An official website of the United States government
The dynamic properties of liquid phase-change materials (PCMs), such as viscosity η and the atomic self-diffusion coefficient D , play an essential role in the ultrafast phase switching behavior of novel nonvolatile phase-change memory applications. To connect η to D , the Stokes-Einstein relation (SER) is commonly assumed to be valid at high temperatures near or above the melting temperature T m and is often used for assessing liquid fragility (or crystal growth velocity) of technologically important PCMs. However, using quasi-elastic neutron scattering, we provide experimental evidence for a breakdown of the SER even at temperatures above T m in the high–atomic mobility state of a PCM, Ge 1 Sb 2 Te 4 . This implies that although viscosity may have strongly increased during cooling, diffusivity can remain high owing to early decoupling, being a favorable feature for the fast phase switching behavior of the high-fluidity PCM. We discuss the origin of the observation and propose the possible connection to a metal-semiconductor and fragile-strong transition hidden below T m .
more »
« less
Predictions of diffusion rates of large organic molecules in secondary organic aerosols using the Stokes–Einstein and fractional Stokes–Einstein relations
Abstract. Information on the rate of diffusion of organic moleculeswithin secondary organic aerosol (SOA) is needed to accurately predict theeffects of SOA on climate and air quality. Diffusion can be important forpredicting the growth, evaporation, and reaction rates of SOA under certainatmospheric conditions. Often, researchers have predicted diffusion rates oforganic molecules within SOA using measurements of viscosity and theStokes–Einstein relation (D∝1/η, where D is the diffusioncoefficient and η is viscosity). However, the accuracy of thisrelation for predicting diffusion in SOA remains uncertain. Usingrectangular area fluorescence recovery after photobleaching (rFRAP), wedetermined diffusion coefficients of fluorescent organic molecules over8 orders in magnitude in proxies of SOA including citric acid, sorbitol,and a sucrose–citric acid mixture. These results were combined withliterature data to evaluate the Stokes–Einstein relation for predictingthe diffusion of organic molecules in SOA. Although almost all the data agreewith the Stokes–Einstein relation within a factor of 10, a fractionalStokes–Einstein relation (D∝1/ηξ) with ξ=0.93is a better model for predicting the diffusion of organic molecules in the SOAproxies studied. In addition, based on the output from a chemical transportmodel, the Stokes–Einstein relation can overpredict mixing times of organicmolecules within SOA by as much as 1 order of magnitude at an altitudeof ∼3 km compared to the fractional Stokes–Einstein relation with ξ=0.93. These results also have implications for other areas such as infood sciences and the preservation of biomolecules.
more »
« less
- Award ID(s):
- 1654104
- PAR ID:
- 10142829
- Date Published:
- Journal Name:
- Atmospheric Chemistry and Physics
- Volume:
- 19
- Issue:
- 15
- ISSN:
- 1680-7324
- Page Range / eLocation ID:
- 10073 to 10085
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Internally-mixed aerosol particles containing organic molecules and inorganic salts are prevalent in the atmosphere, arising from direct emission ( e.g., from the ocean) or indirect production by condensation of organic vapors onto existing inorganic particle seeds. Aerosol particles co-exist with water vapor and, under humid conditions, will exist as dilute aqueous solution particles that can be well described by thermodynamic models. Under low humidity conditions, the increase in solute concentrations leads to molecular interactions and significant non-ideality effects that drive changes in important physical properties, such as viscosity and phase state, that are not predicted using simple models. Here, we explore a model system containing ammonium sulfate (AS) and citric acid (CA). We measure the hygroscopicity, viscosity, and rate of water diffusion in particles across a range of RH conditions and organic fractions to better understand the influence of organic–inorganic mixtures on particle properties. We report the RH dependence of these properties and explore the applicability of commonly used methods that connect them together, such as the Stokes–Einstein relationship and thermodynamic modelling methods. We show that at low RH, the addition of AS to CA leads to a reduction in the amount of water as indicated by the radial growth factor at a fixed RH, while observing an increase in the viscosity over several orders of magnitude. Contrary to the viscosity, only minor changes in water diffusion were measured, and analysis with the fractional Stokes–Einstein relationship indicates that changes in the molecular matrix due to the presence of AS could explain the observed phenomena. This work reveals that small additions of electrolytes can drive large changes in particle properties, with implications for chemical reactivity, lifetime, and particle phase that will influence the environmental impacts and chemistry of aerosol particles.more » « less
-
Abstract. Information on liquid–liquid phase separation (LLPS) and viscosity (ordiffusion) within secondary organic aerosol (SOA) is needed to improvepredictions of particle size, mass, reactivity, and cloud nucleatingproperties in the atmosphere. Here we report on LLPS and viscosities withinSOA generated by the photooxidation of diesel fuel vapors. Diesel fuelcontains a wide range of volatile organic compounds, and SOA generated bythe photooxidation of diesel fuel vapors may be a good proxy for SOA fromanthropogenic emissions. In our experiments, LLPS occurred over the relativehumidity (RH) range of ∼70 % to ∼100 %,resulting in an organic-rich outer phase and a water-rich inner phase. Theseresults may have implications for predicting the cloud nucleating propertiesof anthropogenic SOA since the presence of an organic-rich outer phase athigh-RH values can lower the supersaturation with respect to water requiredfor cloud droplet formation. At ≤10 % RH, the viscosity was ≥1×108 Pa s, which corresponds to roughly the viscosity of tarpitch. At 38 %–50 % RH, the viscosity was in the range of 1×108 to 3×105 Pa s. These measured viscosities areconsistent with predictions based on oxygen to carbon elemental ratio (O:C)and molar mass as well as predictions based on the number of carbon,hydrogen, and oxygen atoms. Based on the measured viscosities and theStokes–Einstein relation, at ≤10 % RH diffusion coefficients oforganics within diesel fuel SOA is ≤5.4×10-17 cm2 s−1 and the mixing time of organics within 200 nm diesel fuel SOAparticles (τmixing) is 50 h. These small diffusion coefficientsand large mixing times may be important in laboratory experiments, where SOAis often generated and studied using low-RH conditions and on timescales ofminutes to hours. At 38 %–50 % RH, the calculated organic diffusioncoefficients are in the range of 5.4×10-17 to 1.8×10-13 cm2 s−1 and calculated τmixing values arein the range of ∼0.01 h to ∼50 h. These valuesprovide important constraints for the physicochemical properties ofanthropogenic SOA.more » « less
-
Applying an excess entropy scaling formalism to the coarse-grained (CG) dynamics of liquids, we discovered that missing rotational motions during the CG process are responsible for artificially accelerated CG dynamics. In the context of the dynamic representability between the fine-grained (FG) and CG dynamics, this work introduces the well-known Stokes–Einstein and Stokes–Einstein–Debye relations to unravel the rotational dynamics underlying FG trajectories, thereby allowing for an indirect evaluation of the effective rotations based only on the translational information at the reduced CG resolution. Since the representability issue in CG modeling limits a direct evaluation of the shear stress appearing in the Stokes–Einstein and Stokes–Einstein–Debye relations, we introduce a translational relaxation time as a proxy to employ these relations, and we demonstrate that these relations hold for the ambient conditions studied in our series of work. Additional theoretical links to our previous work are also established. First, we demonstrate that the effective hard sphere radius determined by the classical perturbation theory can approximate the complex hydrodynamic radius value reasonably well. Furthermore, we present a simple derivation of an excess entropy scaling relationship for viscosity by estimating the elliptical integral of molecules. In turn, since the translational and rotational motions at the FG level are correlated to each other, we conclude that the “entropy-free” CG diffusion only depends on the shape of the reference molecule. Our results and analyses impart an alternative way of recovering the FG diffusion from the CG description by coupling the translational and rotational motions at the hydrodynamic level.more » « less
-
Abstract. The role of secondary organic aerosol (SOA) in atmospheric ice nucleation is not well understood, limiting accurate predictions of aerosol indirect effects in global climate simulations. This article details experiments performed to characterize the ice-nucleating properties of proxy SOA. Experimental techniques in conditioning aerosol to glass transition temperatures (Tg) as low as −70 °C using a pre-cooling unit are described. Ice nucleation measurements of proxy organosulfates (i.e., methyl, ethyl, and dodecyl sulfates) and citric acid were performed using the SPectrometer for ice nucleation (SPIN), operating at conditions relevant to upper-tropospheric cirrus temperatures (−45 °C, −40 °C, −35 °C) and ice saturation ratios (1.0<1.6). Methyl, ethyl, and dodecyl sulfates did not nucleate ice, despite dodecyl sulfate possessing a Tg higher than ambient temperature. Citric acid nucleated ice heterogeneously at −45 and −40 °C (1.2<1.4) but required pre-cooling temperatures of −70 °C, notably colder than the lowest published Tg. A kinetic flux model was used to numerically estimate water diffusion timescales to verify experimental observations and predict aerosol phase state. Diffusion modeling showed rapid liquefaction of glassy methyl and ethyl sulfates due to high hygroscopicity, preventing heterogeneous ice nucleation. The modeling results suggest that citric acid nucleated ice heterogeneously via deposition freezing or immersion freezing after surface liquefaction. We conclude that Tg alone is not sufficient for predicting heterogeneous ice formation for proxy SOA using the SPIN.more » « less
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.5194/acp-19-10073-2019
