Max Planck Institute for Polymer Research, Ackermannweg 10, 55128 Mainz, Germany.
Phys Chem Chem Phys. 2019 Feb 13;21(7):3734-3741. doi: 10.1039/c8cp05604h.
The interfacial premelting in ice/clay nano composites was studied by high energy X-ray diffraction. Below the melting point of bulk water, the formation of liquid water was observed for the ice/vermiculite and ice/kaolin systems. The liquid fraction is gradually increasing with temperature. For both minerals, similar effective premelting layer thicknesses of 2-3 nm are reached 3 K below the bulk melting point. For the quantitative description of the molten water fraction in wet clay minerals we developed a continuum model for short range interactions and arbitrary pore size distributions. This model quantitatively describes the experimental data over the entire temperature range. Model parameters were obtained by fitting using a maximum entropy (MaxEnt) approach. Pronounced differences in the deviation from Antonow's rule relating interfacial free energy between ice, water, and clay are observed for the charged vermiculite and uncharged kaolin minerals. The resultant parameters are discussed in terms of their ice nucleation efficiency. Using well defined and characterized ice/clay nano composite samples, this work bridges the gap between studies on single crystalline ice/solid model interfaces and naturally occurring soils and permafrost.
采用高能 X 射线衍射研究了冰/粘土纳米复合材料的界面预熔。在 bulk water 的熔点以下,观察到冰/蒙脱石和冰/高岭石体系中液态水的形成。液态分数随温度逐渐增加。对于这两种矿物,在 bulk melting point 以下 3 K 时,达到了类似的有效预熔层厚度 2-3 nm。为了定量描述湿粘土矿物中熔融水的分数,我们开发了一个用于短程相互作用和任意孔径分布的连续体模型。该模型在整个温度范围内定量描述了实验数据。使用最大熵(MaxEnt)方法拟合得到模型参数。观察到带电荷的蒙脱石和不带电荷的高岭石矿物的界面自由能与 Antonow 定律之间的偏差与冰、水和粘土之间的界面自由能有明显的差异。根据冰成核效率对得到的参数进行了讨论。使用定义明确且具有特征的冰/粘土纳米复合材料样品,这项工作填补了单晶冰/固体模型界面与天然土壤和永冻层之间研究的空白。