Equilibrium and Reaction of Mineral-water interaction in upper crust

设计了一个环境控制的原位观察样品室，用于200℃和200℃下（高达1.55 MPa）的欠饱和条件下的x射线衍射实验，以研究矿物-蒸汽平衡和反应。设计了一种更高温度和压力的装置来研究欠饱和和过饱和条件。实验：采用碱金属离子、Li+-Cs+、碱土金属离子、Mg2+-Ba2+、La3+等阳离子交换蒙脱石、库尼皮亚F，考察其在150℃下的溶胀性能。不同阳离子对蒙脱石在150℃温度范围内的溶胀行为的影响分子模拟：我们编制了一个程序来产生具有流体相表面的初始结构。分子动力学模拟程序，MXORTO/MXDTRICL，更新了非常大的系统。在MPI并行PC系统上使用这些程序，可以实现超过50,000个原子系统的MD模拟。通过计算得到了粘土矿物层间区h2o和可交换阳离子的过量混合焓和扩散常数。使用这些程序，我们进行了一些多相复杂体系，如蒙脱石与边水/水溶液（NaCl，CaCl2等）。蛇纹石类矿物-水/溶液系统。分子筛表面-氨气体体系的动力学计算揭示了分子筛结构中通道窗处和通道窗附近氨分子的动力学过程。分析：结合实验数据和分子模拟结果，分析了不同物理化学条件下结构变化和吸附行为与平衡和非平衡过程的关系。

A sample chamber for environment controlled in-situ observation was designed and made for x-ray diffraction experiments under 200℃, and under-saturated condition (up to 1.55 MPa at 200℃) to investigate mineral-vapor equilibrium and reactions. An apparatus for higher temperature and pressure was designed to investigate under-and over-saturated conditions.Experiments : Cation exchanged smectite, Kunipia F by alkali metal ion, Li+-Cs+, alkali earth metal ion, Mg2+-Ba2+ and La3+were used to investigate swelling property in terms of cations up to 150℃. The swelling behavior of smectite with various cations for temperature rage up to 150℃Molecular simulations : We made a program to produce initial structures having surfaces with fluid phase. Molecular dynamics simulation programs, MXORTO/MXDTRICL, were updated for the very large systems. Using these programs on MPI parallel PC systems, MD simulations with more than 50,000 atoms systems became possible. We performed calculations to derive excess mixing enthalpy and diffusion constant of H20 and exchangeable cations in interlayer region of clay minerals. Using these programs, we performed some multi-phase complex systems, such as smectite with edge-water/aqueous solution (NaCl,CaCl2 etc.). serpentine group minerals-water/solution systems. MD calculations of zeolite surface-ammonium gas system revealed the dynamic process of ammonium molecules at and near channel windows in zeolite structures.Analysis : Combining the data by experiments and molecular simulation results, we analyzed the relation between structural change and adsorption behavior with equilibrium and non-equilibrium processes under various physico-chemical conditions.