skip to main content


Title: Pre-nucleation Clusters and Complex Nucleation in Soft Matter and the Potential Roles of Space Experiments
For more than a century, Classical Nucleation Theory (CNT) has been used to explain the process of crystallization in supersaturated solutions. According to CNT, nucleation is a single-step process that occurs via monomer-by-monomer addition. However, recent findings from experiments and numerical simulations have shown that nucleation is a multi-step process that occurs via more complex pathways that involve intermediate species such as ion complexes, dense liquid precursors, or even nanocrystals. Such non-classical pathways observed in protein solutions, colloidal suspensions and electrolytes are reviewed in this paper. The formation of stable Pre-nucleation Clusters (PNCs) in the crystallization of biominerals is also discussed. In spite of the mounting evidence for non-classical nucleation behaviors, the knowledge about the structural evolution of the intermediate phases and their role in polymorph selection is still limited. It has also been observed that gravitational force interferes with the crystallization behavior of materials thereby posing limitation to ground-based experiments. Microgravity conditions, coupled with containerless processing techniques provide a suitable alternative to overcome these limitations.  more » « less
Award ID(s):
2132131
NSF-PAR ID:
10383409
Author(s) / Creator(s):
; ; ; ;
Date Published:
Journal Name:
IJMSA
Volume:
39
Issue:
3
ISSN:
2188-9783
Page Range / eLocation ID:
390302
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. null (Ed.)
    Crystallization is fundamental to materials science and is central to a variety of applications, ranging from the fabrication of silicon wafers for microelectronics to the determination of protein structures. The basic picture is that a crystal nucleates from a homogeneous fluid by a spontaneous fluctuation that kicks the system over a single free-energy barrier. However, it is becoming apparent that nucleation is often more complicated than this simple picture and, instead, can proceed via multiple transformations of metastable structures along the pathway to the thermodynamic minimum. In this article, we observe, characterize, and model crystallization pathways using DNA-coated colloids. We use optical microscopy to investigate the crystallization of a binary colloidal mixture with single-particle resolution. We observe classical one-step pathways and nonclassical two-step pathways that proceed via a solid–solid transformation of a crystal intermediate. We also use enhanced sampling to compute the free-energy landscapes corresponding to our experiments and show that both one- and two-step pathways are driven by thermodynamics alone. Specifically, the two-step solid–solid transition is governed by a competition between two different crystal phases with free energies that depend on the crystal size. These results extend our understanding of available pathways to crystallization, by showing that size-dependent thermodynamic forces can produce pathways with multiple crystal phases that interconvert without free-energy barriers and could provide approaches to controlling the self-assembly of materials made from colloids. 
    more » « less
  2. A bstract Membrane nucleation, a higher dimensional analog of the Schwinger effect, is a useful toy model for vacuum decay. While a non-perturbative effect, the computation of nucleation rates has only been accomplished at weak coupling in the field theory. Here we compute the nucleation rates of spherical membranes using AdS/CFT duality, thus naturally including the effects of strong coupling. More precisely, we consider the nucleation of spherical membranes coupled to an antisymmetric tensor field, a process which renders the vacuum unstable above a critical value of the field strength. We analyze membrane creation in flat and de Sitter space using various foliations of AdS. This is accomplished via instanton methods, where the rate of nucleation is dominated by the semi-classical on-shell Euclidean action. Our findings generalize the holographic Schwinger effect and provide a step toward holographic false vacuum decay mediated by Coleman-De Luccia instantons. 
    more » « less
  3. Hierarchical nucleation pathways are ubiquitous in the synthesis of minerals and materials. In the case of zeolites and metal–organic frameworks, pre-organized multi-ion “secondary building units” (SBUs) have been proposed as fundamental building blocks. However, detailing the progress of multi-step reaction mechanisms from monomeric species to stable crystals and defining the structures of the SBUs remains an unmet challenge. Combining in situ nuclear magnetic resonance, small-angle X-ray scattering, and atomic force microscopy, we show that crystallization of the framework silicate, cyclosilicate hydrate, occurs through an assembly of cubic octameric Q38 polyanions formed through cross-linking and polymerization of smaller silicate monomers and other oligomers. These Q38 are stabilized by hydrogen bonds with surrounding H2O and tetramethylammonium ions (TMA+). When Q38 levels reach a threshold of ≈32 % of the total silicate species, nucleation occurs. Further growth proceeds through the incorporation of [(TMA)x(Q38)⋅n H2O](x−8) clathrate complexes into step edges on the crystals. 
    more » « less
  4. Abstract Hierarchical nucleation pathways are ubiquitous in the synthesis of minerals and materials. In the case of zeolites and metal–organic frameworks, pre‐organized multi‐ion “secondary building units” (SBUs) have been proposed as fundamental building blocks. However, detailing the progress of multi‐step reaction mechanisms from monomeric species to stable crystals and defining the structures of the SBUs remains an unmet challenge. Combining in situ nuclear magnetic resonance, small‐angle X‐ray scattering, and atomic force microscopy, we show that crystallization of the framework silicate, cyclosilicate hydrate, occurs through an assembly of cubic octameric Q 3 8 polyanions formed through cross‐linking and polymerization of smaller silicate monomers and other oligomers. These Q 3 8 are stabilized by hydrogen bonds with surrounding H 2 O and tetramethylammonium ions (TMA + ). When Q 3 8 levels reach a threshold of ≈32 % of the total silicate species, nucleation occurs. Further growth proceeds through the incorporation of [(TMA) x (Q 3 8 )⋅ n  H 2 O] ( x −8) clathrate complexes into step edges on the crystals. 
    more » « less
  5. null (Ed.)
    Abstract Electron back scattered diffraction data of garnet crystals from the Nelson Aureole, British Columbia and the Mosher’s Island formation, Nova Scotia, reveals that 22 garnet crystals are all oriented with one of three crystal directions parallel to the trace of the foliation plane in thin section. Structural models suggest that these relationships are due to preferential garnet nucleation onto muscovite, with the alignment of repeating rows of Al octahedra and Si tetrahedra in each leading to inheritance of garnet orientation from the muscovite. These results highlight that epitaxial nucleation may be a prevalent process by which porphyroblast minerals nucleate during metamorphism and carry implications for the role that non-classic nucleation pathways play in the crystallization of metamorphic minerals, the distribution of porphyroblasts in metamorphic rocks, and, in cases in which nucleation is the rate limiting step for crystallization, the energetics of metamorphic reactions. 
    more » « less