The Effect of Additives on the Early Stages of Growth of Calcite Single Crystals.

The Effect of Additives on the Early Stages of Growth of Calcite Single Crystals.
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DOI:
10.1002/anie.201706800
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发表时间:
2017-09-18
期刊:
Angewandte Chemie (International ed. in English)
影响因子:
--
通讯作者:
Meldrum FC
Meldrum FC
中科院分区:
其他
文献类型:
--
作者:
Kim YY;Freeman CL;Gong X;Levenstein MA;Wang Y;Kulak A;Anduix-Canto C;Lee PA;Li S;Chen L;Christenson HK;Meldrum FC

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由于结晶过程往往是快速的,很难监测它们的生长机制。在本研究中,我们利用在小体积中结晶过程比在散装溶液中更慢的事实来研究可溶性添加剂Mg2+和聚苯乙烯磺酸盐(PSS)对方解石晶体生长早期阶段的影响。使用“Crystal Hotel”微流体装置提供明确的纳升体积,我们观察到方解石晶体通过无定形前驱相形成。令人惊讶的是,最初形成的方解石晶体是完美的菱角体,直到Mg2+和PSS的晶体尺寸分别达到0.1 ~ 0.5 μm和1 ~ 2 μm时,可溶性添加剂才对形貌产生影响。然后晶体继续生长,形成具有这些添加剂特征的形态。这些结果可以通过考虑扭结位点的加性结合来合理化,这与晶体生长的经典机制是一致的。
As crystallization processes are often rapid, it can be difficult to monitor their growth mechanisms. In this study, we made use of the fact that crystallization proceeds more slowly in small volumes than in bulk solution to investigate the effects of the soluble additives Mg2+ and poly(styrene sulfonate) (PSS) on the early stages of growth of calcite crystals. Using a “Crystal Hotel” microfluidic device to provide well‐defined, nanoliter volumes, we observed that calcite crystals form via an amorphous precursor phase. Surprisingly, the first calcite crystals formed are perfect rhombohedra, and the soluble additives have no influence on the morphology until the crystals reach sizes of 0.1–0.5 μm for Mg2+ and 1–2 μm for PSS. The crystals then continue to grow to develop morphologies characteristic of these additives. These results can be rationalized by considering additive binding to kink sites, which is consistent with crystal growth by a classical mechanism.
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