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Title: Induction time of a polymorphic transformation

Abstract

When a solution is supersaturated with respect to multiple polymorphs, the polymorph with the lowest nucleation barrier will form first. If this is a metastable polymorph, it will persist until the induction of nuclei of a lower free-energy phase, marking the onset of a polymorphic transformation. Induction of a more stable polymorph can occur under two conditions: a.) during steady-state nucleation, or b.) after complete crystal growth of the metastable phase. Using the theory of competing stochastic processes, we derive the rare probability of forming a higher-barrier, more-stable polymorph during steady-state nucleation, and use this to explain variations in crystallization products between repeat experiments, which may underlie the phenomenon of "Disappearing Polymorphs". We also derive the induction time of a stable phase from a solution equilibrated with a metastable phase, and show that once the stable phase nucleates, bulk metastable crystals will spontaneously ripen onto nanoscale nuclei or seeds of a more stable phase, thermodynamically driving dissolution-reprecipitation processes. Existing strategies to prolong or shorten the lifetimes of transient metastable phases are reviewed and interpreted within the context of polymorphic induction. Finally, the analyses in this work are conducted from classical nucleation and crystal growth theories, suggesting that paradigms shifts tomore » 'non-classical' nucleation theories may not be necessary to rationalize multistage crystallization.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]
  1. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Materials Science and Engineering; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
  2. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Materials Science and Engineering; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division; Univ. of California, Berkeley, CA (United States). Dept. of Materials Science and Engineering
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1474991
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
CrystEngComm
Additional Journal Information:
Journal Volume: 19; Journal Issue: 31; Journal ID: ISSN 1466-8033
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Sun, Wenhao, and Ceder, Gerbrand. Induction time of a polymorphic transformation. United States: N. p., 2017. Web. doi:10.1039/c7ce00766c.
Sun, Wenhao, & Ceder, Gerbrand. Induction time of a polymorphic transformation. United States. doi:10.1039/c7ce00766c.
Sun, Wenhao, and Ceder, Gerbrand. Fri . "Induction time of a polymorphic transformation". United States. doi:10.1039/c7ce00766c. https://www.osti.gov/servlets/purl/1474991.
@article{osti_1474991,
title = {Induction time of a polymorphic transformation},
author = {Sun, Wenhao and Ceder, Gerbrand},
abstractNote = {When a solution is supersaturated with respect to multiple polymorphs, the polymorph with the lowest nucleation barrier will form first. If this is a metastable polymorph, it will persist until the induction of nuclei of a lower free-energy phase, marking the onset of a polymorphic transformation. Induction of a more stable polymorph can occur under two conditions: a.) during steady-state nucleation, or b.) after complete crystal growth of the metastable phase. Using the theory of competing stochastic processes, we derive the rare probability of forming a higher-barrier, more-stable polymorph during steady-state nucleation, and use this to explain variations in crystallization products between repeat experiments, which may underlie the phenomenon of "Disappearing Polymorphs". We also derive the induction time of a stable phase from a solution equilibrated with a metastable phase, and show that once the stable phase nucleates, bulk metastable crystals will spontaneously ripen onto nanoscale nuclei or seeds of a more stable phase, thermodynamically driving dissolution-reprecipitation processes. Existing strategies to prolong or shorten the lifetimes of transient metastable phases are reviewed and interpreted within the context of polymorphic induction. Finally, the analyses in this work are conducted from classical nucleation and crystal growth theories, suggesting that paradigms shifts to 'non-classical' nucleation theories may not be necessary to rationalize multistage crystallization.},
doi = {10.1039/c7ce00766c},
journal = {CrystEngComm},
number = 31,
volume = 19,
place = {United States},
year = {2017},
month = {7}
}

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Works referenced in this record:

Kinetics of Phase Change. I General Theory
journal, December 1939

  • Avrami, Melvin
  • The Journal of Chemical Physics, Vol. 7, Issue 12, p. 1103-1112
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Manipulating the Crystalline State of Pharmaceuticals by Nanoconfinement
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