On the homogeneous and heterogeneous nucleation of some organic compounds

The conversion of a metastable phase into a thermodynamically stable phase takes place via the formation of clusters. Clusters of different sizes are formed spontaneously within the metastable mother phase, but only those larger than a certain size, called the critical size, will end up growing into a new phase. There are two types of nucleation: homogeneous, where the clusters appear in a uniform phase, and heterogeneous, when pre-existing surfaces are available and clusters form on them. The nucleation of aerosol particles from gas-phase molecules is connected not only with inorganic compounds, but also with nonvolatile organic substances found in atmosphere. The question is which ones of the myriad of organic species have the right properties and are able to participate in nucleation phenomena. This thesis discusses both homogeneous and heterogeneous nucleation, having as theoretical tool the classical nucleation theory (CNT) based on thermodynamics. Different classes of organics are investigated. The members of the first class are four dicarboxylic acids (succinic, glutaric, malonic and adipic). They can be found in both the gas and particulate phases, and represent good candidates for the aerosol formation due to their low vapor pressure and solubility. Their influence on the nucleation process has not been largely investigated in the literature and it is not fully established. The accuracy of the CNT predictions for binary water-dicarboxylic acid systems depends significantly on the good knowledge of the thermophysical properties of the organics and their aqueous solutions. A large part of the thesis is dedicated to this issue. We have shown that homogeneous and heterogeneous nucleation of succinic, glutaric and malonic acids in combination with water is unlikely to happen in atmospheric conditions. However, it seems that adipic acid could participate in the nucleation process in conditions occurring in the upper troposphere. The second class of organics is represented by n-nonane and n-propanol. Their thermophysical properties are well established, and experiments on these substances have been performed. The experimental data of binary homogeneous and heterogeneous nucleation have been compared with the theoretical predictions. Although the n-nonane - n-propanol mixture is far from being ideal, CNT seems to behave fairly well, especially when calculating the cluster composition. In the case of heterogeneous nucleation, it has been found that better characterization of the substrate - liquid interaction by means of line tension and microscopic contact angle leads to a significant improvement of the CNT prediction. Unfortunately, this can not be achieved without well defined experimental data.

Theoretical and computational approaches on heterogeneous nucleation

Nucleation is the first step of a first order phase transition. A new phase is always sprung up in nucleation phenomena. The two main categories of nucleation are homogeneous nucleation, where the new phase is formed in a uniform substance, and heterogeneous nucleation, when nucleation occurs on a pre-existing surface. In this thesis the main attention is paid on heterogeneous nucleation. This thesis wields the nucleation phenomena from two theoretical perspectives: the classical nucleation theory and the statistical mechanical approach. The formulation of the classical nucleation theory relies on equilibrium thermodynamics and use of macroscopically determined quantities to describe the properties of small nuclei, sometimes consisting of just a few molecules. The statistical mechanical approach is based on interactions between single molecules, and does not bear the same assumptions as the classical theory. This work gathers up the present theoretical knowledge of heterogeneous nucleation and utilizes it in computational model studies. A new exact molecular approach on heterogeneous nucleation was introduced and tested by Monte Carlo simulations. The results obtained from the molecular simulations were interpreted by means of the concepts of the classical nucleation theory. Numerical calculations were carried out for a variety of substances nucleating on different substances. The classical theory of heterogeneous nucleation was employed in calculations of one-component nucleation of water on newsprint paper, Teflon and cellulose film, and binary nucleation of water-n-propanol and water-sulphuric acid mixtures on silver nanoparticles. The results were compared with experimental results. The molecular simulation studies involved homogeneous nucleation of argon and heterogeneous nucleation of argon on a planar platinum surface. It was found out that the use of a microscopical contact angle as a fitting parameter in calculations based on the classical theory of heterogeneous nucleation leads to a fair agreement between the theoretical predictions and experimental results. In the presented cases the microscopical angle was found to be always smaller than the contact angle obtained from macroscopical measurements. Furthermore, molecular Monte Carlo simulations revealed that the concept of the geometrical contact parameter in heterogeneous nucleation calculations can work surprisingly well even for very small clusters.

Heterogeneous nucleation of solidification of cadmium particles embedded in an aluminium matrix

A hypomonotectic alloy of Al-4.5wt%Cd has been manufactured by melt spinning and the resulting microstructure examined by transmission electron microscopy. As-melt spun hypomonotectic Al-4.5wt%Cd consists of a homogeneous distribution of faceted 5 to 120 nm diameter cadmium particles embedded in a matrix of aluminium, formed during the monotectic solidification reaction. The cadmium particles exhibit an orientation relationship with the aluminium matrix of {111}Al//{0001}Cd and lang110rangAlAl//lang11¯20> Cd, with four cadmium particle variants depending upon which of the four {111}Al planes is parallel to {0001}Cd. The cadmium particles exibit a distorted cuboctahedral shape, bounded by six curved {100}Al//{20¯23}Cd facets, six curved {111}Al/{40¯43}Cd facets and two flat {111}Al//{0001}Cd facets. The as-melt spun cadmium particle shape is metastable and the cadmium particles equilibrate during heat treatment below the cadmium melting point, becoming elongated to increase the surface area and decrease the separation of the {111}Al//{0001}Cd facets. The equilibrium cadmium particle shape and, therefore, the anisotropy of solid aluminium-solid cadmium and solid aluminium -liquid cadmium surface energies have been monitored by in situ heating in the transmission electron microscope over the temperature range between room temperature and 420 °C. The anisotropy of solid aluminium-solid cadmium surface energy is constant between room temperature and the cadmium melting point, with the {100}Al//{20¯23}Cd surface energy on average 40% greater than the {111}Al//{0001}Cd surface energy, and 10% greater than the {111}Al//{40¯43Cd surface energy. When the cadmium particles melt at temperatures above 321 °C, the {100}Al//{20¯23}Cd facets disappear and the {111}Al//{40¯43}Cd and {111}A1//{0001}Cd surface energies become equal. The {111}Al facets do not disappear when the cadmium particles melt, and the anisotropy of solid aluminium-liquid cadmium surface energy decreases gradually with increasing temperature above the cadmium melting point. The kinetics of cadmium solidification have been examined by heating and cooling experiments in a differential scanning calorimeter over a range of heating and cooling rates. Cadmium particle solidification is nucleated catalytically by the surrounding aluminium matrix on the {111}Al faceted surfaces, with an undercooling of 56 K and a contact angle of 42 °. The nucleation kinetics of cadmium particle solidification are in good agreement with the hemispherical cap model of heterogeneous nucleation.

Heterogeneous nucleation of pb particles embedded in a Zn matrix

Zinc-10 and 20 wt pct Pb alloys have been rapidly solidified by melt spinning to obtain a very fine scale dispersion of nanometer-sized Pb particles embedded in Zn matrix. The microstructure and crystallography of the Pb particles have been studied using transmission electron microscopy (TEM). Each embedded Pb particle is a single crystal, with a truncated hexagonal biprism shape with the 6/mmm Zn matrix point group symmetry surrounded by and { 0001 á },\text { \text10[`\text1] \text0 },\text and { \text10[`\text1] \text1 }0001 1010 and 1011 facets. The Pb particles solidify with a well-defined orientation relationship with the Zn matrix of ( 0001 )Zn ||(111)Pb\text and\text [ \text11[`\text2] \text0 ]Zn| ||[ 1[`1] 0 ]Pb 0001Zn(111)Pb and 1120Zn110Pb . The melting and solidification behavior of the Pb particle have been studied using differential scanning calorimetry (DSC). The Pb particles solidify with an undercooling of approximately 30 K, by heterogeneous nucleation on the {0001} facets of the surrounding Zn matrix, with an apparent contact angle of 23 deg.

Heterogeneous nucleation of nanometre-sized Bi particles embedded in a Zn matrix

It is argued that the nanometric dispersion of Bi in a Zn matrix is an ideal model system for heterogeneous nucleation experiments. The classical theory of heterogeneous nucleation with a hemispherical cap model is applied to analyse the nucleation data. It is shown that, unlike the results of earlier experiments, the derived site density for catalytic nucleation and contact angle are realistic and strongly suggest the validity of the classical theory. The surface energy between the 0001 plane of Zn and the <10(1)over bar 2> plane of Bi, which constitute the epitaxial nucleation interface, is estimated to be 39 mJ m(-2).

New Insights into Selective Heterogeneous Nucleation of Metal Nanoparticles on Oxides by Microwave-Assisted Reduction: Rapid Synthesis of High-Activity Supported Catalysts

Microwave-based methods are widely employed to synthesize metal nanoparticles on various substrates. However, the detailed mechanism of formation of such hybrids has not been addressed. In this paper, we describe the thermodynamic and kinetic aspects of reduction of metal salts by ethylene glycol under microwave heating conditions. On the basis of this analysis, we identify the temperatures above which the reduction of the metal salt is thermodynamically favorable and temperatures above which the rates of homogeneous nucleation of the metal and the heterogeneous nucleation of the metal on supports are favored. We delineate different conditions which favor the heterogeneous nucleation of the metal on the supports over homogeneous nucleation in the solvent medium based on the dielectric loss parameters of the solvent and the support and the metal/solvent and metal/support interfacial energies. Contrary to current understanding, we show that metal particles can be selectively formed on the substrate even under situations where the temperature of the substrate Is lower than that of the surrounding medium. The catalytic activity of the Pt/CeO(2) and Pt/TiO(2) hybrids synthesized by this method for H(2) combustion reaction shows that complete conversion is achieved at temperatures as low as 100 degrees C with Pt-CeO(2) catalyst and at 50 degrees C with Pt-TiO(2) catalyst. Our method thus opens up possibilities for rational synthesis of high-activity supported catalysts using a fast microwave-based reduction method.

Insights on Defect-Mediated Heterogeneous Nucleation of Graphene on Copper

The grain size of monolayer large area graphene is key to its performance. Microstructural design for the desired grain size requires a fundamental understanding of graphene nucleation and growth. The two levers that can be used to control these aspects are the defect density, whose population can be controlled by annealing, and the gas-phase supersaturation for activation of nucleation at the defect sites. We observe that defects on copper surface, namely dislocations, grain boundaries, triple points, and rolling marks, initiate nucleation of graphene. We show that among these defects dislocations are the most potent nucleation sites, as they get activated at lowest supersaturation. As an illustration, we tailor the defect density and supersaturation to change the domain size of graphene from <1 mu m(2) to >100 mu m(2). Growth data reported in the literature has been summarized on a supersaturation plot, and a regime for defect-dominated growth has been identified. In this growth regime, we demonstrate the spatial control over nucleation at intentionally introduced defects, paving the way for patterned growth of graphene. Our results provide a unified framework for understanding the role of defects in graphene nucleation and can be used as a guideline for controlled growth of graphene.

Heterogeneous nucleation effects of neodymium oxide on polyamide-1010

In this paper microcrystalline structures of polyamide-1010 (PA1010) mixed with neodymium oxide (Nd2O3) were studied by Wide Angle X-ray Diffraction (WAXD) and Small Angle X-ray Scattering (SAXS). Crystallization behavior was investigated by DSC. The transition and relaxation of macromolecules in the crystalline phase were explored by Differential Scanning Calorimetry (DSC). It was revealed that neodymium oxide plays an important role in PA1010 crystallization as a heterogeneous nucleating agent. It can improve the crystallization rate, reduce crystallite size and introduce crystal imperfections. The microcrystalline structure was imposed by the addition of Nd2O3 However, the heterogeneous nucleation effect obviously does not exert its influence on the transition and relaxation of macromolecules in the crystalline phase.

INVESTIGATING THE ROLE OF THE CONTACT LINE IN HETEROGENEOUS NUCLEATION WITH HIGH SPEED IMAGING

While nucleation of solids in supercooled liquids is ubiquitous [15, 65, 66], surface crystallization, the tendency for freezing to begin preferentially at the liquid-gas interface, has remained puzzling [74, 18, 68, 69, 51, 64, 72, 16]. Here we employ high-speed imaging of supercooled water drops to study the phenomenon of heterogeneous surface crystallization. Our geometry avoids the "point-like contact" of prior experiments by providing a simple, symmetric contact line (triple line defined by the substrate-liquid-air interface) for a drop resting on a homogeneous silicon substrate. We examine three possible mechanisms that might explain these laboratory observations: (i) Line Tension at the triple line, (ii) Thermal Gradients within the droplets and (iii) Surface Texture. In our first study we record nearly perfect spatial uniformity in the immersed (liquid-substrate) region and, thereby, no preference for nucleation at the triple line. In our second study, no influence of thermal gradients on the preference for freezing at the triple line was observed. Motivated by the conjectured importance of line tension (τ) [1, 66] for heterogeneous nucleation, we also searched for evidence of a transition to surface crystallization at length scales on the order of δ ∼ τ/σ, where σ is the surface tension [14]; poorly constrained τ [49] leads to δ ranging from microns to nanometers. We demonstrate that nano-scale texture causes a shift in the nucleation to the three-phase contact line, while micro-scale texture does not. The possibility of a critical length scale has implications for the effectiveness of nucleation catalysts, including formation of ice in atmospheric clouds [7].

Heterogeneous nucleation of Mg-Al alloys

Grain size is one of the most important microstructural characteristics determining the mechanical properties and therefore the service performance of polycrystalline materials. Heterogeneous nucleation involves the addition or in situ formation of potent nuclei in the system to promote nucleation events, leading to a fine grain structure. This paper reports experimental results using graphite and SiC as potential grain refining agents to form in situ nuclei for Mg in Mg-Al alloys, and demonstrates the key role of Al4C3 in grain refilling this important alloy system. This insight will contribute to the design and development of the most cost effective, eco-friendly grain refining agents for Mg-Al alloys. (c) 2006 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Numerical study of homogeneous and heterogeneous crystal nucleation in colloidal systems

Im Rahmen dieser Arbeit wurden Computersimulationen von Keimbildungs- und Kris\-tallisationsprozessen in rnkolloidalen Systemen durchgef\"uhrt. rnEine Kombination von Monte-Carlo-Simulationsmethoden und der Forward-Flux-Sampling-Technik wurde rnimplementiert, um die homogene und heterogene Nukleation von Kristallen monodisperser Hart\-kugeln zu untersuchen. rnIm m\"a\ss{ig} unterk\"uhlten Bulk-Hartkugelsystem sagen wir die homogenen Nukleationsraten voraus und rnvergleichen die Resultate mit anderen theoretischen Ergebnissen und experimentellen Daten. rnWeiterhin analysieren wir die kristallinen Cluster in den Keimbildungs- und Wachstumszonen, rnwobei sich herausstellt, dass kristalline Cluster sich in unterschiedlichen Formen im System bilden. rnKleine Cluster sind eher l\"anglich in eine beliebige Richtung ausgedehnt, w\"ahrend gr\"o\ss{ere} rnCluster kompakter und von ellipsoidaler Gestalt sind. rn rnIm n\"achsten Teil untersuchen wir die heterogene Keimbildung an strukturierten bcc (100)-W\"anden. rnDie 2d-Analyse der kristallinen Schichten an der Wand zeigt, dass die Struktur der rnWand eine entscheidende Rolle in der Kristallisation von Hartkugelkolloiden spielt. rnWir sagen zudem die heterogenen Kristallbildungsraten bei verschiedenen \"Ubers\"attigungsgraden voraus. rnDurch Analyse der gr\"o\ss{ten} Cluster an der Wand sch\"atzen wir zus\"atzlich den Kontaktwinkel rnzwischen Kristallcluster und Wand ab. rnEs stellt sich heraus, dass wir in solchen Systemen weit von der Benetzungsregion rnentfernt sind und der Kristallisationsprozess durch heterogene Nukleation stattfindet. rn rnIm letzten Teil der Arbeit betrachten wir die Kristallisation von Lennard-Jones-Kolloidsystemen rnzwischen zwei ebenen W\"anden. rnUm die Erstarrungsprozesse f\"ur ein solches System zu untersuchen, haben wir eine Analyse des rnOrdnungsparameters f\"ur die Bindung-Ausrichtung in den Schichten durchgef\"urt. rnDie Ergebnisse zeigen, dass innerhalb einer Schicht keine hexatische Ordnung besteht, rnwelche auf einen Kosterlitz-Thouless-Schmelzvorgang hinweisen w\"urde. rnDie Hysterese in den Erhitzungs-Gefrier\-kurven zeigt dar\"uber hinaus, dass der Kristallisationsprozess rneinen aktivierten Prozess darstellt.

Computational fluid dynamics simulations in aerosol and nucleation studies

Nucleation is the first step in the formation of a new phase inside a mother phase. Two main forms of nucleation can be distinguished. In homogeneous nucleation, the new phase is formed in a uniform substance. In heterogeneous nucleation, on the other hand, the new phase emerges on a pre-existing surface (nucleation site). Nucleation is the source of about 30% of all atmospheric aerosol which in turn has noticeable health effects and a significant impact on climate. Nucleation can be observed in the atmosphere, studied experimentally in the laboratory and is the subject of ongoing theoretical research. This thesis attempts to be a link between experiment and theory. By comparing simulation results to experimental data, the aim is to (i) better understand the experiments and (ii) determine where the theory needs improvement. Computational fluid dynamics (CFD) tools were used to simulate homogeneous onecomponent nucleation of n-alcohols in argon and helium as carrier gases, homogeneous nucleation in the water-sulfuric acid-system, and heterogeneous nucleation of water vapor on silver particles. In the nucleation of n-alcohols, vapor depletion, carrier gas effect and carrier gas pressure effect were evaluated, with a special focus on the pressure effect whose dependence on vapor and carrier gas properties could be specified. The investigation of nucleation in the water-sulfuric acid-system included a thorough analysis of the experimental setup, determining flow conditions, vapor losses, and nucleation zone. Experimental nucleation rates were compared to various theoretical approaches. We found that none of the considered theoretical descriptions of nucleation captured the role of water in the process at all relative humidities. Heterogeneous nucleation was studied in the activation of silver particles in a TSI 3785 particle counter which uses water as its working fluid. The role of the contact angle was investigated and the influence of incoming particle concentrations and homogeneous nucleation on counting efficiency determined.

Mechanism of nucleation and precipitation in Li containing Al-Zn-Mg-Cu alloys

Investigations on the aging hardening behavior of four Al-Li-Zn-Mg-Cu alloys were carried out using differential scanning calorimetry, transmission electron microscopy and hardness measurement. It is shown that the addition of Li inhibits the formation of Zn-rich G.P. zones in Al-Zn-Mg-Cu alloys. The dominant aging hardening precipitates is delta'(Al3Li) phase. Coarse T ((AlZn)(49)Mg-32) phase, instead of MgZn2, precipitates primarily on grain boundaries, and provides little strengthening. The multi-stop aging involving plastic deformation introduces in the matrix a high concentration of structural defects. These defects play different role on the nucleation of Zn-rich G.P. zones in different alloys. For the Li free alloy, structural defects act as vacancy sinks and tend to suppress the homogeneous precipitation of G.P. zones, while for the Li containing alloys, these defects promote the heterogeneous nucleation of G.P. zones and metastable MgZn2. A significant aging hardening effect is attained in deformed Li containing alloys due to the extra precipitation of fine MgZn2 in the matrix combined with deformation hardening.

Self-nucleation and crystallization kinetics of double crystalline poly(p-dioxanone)-b-poly(epsilon-caprolactone) diblock copolymers

The crystallization kinetics of each constituent of poly(p-dioxanone)-b-poly(epsilon-caprolactone) diblock copolymers (PPDX-b-PCL) has been determined in a wide composition range by differential scanning calorimetry and compared to that of the equivalent homopolymers. Spherulitic growth rates were also measured by polarized optical microscopy while atomic force microscopy was employed to reveal the morphology of one selected diblock copolymer. It was found that crystallization drives structure formation and both components form lamellae within mixed spherulitic superstructures. The overall isothermal crystallization kinetics of the PPDX block at high temperatures, where the PCL is molten, was determined by accelerating the kinetics through a previous self-nucleation procedure. The application of the Lauritzen and Ho. man theory to overall growth rate data yielded successful results for PPDX and the diblock copolymers. The theory was applied to isothermal overall crystallization of previously self-nucleated PPDX ( where growth should be the dominant factor if self-nucleation was effective) and the energetic parameters obtained were perfectly matched with those obtained from spherulitic growth rate data of neat PPDX. A quantitative estimate of the increase in the energy barrier for crystallization of the PPDX block, caused by the covalently bonded molten PCL as compared to homo-PPDX, was thus determined. This energy increase can dramatically reduce the crystallization rate of the PPDX block as compared to homo-PPDX. In the case of the PCL block, both the crystallization kinetics and the self-nucleation results indicate that the PPDX is able to nucleate the PCL within the copolymers and heterogeneous nucleation is always present regardless of composition. Finally, preliminary results on hydrolytic degradation showed that the presence of relatively small amounts of PCL within PPDX-bPCL copolymers substantially retards hydrolytic degradation of the material in comparison to homo-PPDX. This increased resistance to hydrolysis is a complex function of composition and its knowledge may allow future prediction of the lifetime of the material for biomedical applications.

Crystal nucleation kinetics of a metastable phase on cordierite glass surfaces

The crystal nucleation rates of a metastable phase (chi) on the surface of a near stoichiometric cordierite glass were determined for temperatures between 839 and 910 degrees C (T-g similar to 800 degrees C). The surface nucleation kinetics of that phase on our glass, as well as on a stoichiometric glass (2 MgO-2Al(2)O(3)-5SiO(2)) studied by other authors, were analysed in terms of the classical nucleation theory; for the first time. It was shown that the effective interfacial energy for surface nucleation is substantially lower than that for homogeneous volume nucleation in silicate glasses, vindicating the assumption of heterogeneous nucleation on free glass surfaces. The average wetting angle between the nucleating crystals and the active solid particles was estimated to be around 46 degrees C. The pre-exponential constant was several orders of magnitude higher than the theoretical values as found for volume homogeneous nucleation in oxide glasses.