工程科学学报，第37卷，第8期：976983,2015年8月 Chinese Journal of Engineering,Vol.37,No.8:976-983,August 2015 DOI:10.13374/j.issn2095-9389.2015.08.002:http://journals.ustb.edu.cn 碳酸盐溶液中富水充填材料的腐蚀及劣化机理 高 萌，刘娟红四，吴爱祥 北京科技大学土木与环境工程学院，北京100083 ☒通信作者，Email:juanhongl966@hotmail.com 摘要为了研究碳酸根离子对富水充填材料的影响，通过强度检测、扫描电镜观察、X射线衍射分析和红外光谱测试，分析 富水充填材料在碳酸钠溶液中浸泡后的宏观及微观结构变化，并对其腐蚀及劣化机理进行探讨，富水充填材料在质量分数 为10%的碳酸钠溶液中浸泡后，抗压强度随浸泡时间延长大幅度降低，浸泡90d后抗压强度比标养28d抗压强度降低 72.5%,浸泡28d后出现泥化现象.X射线衍射图谱显示，富水充填材料在质量分数为10%的碳酸钠溶液中浸泡后有碳硫硅 钙石生成，且随浸泡时间延长碳硫硅钙石的生成量增大.红外光谱结果未发现O。]存在，证实在碳酸钠溶液中富水充填材 料硬化体中钙矾石急剧减少，转变为烂泥状的碳硫硅钙石：碳硫硅钙石作为无胶结力物质，会对富水充填材料硬化体造成严 重破坏，表明碳酸盐溶液对富水充填材料具有腐蚀作用 关键词充填材料：疏铝酸盐：碳酸盐；腐蚀：劣化 分类号TD823.7 Corrosion and deterioration mechanism of water-rich filling materials in carbonate solutions GAO Meng,LIU Juan-hong,WU Ai-xiang School of Civil and Environmental Engineering,University of Science and Technology Beijing,Beijing 100083,China Corresponding author,E-mail:juanhong1966@hotmail.com ABSTRACT In order to research the impact of carbonate ions on water-rich filling materials,strength testing,scanning electron microscopy,X-ray diffraction analysis and IR spectrum testing were used to analyze the macro-and micro-structural change and the corrosion and deterioration mechanism of the materials in sodium carbonate solutions.It is found that the compressive strength of the materials in a sodium carbonate solution whose mass fraction is 10%decreases significantly with increasing soaking time.When the soak age is 90 d,the compressive strength of the materials decreases by 72.5%compared with standard curing for 28 d.After soaking for 28d the specimen surface is muddy.XRD patterns show that after soaking in a sodium carbonate solution whose mass fraction is 10%,thaumasite generates in the materials.With increasing soaking time the amount of thaumasite increases.Infrared spectroscopy results show that there does not exist [AlOJ.This confirms that ettringite in the materials soaking in the sodium carbonate solution drastically reduces and transforms into pulpy thaumasite.As non-cemented materials,thaumasite will cause serious damage to the hardening body of the materials.This shows that the carbonate solution has corrosive action on water-rich filling materials. KEY WORDS filling materials:sulphoaluminates:carbonates;corrosion:deterioration 为了解决地下大量采空区造成的部分矿井无煤可 充填开采的核心是充填材料，充填开采所用胶凝材料 采的问题，同时减轻资源开采对地面的损坏程度，必须 主要包括高水固结材料、赤泥胶结材料、矿渣胶结材 采取保护性开采措施，其中最为有效的是充填开采. 料、全砂土固结材料、矿山尾砂固结材料等四.充填 收稿日期：2014-2-10 基金项目：国家自然科学基金资助项目(51374030：“十二五”国家科技支撑计划资助项目(2012BAB08B02)工程科学学报，第 37 卷，第 8 期: 976--983，2015 年 8 月 Chinese Journal of Engineering，Vol． 37，No． 8: 976--983，August 2015 DOI: 10． 13374 /j． issn2095--9389． 2015． 08． 002; http: / /journals． ustb． edu． cn 碳酸盐溶液中富水充填材料的腐蚀及劣化机理 高 萌，刘娟红，吴爱祥 北京科技大学土木与环境工程学院，北京 100083  通信作者，E-mail: juanhong1966@ hotmail． com 摘 要 为了研究碳酸根离子对富水充填材料的影响，通过强度检测、扫描电镜观察、X 射线衍射分析和红外光谱测试，分析 富水充填材料在碳酸钠溶液中浸泡后的宏观及微观结构变化，并对其腐蚀及劣化机理进行探讨． 富水充填材料在质量分数 为 10% 的碳酸钠溶液中浸泡后，抗压强度随浸泡时间延长大幅度降低，浸泡 90 d 后抗压强度比标养 28 d 抗压强度降低 72. 5% ，浸泡 28 d 后出现泥化现象． X 射线衍射图谱显示，富水充填材料在质量分数为 10% 的碳酸钠溶液中浸泡后有碳硫硅 钙石生成，且随浸泡时间延长碳硫硅钙石的生成量增大． 红外光谱结果未发现［AlO6］存在，证实在碳酸钠溶液中富水充填材 料硬化体中钙矾石急剧减少，转变为烂泥状的碳硫硅钙石; 碳硫硅钙石作为无胶结力物质，会对富水充填材料硬化体造成严 重破坏，表明碳酸盐溶液对富水充填材料具有腐蚀作用． 关键词 充填材料; 硫铝酸盐; 碳酸盐; 腐蚀; 劣化 分类号 TD823. 7 Corrosion and deterioration mechanism of water-rich filling materials in carbonate solutions GAO Meng，LIU Juan-hong ，WU Ai-xiang School of Civil and Environmental Engineering，University of Science and Technology Beijing，Beijing 100083，China  Corresponding author，E-mail: juanhong1966@ hotmail． com ABSTＲACT In order to research the impact of carbonate ions on water-rich filling materials，strength testing，scanning electron microscopy，X-ray diffraction analysis and IＲ spectrum testing were used to analyze the macro- and micro-structural change and the corrosion and deterioration mechanism of the materials in sodium carbonate solutions． It is found that the compressive strength of the materials in a sodium carbonate solution whose mass fraction is 10% decreases significantly with increasing soaking time． When the soak age is 90 d，the compressive strength of the materials decreases by 72. 5% compared with standard curing for 28 d． After soaking for 28 d the specimen surface is muddy． XＲD patterns show that after soaking in a sodium carbonate solution whose mass fraction is 10% ，thaumasite generates in the materials． With increasing soaking time the amount of thaumasite increases． Infrared spectroscopy results show that there does not exist ［AlO6］． This confirms that ettringite in the materials soaking in the sodium carbonate solution drastically reduces and transforms into pulpy thaumasite． As non-cemented materials，thaumasite will cause serious damage to the hardening body of the materials． This shows that the carbonate solution has corrosive action on water-rich filling materials． KEY WOＲDS filling materials; sulphoaluminates; carbonates; corrosion; deterioration 收稿日期: 2014--12--10 基金项目: 国家自然科学基金资助项目( 51374036) ; “十二五”国家科技支撑计划资助项目( 2012BAB08B02) 为了解决地下大量采空区造成的部分矿井无煤可 采的问题，同时减轻资源开采对地面的损坏程度，必须 采取保护性开采措施，其中最为有效的是充填开采． 充填开采的核心是充填材料，充填开采所用胶凝材料 主要包括高水固结材料、赤泥胶结材料、矿渣胶结材 料、全砂土固结材料、矿山尾砂固结材料等［1 － 2］． 充填