Study on the evolution of pore structure of manufactured aggregate concrete under sulfate freeze-thaw based on nuclear magnetic resonance technology
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摘要: 我国西北地区昼夜温差大且存在大量盐渍土环境，因此西北地区的大量建筑无法避免地受到硫酸盐与冻融的耦合作用，使结构内部产生大量孔隙并最终导致其损伤失效。本文采用核磁共振(NMR)对硫酸盐与冻融耦合作用下机制骨料混凝土的孔径分布和孔隙率等孔结构参数进行分析，并探究了硫酸盐浓度、冻融循环次数以及石粉掺量对机制骨料混凝土孔结构的影响规律。结果表明：硫酸盐降低了机制骨料混凝土的冻融劣化速率，随着硫酸盐浓度的增加降低效果更显著；机制骨料混凝土的孔隙率随冻融循环次数增加而增大；机制骨料混凝土孔隙率随着石粉掺量的增多先减小后增大，当石粉掺量控制在10wt%左右时具有最佳的孔结构；硫酸盐冻融的耦合作用下的化学侵蚀产物除了钙矾石和石膏外还存在无水芒硝，但是低温抑制了硫酸盐的化学侵蚀使得物理侵蚀占据主导作用。Abstract: There is a large temperature difference between day and night in the northwest region of China and there is a large amount of saline soil environment. Therefore, a large number of buildings in the northwest region are inevitably subjected to the coupling effect of sulfate and freeze-thaw, resulting in a large number of pores inside the structure and ultimately leading to its damage and failure. Nuclear magnetic resonance (NMR) was used to analyze the pore size distribution, porosity and other pore structure parameters of manufactured aggregate concrete under the coupling effect of sulfate and freeze-thaw, and the influences of sulfate concentration, freeze-thaw cycles and stone powder contents on the pore structure of manufactured aggregate concrete were explored. The results show that sulfate reduces the freeze-thaw deterioration rate of the mechanism aggregate concrete, and the deterioration effect is more significant with the increase of sulfate concentration. The porosity of manufactured aggregate concrete increases with the increase of freeze-thaw cycles. The porosity of mechanism aggregate concrete decreases first and then increases with the increase of stone powder content. It has the best pore structure when the content of stone powder is controlled at about 10wt%. In addition to ettringite and gypsum, there is also anhydrous mirabilite in the chemical erosion products under the coupling effect of sulfate freeze-thaw, but the low temperature inhibits the chemical erosion of sulfate and makes physical erosion dominant.
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图 3 冻融循环作用下机制骨料混凝土性能退化规律
Figure 3. Degradation law of manufactured aggregate concrete performance under freeze-thaw cycles
S1, S2, S3—0.89wt%, 3.7wt% and 7.4wt% mass fraction of sodium sulfate solution, respectively
图 4 机制骨料混凝土150次冻融循环后宏观截面图
Figure 4. Macroscopic cross section of manufactured aggregate concrete after 150 freeze-thaw cycles
图 5 冻融作用下不同石粉掺量的机制骨料混凝土性能退化规律
Figure 5. Performance degradation law of manufactured aggregate concrete with different stone powder contents under freeze-thaw action
图 6 不同冻融循环次数下机制骨料混凝土的横向弛豫时间T2分布
Figure 6. Transverse relaxation time T2 distribution of manufactured aggregate concrete under different freeze-thaw cycles
图 7 机制骨料混凝土孔隙度损失率γ与冻融循环次数关系
Figure 7. Relationship between porosity loss rate γ of manufactured aggregate concrete and freeze-thaw cycles
图 9 机制骨料混凝土的孔喉尺寸随冻融循环次数的变化
Figure 9. Change of pore throat size of manufactured aggregate concrete with the number of freeze-thaw cycle
图 10 不同石粉掺量的机制骨料混凝土在不同冻融循次数下的T2图谱
Figure 10. T2 map of manufactured aggregate concrete with different stone powder contents under different freeze-thaw cycles
图 11 不同石粉掺量机制骨料混凝土试件在200次冻融循环后的γ值
Figure 11. γ values of the manufactured aggregate concrete specimens with different stone powder contents after 200 freeze-thaw cycles
图 12 不同石粉掺量机制骨料混凝土的孔喉尺寸占比随冻融循环次数的变化
Figure 12. The proportion of pore throat size of manufactured aggregate concrete with different stone powder content varies with the number of freeze-thaw cycles
图 13 机制骨料混凝土150次冻融循环后的XRD图谱
Figure 13. XRD patterns of manufactured aggregate concrete after 150 freeze-thaw cycles
图 14 机制骨料混凝土硫酸盐冻融循环前的SEM图像
Figure 14. SEM images of manufactured aggregate concrete before sulfate freeze-thaw cycle
C-S-H—Hydrate calcium silicate
图 15 机制骨料混凝土50次硫酸盐冻融循环后的SEM图像和EDS图谱
Figure 15. SEM images and EDS spectra of manufactured aggregate concrete after 50 sulfate freeze-thaw cycles
图 16 机制骨料混凝土150次硫酸盐冻融循环后的SEM图像和EDS图谱
Figure 16. SEM images and EDS spectra of manufactured aggregate concrete after 150 sulfate freeze-thaw cycles
表 1 机制骨料混凝土配合比(kg/m3)
Table 1. Mix proportion of manufactured aggregate concrete (kg/m3)
Numbering Fly ash Cement Water Powder content Manufactured sand Manufactured gravel Water reducing admixture H 100 320 160 0 765 1015 6 H-5 100 320 160 38 727 1015 6 H-10 100 320 160 77 689 1015 6 H-15 100 320 160 115 651 1015 6 Notes: H—Benchmark group of granite mechanism aggregate concrete; H-5, H-10 and H-15—Mechanism aggregate concrete with 5wt%, 10wt% and 15wt% mass fraction of stone powder, respectively. 
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表 2 机制骨料混凝土反演曲线峰面积
Table 2. Peak area of inversion curve of manufactured aggregate concrete
Type of solution Peak area of inversion curve 0 cycle 50 cycles 100 cycles 150 cycles 200 cycles S1 452.314 561.025 614.135 881.399 1042.084 S2 452.314 566.348 543.383 868.502 976.961 S3 452.314 456.477 525.213 861.833 945.207 Water 452.314 598.368 813.333 1136.531 –
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