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NPLIN was studied in supersaturated solutions (S = 1.06) of potassium chloride (KCl) and bromide (KBr). The fraction of samples nucleated (f) follows a nonlinear dependence on peak power density that approaches f = 1 at higher incident powers. It is shown that a lower threshold power is required for nucleation using 532 nm laser pulses than at 1064 nm, and that a higher fraction of samples nucleate when exposed to 532 nm pulses at a given laser power. Comparison with KCl shows higher fractions of KBr samples nucleate with lower threshold values at both wavelengths. Samples of KCl of equal supersaturation at two different temperatures (23 and 33 °C) exposed to 1064 nm pulses show that those at 33 °C are significantly more labile to nucleation. The ratio of samples nucleated at 33 °C compared to those at 23 °C was 2.11 ± 0.47. A classical nucleation model based on activation of subcritical solute clusters accounts remarkably well for the experimental data and provides phenomological values of the crystal–solution interfacial tension (γ) at 23 °C for KCl and KBr of 5.283 and 4.817 mJ m-2. At 33 °C, the model yields a best-fit value of γ = 5.429 mJ m-2 for KCl. As an extension of this work the use of an evanescent wave (ew) generated by total internal reflection was investigated as a method to cause nucleation in supersaturated KCl solution. Evanescent wave NPLIN (ew-NPLIN) was shown to cause nucleation. The results showed a higher laser-power threshold required for nucleation and sample lability greater than that of bulk NPLIN. In a second approach to understanding NPLIN, the structures of concentrated solutions were probed by a series of laser scattering experiments. Evidence showing populations of particles in solution was provided by Rayleigh laser scattering (RLS) experiments. Scattering in solutions prepared to be nearly saturated (S = 0.95) was observed using a low magnification (×10) microscope objective; almost all solutions showed the presence of scattering objects moving freely in solution. For those that showed no particles, it was noted that the solutions were typically of higher solute concentration (> 11 mol% solute). Ammonium nitrate solution showed no particles using ×10 magnification, however particles were identified when higher magnification was used (×50 and ×100). Video footage of the Rayleigh scattering observed in aqueous solutions of glycine, urea and ammonium nitrate obtained using ×50 magnification were analysed using a custom nanoparticle tracking software. The results showed a population of particles in aqueous urea and glycine solutions with particle concentrations of the order 108 particles cm-3 and mean hydrodynamic diameter of approximately 267 ± 1 and 173 ± 2 nm respectively. Not enough particles were identified in ammonium nitrate solution to complete the tracking analysis; however a fluctuating background scatter suggested a population of particles with sizes below the limit of resolution of the optical system. Using aqueous urea solution as a model system the structure of the particles identified in solution was investigated using scanning microscopy. The second-harmonic scattering (SHS) signal measured in concentrated aqueous urea solution was measured as a function of solution concentration (C) over a range of saturation conditions from undersaturated (S = 0.15) to supersaturated (S = 1.86). The results show a non-linear increase in SHS signal with local maxima near S = 0.95 and 1.75 suggesting a change in solution structure near these points. Rayleigh scattering images indicate the presence of particles in nearly saturated (S = 0.95) urea solutions. Time-dependent SHS measurements indicate that signals originate from individual events encountered during scanning of the sample through the focal volume of the probe laser, consistent with second harmonic generation (SHG) from particles. SHG from aqueous dispersions of barium titanate (BaTiO3) nanoparticles with diameters < 200 nm, showed signals ~20 times larger than urea solutions. The results suggest the existence of a population of semi-ordered clusters of urea that changes with solution concentration.

Approved for public release; distribution is unlimited / "Superplastic forming is an emerging industrial technology that allows the production of complex shapes in metallic materials including aluminum. A critical characteristic of materials that are capable of sustaining superplastic forming is a fine grain size. In this study a commercial aluminum-magnesium-manganese alloy received in the as-cast condition was subjected to various thermomechanical processes intended to refine the grain size. Particle stimulated nucleation (PSN) theory was employed to develop the thermomechanical processes. These processes all involved initial homogenization and hot working. Subsequent annealing treatments were intended to control the size and size distribution of second phase particles, such as Al6Mn. Strain energy was introduced through cold rolling followed by recrystallization anneals. Samples were analyzed using orientation-imaging microscopy to examine the effect of processing variables on the recrystallized grain size." p. i. / Ensign, United States Navy

by Yang Hua. / "August 1999." / Thesis (Ph.D.)--Chinese University of Hong Kong, 1999. / Includes bibliographical references. / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Mode of access: World Wide Web. / Abstracts in English and Chinese. / by Yang Hua.

Nucleation is the process by which a metastable phase decays into a stable phase. It is widely observed in nature, and is responsible for many phenomena such as the formation clouds and domains in crystalline solids. The classical theory of nucleation predicts that the objects that initiate the decay from the metastable to the stable phase are compact droplets whose interior has the structure of the stable phase. For quenches deep into the metastable phase, however, the droplets may be ramified, with a structure very different from the stable phase. This difference has profound implications for material properties, especially because predicting the onset of structure early enough is useful for manipulating and controlling nucleation processes. I used molecular dynamics to simulate nucleation in Lennard-Jonesium, a model system for liquid-solid transformations. The system is quenched from a high temperature, where the liquid is stable, to a temperature where the liquid is metastable, and is allowed to nucleate via fluctuation-driven clusters referred to as critical droplets. I determined the occurrence of critical droplets by the intervention method, but found a non-monotonic variation in droplet survival rates near the saddle point. I determined the structure of the critical droplet and found evidence for a core consisting of mostly solid-like particles with hcp symmetry and a previously unknown planar structure around it. Using perturbative techniques, I showed that the planar particles have a significant influence on the nucleation and growth of critical droplets. I also introduced a novel method of learning symmetries to predict the structure and appearance of precursors to the critical nucleus. My results give added evidence for the presence of spinodal nucleation at deep quenches.

by Leung Kwok Kuen. / Thesis (Ph.D.)--Chinese University of Hong Kong, 1997. / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Mode of access: World Wide Web. / by Leung Kwok Kuen.

The aim of this thesis was to discover the mechanism for non-photochemical laser-induced nucleation (NPLIN), which is a technique for inducing nucleation of crystals with laser light without absorption. The mechanism of the optical Kerr effect (OKE) was suggested by Garetz et al. [Physical Review Letters 77, 3475–3476 (1996)] to give an explanation for NPLIN. Since the feasibility of the OKE mechanism for NPLIN has been questioned, a series of experiments on NPLIN of aqueous supersaturated urea were carried out to quantify the relationship between crystal alignment and laser polarization. Digital imaging of crystal growth during laser irradiation showed that nascent needle-shaped crystals of urea were not aligned with the direction of the electric field of the laser. Additionally, work on glycine was aimed at verifying the possibility to control the polymorph of the obtained crystal via the laser polarization. However, our finding shows that the probability of γ-glycine is more likely to increase with increasing supersaturation; and the influence of laser polarization on the resulting morphologies is not strong as reported by Sun et al. [Crystal Growth & Design 6, 684–689 (2006)]. Furthermore, in another work on NPLIN of L-histidine, based on Sun et al. [Crystal Growth & Design 8, 1720–1722 (2008)], we were unable to reproduce the results as stated in Sun’s published paper. We find their results exhibit a large uncertainty when recalculated through the Wilson score interval for binomial distributions. On account of these revised uncertainties, it is unlikely that laser polarization gives polymorphism control. Comparison with the nucleation probability of unfiltered samples in the work of urea and glycine shows that the number of filtered samples nucleated as a result of NPLIN was largely decreased. Moreover, experiments on NPLIN of NaCl and KCl also exhibited that the number of filtered samples nucleated was significantly lower than that of unfiltered samples. This downward tendency in nucleation probability after filtration cannot be explained by Garetz’s OKE mechanism. On account of this, an alternative mechanism named particle-heating mechanism was proposed, and supported by experiments on NPLIN of sodium acetate. Sodium acetate experiments showed that the crystallization of sodium acetate can be induced by a single pulse of a nanosecond laser (1064 nm) with minimum power of 0.1 J cm−2. As discovered by Oliver et al. [D. Oliver, PhD Thesis, Edinburgh University, 2014], anhydrous or trihydrate sodium acetate can be formed under the effects of different organic and inorganic additives, such as poly- (methacrylic acid) and disodium hydrogen phosphate. We demonstrate that crystalline growth velocities and crystal morphology can be influenced by these additives. We find that high levels of additive cause only nucleation of bubbles. By counting the number of crystals, which is approximately consistent to the number of bubbles observed, video microscopy of laser-induced crystallization of sodium acetate has revealed that the general mechanism of NPLIN is most likely to be caused by a particle-heating mechanism. Chapter 8 of the thesis describes a number of solute molecules that were tested using NPLIN, but failed. In terms of improvements for future work or a perspective on NPLIN, detailed suggestions have been described in Chapter 9, which also gives a summary of all work presented.

The role of heterogeneity in two long-range systems is explored with a focus on the interplay of this heterogeneity with the component system interactions. The first will be the heterogeneous Ising model with long-range interactions. Earthquake fault systems under long-range stress transfer with varying types of heterogeneity will be the second system of interest. First I will review the use of the intervention method to determine the time and place of nucleation and extend its use as an indicator for spinodal nucleation. The heterogeneous Ising model with fixed magnetic sites will then be reformulated as a dilute random field Ising model. This reformulation will allow for the application of spinodal nucleation theory to the heterogeneous Ising model by correcting the spinodal field and the critical exponent sigma describing the critical behavior of clusters in spinodal nucleation theory. The applicability of this correction is shown by simulations that determine the cluster scaling of the nucleating droplets near the spinodal. Having obtained a reasonable definition of the saddle point object describing the nucleation droplet, the density profile of the nucleating droplet is measured and deviations from homogeneous spinodal nucleation are found due to the excess amount of sparseness in the nucleating droplet due to the heterogeneity. Earthquake fault systems are then introduced and a connection is shown of two earthquake models. Heterogeneity is introduced in the form of asperities with the intent of modeling the effect of hard rocks on earthquake statistics. The asperities are observed to be a crucial element in explaining the behavior of aftershocks resulting in Omori's law. A second form of heterogeneity is introduced by coupling the Olami-Feder-Christensen model to an invasion percolation model for the purpose of modeling an earthquake fault system undergoing hydraulic fracturing. The ergodicty and event size statistics are explored in this extended model. The robustness of the event size statistics results are explored by allowing for the dissipation parameter in the Olami-Feder-Christensen model to vary.

We report the results of a series of experimental studies in two interrelated areas: homogeneous nucleation and transient heat transfer in cryogenic liquids. We report the first determination of the homogeneous nucleation temperature of liquid helium I and liquid nitrogen employing a transient superheating technique. This technique in liquid helium involved the development of a new transient magnetoresistive thermometer which relies on the strong temperaure dependence of magnetoresistance in bismuth as a thermometric property. Our measurements of the homogeneous nucleation temperature for both liquid helium I and nitrogen are in good agreement with the predictions from the Becker-Doring Volmer-Zel'dovich-Frenkel nucleation theory. On the basis of such agreement between theory and experiment in both liquid helium and liquid nitrogen we have developed a corresponding state analysis applicable to the case of homogeneous nucleation in liquid noble gases, both quantum and classical. Predictions of the homogeneous nucleation temperature and surface tension of several hydrogen isotopes are made from such a quantum mechanical law of corresponding states. We also comment on the limiting superheat temperature of liquid helium I. It is suggested that a comparison between the limiting superheat temperaure and the peak nucleate boiling temperature is meaningless and that the reported agreement between the two is largely fortuitous. In the studies of transient heat transfer in helium we find that the heat transfer from a solid into liquid helium is markedly enhanced by the application of a visible pulse of light. In liquid nitrogen we find that a transition to stable film boiling can be observed for power values as low as 40 per cent of the steady-state peak heat flux.

The freezing of model atmospheric aerosols – specifically, model cirrus cloud particles – was investigated through laboratory studies of supercooled water aerosols. Water droplets with radii of 1 – 2.7 µm were exposed to well-defined temperature profiles ranging from 240 – 230 K in a cryogenic flow tube apparatus, and observed using infrared extinction spectroscopy. A computational characterization procedure, based on theories of light scattering, was used to determine the size and phase composition of aerosols from extinction spectra. The procedure showed large ice fractions at uncharacteristically warm temperatures, which was attributed to the formation of ordered, “ice-like” clusters of molecules in supercooled water. Temperature-dependent complex indices of refraction were determined from the supercooled water extinction spectra, and showed changes reflecting this ordered formation. Taking the “ice-like” character of clusters into account, the homogeneous nucleation point for micrometre-sized water aerosols was determined to be 236.2 K. A microphysical model was developed to determine temperature-dependent, volume- and surface-based homogeneous nucleation rates from experimental freezing data. The model results indicated that surface nucleation was the dominant process for our range of experimental conditions. This was supported by separate studies of smaller, 0.63 and 0.75 µm radius aerosols, with larger surface-to-volume ratios. An optical microscopy apparatus was placed in the cryogenic flow tube to allow real-time imaging of particles in freezing experiments. The imaging studies demonstrated the utility of the microscopy apparatus for the observation and classification of ice crystal habits. Ray tracing and image processing algorithms were used to analyze particle geometry and size. The latter was used to validate the size retrievals from the aerosol characterization procedure. Additional studies probed the changes in the optical properties of crystalline ammonium sulfate, (NH₄)₂SO₄, due to the paraelectric-to-ferroelectric transition at 223 K. Temperature- dependent refractive indices were determined from crystalline (NH₄)₂SO₄ extinction spectra. Only small changes in these values were observed down to 223 K, below which significant changes were observed, due to the changes in lattice structure accompanying the ferroelectric transition.