尽管熟料矿物的晶体结构与水化活性已经研究了一百多年，但目前实验研究仍然没能阐明熟料矿物性质与电子结构之间的本质联系。为此，本文基于第一性原理计算和分子动力学模拟系统研究了C₃S、C₂S、C₃A和C₄AF四种熟料矿物的晶体结构与水化活性，从原子尺度揭示了熟料矿物本征水化活性与其晶体结构和电子结构的本质联系，探讨了掺杂离子对熟料矿物反应活性的影响机制，同时对熟料水化热-动力学模拟进行了初步探索，主要结论如下：
（1）C₄AF晶体结构中Fe和Al原子的占位机制
C₄AF中Fe和Al的占位遵循“均质层原理”，即Fe和Al原子并不是随意地占据八面体和四面体位置，它们更倾向于在b轴方向上逐层交替地排列而在每一层只包含Fe或Al原子。Fe原子倾向于占据八面体位置，但不能完全占据八面体位置。因为尽管Fe原子完全占据八面体位置时体系的焓最低，但随着温度升高，Fe部分占据八面体位置时体系的熵增加更快，并且在室温时熵对自由能的贡献超过了焓，导致Fe部分占据八面体位置时体系更加稳定。
（2）C₃S、C₂S、C₃A和C₄AF的反应活性位点和水化特征
四种熟料晶体的亲电反应活性位点都位于O离子周围，但C₃S中的亲电反应位点主要位于离子化的O而不是[SiO₄]四面体中的O，表明离子化O具有更高的反应活性。C₂S、C₃S和C₃A的亲核反应活性位点主要位于Ca离子周围，而C₄AF的亲核反应活性位点位于Fe离子周围，这是由于C₄AF的导带底主要由Fe3d能级贡献，而其他三种熟料晶体的导带底主要由Ca3d能级贡献。C₄AF中Al比Fe具有更高的反应活性。不论是Al还是Fe，它们的四配位结构都比六配位结构具有更高的反应活性。
（3）Mn、Zn和Cu离子在熟料矿相中的缺陷形成机制及其对熟料水化活性的影响机制
C₄AF是四种熟料矿相中最有利于固溶Mn、Zn和Cu的矿相，且它们的引入有利于C₄AF晶体的稳定。Ca离子置换是硅酸盐和铝酸盐相中Mn、Zn和Cu杂质离子最有利的缺陷形式。熟料晶体中引入的杂质离子总是倾向于取代与杂质元素本身电子结构最相似的原子，以保持形成的化学键的失配最低。这种化学键的失配程度可以通过键级差异来评价。
对于C₃S、C₂S和C₃A，掺杂离子在能带间隙引入了杂质能级，导致亲核反应活性位点从Ca离子转移到缺陷离子。而对于C₄AF，引入的杂质能级被本身的Fe3d能级所掩盖，因此无法改变C₄AF的亲核反应活性位点。Cu和Zn掺杂在多数情况下导致Ca离子的有效电荷降低，但增加了Fe离子的有效电荷，意味着Cu和Zn掺杂对C₄AF的影响作用与其他三种熟料矿相有所不同。
（4）β-C₂S的溶解热力学和动力学
本文基于经典的ClayFF力场开发了可用于模拟硅酸盐溶解过程的新力场ClinkerFF。β-C₂S的Ca离子溶解反应过程需要经历kink结构、双配体结构、“内球形吸附”和“外球形吸附”四个阶段。计算得到的Ca离子溶解自由能势垒为33.8 kJ/mol，与实验结果32 kJ/mol十分接近。溶解的Ca离子并不能完全自由地运动，而是在表层水（约2~3个水分子层）中不断振荡。Ca离子需要克服表层水的扩散自由能势垒（23 kJ/mol）才能进入溶液深处成为自由移动的离子。动力学模拟计算了Ca离子溶解的每个反应步骤的速率常数、平衡常数和Ca离子活度。计算的Ca离子活度为3.60×10^-5，位于实验结果的区间范围2.44×10^-5 ~ 8.75×10^-5。

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