Dissolution characteristics and mechanical properties of limestone with different mineral composition contents eroded by acid chemical solution
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摘要: 以灰岩、方解石为研究对象,配置不同酸性水化学溶液,对酸性水化学溶液侵蚀下灰岩、方解石试件进行溶解动力学试验及力学试验,获得水化学溶液侵蚀过程中灰岩、方解石试件溶解行为及抗压强度的变化规律,研究不同矿物成分含量对灰岩溶解特性及强度损伤特性的影响。试验结果表明：①浸泡灰岩、方解石试件水化学溶液中离子浓度随着浸泡时间的增加呈幂函数上升趋势,试件在酸性水化学溶液中的溶解过程分为酸岩反应、水解反应两个阶段；②在酸性水化学溶液侵蚀过程中,灰岩试件酸岩反应速率小于方解石试件,但其水解反应速率大于方解石试件,最终灰岩溶蚀破坏程度大于方解石；③酸性水化学溶液侵蚀下灰岩、方解石试件的力学损伤规律与其溶解动力学行为之间呈现良好的相关性,灰岩、方解石试件单轴抗压强度随着浸泡时间的增加呈幂函数下降趋势,酸岩反应阶段,灰岩强度损伤程度低于方解石,水解反应阶段,其强度损伤程度高于方解石。Abstract: In order to investigate the effects of different mineral composition contents on the dissolution characteristics and strength damage characteristics of limestone, the dissolution kinetics and mechanical tests of limestone and calcite specimens eroded by acidic aqueous chemical solution are carried out to obtain the variation laws of dissolution characteristics and strength damage characteristics of limestone and calcite specimens during the erosion process of acidic aqueous chemical solution. The test results show that: (1) The ion concentration in the chemical solution exhibits an increasing of power function trend with the increase of immersion time, and the dissolution process of limestone and calcite specimens in acidic aqueous chemical solution is divided into acid rock reaction and hydrolysis reaction. (2) In the erosion process of acidic aqueous chemical solution, the acid rock reaction rate of limestone specimens is lower than that of calcite ones, while the hydrolysis reaction rate is higher than that of calcite ones, and finally the limestone dissolution damage degree is greater than that of calcite specimens. (3) The mechanical damage laws of limestone and calcite specimens eroded by acidic chemical solution show a good correlation with their dissolution kinetics behavior. The uniaxial compressive strength of limestone and calcite specimens shows a decreasing trend of power function with the increase of immersion time. The strength damage degree of limestone is lower than that of calcite at the acid rock reaction stage, while the strength damage degree of limestone is higher than that of calcite at the hydrolysis reaction stage.
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Keywords:
- chemical corrosion /
- mineral composition /
- dissolution kinetics /
- compressive strength /
- limestone
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图 2 水化学溶液pH值与侵蚀时间关系图
Figure 2. Relationship between pH value and erosion time for specimens eroded by chemical solution
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图 3 水化学溶液Ca2+浓度与侵蚀时间关系图
Figure 3. Relationship between concentration of Ca2+ and erosion time for specimens eroded by chemical solution
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图 4 灰岩、方解石试件在pH=4时NaCl溶液中离子浓度与侵蚀时间关系
Figure 4. Relationship between ion concentration and erosion time for different rock specimens eroded by chemical solution
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图 6 水化学溶液侵蚀下试件抗压强度与侵蚀时间关系
Figure 6. Relationship between uniaxial compressive strength and erosion time for specimens eroded by chemical solution
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图 7 酸性水化学侵蚀下试件抗压强度与溶液离子浓度关系
Figure 7. Relationship between ion concentration and compressive strength for specimens eroded by chemical solution
表 1 岩石试样矿物成分及含量
Table 1 Mineral composition and content of rock samples
(%) 岩石种类 方解石 白云石 其他 灰岩 75.1 22.6 2.3 方解石 97.2 — 2.8 
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表 2 水化学溶液的配制
Table 2 Artificially made chemical solutions for tests
名称 浓度/(mol·L-1) pH值 蒸馏水 — 6.6 NaCl溶液 0.01 4,6 CaCl2溶液 0.01 6
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表 3 试件基本物理参数
Table 3 Basic physical parameters of specimens
岩石种类 质量/g 密度/(g·cm-3) 相对质量密度 含水率/% 孔隙度/% 纵波波速/(m·s-1) 灰岩 511.571 2.717 2.727 0.021 0.35 5181 方解石 510.123 2.680 2.746 0.008 2.40 5067
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表 4 浸泡灰岩试件不同时间下水化学溶液Ca2+、Mg2+浓度
Table 4 Concentrations of Ca2+ and Mg2+ in chemical solution of soaked limestone specimens at different time
离子种类 浸泡时长/d 离子浓度/(mmol·L-1) pH=4NaCl pH=6NaCl pH=6CaCl2 蒸馏水 Ca2+ 10 0.2767 0.2029 0.0516 0.2011 20 0.5065 0.3628 0.0573 0.3240 30 0.6673 0.5227 0.0619 0.3978 60 0.9163 0.7871 0.0690 0.6447 90 0.9701 0.8485 0.0757 0.7348 120 1.0159 0.8839 0.0765 0.7886 150 1.0592 0.9260 0.0782 0.8455 Mg2+ 10 0.0553 0.0369 0.0017 0.0321 20 0.0892 0.0594 0.0018 0.0534 30 0.1015 0.0813 0.0018 0.0640 60 0.1391 0.1194 0.0021 0.1038 90 0.1472 0.1312 0.0024 0.1173 120 0.1566 0.1369 0.0024 0.1243 150 0.1682 0.1401 0.0024 0.1361
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表 5 浸泡方解石试件不同时间下水化学溶液Ca2+浓度
Table 5 Concentrations of Ca2+ in chemical solution of soaked calcite specimens at different time
离子种类 浸泡时长/d 离子浓度/(mmol·L-1) pH=4NaCl pH=6NaCl pH=6CaCl2 蒸馏水 Ca2+ 10 0.3035 0.2275 0.0541 0.2460 20 0.5273 0.4612 0.0586 0.2767 30 0.6210 0.5534 0.0610 0.4243 60 0.8148 0.7133 0.0649 0.5165 90 0.8608 0.7440 0.0664 0.6272 120 0.8983 0.7694 0.0679 0.6456 150 0.9169 0.7934 0.0686 0.7071 注： 方解石试件矿物成分中不含白云石,溶解过程中未产生Mg2+。
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表 6 试件在不同水化学溶液中溶解速率常数及相关系数
Table 6 Dissolution rate constants and correlation coefficients of specimens eroded by chemical solutions
水化学溶液 灰岩 方解石 a R2 a R2 pH=4 NaCl 1.1442 0.9960 0.7308 0.9931 pH=6 NaCl 0.9115 0.9929 0.5703 0.9719 pH=6 CaCl2 0.2619 0.9548 0.0503 0.9909 蒸馏水 0.7972 0.9968 0.4405 0.9675
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表 7 不同水化学溶液侵蚀不同时间下试件抗压强度
Table 7 Uniaxial compressive strengths of specimens eroded by different chemical solutions at different time
水化学溶液 抗压强度/MPa 灰岩 方解石 30 d 90 d 150 d 30 d 90 d 150 d pH=4NaCl 115.179 105.558 96.197 71.766 65.988 63.234 pH=6NaCl 118.298 109.685 101.486 72.371 68.317 65.942 pH=6CaCl2 120.425 113.333 106.683 75.343 73.580 72.756 蒸馏水 119.437 112.985 104.194 76.974 72.576 71.325
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表 8 水化学溶液侵蚀下试件强度损伤相关系数
Table 8 Correlation coefficients of strength damage of specimens under chemical solution erosion
水化学溶液 灰岩 方解石 b R2 b R2 pH=4NaCl 0.8649 0.9987 0.8275 0.9887 pH=6NaCl 0.6890 0.9943 0.6874 0.9785 pH=6CaCl2 0.5275 0.9858 0.3312 0.9461 蒸馏水 0.5859 0.9768 0.3777 0.9550
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