Time and space resolved methods : General discussion

Sun, Wenhao and Booth, Samuel and Myerson, Allan and Hughes, Colan and Pan, Haihua and Coquerel, Gerard and Brandel, Clement and Meekes, Hugo and Mazzotti, Marco and Fabian, Laszlo and Black, Simon and Vekilov, Peter and Back, Kevin and Toroz, Dimitrios and Lovelock, Jessica and Sefcik, Jan and Rasmuson, Ake and Breynaert, Eric and Sear, Richard and Hammond, Robert and Ward, Martin and Threlfall, Terence and De Yoreo, Jim and Davey, Roger and Ristic, Radoljub and Lewtas, Ken and Roberts, Kevin and Hare, Alan and Gich, Martí and Cölfen, Helmut and Likhatskiy, Maxim and Ter Horst, Joop and Sommerdijk, Nico (2015) Time and space resolved methods : General discussion. Faraday Discussions, 179. pp. 247-267. ISSN 1359-6640 (https://doi.org/10.1039/c5fd90037a)

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Jim De Yoreo presented some slides on in situ AFM, TEM, dynamic force spectroscopy (DFS) and optical spectroscopy investigations of nucleation in the calcium carbonate system: The free energy barrier to homogeneous nucleation of calcite calculated within the framework of classical nucleation theory (CNT) is prohibitive, even at concentrations exceeding the solubility limits of the amorphous phases. Consistent with this analysis, during nucleation in pure solutions, in our in situ TEM experiments we observed direct formation of all phases, including amorphous calcium carbonate (ACC), as well as the three predominant crystalline phases: calcite, vaterite, and aragonite, even under conditions in which ACC readily forms. In addition to direct formation pathways, we observed indirect pathways in which ACC transforms to aragonite and vaterite through nucleation within or on the precursors, rather than via dissolution and reprecipitation. We also observed aragonate transformation to calcite, but never recorded an instance in which ACC transforms into calcite, except via dissolution–reprecipitation reactions.