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材料导报  2021, Vol. 35 Issue (8): 8034-8041    https://doi.org/10.11896/cldb.20030217
  无机非金属及其复合材料 |
氯离子与硫酸根离子在水化硅酸钙表面竞争吸附的分子动力学研究
郭丽萍1,2,†, 费香鹏1,†, 曹园章1, 薛晓丽1, 丁聪1
1 东南大学材料科学与工程学院,南京 211189
2 江苏省土木工程材料重点实验室,江苏省先进土木工程材料协同创新中心,南京 211189
Molecular Kinetics of Competitive Adsorption of Chloride and Sulphate Ions on C-S-H Surface
GUO Liping1,2,†, FEI Xiangpeng1,†, CAO Yuanzhang1, XUE Xiaoli1, DING Cong1
1 School of Materials Science and Engineering, Southeast University, Nanjing 211189, China
2 Jiangsu Key Laboratory of Construction Materials, Jiangsu Collaborative Innovation Center for Sustainable Civil Engineering Materials & Structures, Nanjing 211189, China
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摘要 水化硅酸钙凝胶(C-S-H)是水泥基材料中主要起粘结作用的胶体,也是发生氯离子和硫酸根离子物理吸附的主要原因。由于实验方法无法直观表现C-S-H物理吸附的过程以及吸附量随时间的变化规律,本研究采用分子动力学模型模拟C-S-H物理吸附氯离子及硫酸根离子的过程,探究吸附过程中氯离子和硫酸根离子之间的交互作用关系。模拟利用配位数并结合等温吸附法计算了3.5%NaCl溶液及3.5%NaCl+3.5%Na2SO4复合溶液中Cl-和SO42-的吸附量。研究发现:物理吸附作用包括离子间的近程库伦(Coulomb)作用以及长程范德华(VDW)作用,SO42-抑制了C-S-H对Cl-的吸附,减弱了C-S-H对Cl-的长程VDW作用,但并没有减少位点对Cl-的吸附量,只是延缓了吸附发生的时间;SiOCa+是Cl-及SO42-的主要吸附位点,SiOH可以吸附少量Cl-,但对SO42-无明显吸附作用,且SiOCa+与SiOH位点存在竞争关系。两种溶液中C-S-H凝胶对Cl-的吸附量相差不大,约为0.06 mmol/g,对SO42-的吸附量约为0.02 mmol/g。由分子动力学计算得出的C-S-H的离子吸附量,与通过测试实验合成的C-S-H及水泥浆体中的C-S-H的离子吸附量相符,由此可以证明分子动力学模拟可准确、可靠地表征侵蚀离子在水泥基材料内的复杂交互作用。
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郭丽萍
费香鹏
曹园章
薛晓丽
丁聪
关键词:  C-S-H吸附  动力学模型  氯离子  硫酸根离子  物理吸附    
Abstract: Hydrated calcium silicate (C-S-H) gel is the main bonding colloid in cement-based materials, and it is also the main source of physical adsorption of chloride and sulphate ions. Due to that the process of C-S-H physical adsorption and the change of the adsorption amount with time cannot be reflected directly by experimental methods. In this paper, a molecular dynamics model was used to simulate the process of C-S-H phy-sical adsorption of chloride and sulphate ions. The interaction between chloride and sulfate ions during the adsorption process was investigated. The coordination number and the isothermal adsorption method were used to calculate the adsorption amount of Cl- and SO42- in 3.5% NaCl and 3.5% NaCl + 3.5% Na2SO4 solution. The research results show that the adsorption capacity of C-S-H gel for Cl- in the two solutions is almost the same, about 0.1 mmol/g, and the adsorption capacity for SO42- is about 0.04 mmol/g in compound salts solution .The physical adsorption includes short-range Coulomb interaction between ions and long-range van der Waals (VDW) interaction. The adsorption of C-S-H to Cl- is delayed and the long-range VDW effect of C-S-H on Cl- is weakened by SO42-. However, the presence of SO42- doesn't reduce the amount of Cl- adsorption at the site, it only delays the time of adsorption. SiOCa+ is the main adsorption site for Cl- and SO42-. The SiOH sites which have no obvious adsorption effect on SO42- have ability to adsorb Cl-, but the amount is negligible. Moreover, there is also a competitive relationship between SiOCa+ and SiOH sites. The ions adsorption of C-S-H calculated by molecular dynamic is consistent with the ion adsorption of the C-S-H synthesized by experimental methods or the C-S-H in cement slurry. It can be proved that molecular dynamics simulations can be used to accurately and reliably characterize the complex interactions of aggressive ions in cement-based materials.
Key words:  C-S-H adsorption    kinetics model    chloride ions    sulphate ions    physical adsorption
               出版日期:  2021-04-25      发布日期:  2021-05-10
ZTFLH:  TU528  
基金资助: 国家自然科学基金(51778133);国家重点研发计划(973计划,2015CB655102)
作者简介:  郭丽萍,博士,教授,博导。主要研究方向有超高延性水泥基复合材料、混凝土耐久性、固废物再生自清洁无机涂层。主持国家自然科学基金项目(51778133) 和国家973项目“严酷环境下混凝土材料与结构长寿命的基础研究”(项目编号:2015CB655102)第二课题第一子题研究等。
费香鹏,东南大学硕士研究生,主要从事混凝土耐久性的研究,参与国家973项目“严酷环境下混凝土材料与结构长寿命的基础研究”(项目编号:2015CB655102)的研究。
引用本文:    
郭丽萍, 费香鹏, 曹园章, 薛晓丽, 丁聪. 氯离子与硫酸根离子在水化硅酸钙表面竞争吸附的分子动力学研究[J]. 材料导报, 2021, 35(8): 8034-8041.
GUO Liping, FEI Xiangpeng, CAO Yuanzhang, XUE Xiaoli, DING Cong. Molecular Kinetics of Competitive Adsorption of Chloride and Sulphate Ions on C-S-H Surface. Materials Reports, 2021, 35(8): 8034-8041.
链接本文:  
http://www.mater-rep.com/CN/10.11896/cldb.20030217  或          http://www.mater-rep.com/CN/Y2021/V35/I8/8034
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