Kim Joonsoo, Kimura Yuki, Puchala Brian, Yamazaki Tomoya, Becker Udo, Sun Wenhao
Department of Materials Science and Engineering, University of Michigan, Ann Arbor, MI, USA.
Institute of Low Temperature Science, Hokkaido University, Sapporo, Japan.
Science. 2023 Nov 24;382(6673):915-920. doi: 10.1126/science.adi3690. Epub 2023 Nov 23.
Crystals grow in supersaturated solutions. A mysterious counterexample is dolomite CaMg(CO), a geologically abundant sedimentary mineral that does not readily grow at ambient conditions, not even under highly supersaturated solutions. Using atomistic simulations, we show that dolomite initially precipitates a cation-disordered surface, where high surface strains inhibit further crystal growth. However, mild undersaturation will preferentially dissolve these disordered regions, enabling increased order upon reprecipitation. Our simulations predict that frequent cycling of a solution between supersaturation and undersaturation can accelerate dolomite growth by up to seven orders of magnitude. We validated our theory with in situ liquid cell transmission electron microscopy, directly observing bulk dolomite growth after pulses of dissolution. This mechanism explains why modern dolomite is primarily found in natural environments with pH or salinity fluctuations. More generally, it reveals that the growth and ripening of defect-free crystals can be facilitated by deliberate periods of mild dissolution.
晶体在过饱和溶液中生长。一个神秘的反例是白云石CaMg(CO₃)₂,它是一种在地壳中储量丰富的沉积矿物,在环境条件下不易生长,即使在高度过饱和溶液中也不行。通过原子模拟,我们发现白云石最初沉淀出一个阳离子无序的表面,高表面应变会抑制晶体的进一步生长。然而,轻度欠饱和会优先溶解这些无序区域,使得再沉淀时有序度增加。我们的模拟预测,溶液在过饱和和欠饱和之间频繁循环可使白云石的生长速度加快多达七个数量级。我们通过原位液体池透射电子显微镜验证了我们的理论,直接观察到溶解脉冲后块状白云石的生长。这种机制解释了为什么现代白云石主要存在于pH值或盐度有波动的自然环境中。更普遍地说,它揭示了通过适度溶解的有意阶段可以促进无缺陷晶体的生长和熟化。