SAXS Study of the Nucleation of Glycine Crystals from a Supersaturated Solution

Chattopadhyay, Soma; Erdemir, Deniz; Evans, James G.; Ilavský, Ján; Amenitsch, Heinz; Segre, Carlo U.; Myerson, Allan S.

doi:10.1021/cg0497344

Cited by 135 publications

(158 citation statements)

References 34 publications

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“…The first example came from experimental studies of lysozyme crystals, which were found to crystallize more easily just outside the metastable gas-liquid phase separation transition [96,97]. Similar processes have been found in both small molecules, like glycine [98] and calcium carbonate [91], and colloidal systems [88]. Two-step crystallization in absence of a metastable liquid phase was also confirmed theoretically in spin models [99] and density functional theory [93].…”

Section: Two-step Nucleation: Coupling Between Density Fluctuatiomentioning

confidence: 67%

Crystal nucleation as the ordering of multiple order parameters

Russo

Tanaka

2016

The Journal of Chemical Physics

107

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Nucleation is an activated process in which the system has to overcome a free energy barrier in order for a first-order phase transition between the metastable and the stable phases to take place. In the liquid-to-solid transition the process occurs between phases of different symmetry, and it is thus inherently a multi-dimensional process, in which all symmetries are broken at the transition. In this Focus Article, we consider some recent studies which highlight the multi-dimensional nature of the nucleation process. Even for a single-component system, the formation of solid crystals from the metastable melt involves fluctuations of two (or more) order parameters, often associated with the decoupling of positional and orientational symmetry breaking. In other words, we need at least two order parameters to describe the free-energy of a system including its liquid and crystalline states. This decoupling occurs naturally for asymmetric particles or directional interactions, focusing here on the case of water, but we will show that it also affects spherically symmetric interacting particles, such as the hard-sphere system. We will show how the treatment of nucleation as a multi-dimensional process has shed new light on the process of polymorph selection, on the effect of external fields on the nucleation process, and on glass-forming ability.

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Section: Two-step Nucleation: Coupling Between Density Fluctuatiomentioning

confidence: 67%

Crystal nucleation as the ordering of multiple order parameters

Russo

Tanaka

2016

The Journal of Chemical Physics

107

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“…The number and variety of solutions that have been found to crystallize from dense liquid precursors lead to the idea that two-step crystallization pathways are quite universal crystallization processes. For example, two-step crystallization processes have been suggested for systems outside the region of stability of the dense fluid phase [38,41,[45][46][47][48].…”

Section: Two-step Nucleation and Precursorsmentioning

confidence: 99%

Nonclassical pathways of crystallization in colloidal systems

Russo

Tanaka

2016

MRS Bull.

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Colloidal systems offer the ideal conditions to study the nucleation process, both from an experimental viewpoint, due to their relative large size and long time-scales, and from a modeling point of view, due to the tunability of their interactions. Here we review some recent works that study the process of colloidal crystallization from a microscopic perspective. We focus in particular on non-classical pathways to nucleation where the appearance of the solid crystals involves fluctuations of two (or more) order parameters. We interpret the non-classical behavior as a decoupling of positional and orientational symmetry breaking. We then consider how the nucleation pathway determines which polymorph is selected upon nucleation from the melt. Moreover we show how the study of nucleation pathways not only sheds new light on the microscopic mechanism of nucleation, but also provides important information regarding its avoidance, thus suggesting a deep link between crystallization and vitrification.

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“…A magnetic stirrer bar was added to each test tube, which was then promptly sealed to prevent solvent evaporation and contamination. The test tubes were then moved directly to a second thermostatic bath at a temperature corresponding to a slight undersaturation with respect to form I (52, 55 or 60 °C) for a controlled period of time (8,30 or >360 min). The temperature levels and time limits are marked with horizontal and vertical lines, respectively, in Figure 3.…”

Section: Cooling Crystallizationsmentioning

confidence: 99%

Influence of Solution Thermal and Structural History on the Nucleation of m-Hydroxybenzoic Acid Polymorphs

Nordström

Svärd

Malmberg

et al. 2012

Crystal Growth & Design

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The influence of solution pre-treatment on primary nucleation of m-hydroxybenzoic acid has been investigated through 550 cooling crystallization experiments. The metastable zone width has been determined at constant cooling rate and the time and temperature of the preceding superheating step have been varied. m-Hydroxybenzoic acid has two polymorphs and the influence of the polymorph used to prepare the solutions has also been investigated. There is an overall tendency in the experiments for the solution to exhibit a larger metastable zone width if it is superheated for a longer time and at a higher temperature, but under the investigated conditions this tendency is not very strong. The results show that the metastable form II preferentially crystallizes in all experiments and in particular when the solution has been more strongly superheated for several hours. However, when the time and/or the temperature of superheating is reduced there is an increasing tendency to obtain the stable form I. This is most clearly found for solutions prepared by dissolving form I. When the solutions are prepared by dissolution of form II, this tendency is weaker in what appears to be a systematic way. It is hypothesized that, unless the solution is strongly superheated for several hours, it will contain for a significant period of time clusters of solute molecules which can retain some degree of structure from the dissolved crystal. This leads to "memory" effects in the solution which may influence subsequent nucleation. The work includes a comprehensive review of previous published work on the influence of thermal history on nucleation in solutions and melts.

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SAXS Study of the Nucleation of Glycine Crystals from a Supersaturated Solution

Cited by 135 publications

References 34 publications

Crystal nucleation as the ordering of multiple order parameters

Crystal nucleation as the ordering of multiple order parameters

Nonclassical pathways of crystallization in colloidal systems

Influence of Solution Thermal and Structural History on the Nucleation of m-Hydroxybenzoic Acid Polymorphs

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