Degree Of Supersaturation Research Articles

Nucleation of multi-species crystals: methane cleatrate hydrates, a playground for classical force models

Nucleation and growth of methane clathrate hydrates is an exceptional playground to study crystallisation of multi-component, host-guest crystallites when one of the species forming the crystal, the guest, has a higher concentration in the solid than in the liquid phase. This adds problems related to the transport of the low concentration species, here methane. A key aspect in the modelling of clathrates is the water model employed in the simulation. In previous articles, we compared an all-atom force model, TIP4P/Ewald, with a coarse grain one, which is highly appreciated for its computational efficiency. Here, we perform a complementary analysis considering three all-atoms water models: TIP4P/Ewald, TIP4P/ice and TIP5P. A key difference between these models is that the former predicts a much lower freezing temperature. Intuitively, one expects that to lower freezing temperatures of water correspond to lower water/methane–methane gas–clathrate coexistence ones, which determines the degree of supercooling and the degree of supersaturation. Hence, in the simulation conditions, 250 K (500 atm, and fixed methane molar fraction), one expects computational samples made of TIP4P-ice and TIP5P, with a similar freezing temperature ( T f ∼ 273 K), to be more supersaturated with respect to the case of TIP4P-Ew ( T f ∼ 245 K), and crystallisation to be faster. Surprisingly, we find that while the nucleation rate is consistent with this prediction, growth rate with TIP4P-ice and TIP5P is much slower than with TIP4P-Ew. The latter was attributed to the slower reorientation of water molecules in strong supercooled conditions, resulting in a lower growth rate. This suggests that the freezing temperature is not a suitable parameter to evaluate the adequacy of a water model.

Phase behavior and crystal nucleation of hard triangular prisms.

The interplay between densification and positional ordering during the process of crystal nucleation is a greatly investigated topic. Even for the simplest colloidal model-hard spheres-there has been much debate regarding the potential foreshadowing of nucleation by significant fluctuations in either local density or local structure. Considering anisotropic particles instead of spheres adds a third degree of freedom to the self-organization process of crystal nucleation: orientational ordering. Here, we investigate the crystal nucleation of hard triangular prisms. Using Monte Carlo simulations, we first carefully determine the crystal-fluid coexistence values and calculate the nucleation barriers for two degrees of supersaturation. Next, we use brute force simulations to obtain a large set of spontaneous nucleation events. By studying the time evolution of the local density, positional ordering, and orientational ordering in the region in which the nucleus first arises, we demonstrate that all local order parameters increase simultaneously from the very start of the nucleation process. We thus conclude that we observe no precursor for the crystal nucleation of hard triangular prisms.

Mechanisms of dissolution and crystallization of amorphous glibenclamide

Amorphous solid dispersions enhance the dissolution and oral bioavailability of poorly water-soluble drugs. However, the link between polymer properties and formulation performance has not been fully clarified yet. We studied the effect of hydroxypropyl cellulose (HPC) polymers molecular weight (Mw) on the storage stability, dissolution kinetics and supersaturation stability of spray-dried amorphous glibenclamide (GLB) formulations. The solid-state stability of amorphous GLB during storage was significantly enhanced by both the 40 kDa (HPC-SSL) and 84 kDa (HPC-L) polymers, regardless of Mw differences. In contrast, HPC-SSL maintained significantly higher aqueous drug concentrations during dissolution, compared to HPC-L (its higher Mw analogue). Dedicated dissolution experiments, in situ optical microscopy and solid-state characterization revealed that aqueous drug concentrations were determined by the interplay between crystallization inhibition, drug ionization, wetting and solubilization effects: (1) HPC prevents surface nucleation, hence inhibiting crystallization, (2) intestinal colloids (bile salts and phospholipids) increase supersaturated drug concentrations via wetting and solubilization effects and (3) pH and drug ionization severely impact the degree of supersaturation. The better performance of the lower Mw HPC-SSL was due to its superior inhibition of surface crystallization. These insights into the molecular mechanisms of dissolution and crystallization of amorphous solids provide foundation for rational formulation development.

Microstructure Evolution and Mechanical Properties of In Situ TiB2/Al–Zn–Mg–Cu Composites by Electropulsing‐Assisted Solution Treatment

The traditional solution treatment is not completely applicable for in situ TiB2/Al–Zn–Mg–Cu composite due to the influence of TiB2 particles. This study investigates the impact of the electropulsing‐assisted solution (EAS) process on the microstructure evolution and mechanical properties of TiB2/Al–Zn–Mg–Cu composites. The nonuniform microstructure evolution related to the difference in temperature and current density is supported by simulative and experimental results. EAS treatment significantly enhances the degree of supersaturation, allowing phases surrounding TiB2 particles to dissolve without extensive overburning, unlike traditional solution treatments. This improvement is attributed to the reduced thermodynamic barrier and accelerated atomic diffusion, facilitated by both localized and average Joule heating effects and enhanced thermal electron/phonon scattering. Meanwhile, grain size remains stable during the temperature rise induced by EAS treatment. Furthermore, the mechanical properties of composites increase, among which the increase in strength is mainly ascribed to solid–solution strengthening, and the increase in elongation is related to multiple factors referring to TiB2 particles fracture and interface crack between the undissolved phases and matrix. This study provides an approach to achieve an efficient dissolution of phases aggregated with particles and without widespread overburning in particle‐reinforced Al matrix composites via electropulsing techniques.

Topochemical transformation mechanism and piezoelectric response of B-site complex BaZr0.1Ti0.9O3 microplatelets

The B-site complex BaZr0.1Ti0.9O3 (BZT) microplatelets with perovskite-structured were synthesized, using the Bi4(Zr0.1Ti0.9)3O12 (BIZ0.1T0.9) as a precursor. The precursor had a high aspect ratio, with an average size of ∼8.0 μm. Later, B-site complex BZT microplatelets were obtained via molten salt methods. The influence of n(BIZ0.1T0.9):n(BaCO3) ratio and calcined temperature in the composition, morphology and local piezoelectric and ferroelectric behaviour for BZT microplatelets was deeply discussed. The result showed that the reactants ratio determined the supersaturation degree in the molten salt environment, while the calcined temperature determined the crystallinity of BZT microcrystals. Overall, with the n(BIZ0.1T0.9):n(BaCO3) ratio was 1:4, the BZT microcrystal calcined at 900 °C had a better plate-like morphology. Manwhile, the micropizoelectric properties of BZT microplatelet was studied, achieving a maximum d33* of ∼330 pm/V. The result indicated that the B-site complex BZT microplatelets is a potential templates for textured ceramics.

Evaluation of the impact of mucin on supersaturation and permeation of BCS class 2 basic drugs

This study evaluated the impact of mucin on supersaturation and permeation of BCS Class 2 basic drugs in a pH-shift, 2-stage model using three model compounds, dipyridamole, ricobendazole, and Compound A. The three compounds showed various degrees of supersaturation (DoS) in Stage 2 and modest to no increases in flux with the presence of mucin in the dissolution media. Mucin's impact on DoS and flux, if any, appeared to be compound specific and possibly related to its pKa and ionization state. Overall, the increases in supersaturation and permeation due to mucin ranged from modest to minimal for the three model compounds under the conditions tested. The pH-shift model using MacroFLUX was able to monitor gastric and intestinal dissolution and simultaneously assess the effect of intestinal mucin on supersaturation and flux.

Thermally-Induced Supersaturation Approach for Optimizing Drug Loading and Biopharmaceutical Properties of Supersaturated Lipid-Based Formulations: Case Studies with Ibrutinib and Enzalutamide.

Lipid-based formulations (LbFs) have demonstrated success in pharmaceutical applications; however, challenges persist in dissolving entire doses of the drug into defined liquid volumes. In this study, the temperature-induced supersaturation method was employed in LbF to address drug loading and pill burden issues. Supersaturated LbFs (super-LbF) were prepared using the temperature-induced supersaturation method, where the drug load is above its equilibrium solubility. Further, the influence of the drug's physicochemical and thermal characteristics on drug loading and their relevance with an apparent degree of supersaturation (aDS) was studied using two model drugs, ibrutinib and enzalutamide. All the prepared LbFs were evaluated in terms of physical stability, dispersion, and solubilization capacity, as well as pharmacokinetic assessments. Drug re-crystallization was observed in the lipid solution on long-term storage at higher aDS values of 2-2.5. Furthermore, high-throughput lipolysis studies demonstrated a significant decrease in drug concentration across all LbFs (regardless of drug loading) due to a decline in the formulation solvation capacity and subsequent generation of in-situ supersaturation. Further, the in vivo results demonstrated comparable pharmacokinetic parameters between conventional LbF and super-LbF. The short duration of the thermodynamic metastable state limits the potential absorption benefits. However, super-LbFs of Ibr and Enz showed superior profiles, with 1.7-fold and 5.2-fold increased drug exposure compared to their respective crystalline suspensions. In summary, this study emphasizes the potential of temperature-induced supersaturation in LbF for enhancing drug loading and highlights the intricate interplay between drug properties, formulation characteristics, and in vivo performance.

Antiscaling Pickering Emulsions Enabled by Amphiphilic Hairy Cellulose Nanocrystals.

Nucleation and growth of sparingly soluble salts, referred to as scaling, has posed substantial challenges in industrial processes that deal with multiphase flows, including enhanced oil recovery (EOR). During crude oil extraction/recovery, seawater is injected into oil reservoirs and yields water-in-oil (W/O) emulsions that may undergo calcium carbonate (CaCO3) scaling. Common antiscaling macromolecules and nanoparticles have adverse environmental impacts and/or are limited to functioning only in single-phase aqueous media. Here, we develop a novel antiscaling cellulose-based nanoparticle that enables scale-resistant Pickering emulsions. Cellulose fibrils are rationally nanoengineered to yield amphiphilic hairy cellulose nanocrystals (AmHCNC), bearing hydrophilic dicarboxylate groups and hydrophobic alkyl chains on disordered cellulose chains (hairs) protruding from nanocrystal ends. The unique chemical and structural properties of AmHCNC render them the first dual functional antiscaling and emulsion stabilizing nanoparticle. AmHCNC stabilize W/O Pickering emulsions at a concentration of 1.00 wt % for 1 week while inhibiting CaCO3 scale formation up to 70% by mass at a supersaturation degree of ∼101 compared with the synthetic surfactant Span 80. To the best of our knowledge, this study presents the first biopolymer-based solution for the long-lasting scaling challenge in multiphase media, which may set the stage for developing sustainable scale-resistant multiphase flows in a broad spectrum of industrial sectors.

Effect of friction-stir processing and subsequent aging treatment on microstructure and service properties of Cu-Cr-Zr alloy

The effect of friction-stir processing (FSP) and the subsequent aging treatment on the microstructure, electrical conductivity, and mechanical properties of a Cu-0.3%Cr-0.5%Zr alloy was studied. FSP promoted complex microstructural changes, including significant grain refinement and dissolution of secondary particles within the stir zone and particle coarsening within the heat-affected zone. The particle phenomena resulted in the essential material softening and degradation of electrical conductivity. The subsequent aging treatment provided particle reprecipitation within the stir zone and thus essentially recovered material properties in this area. In the heat-affected zone, however, the recovery effect was less pronounced, thus leading to the characteristic W-shaped profiles of microhardness and electrical conductivity. This result was attributed to the insufficient degree of supersaturation of the solid solution in this microstructural region, which, in turn, promoted the relatively slow precipitation kinetics.

Refined simple model of stable water isotopic content in central Antarctic precipitation including Oxygen 17 fractionation

Modeling the isotopic composition of atmospheric precipitation is an important tool for climatic, paleoclimatic and hydrological studies. This paper presents an improved simple model of the isotopic composition of precipitation in Central Antarctica. It differs from the previous version published by Salamatin et al. (2004) by 1) the included geochemical cycle of oxygen 17 and 2) the possibility of solving the inverse problem (i.e., finding the trajectory parameters that could form the isotopic composition of the precipitation observed at the end of the trajectory). The paper examines in detail the main tuning parameters of the model, among which the most important are the temperature and humidity in the moisture source, the “circulation parameter”, which takes into account the advection of vapor into the moisture source, the condensation temperature and the degree of air supersaturation with moisture in ice clouds. Based on the analysis of data on the isotopic composition (including “excess of oxygen 17”, 17O-xs) of water vapor in the surface layer of the atmosphere over the ocean and surface snow sampled along meridional profiles in East Antarctica, the optimal tuning of the model for calculating the isotopic composition of atmospheric precipitation at the Antarctic Vostok station was performed. In particular, it is shown that the temperature and humidity of the air in the moisture source are +17.4°C and 72%, respectively, and the condensation temperature is –41.3°C. The possibilities of using the model to analyze the isotopic composition of liquid precipitation falling on other continents are discussed. The final part of the paper discusses the limitations of the model. In particular, it is noted that the model does not take into account such processes as the evaporation of precipitation when it falls in arid conditions, mixing of trajectories, the influence of local sources of moisture, as well as the features of isotope fractionation during the evaporation of moisture from the continents.

How well can persistent contrails be predicted? An update

Abstract. The total aviation effective radiative forcing is dominated by non-CO2 effects. The largest contributors to the non-CO2 effects are contrails and contrail cirrus. There is the possibility of reducing the climate effect of aviation by avoiding flying through ice-supersaturated regions (ISSRs), where contrails can last for hours (so-called persistent contrails). Therefore, a precise prediction of the specific location and time of these regions is needed. But a prediction of the frequency and degree of ice supersaturation (ISS) on cruise altitudes is currently very challenging and associated with great uncertainties because of the strong variability in the water vapour field, the low number of humidity measurements at the air traffic altitude, and the oversimplified parameterisations of cloud physics in weather models. Since ISS is more common in some dynamical regimes than in others, the aim of this study is to find variables/proxies that are related to the formation of ISSRs and to use these in a regression method to predict persistent contrails. To find the best-suited proxies for regressions, we use various methods of information theory. These include the log-likelihood ratios, known from Bayes' theorem, a modified form of the Kullback–Leibler divergence, and mutual information. The variables (the relative humidity with respect to ice, RHiERA5; the temperature, T; the vertical velocity, ω; the divergence, DIV; the relative vorticity, ζ; the potential vorticity, PV; the normalised geopotential height, Z; and the local lapse rate, γ) come from ERA5, and RHiM/I, which we assume as the truth, comes from MOZAIC/IAGOS (Measurement of Ozone and Water Vapour on Airbus In-service Aircraft/In-service Aircraft for a Global Observing System; commercial aircraft measurements). It turns out that RHiERA5 is the most important predictor of ice supersaturation, in spite of its weaknesses, and all other variables do not help much to achieve better results. Without RHiERA5, a regression to predict ISSRs is not successful. Certain modifications of RHiERA5 before the regression (as suggested in recent papers) do not lead to improvements of ISSR prediction. Applying a sensitivity study with artificially modified RHiERA5 distributions points to the origin of the problems with the regression: the conditional distributions of RHiERA5 (conditioned on ISS and non-ISS, from RHiM/I) overlap too heavily in the range of 70 %–100 %, so for any case in that range, it is not clear whether it belongs to an ISSR or not. Evidently, this renders the prediction of contrail persistence very difficult.

Influence of silica on the crystallization of sodium hydroaluminate

To extract aluminium from highly concentrated aluminate solutions of alumina-containing raw materials, decomposition is performed through the crystallization of sodium hydroaluminate. This paper presents the results of a study on the stability of aluminate solutions. To calculate the probable yield of Al2O3 in the solid phase, it is necessary to determine the crystallization rate of sodium hydroaluminate according to the composition of the initial solutions and the conditions of the process. The influences of SiO2 content on the decomposition of aluminate solutions with Na2Ok concentrations of 540 g/dm3 and 590 g/dm3 with and without inoculum were studied. In addition, the influence of silica on the appearance of precipitating crystals of sodium hydroaluminate was considered. A sharp increase in the stability of the aluminate solutions at rest in the presence of silica was observed. Different crystallization conditions for sodium hydroaluminate have been investigated. Silica slows the crystallization process of sodium hydroaluminate, affecting both the nucleation and crystal growth rates. The effect of SiO₂ on the rate of decomposition is similar to the reduction in the degree of supersaturation.

Innovative synthesis of high-strength α-hemihydrate gypsum: Effects and mechanisms of TA modification under microwave hydrothermal conditions

Titanium gypsum (TG), a byproduct of the titanium dioxide industry, is recognized as a significant contributor to environmental pollution due to high water content, poor crystallinity and other characteristics that make it difficult to be reused/recycled effectively. This study evaluated the feasibility to recycle TG to produce α-hemihydrate gypsum via microwave hydrothermal method, wherein tricarballylic acid (TA) was employed as modifier to modulate the crystallization of α-HH. The impact of TA dosage on the characteristics of α-HH crystals is comprehensively assessed through a series of microscale analyses. The findings reveal a notable reduction in the Length/Diameter ratio (L/D ratio) of α-HH crystals, diminishing from 17.79 to 0.96, in response to the incremental introduction of TA, ranging from 0 % to 0.13 %. An optimum TA dosage of 0.1 % is found to yield a commendable compressive strength of 37.4 MPa. Additionally, this study validates the interaction between TA and α-HH crystals. Based on the experimental results, it is further postulated that microwave heating is conducive to expediting the rate of Ca2+ and SO42− ion accumulation at the (002) surface, thus altering the degree of solution supersaturation and consequently accelerating the growth kinetics of α-HH crystals. This study offers valuable insights into the utilisation of this methodology in various industrial and scientific applications.

STRUCTURAL CHANGES DURING THERMAL STRENGTHENING OF THE RAILWAY WHEEL

Purpose. Justification of mechanism of the structure transformations in the carbon steel of the railway wheel during disk thermal strengthening. Research methods. The material for the study was carbon steel of a railway wheel with a content of 0.57 % C, 0.65 % Si, 0.45 % Mn, 0.0029 % S, 0.014 % P and 0.11 % Cr. The railway wheel was heated to temperatures higher than Ac3, kept at this temperature to complete austenite homogenization process, and disk was rapidly cooled to the specified temperature. Degree defectiveness structure of the metal after accelerated cooling was assessed using technique of X-ray structural analysis. Strength stress, yield stress and relative elongation of the carbon steel were determined at stretching at rate of deformation 10-3 s-1. Results. At accelerated cooling of the carbon steel, the sources of strengthening are the processes of blocking mobile dislocations due to the condensation of carbon atoms on them and dispersion strengthening from the formed particles of the carbide phase. At temperatures of termination of forced cooling of carbon steel above 300…350 °C, the reduction rate of strength properties is determined by the excess of total effect of softening from decomposition of the solid solution, acceleration of spheroidization and coalescence of cementite particles over the blocking of dislocations by carbon atoms and dispersion hardening. Scientific novelty. The level of strength and plasticity characteristics of carbon steel of the railway wheel disc, depending on the temperature end forced cooling, is determined by the ratio of the influence of degree super saturation of the solid solution and the dispersion strengthening by carbide phase. Practical value. For temperatures termination of accelerated cooling of 200…300 °C, degree of super saturation of the solid solution is the main factor that determines the level of strength and plasticity characteristics. When manufacturing an all-rolled railway wheel, the strength limit of the disc metal can be increased by accelerated cooling to the middle range of temperature.

Influence of the Isothermal Transformation Temperature on the Structure and Properties of Low-Carbon Steel

Purpose. The study is aimed at evaluating the effect of the isothermal transformation temperature on the structure and properties of low-carbon steel. Methodology. The material for the study was a 3 mm diameter wire made of mild steel with the following chemical composition: 0.21% C, 0.47% Mn, 1.2% Si, 0.1% Cr, 0.03% S, 0.012% P. The 0.3 m long wire samples were subjected to austenitizing at 920 °C for 8...9 min, after which they were held isothermally for 11 min at temperatures of 650...200 °C, followed by cooling in air. The strength, plastic properties, and strain hardening coefficient were determined from the analysis of tensile curves. Findings. It was found that a decrease in the temperature of isothermal transformation, starting from 450...400 °C, increases the amount of Widmannstätten ferrite due to the disappearance of polyhedral ferrite grains. At the same time, the number of areas with locally located dispersed cementite particles similar to pearlite colonies increases, and bainite crystals appear. Against the background of a sharp decrease in the strain hardening coefficient in the range of 450...400 °C, the ability of the bainite phase to undergo plastic deformation should be considered one of the reasons for the delay in density reduction. Originality. The effect of steel hardening with a decrease in the pearlite transformation temperature is based on the grinding of ferrite grains, an increase in the amount of Widmannstätten ferrite, and the dispersion of pearlite colonies. The strengthening effect of steel with a bainite structure is based on an increase in the degree of supersaturation of the solid solution with carbon atoms and dispersion hardening by particles of the carbide phase. Practical value. The optimal structural state of steel intended for the manufacture of such critical elements as a support beam, railroad car bogie, etc. is a mixture of phase components with different dispersion and morphology, and their quantitative ratio is determined by the operating conditions of a particular product.

Bulk Nanobubbles through Gas Supersaturation Originated by Hot and Cold Solvent Mixing.

The nucleation mechanism of bulk nanobubbles remains unclear despite the considerable attention they have received in recent years. We propose two hypotheses: (i) The gas supersaturation in the bulk liquid is the primary factor for nanobubble nucleation, and (ii) the mixing of the same solvent at varying gas solubilities should produce nanobubbles, provided that the first hypothesis is correct. To test this hypothesis, we performed extensive experiments on nanobubble nucleation in both water and organic solvents. The temperature difference between hot and cold samples ranged from 10 to 80 °C in pure solvents such as water, methanol, ethanol, propanol, and butanol prepared and mixed in equal proportions. To the best of our knowledge, we report bulk nanobubble nucleation by mixing hot and cold solvents for the first time. The refractive index value calculations using Mie scattering theory confirmed the existence of nanobubbles. When surface tension dominates over surface charge, the critical work for nanobubble formation is ΔFc ∝ 1/ξ2, and when surface charge dominates over surface tension, the critical work is ΔFc ∝ ξ1/4. Our experimental results verify such dependency by measuring nanobubbles nucleated with varying degrees of gas supersaturation.

Fast formation of large ice pebbles after FU Orionis outbursts

During their formation, nascent planetary systems are subject to FU Orionis outbursts that heat a substantial part of the disc. This causes water ice in the affected part of the disc to sublimate as the ice line moves outwards to several to tens of astronomical units. In this paper, we investigate how the subsequent cooling of the disc impacts the particle sizes. We calculate the resulting particle sizes in a disc model with cooling times between 100 and 1000 yr, corresponding to typical FU Orionis outbursts. As the disc cools and the ice line retreats inwards, water vapour forms icy mantles on existing silicate particles. This process is called heterogeneous nucleation. The nucleation rate per surface area of silicate substrate strongly depends on the degree of super-saturation of the water vapour in the gas. Fast cooling results in high super-saturation levels, high nucleation rates, and limited condensation growth because the main ice budget is spent in the nucleation. Slow cooling, on the other hand, leads to rare ice nucleation and efficient growth of ice-nucleated particles by subsequent condensation. We demonstrate that close to the quiescent ice line, pebbles with a size of about centimetres to decimetres form by this process. The largest of these are expected to undergo cracking collisions. However, their Stokes numbers still reach values that are high enough to potentially trigger planetesimal formation by the streaming instability if the background turbulence is weak. Stellar outbursts may thus promote planetesimal formation around the water ice line in protoplanetary discs.

Thermodynamic assessment of two-step nucleation occurrence in supercritical fluid

For the crystallization of an API in supercritical CO2, a two – step nucleation mechanism involves the apparition of metastable liquid droplets in the vapour phase composed of the API dissolved in the CO2, before crystallization. To find out the pressure and temperature conditions such a two – step mechanism could be observed, we studied the stability / metastability / instability for {(S)-Naproxen + CO2} and {(RS)-Ibuprofen + CO2} vapour binary mixtures. Thermodynamic computations proposed in the paper, have shown that a mixture of API and CO2 at elevated pressures can be unstable and/or metastable with respect to a liquid-vapour equilibrium and at the same time with respect to a solid-vapour equilibrium. Depending on the degree of supersaturation, such a mixture can potentially first decompose via spinodal decomposition into coexisting liquid and vapour phases, which turn due to nucleation and growth theory to a solid-fluid equilibrium.

A numerical study of heterogeneous nucleation of ice crystals and frost layer growth on horizontal cold surfaces

In engineering applications, the formation and growth of frost layers can significantly affect the normal operation of equipment, leading to undesirable influences. Therefore, it is imperative to understand the frost formation mechanisms as a basis for developing effective anti-frosting and defrosting methodologies. This study proposes a model for the growth of horizontal cold surface frost layers using the classical nucleation theory and the Eulerian multiphase flow model. Compared to numerous models that investigate the frost formation issues using the computational fluid dynamics (CFD) method, our proposed model takes into account the crystal growth period (the heterogeneous nucleation process of ice). The predicted results of the proposed model were found to be in good agreement with the data collected from five related experimental studies. In this regard, the maximum frost layer thickness error was 23.9 % with a mean error of 5.1 %, and the maximum density error was 22.8 % with a mean error of 8.1 %. Compared to existing models in the literature, the proposed model can reduce the maximum thickness and density uncertainties by 17.4 % and 10.2 %, respectively. Additionally, the effects of the surface contact angle and environmental parameters on the nucleation process were analyzed using the established model. It was found that a larger contact angle, higher cold surface temperature, and lower air temperature, humidity, and velocity were unfavorable conditions for supporting the formation and growth of ice crystals. Moreover, the nucleation completion time was shortened with the increase in the moist air supersaturation degree, varying as an exponential function. The findings of this study provide an important theoretical basis for the development of optimizing strategies for anti-frosting and defrosting.

Transformation of Precursor Iron(III) Minerals in Diagenetic Fluids: Potential Origin of Gray Hematite at Vera Rubin Ridge

AbstractCoarse‐grained (>3–5 μm) gray hematite particles occur at Vera Rubin ridge (VRR) within Gale crater, Mars. VRR has likely undergone multiple episodes of diagenesis, at least one of which resulted in the formation of gray hematite. The precursor mineralogy and nature of the diagenetic fluids that produced coarse‐grained hematite remain unknown. Analog laboratory experiments were performed on a variety of iron(III) minerals to assess the potential fluid conditions and precursor mineralogy that form coarse‐grained hematite. Gray hematite formed from the transformation of jarosite after 20 days at 200°C. Conversion was complete in chloride‐rich fluids; however, modeling indicates that at lower jarosite‐to‐water ratios, conversion is complete even in chloride‐free, sulfate‐rich conditions. No transformations of jarosite occurred when aged at 98°C. All other precursor minerals (akaganeite, ferrihydrite, goethite, and schwertmannite) did not transform or produced red, fine‐grained hematite under all conditions assessed. Additionally, seeding precursor iron(III) phases with red hematite and coarsening pre‐existing red hematite failed to produce gray hematite. These results suggest that jarosite could have been the precursor of gray hematite at VRR and that transformation is possible in both sulfate‐bearing and chloride‐bearing fluids. Jarosite produces gray hematite because the acidic conditions it generates yield both a low degree of hematite supersaturation, producing few nuclei, and high dissolved iron concentrations, enabling rapid hematite growth. Gray hematite readily forms under oxic conditions and its occurrence at VRR is not a marker for a redox interface. The associated diagenetic event was thus unlikely to have generated substantial new chemical energy for life.