Showing papers on "Nucleation published in 2011"

Role of sulphuric acid, ammonia and galactic cosmic rays in atmospheric aerosol nucleation

Abstract: Atmospheric aerosols exert an important influence on climate through their effects on stratiform cloud albedo and lifetime and the invigoration of convective storms. Model calculations suggest that almost half of the global cloud condensation nuclei in the atmospheric boundary layer may originate from the nucleation of aerosols from trace condensable vapours, although the sensitivity of the number of cloud condensation nuclei to changes of nucleation rate may be small. Despite extensive research, fundamental questions remain about the nucleation rate of sulphuric acid particles and the mechanisms responsible, including the roles of galactic cosmic rays and other chemical species such as ammonia. Here we present the first results from the CLOUD experiment at CERN. We find that atmospherically relevant ammonia mixing ratios of 100 parts per trillion by volume, or less, increase the nucleation rate of sulphuric acid particles more than 100–1,000-fold. Time-resolved molecular measurements reveal that nucleation proceeds by a base-stabilization mechanism involving the stepwise accretion of ammonia molecules. Ions increase the nucleation rate by an additional factor of between two and more than ten at ground-level galactic-cosmic-ray intensities, provided that the nucleation rate lies below the limiting ion-pair production rate. We find that ion-induced binary nucleation of H_(2)SO_(4)–H_(2)O can occur in the mid-troposphere but is negligible in the boundary layer. However, even with the large enhancements in rate due to ammonia and ions, atmospheric concentrations of ammonia and sulphuric acid are insufficient to account for observed boundary-layer nucleation.

Controlling Zeolitic Imidazolate Framework Nano- and Microcrystal Formation: Insight into Crystal Growth by Time-Resolved In Situ Static Light Scattering

Abstract: We report on a simple and straightforward method that enables the rapid room-temperature production of nanocrystals (finely tuned in size between ∼10 and 65 nm) and microcrystals (∼1 μm) of the prototypical microporous zeolitic imidazolate framework (ZIF) material ZIF-8. Control of crystal size is achieved in a novel approach by employing an excess of the bridging bidentate ligand and various simple auxiliary monodentate ligands with different chemical functionalities (carboxylate, N-heterocycle, alkylamine). The function of the monodentate ligands can be understood as a modulation of complex formation and deprotonation equilibria during crystal nucleation and growth. Using time-resolved static light scattering, the functioning of modulating ligands is monitored for the first time by in situ experiments, which offered significant insight into the crystal growth processes. Formation of nanocrystals is characterized by continuous, comparatively slow nucleation and fast crystal growth occurring on a time sca...

From point defects in graphene to two-dimensional amorphous carbon.

Abstract: While crystalline two-dimensional materials have become an experimental reality during the past few years, an amorphous 2D material has not been reported before. Here, using electron irradiation we create an $s{p}^{2}$-hybridized one-atom-thick flat carbon membrane with a random arrangement of polygons, including four-membered carbon rings. We show how the transformation occurs step by step by nucleation and growth of low-energy multivacancy structures constructed of rotated hexagons and other polygons. Our observations, along with first-principles calculations, provide new insights to the bonding behavior of carbon and dynamics of defects in graphene. The created domains possess a band gap, which may open new possibilities for engineering graphene-based electronic devices.

Structural transformation in supercooled water controls the crystallization rate of ice

Abstract: The various anomalous properties of water have puzzled scientists for decades, and many hypotheses have been put forward to explain their origin. One mystery is the question of what determines the lowest temperature to which water can be cooled before it freezes to ice. Rapid crystallization at low temperatures hampers experimental studies, and simulations are usually prohibitively costly in terms of computer time. Using a simple water model that allows demanding calculations, Emily Moore and Valeria Molinero now show that a sharp increase in the fraction of four-coordinated molecules in supercooled liquid water controls the rate and mechanism of ice formation. The structural change also results in a peak in the rate of crystallization at 225 K; below this temperature, ice nuclei form faster than liquid water can equilibrate. This finding explains the observed thermodynamic anomalies, and why homogeneous ice nucleation rates depend on the thermodynamics of water. One of water’s unsolved puzzles is the question of what determines the lowest temperature to which it can be cooled before freezing to ice. The supercooled liquid has been probed experimentally to near the homogeneous nucleation temperature, TH ≈ 232 K, yet the mechanism of ice crystallization—including the size and structure of critical nuclei—has not yet been resolved. The heat capacity and compressibility of liquid water anomalously increase on moving into the supercooled region, according to power laws that would diverge (that is, approach infinity) at ∼225 K (refs 1, 2), so there may be a link between water’s thermodynamic anomalies and the crystallization rate of ice. But probing this link is challenging because fast crystallization prevents experimental studies of the liquid below TH. And although atomistic studies have captured water crystallization3, high computational costs have so far prevented an assessment of the rates and mechanism involved. Here we report coarse-grained molecular simulations with the mW water model4 in the supercooled regime around TH which reveal that a sharp increase in the fraction of four-coordinated molecules in supercooled liquid water explains its anomalous thermodynamics and also controls the rate and mechanisms of ice formation. The results of the simulations and classical nucleation theory using experimental data suggest that the crystallization rate of water reaches a maximum around 225 K, below which ice nuclei form faster than liquid water can equilibrate. This implies a lower limit of metastability of liquid water just below TH and well above its glass transition temperature, 136 K. By establishing a relationship between the structural transformation in liquid water and its anomalous thermodynamics and crystallization rate, our findings also provide mechanistic insight into the observed5 dependence of homogeneous ice nucleation rates on the thermodynamics of water.

Nanograssed Micropyramidal Architectures for Continuous Dropwise Condensation

Abstract: Engineering the dropwise condensation of water on surfaces is critical in a wide range of applications from thermal management (e.g. heat pipes, chip cooling etc.) to water harvesting technologies. Surfaces that enable both effi cient droplet nucleation and droplet self-removal (i.e. droplet departure) are essential to accomplish successful dropwise condensation. However it is extremely challenging to design such surfaces. This is because droplet nucleation requires a wettable surface while droplet departure necessitates a super-hydrophobic surface. Here we report that these confl icting requirements can be satisfi ed using a hierarchical (multiscale) nanograssed micropyramid architecture that yield a gobal superhydrophobicity as well as locally wettable nucleation sites, allowing for ˜65% increase in the drop number density and ˜450% increase in the drop self-removal volume as compared to a superhydrophobic surface with nanostructures alone. Further we fi that synergistic co-operation between the hierarchical structures contributes directly to a continuous process of nucleation, coalescence, departure, and re-nucleation enabling sustained dropwise condensation over prolonged periods. Exploiting such multiscale coupling effects can open up novel and exciting vistas in surface engineering leading to optimal condensation surfaces for high performance electronics cooling and water condenser systems.

Kinetics of non-equilibrium lithium incorporation in LiFePO4

Abstract: Lithium-ion batteries are a key technology for multiple clean energy applications. Their energy and power density is largely determined by the cathode materials, which store Li by incorporation into their crystal structure. Most commercialized cathode materials, such as LiCoO(2) (ref. 1), LiMn(2)O(4) (ref. 2), Li(Ni,Co,Al)O(2) or Li(Ni,Co,Mn)O(2) (ref. 3), form solid solutions over a large concentration range, with occasional weak first-order transitions as a result of ordering of Li or electronic effects. An exception is LiFePO(4), which stores Li through a two-phase transformation between FePO(4) and LiFePO(4) (refs 5-8). Notwithstanding having to overcome extra kinetic barriers, such as nucleation of the second phase and growth through interface motion, the observed rate capability of LiFePO(4) has become remarkably high. In particular, once transport limitations at the electrode level are removed through carbon addition and particle size reduction, the innate rate capability of LiFePO(4) is revealed to be very high. We demonstrate that the reason LiFePO(4) functions as a cathode at reasonable rate is the availability of a single-phase transformation path at very low overpotential, allowing the system to bypass nucleation and growth of a second phase. The Li(x)FePO(4) system is an example where the kinetic transformation path between LiFePO(4) and FePO(4) is fundamentally different from the path deduced from its equilibrium phase diagram.

Effects of Polycrystalline Cu Substrate on Graphene Growth by Chemical Vapor Deposition

Abstract: Chemical vapor deposition of graphene on Cu often employs polycrystalline Cu substrates with diverse facets, grain boundaries (GBs), annealing twins, and rough sites. Using scanning electron microscopy (SEM), electron-backscatter diffraction (EBSD), and Raman spectroscopy on graphene and Cu, we find that Cu substrate crystallography affects graphene growth more than facet roughness. We determine that (111) containing facets produce pristine monolayer graphene with higher growth rate than (100) containing facets, especially Cu(100). The number of graphene defects and nucleation sites appears Cu facet invariant at growth temperatures above 900 °C. Engineering Cu to have (111) surfaces will cause monolayer, uniform graphene growth.

Suppression of Phase Separation in LiFePO4 Nanoparticles During Battery Discharge

Abstract: Using a novel electrochemical phase-field model, we question the common belief that LiXFePO4 nanoparticles always separate into Li-rich and Li-poor phases during battery discharge. For small currents, spinodal decomposition or nucleation leads to moving phase boundaries. Above a critical current density (in the Tafel regime), the spinodal disappears, and particles fill homogeneously, which may explain the superior rate capability and long cycle life of nano-LiFePO4 cathodes.

Influence of Copper Morphology in Forming Nucleation Seeds for Graphene Growth

Abstract: We report that highly crystalline graphene can be obtained from well-controlled surface morphology of the copper substrate. Flat copper surface was prepared by using a chemical mechanical polishing method. At early growth stage, the density of graphene nucleation seeds from polished Cu film was much lower and the domain sizes of graphene flakes were larger than those from unpolished Cu film. At later growth stage, these domains were stitched together to form monolayer graphene, where the orientation of each domain crystal was unexpectedly not much different from each other. We also found that grain boundaries and intentionally formed scratched area play an important role for nucleation seeds. Although the best monolayer graphene was grown from polished Cu with a low sheet resistance of 260 Ω/sq, a small portion of multilayers were also formed near the impurity particles or locally protruded parts.

Suppression of Phase Separation in LiFePO4 Nanoparticles During Battery Discharge

Abstract: Using a novel electrochemical phase-field model, we question the common belief that LixFePO4 nanoparticles separate into Li-rich and Li-poor phases during battery discharge. For small currents, spinodal decomposition or nucleation leads to moving phase boundaries. Above a critical current density (in the Tafel regime), the spinodal disappears, and particles fill homogeneously, which may explain the superior rate capability and long cycle life of nano-LiFePO4 cathodes.

Structure and morphology control in thin films of regioregular poly(3‐hexylthiophene)

Abstract: This review focuses on the structural control in thin films of regioregular poly(3-hexylthiophene) (P3HT), a workhorse among conjugated semiconducting polymers. It highlights the correlation existing between processing conditions and the resulting structures formed in thin films and in solution. Particular emphasis is put on the control of nucleation, crystallinity and orientation. P3HT can generate a large palette of morphologies in thin films including crystalline nanofibrils, spherulites, interconnected semicrystalline morphologies and nanostructured fibers, depending on the elaboration method and on the macromolecular parameters of the polymer. Effective means developed in the recent literature to control orientation of crystalline domains in thin films, especially by using epitaxial crystallization and controlled nucleation conditions are emphasized. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 49: 1218–1233, 2011

Cubic crystals from cubic colloids

Abstract: We have studied the crystallization behavior of colloidal cubes by means of tunable depletion interactions. The colloidal system consists of novel micron-sized cubic particles prepared by silica deposition on hematite templates and various non-adsorbing watersoluble polymers as depletion agents. We have found that under certain conditions the cubes self-organize into crystals with a simple cubic symmetry, which is set by the size of the depletant. The dynamic of crystal nucleation and growth is investigated, monitoring the samples in time by optical microscopy. Furthermore, by using temperature sensitive microgel particles as depletant it is possible to fine tune depletion interactions to induce crystal melting. Assisting crystallization with an alternating electric field improves the uniformity of the cubic pattern allowing the preparation of macroscopic (almost defect-free) crystals that show visible Bragg colors.

Theory and Practice of Metal Electrodeposition

Abstract: Basic terms and concepts.- The structure of the metal-solution interface.- Electrochemical thermodynamics and electrochemical kinetics.- Influence of diffusion on the rate of electrochemical process.- Nucleation.- Morphology of the growing metal surface.- Potential distribution in the volume of solution and current distribution on the electrode surface.- Current density distribution on rough surfaces.- Using of pulse and periodic currents in electrodeposition and in electrochemical experiments.- Electrodeposition of alloys.- Codeposition of impurities. Hydrogenation.- Technologies for deposition of several metals and alloys.- Structure of electrodeposited metals and alloys.- Physical properties of deposited macrolayers of metals and alloys. Control of quality and testing methods.- Conclusion

Oxygen-Aided Synthesis of Polycrystalline Graphene on Silicon Dioxide Substrates

Abstract: We report the metal-catalyst-free synthesis of high-quality polycrystalline graphene on dielectric substrates [silicon dioxide (SiO2) or quartz] using an oxygen-aided chemical vapor deposition (CVD) process The growth was carried out using a CVD system at atmospheric pressure After high-temperature activation of the growth substrates in air, high-quality polycrystalline graphene is subsequently grown on SiO2 by utilizing the oxygen-based nucleation sites The growth mechanism is analogous to that of growth for single-walled carbon nanotubes Graphene-modified SiO2 substrates can be directly used in transparent conducting films and field-effect devices The carrier mobilities are about 531 cm2 V–1 s–1 in air and 472 cm2 V–1 s–1 in N2, which are close to that of metal-catalyzed polycrystalline graphene The method avoids the need for either a metal catalyst or a complicated and skilled postgrowth transfer process and is compatible with current silicon processing techniques

Field assisted and flash sintering of alumina and its relationship to conductivity and MgO-doping

Abstract: We show that flash-sintering in MgO-doped alumina is accompanied by a sharp increase in electrical conductivity. Experiments that measure conductivity in fully dense specimens, prepared by conventional sintering, prove that this is not a cause-and-effect relationship, but instead that the concomitant increase in the sintering rate and the conductivity share a common mechanism. The underlying mechanism, however, is mystifying since electrical conductivity is controlled by the transport of the fastest moving charged species, while sintering, which requires molecular transport or chemical diffusion, is limited by the slow moving charged species. Joule heating of the specimen during flash sintering cannot account for the anomalously high sintering rates. The sintering behavior of MgO-doped alumina is compared to that of nominally pure-alumina: the differences provide insight into the underlying mechanism for flash-sintering. We show that the pre-exponential in the Arrhenius equation for conductivity is enhanced in the non-linear regime, while the activation energy remains unchanged. The nucleation of Frenkel pairs is proposed as a mechanism to explain the coupling between flash-sintering and the non-linear increase in the conductivity.

Coherency strain and the kinetics of phase separation in LiFePO4

Abstract: A theoretical investigation of the effects of elastic coherency on the thermodynamics, kinetics, and morphology of intercalation in single LiFePO4 nanoparticles yields new insights into this important battery material Anisotropic elastic stiffness and misfit strains lead to the unexpected prediction that low-energy phase boundaries occur along {101} planes, while conflicting reports of phase boundary orientations are resolved by a partial loss of coherency in the {100} direction Elastic relaxation near surfaces leads to the formation of a striped morphology, whose characteristic length scale is predicted by the model and yields an estimate of the interfacial energy The effects of coherency strain on solubility and galvanostatic discharge are studied with a reaction-limited phase-field model, which quantitatively captures the influence of misfit strain, particle size, and temperature on solubility seen in experiments Coherency strain strongly suppresses phase separation during discharge, which enhances rate capability and extends cycle life The effects of elevated temperature and the feasibility of nucleation are considered in the context of multi-particle cathodes

Effect of microstructure on the nucleation of deformation twins in polycrystalline high-purity magnesium: A multi-scale modeling study

Abstract: A multi-scale, theoretical study of twin nucleation from grain boundaries in polycrystalline hexagonal close packed (hcp) metals is presented. A key element in the model is a probability theory for the nucleation of deformation twins based on the idea that twins originate from a statistical distribution of defects in the grain boundaries and are activated by local stresses at the grain boundaries. In this work, this theory is integrated into a crystal plasticity constitutive model in order to study the influence of these statistical effects on the microstructural evolution of the polycrystal, such as texture and twin volume fraction. Recently, a statistical analysis of exceptionally large data sets of {1012} deformation twins was conducted for high-purity Mg ( Beyerlein et al., 2010a ). To demonstrate the significantly enhanced accuracy of the present model over those employing more conventional, deterministic approaches to twin activation, the model is applied to the case of {1012} twinning in Mg to quantitatively interpret the many statistical features reported for these twins (e.g., variant selection, thickness, numbers per grain) and their relationship to crystallographic grain orientation, grain size, and grain boundary misorientation angle. Notably the model explains the weak relationship observed between crystal orientation and twin variant selection and the strong correlation found between grain size and the number of twins formed per grain. The predictions suggest that stress fluctuations generated at grain boundaries are responsible for experimentally observed dispersions in twin variant selection.

Nucleation mechanism for the direct graphite-to-diamond phase transition

Abstract: Graphite remains stable at pressures higher than those of its equilibrium coexistence with diamond This has proved hard to explain, owing to the difficulty in simulating the transition with accuracy Ab initio calculations using a trained neural-network potential now show that the stability of graphite and the direct transformation of graphite to diamond can be accounted for by a nucleation mechanism

Graphene Nucleation on Transition Metal Surface: Structure Transformation and Role of the Metal Step Edge

Abstract: The nucleation of graphene on a transition metal surface, either on a terrace or near a step edge, is systematically explored using density functional theory calculations and applying the two-dimensional (2D) crystal nucleation theory. Careful optimization of the supported carbon clusters, CN (with size N ranging from 1 to 24), on the Ni(111) surface indicates a ground state structure transformation from a one-dimensional C chain to a 2D sp2 C network at N ≈ 10−12. Furthermore, the crucial parameters controlling graphene growth on the metal surface, nucleation barrier, nucleus size, and nucleation rate on a terrace or near a step edge are calculated. In agreement with numerous experimental observations, our analysis shows that graphene nucleation near a metal step edge is superior to that on a terrace. On the basis of our analysis, we propose the use of graphene seeds to synthesize high-quality graphene in large area.

Sequential crystallization of sea urchin-like bimetallic (Ni, Co) carbonate hydroxide and its morphology conserved conversion to porous NiCo2O4 spinel for pseudocapacitors

Abstract: We report kinetic control over and mechanistic studies on the formation of sea urchin-like, bimetallic (Ni, Co) carbonate hydroxidevia a sequential crystallization process, which was facilely converted to porous NiCo2O4 spinel with a conserved morphology, an excellent candidate material for pseudocapacitors. The formation of bimetallic carbonate hydroxide was found to start with the nucleation of monometallic nickel carbonate hydroxide evolving into flower-like microspheres. This was followed by the nucleation and growth of the bimetallic carbonate hydroxide nanorods from and on the nanoplates in the flower-like microspheres by localized dissolution-recrystallization, leading finally to the sea urchin structure. After calcination, a morphology conserved NiCo2O4 spinel nanostructure was formed, which uniquely comprises hierarchical, interconnected pores with high specific surface areas suitable for fast electron and electrolyte transport. This, in tandem with the rich redox reactions of nickel cobaltite spinel and their at least two orders of magnitude higher electric conductivity than those of nickel oxides and cobalt oxides alone, renders the novel nanostructures ideal candidates for pseudocapacitors. Indeed, the porous NiCo2O4 nanostructure with a specific surface area of up to 198.9 m2 g−1 has exhibited higher specific capacitances (658 F g−1 at 1 A g−1) than the monometallic cobalt oxides (60 F/g at 1 A g−1) and nickel oxides (194 F g−1 at 1 A g−) with similar porous nanostructures. Significantly, even at a high current density of 10 A g−1, the pseudocapacitor made of NiCo2O4 porous materials retained high specific capacitances of 530 F g−1 with excellent cycling stability. In all, the simple, scalable syntheses and the excellent supercapacitor performance reported here portend large scale applications of these novel materials in energy storage.

Crystal Nucleation Rates from Probability Distributions of Induction Times

Abstract: A novel method for the determination of stationary crystal nucleation rates in solutions has been developed. This method makes use of the stochastic nature of nucleation, which is reflected in the variation of the induction time in many measurements at a constant supersaturation. A probability distribution function was derived which describes, under the condition of constant supersaturation, the probability of detecting crystals as a function of time, stationary nucleation rate, sample volume, and a time needed to grow the formed nuclei to a detectable size. Cumulative probability distributions of the induction time at constant supersaturation were experimentally determined using at least 80 induction times per supersaturation in 1 mL stirred solutions. The nucleation rate was determined by the best fit of the derived equation to the experimentally obtained distribution. This method was successfully applied to measure the nucleation rates at different supersaturations of two model compounds, m-aminobenzoi...

In situ characterization of alloy catalysts for low-temperature graphene growth.

Abstract: Low-temperature (∼450 °C), scalable chemical vapor deposition of predominantly monolayer (74%) graphene films with an average D/G peak ratio of 0.24 and domain sizes in excess of 220 μm(2) is demonstrated via the design of alloy catalysts. The admixture of Au to polycrystalline Ni allows a controlled decrease in graphene nucleation density, highlighting the role of step edges. In situ, time-, and depth-resolved X-ray photoelectron spectroscopy and X-ray diffraction reveal the role of subsurface C species and allow a coherent model for graphene formation to be devised.

Graphene Nucleation on Transition Metal Surface: Structure Transformation and Role of the Metal Step Edge

Abstract: The nucleation of graphene on a transition metal (TM) surface, either on a terrace or near a step edge, is systematically explored using density functional theory (DFT) calculations and applying the two-dimensional (2D) crystal nucleation theory. Careful optimization of the supported carbon clusters, CN (with size N ranging from 1 to 24), on the Ni(111) surface indicates a ground state structure transformation from a one-dimensional (1D) C chain to a two-dimensional (2D) sp2 C network at N ~ 10-12. Furthermore, the crucial parameters controlling graphene growth on the metal surface, nucleation barrier, nucleus size, and the nucleation rate on a terrace or near a step edge, are calculated. In agreement with numerous experimental observations, our analysis shows that graphene nucleation near a metal step edge is superior to that on a terrace. Based on our analysis, we propose the use of seeded graphene to synthesize high-quality graphene in large area.

Homogeneous ice nucleation from supercooled water

Abstract: Homogeneous ice nucleation from supercooled water was studied in the temperature range of 220–240 K through combining the forward flux sampling method (Allen et al., J. Chem. Phys., 2006, 124, 024102) with molecular dynamics simulations (FFS/MD), based on a recently developed coarse-grained water model (mW) (Molinero et al., J. Phys. Chem. B, 2009, 113, 4008). The calculated ice nucleation rates display a strong temperature dependence, ranging from 2.148 ± 0.635 × 1025 m−3 s−1 at 220 K to 1.672 ± 0.970 × 10−7 m−3 s−1 at 240 K. These rates can be fitted according to the classical nucleation theory, yielding an estimate of the effective ice–water interface energy γls of 31.01 ± 0.21 mJ m−2 for the mW water model. Compared to experiments, our calculation underestimates the homogeneous ice nucleation rate by a few orders of magnitude. Possible reasons for the discrepancy are discussed. The nucleating ice embryo contains both cubic ice Ic and hexagonal ice Ih, with the fraction of each structure being roughly 50% when the critical size is reached. In particular, a novel defect structure containing nearly five-fold twin boundaries is identified in the ice clusters formed during nucleation. The way such defect structure is formed is found to be different from mechanisms proposed for the formation of the same defect in metallic nanoparticles and thin film. The quasi five-fold twin boundary structure found here is expected to occur in the crystallization of a wide range of materials with the diamond cubic structure, including ice.

Nucleation of the Electroactive γ Phase and Enhancement of the Optical Transparency in Low Filler Content Poly(vinylidene)/Clay Nanocomposites

Abstract: Poly(vinylidene fluoride), PVDF, based nanocomposites with different clay structures have been processed by solvent casting and melt crystallization. Depending on the melting temperature of the polymer, the nanocomposite recrystalises in the electroactive γ or nonelectroactive α phase of the polymer. This fact is related to the thermal behavior of the clay. For montmorillonite clay, the full crystallization of the electroactive γ phase occurs for clay contents lower than 0.5 wt %, allowing the nanocomposites to maintain the mechanical properties of the polymer matrix. The electroactivity of the material has been proven by measuring the piezoelectric d33 response of the material. The obtained value of d33 is −7 pC/N, lower than in β-PVDF obtained by mechanical stretching but still among the largest coefficients obtained for polymers. Further, the optical transmittance in the visible range is strongly enhanced with respect to the transmittance of the pure polymer. Finally, it is demonstrated that the nuclea...

Heterogeneous freezing of water droplets containing kaolinite particles

Abstract: . Clouds composed of both ice particles and supercooled liquid water droplets exist at temperatures above ~236 K. These mixed phase clouds, which strongly impact climate, are very sensitive to the presence of solid particles that can catalyse freezing. In this paper we describe experiments to determine the conditions at which the clay mineral kaolinite nucleates ice when immersed within water droplets. These are the first immersion mode experiments in which the ice nucleating ability of kaolinite has been determined as a function of clay surface area, cooling rate and also at constant temperatures. Water droplets containing a known amount of clay mineral were supported on a hydrophobic surface and cooled at rates of between 0.8 and 10 K min −1 or held at constant sub-zero temperatures. The time and temperature at which individual 10–50 μm diameter droplets froze were determined by optical microscopy. For a cooling rate of 10 K min −1 , the median nucleation temperature of 10–40 μm diameter droplets increased from close to the homogeneous nucleation limit (236 K) to 240.8 ± 0.6 K as the concentration of kaolinite in the droplets was increased from 0.005 wt% to 1 wt%. This data shows that the probability of freezing scales with surface area of the kaolinite inclusions. We also show that at a constant temperature the number of liquid droplets decreases exponentially as they freeze over time. The constant cooling rate experiments are consistent with the stochastic, singular and modified singular descriptions of heterogeneous nucleation; however, freezing during cooling and at constant temperature can be reconciled best with the stochastic approach. We report temperature dependent nucleation rate coefficients (nucleation events per unit time per unit area) for kaolinite and present a general parameterisation for immersion nucleation which may be suitable for cloud modelling once nucleation by other important ice nucleating species is quantified in the future.