factor of 3 to 5 and may also account in part for higher SOA yields obtained in the chambers, where seed particles are routinely used.National Science Foundation (U.S.). Atmospheric Chemistry Program (Grant AGS-1056225)National Science Foundation (U.S.). Atmospheric Chemistry Program (Grant AGS-1245011

Comparison of strength and durability characteristics of a geopolymer produced from fly ash, ground glass fiber and glass powder

Strength and durability characteristics of geopolymers produced using three precursors, consisting of fly ash, Ground Glass Fiber (GGF), and glass-powder were studied. Combinations of sodium hydroxide and sodium silicate were used as the activator solutions, and the effect of different sodium and silica content of the activators on the workability and compressive strength of geopolymers was investigated. The parameters used in this study were the mass ratio of Na2O-to-binder (for sodium content), and SiO2-to-Na2O of the activator (for silica content). Geopolymer mixtures that achieved the highest compressive strength from each precursor were assessed for their resistance to alkali-silica reaction and compared against the performance of portland cement mixtures. Test results revealed that GGF and fly ash-based geopolymers performed better than glass-powder-based geopolymer mixtures. The resistance of GGF-based and fly ash-based geopolymers to alkali-silica reaction was superior to that of portland cement mixtures, while glass-powder-based geopolymer showed inferior performance

The influence of rice husk ash addition on the properties of metakaolin-based geopolymers

This paper investigates the replacement of metakaolin (MK) with rice husk ash (RHA) in the production of alkali-activated binders or geopolymers. The influence of the RHA addition on compressive and flexural strength, as well as water absorption and apparent porosity were determined, in terms of the percentage of RHA in the mixture and molar ratios of the mixes. Fourier Transform Infrared (FTIR) spectroscopy and Energy Dispersive spectroscopy (EDS) were carried out to assess the changes in the microstructure of the geopolymer matrices with the RHA addition. Results have shown that RHA may be a supplementary precursor for geopolymers. The composition of the geopolymer matrices containing 0-40% RHA is very similar, which indicates that the additional Si provided by RHA is not incorporated to the geopolymer matrix. In addition, geopolymers with RHA content higher than 40% present a plastic behavior, characterized by extremely low strength and high deformation, which can be attributed to the formation of silica gel in formulations containing variable Si/Al ratio

Calorimetric study of geopolymer binders based on natural pozzolan

This paper investigates the kinetics of geopolymerisation in an inorganic polymeric binder based on a natural pozzolan. The heat released by the exothermic geopolymerisation reaction process is monitored under isothermal temperature conditions, maintained in a differential scanning calorimeter using a water circulation cell. Calorimetric data are obtained isothermally at 65, 75, and 85 °C with various Na2O/Al2O3 and SiO2/Na2O molar ratios and in the presence and absence of small amounts of calcium aluminate cement (used as an efflorescence control admixture in these binder systems). The first stage of reaction, which is rapid and strongly exothermic, is shortened as the temperature increases. The total heat of reaction increases in the mixes containing calcium aluminate cement, but the apparent activation energy calculated using a pseudo-first-order reaction model is lower than without added calcium aluminate cement. At a constant overall SiO2/Na2O molar ratio, the apparent activation energy is decreased as the Na2O/Al2O3 molar ratio increases. Calcium aluminate cement, therefore, reduces the minimum energy required to initiate geopolymerisation reactions of this natural pozzolan and facilitates the progress of the reactions which lead to formation of a cementitious product

Nanofluidic transport governed by the liquid/vapour interface

Liquid/vapour interfaces govern the behaviour of a wide range of systems but remain poorly understood, leaving ample margin for the exploitation of intriguing functionalities for applications. Here, we systematically investigate the role of liquid/vapour interfaces in the transport of water across apposing liquid menisci in osmosis membranes comprising short hydrophobic nanopores that separate two fluid reservoirs. We show experimentally that mass transport is limited by molecular reflection from the liquid/vapour interface below a certain length scale, which depends on the transmission probability of water molecules across the nanopores and on the condensation probability of a water molecule incident on the liquid surface. This fundamental yet elusive condensation property of water is measured under near-equilibrium conditions and found to decrease from 0.36 ± 0.21 at 30 °C to 0.18 ± 0.09 at 60 °C. These findings define the regime in which liquid/vapour interfaces govern nanofluidic transport and have implications for understanding mass transport in nanofluidic devices, droplets and bubbles, biological components and porous media involving liquid/vapour interfaces.Center for Clean Water and Clean Energy at MIT and KFUPM (Project R10-CW-09

An investigation of the mechanisms for strength gain or loss of geopolymer mortar after exposure to elevated temperature

When fly ash-based geopolymer mortars were exposed to a temperature of 800 °C, it was found that the strength after the exposure sometimes decreased, but at other times increased. This paper shows that ductility of the mortars has a major correlation to this strength gain/loss behaviour. Specimens prepared with two different fly ashes, with strengths ranging from 5 to 60 MPa, were investigated. Results indicate that the strength losses decrease with increasing ductility, with even strength gains at high levels of ductility. This correlation is attributed to the fact that mortars with high ductility have high capacity to accommodate thermal incompatibilities. It is believed that the two opposing processes occur in mortars: (1) further geopolymerisation and/or sintering at elevated temperatures leading to strength gain; (2) the damage to the mortar because of thermal incompatibility arising from non-uniform temperature distribution. The strength gain or loss occurs depending on the dominant process