scholarly journals The Role of Contact Angle and Pore Width on Pore Condensation and Freezing

2019 ◽  
Author(s):  
Robert O. David ◽  
Jonas Fahrni ◽  
Claudia Marcolli ◽  
Fabian Mahrt ◽  
Dominik Brühwiler ◽  
...  
Keyword(s):  
Contact Angle ◽  
Active Sites ◽  
Water Saturation ◽  
Capillary Condensation ◽  
Contact Angles ◽  
Ice Nucleation ◽  
Pore Width ◽  
Kelvin Effect ◽  
Pore Condensation

Abstract. It has recently been shown that pore condensation and freezing (PCF) is a mechanism responsible for ice formation under cirrus cloud conditions. PCF is defined as the condensation of liquid water in narrow capillaries below water saturation due to the Kelvin effect, followed by either heterogeneous or homogeneous nucleation depending on the temperature regime and presence of an ice nucleating active site. By using sol-gel synthesized silica with well-defined pore diameters, morphology and distinct chemical surface-functionalization, the role of the water-silica contact angle and pore width on PCF is investigated. We find that contact angle and pore width play an important role in determining the relative humidity required for capillary condensation as predicted by the Kelvin effect and subsequent ice nucleation at cirrus temperatures. For the pore diameters and contact angles covered in this study, 2.2–9.2 nm and 15–78°, respectively, our results reveal that the contact angle plays an important role in predicting the humidity required for pore filling while the pore diameter determines the ability of pore water to freeze. For T > 235 K and below water saturation, pore diameters and contact angles were not able to predict the freezing ability of the particles suggesting an absence of active sites, thus ice nucleation did not proceed via a PCF mechanism. Rather, the ice nucleating ability of the particles depended solely on chemical functionalization. Therefore, parameterizations for the ice nucleating abilities of particles at cirrus conditions should differ from parameterizations at mixed-phase clouds conditions. Our results support PCF as the atmospherically relevant ice nucleation mechanism below water saturation when porous surfaces are encountered in the troposphere.

scholarly journals The role of contact angle and pore width on pore condensation and freezing

2020 ◽  
Vol 20 (15) ◽  
pp. 9419-9440 ◽  
Author(s):  
Robert O. David ◽  
Jonas Fahrni ◽  
Claudia Marcolli ◽  
Fabian Mahrt ◽  
Dominik Brühwiler ◽  
...  
Keyword(s):  
Contact Angle ◽  
Active Sites ◽  
Water Saturation ◽  
Sol Gel ◽  
Contact Angles ◽  
Ice Nucleation ◽  
Pore Width ◽  
Water Contact ◽  
Pore Condensation

Abstract. It has recently been shown that pore condensation and freezing (PCF) is a mechanism responsible for ice formation under cirrus cloud conditions. PCF is defined as the condensation of liquid water in narrow capillaries below water saturation due to the inverse Kelvin effect, followed by either heterogeneous or homogeneous nucleation depending on the temperature regime and presence of an ice-nucleating active site. By using sol–gel synthesized silica with well-defined pore diameters, morphology and distinct chemical surface-functionalization, the role of the water–silica contact angle and pore width on PCF is investigated. We find that for the pore diameters (2.2–9.2 nm) and water contact angles (15–78∘) covered in this study, our results reveal that the water contact angle plays an important role in predicting the humidity required for pore filling, while the pore diameter determines the ability of pore water to freeze. For T>235 K and below water saturation, pore diameters and water contact angles were not able to predict the freezing ability of the particles, suggesting an absence of active sites; thus ice nucleation did not proceed via a PCF mechanism. Rather, the ice-nucleating ability of the particles depended solely on chemical functionalization. Therefore, parameterizations for the ice-nucleating abilities of particles in cirrus conditions should differ from parameterizations at mixed-phase clouds conditions. Our results support PCF as the atmospherically relevant ice nucleation mechanism below water saturation when porous surfaces are encountered in the troposphere.

scholarly journals Technical note: Fundamental aspects of ice nucleation via pore condensation and freezing including Laplace pressure and growth into macroscopic ice

2020 ◽  
Vol 20 (5) ◽  
pp. 3209-3230 ◽  
Author(s):  
Claudia Marcolli
Keyword(s):  
Negative Pressure ◽  
Active Sites ◽  
Water Saturation ◽  
Particle Surface ◽  
Ice Nucleation ◽  
Nucleation Theory ◽  
Ice Crystal ◽  
Spherical Cap ◽  
Pore Opening ◽  
Pore Condensation

Abstract. Pore condensation and freezing (PCF) is an ice nucleation mechanism that explains ice formation at low ice supersaturation. It assumes that liquid water condenses in pores of solid aerosol particles below water saturation, as described by the Kelvin equation, followed by homogeneous ice nucleation when temperatures are below about 235 K or immersion freezing at higher temperatures, in case the pores contain active sites that induce ice nucleation. Porewater is under tension (negative pressure) below water saturation as described by the Young–Laplace equation. This negative pressure affects the ice nucleation rates and the stability of the pore ice. Here, pressure-dependent parameterizations of classical nucleation theory are developed to quantify the increase in homogeneous ice nucleation rates as a function of tension and to assess the critical diameter of pores that is required to accommodate ice at negative pressures. Growth of ice out of the pore into a macroscopic ice crystal requires ice supersaturation. This supersaturation as a function of the pore opening width is derived, assuming that the ice phase first grows as a spherical cap on top of the pore opening before it starts to expand laterally on the particle surface into a macroscopic ice crystal.

scholarly journals Technical note: Fundamental aspects of ice nucleation via pore condensation and freezing including Laplace pressure and growth into macroscopic ice

2019 ◽  
Author(s):  
Claudia Marcolli
Keyword(s):  
Negative Pressure ◽  
Active Sites ◽  
Water Saturation ◽  
Particle Surface ◽  
Ice Nucleation ◽  
Nucleation Theory ◽  
Ice Crystal ◽  
Spherical Cap ◽  
Pore Opening ◽  
Pore Condensation

Abstract. Pore condensation and freezing (PCF) is an ice nucleation mechanism that explains ice formation at low ice supersaturation. It assumes that liquid water condenses in pores of solid aerosol particles below water saturation, as described by the Kelvin equation, followed by homogeneous ice nucleation when temperatures are below about 235 K or immersion freezing at higher temperatures, in case the pores contain active sites that induce ice nucleation. Pore water is under tension (negative pressure) below water saturation as described by the Young-Laplace equation. This negative pressure affects the ice nucleation rates and the stability of the pore ice. Here, pressure dependent parameterizations of classical nucleation theory are developed to quantify the increase of homogeneous ice nucleation rates as a function of tension and to assess the critical diameter of pores that is required to accommodate ice at negative pressures. For growth out of the pore into a macroscopic ice crystal, ice supersaturation is required. The required supersaturation as a function of the pore opening width is derived, assuming that the ice phase first grows as a spherical cap on top of the pore opening before it starts to expand laterally on the particle surface into a macroscopic ice crystal.

scholarly journals Influence of moisture content on the contact angle and surface tension measured on birch wood surfaces

2021 ◽  
Author(s):  
Rami Benkreif ◽  
Fatima Zohra Brahmia ◽  
Csilla Csiha
Keyword(s):  
Surface Tension ◽  
Contact Angle ◽  
Moisture Content ◽  
Solid Wood ◽  
Contact Angles ◽  
Surface Moisture ◽  
Wood Coatings ◽  
The Relationship ◽  
Wood Surfaces

AbstractSurface tension of solid wood surfaces affects the wettability and thus the adhesion of various adhesives and wood coatings. By measuring the contact angle of the wood, the surface tension can be calculated based on the Young-Dupré equation. Several publications have reported on contact angle measured with different test liquids, under different conditions. Results can only be compared if the test conditions are similar. While the roles of the drop volume, image shooting time etc., are widely recognized, the role of the wood surface moisture content (MC) is not evaluated in detail. In this study, the effect of wood moisture content on contact angle values, measured with distilled water and diiodomethane, on sanded birch (Betula pendula) surfaces was investigated, in order to find the relationship between them. With increasing MC from approximately 6% to 30%, increasing contact angle (decreasing surface tension) values were measured according to a logarithmic function. The function makes possible the calculation of contact angles that correspond to different MCs.

scholarly journals Efficiency of immersion mode ice nucleation on surrogates of mineral dust

2007 ◽  
Vol 7 (19) ◽  
pp. 5081-5091 ◽  
Author(s):  
C. Marcolli ◽  
S. Gedamke ◽  
T. Peter ◽  
B. Zobrist
Keyword(s):  
Contact Angle ◽  
Active Sites ◽  
Quantitative Agreement ◽  
Ice Nucleation ◽  
Nucleation Theory ◽  
Classical Nucleation Theory ◽  
Aqueous Suspensions ◽  
Freezing Temperatures ◽  
Good Agreement ◽  
Heterogeneous Ice Nucleation

Abstract. A differential scanning calorimeter (DSC) was used to explore heterogeneous ice nucleation of emulsified aqueous suspensions of two Arizona test dust (ATD) samples with particle diameters of nominally 0–3 and 0–7 μm, respectively. Aqueous suspensions with ATD concentrations of 0.01–20 wt% have been investigated. The DSC thermograms exhibit a homogeneous and a heterogeneous freezing peak whose intensity ratios vary with the ATD concentration in the aqueous suspensions. Homogeneous freezing temperatures are in good agreement with recent measurements by other techniques. Depending on ATD concentration, heterogeneous ice nucleation occurred at temperatures as high as 256 K or down to the onset of homogeneous ice nucleation (237 K). For ATD-induced ice formation Classical Nucleation Theory (CNT) offers a suitable framework to parameterize nucleation rates as a function of temperature, experimentally determined ATD size, and emulsion droplet volume distributions. The latter two quantities serve to estimate the total heterogeneous surface area present in a droplet, whereas the suitability of an individual heterogeneous site to trigger nucleation is described by the compatibility function (or contact angle) in CNT. The intensity ratio of homogeneous to heterogeneous freezing peaks is in good agreement with the assumption that the ATD particles are randomly distributed amongst the emulsion droplets. The observed dependence of the heterogeneous freezing temperatures on ATD concentrations cannot be described by assuming a constant contact angle for all ATD particles, but requires the ice nucleation efficiency of ATD particles to be (log)normally distributed amongst the particles. Best quantitative agreement is reached when explicitly assuming that high-compatibility sites are rare and that therefore larger particles have on average more and better active sites than smaller ones. This analysis suggests that a particle has to have a diameter of at least 0.1 μm to exhibit on average one active site.

scholarly journals Ice nucleation abilities of soot particles determined with the Horizontal Ice Nucleation Chamber

2018 ◽  
Vol 18 (18) ◽  
pp. 13363-13392 ◽  
Author(s):  
Fabian Mahrt ◽  
Claudia Marcolli ◽  
Robert O. David ◽  
Philippe Grönquist ◽  
Eszter J. Barthazy Meier ◽  
...  
Keyword(s):  
Particle Size ◽  
Water Saturation ◽  
Particle Surface ◽  
Water Vapor Sorption ◽  
Contact Angles ◽  
Ice Nucleation ◽  
Particle Surface Area ◽  
Soot Particles ◽  
Microphysical Properties ◽  
Homogeneous Freezing

Abstract. Ice nucleation by different types of soot particles is systematically investigated over the temperature range from 218 to 253 K relevant for both mixed-phase (MPCs) and cirrus clouds. Soot types were selected to represent a range of physicochemical properties associated with combustion particles. Their ice nucleation ability was determined as a function of particle size using relative humidity (RH) scans in the Horizontal Ice Nucleation Chamber (HINC). We complement our ice nucleation results by a suite of particle characterization measurements, including determination of particle surface area, fractal dimension, temperature-dependent mass loss (ML), water vapor sorption and inferred porosity measurements. Independent of particle size, all soot types reveal absence of ice nucleation below and at water saturation in the MPC regime (T>235 K). In the cirrus regime (T≤235 K), soot types show different freezing behavior depending on particle size and soot type, but the freezing is closely linked to the soot particle properties. Specifically, our results suggest that if soot aggregates contain mesopores (pore diameters of 2–50 nm) and have sufficiently low water–soot contact angles, they show ice nucleation activity and can contribute to ice formation in the cirrus regime at RH well below homogeneous freezing of solution droplets. We attribute the observed ice nucleation to a pore condensation and freezing (PCF) mechanism. Nevertheless, soot particles without cavities of the right size and/or too-high contact angles nucleate ice only at or well above the RH required for homogeneous freezing conditions of solution droplets. Thus, our results imply that soot particles able to nucleate ice via PCF could impact the microphysical properties of ice clouds.

scholarly journals Pre-activation of ice-nucleating particles by the pore condensation and freezing mechanism

2016 ◽  
Vol 16 (4) ◽  
pp. 2025-2042 ◽  
Author(s):  
Robert Wagner ◽  
Alexei Kiselev ◽  
Ottmar Möhler ◽  
Harald Saathoff ◽  
Isabelle Steinke
Keyword(s):  
Capillary Condensation ◽  
Ice Nucleation ◽  
Temperature Cycling ◽  
Activation Mechanism ◽  
Crystal Formation ◽  
Model Calculations ◽  
Surface Samples ◽  
Activation Efficiency ◽  
Kelvin Effect ◽  
Homogeneous Freezing

Abstract. In spite of the resurgence in ice nucleation research a comparatively small number of studies deal with the phenomenon of pre-activation in heterogeneous ice nucleation. Fifty years ago, it was shown that various mineral dust and volcanic ash particles can be pre-activated to become nuclei for ice crystal formation even at temperatures as high as 270–271 K. Pre-activation was achieved under ice-subsaturated conditions without any preceding macroscopic ice growth by just temporarily cooling the particles to temperatures below 228 K. A two-step mechanism involving capillary condensation of supercooled water and subsequent homogeneous freezing was proposed to account for the particles' enhanced ice nucleation ability at high temperatures. This work reinvestigates the efficiency of the proposed pre-activation mechanism in temperature-cycling experiments performed in a large cloud chamber with suspended particles. We find the efficiency to be highest for the clay mineral illite as well as for highly porous materials like zeolite and diatomaceous earth, whereas most aerosols generated from desert dust surface samples did not reveal a measurable pre-activation ability. The pre-activation efficiency is linked to particle pores in a certain size range. As estimated by model calculations, only pores with diameters between about 5 and 8 nm contribute to pre-activation under ice-subsaturated conditions. This range is set by a combination of requirements from the negative Kelvin effect for condensation and a critical size of ice embryos for ice nucleation and melting. In contrast to the early study, pre-activation is only observed for temperatures below 260 K. Above that threshold, the particles' improved ice nucleation ability disappears due to the melting of ice in the pores.

scholarly journals Immersion freezing of water and aqueous ammonium sulfate droplets initiated by humic-like substances as a function of water activity

2013 ◽  
Vol 13 (13) ◽  
pp. 6603-6622 ◽  
Author(s):  
Y. J. Rigg ◽  
P. A. Alpert ◽  
D. A. Knopf
Keyword(s):  
Water Activity ◽  
Active Sites ◽  
Melting Curve ◽  
Contact Angles ◽  
Ice Nucleation ◽  
Nucleation Theory ◽  
Classical Nucleation Theory ◽  
Surface Areas ◽  
Immersion Freezing ◽  
Freezing Temperatures

Abstract. Immersion freezing of water and aqueous (NH4)2SO4 droplets containing leonardite (LEO) and Pahokee peat (PP) serving as surrogates for humic-like substances (HULIS) has been investigated. Organic aerosol containing HULIS are ubiquitous in the atmosphere; however, their potential for ice cloud formation is uncertain. Immersion freezing has been studied for temperatures as low as 215 K and solution water activity, aw, from 0.85 to 1.0. The freezing temperatures of water and aqueous solution droplets containing LEO and PP are 5–15 K warmer than homogeneous ice nucleation temperatures. Heterogeneous freezing temperatures can be represented by a horizontal shift of the ice melting curve as a function of solution aw by Δaw = 0.2703 and 0.2466, respectively. Corresponding hetrogeneous ice nucleation rate coefficients, Jhet, are (9.6 ± 2.5)×104 and (5.4 ± 1.4)×104 cm−2 s−1 for LEO and PP containing droplets, respectively, and remain constant along freezing curves characterized by Δaw. Consequently predictions of freezing temperatures and kinetics can be made without knowledge of the solute type when relative humidity and ice nuclei (IN) surface areas are known. The acquired ice nucleation data are applied to evaluate different approaches to fit and reproduce experimentally derived frozen fractions. In addition, we apply a basic formulation of classical nucleation theory (α(T)-model) to calculate contact angles and frozen fractions. Contact angles calculated for each ice nucleus as a function of temperature, α(T)-model, reproduce exactly experimentally derived frozen fractions without involving free-fit parameters. However, assigning the IN a single contact angle for the entire population (single-α model) is not suited to represent the frozen fractions. Application of α-PDF, active sites, and deterministic model approaches to measured frozen fractions yield similar good representations. Furthermore, when using a single parameterization of α-PDF or active sites distribution to fit all individual aw immersion freezing data simultaneously, frozen fraction curves are not reproduced. This implies that these fitting formulations cannot be applied to immersion freezing of aqueous solutions, and suggests that derived fit parameters do not represent independent particle properties. Thus, from fitting frozen fractions only, the underlying ice nucleation mechanism and nature of the ice nucleating sites cannot be inferred. In contrast to using fitted functions obtained to represent experimental conditions only, we suggest to use experimentally derived Jhet as a function of temperature and aw that can be applied to conditions outside of those probed in laboratory. This is because Jhet(T) is independent of time and IN surface areas in contrast to the fit parameters obtained by representation of experimentally derived frozen fractions.

scholarly journals Exploratory experiments on pre-activated freezing nucleation on mercuric iodide

2020 ◽  
Author(s):  
Gabor Vali
Keyword(s):  
Liquid Water ◽  
Laboratory Experiments ◽  
Ice Nucleation ◽  
Mercuric Iodide ◽  
Multiple Sample ◽  
Pore Condensation ◽  
Basic Level ◽  
Activation Cycle

Abstract. Pre-activation of freezing nucleation was examined in laboratory experiments with mercuric iodide suspensions in water. The experiments followed the procedure designed by Edwards, Evans and Zipper (1970) but employed multiple sample drops and many repetitions of the pre-activation cycle. The results obtained confirm the basic findings of the earlier work and refine it. By also drawing on the results of Seeley and Seidler (2001), pre-activated freezing nucleation (PFN in this work) is analyzed in search of constraints that help define the process responsible for it. No firm conclusions are reached, but evidence is accumulated pointing to the role of definite structures being involved in PFN, similar to the role of sites in heterogeneous freezing nucleation in general. PFN differs from pore condensation and freezing described by Marcolli (2020) and David et al. (2020) in that it takes place in liquid water. Further exploration of this process can help understading ice nucleation at the basic level and in its practical manifestations. The results call attention to an ice nucleation pathway hitherto barely explored and which can be expected to have consequences in how ice nucleation occurs in atmospheric clouds and in other systems.

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