Stawski, TM, Freeman, HM orcid.org/0000-0001-8242-9561, Van Driessche, AES et al. (4 more authors) (2019) Particle-Mediated Nucleation Pathways Are Imprinted in the Internal Structure of Calcium Sulfate Single Crystals. Crystal Growth & Design, 19 (7). pp. 3714-3721. ISSN 1528-7483
Abstract
Calcium sulfate minerals are found in nature as three hydrates: gypsum (CaSO4·2H2O), bassanite (CaSO4·0.5H2O), and anhydrite (CaSO4). Due to their relevance in natural and industrial processes, the formation pathways of calcium sulfates from aqueous solution have been the subject of intensive research, and there is a growing body of literature, suggesting that calcium sulfates form through nonclassical nanoparticle-mediated crystallization processes. We showed earlier (Stawski et al. Nat. Commun.2016, 7, 11177) that at the early stages in the precipitation reaction, calcium sulfate nanocrystals nucleate through the reorganization and coalescence of aggregates rather than through classical unit addition. Here, we used low-dose dark field (DF) transmission electron microscopy (TEM) and electron diffraction and document that these restructuring processes do not continue until a final near-perfectly homogeneous single crystal is obtained. Instead, we show that the growth process yields a final imperfect mesocrystal with an overall morphology resembling that of a single crystal, yet composed of smaller nanodomains. Our data reveal that organic-free calcium sulfate mesocrystals grown by a particle mediated-pathway may preserve in the final crystal structure a “memory” or “imprint” of their nonclassical nucleation process, something that has been overlooked until now. Furthermore, the nanoscale misalignment of the structural subunits within these crystals might propagate through the length-scales, which is potentially expressed macroscopically as misaligned zones/domains in large single crystals. This is akin to observations in some of the giant crystals from the Naica Mine, Chihuahua, Mexico.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2019 American Chemical Society. This is an author produced version of a paper published in Crystal Growth & Design. Uploaded in accordance with the publisher's self-archiving policy. |
Dates: |
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Institution: | The University of Leeds |
Academic Units: | The University of Leeds > Faculty of Engineering & Physical Sciences (Leeds) > School of Chemical & Process Engineering (Leeds) |
Depositing User: | Symplectic Publications |
Date Deposited: | 30 Jul 2019 10:40 |
Last Modified: | 03 Jul 2020 00:40 |
Status: | Published |
Publisher: | American Chemical Society |
Identification Number: | 10.1021/acs.cgd.9b00066 |
Related URLs: | |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:149115 |