Experimental and mechanism exploration of alkali-silica reaction inhibition by microbial mineralization
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摘要: 碱-硅酸反应(ASR)是混凝土中碱性孔隙溶液和骨料中反应性非结晶SiO2之间的反应，会导致混凝土膨胀和开裂及力学性能下降。本文基于巴氏芽孢杆菌微生物诱导碳酸钙沉淀(MICP)技术，采用不同处理次数及方式(表面处理潜在活性骨料及其制成的砂浆棒)，综合评价MICP对ASR的抑制规律与机制。结果表明：MICP处理可以在骨料及砂浆棒表面形成具有黏附作用的致密CaCO3层，从而阻止碱性离子和水的入侵，且抑制效果随处理次数的增多而变强；与对照组相比，处理砂浆棒时，力学性能最大提升了13.8%，膨胀率下降了35%；处理骨料时，由于表面CaCO3层可同时阻隔孔隙溶液中已有及外部入侵的碱性离子与水分，其力学性能提升了25.3%，膨胀率下降了59.6%，具有更好的抑制效果。微观结构和成分分析表明，经MICP处理后骨料表面Si和Na原子比例分别下降了69.6%和88.9%，表明ASR凝胶显著减少。Abstract: Alkali-silica reaction (ASR) is a reaction between alkaline pore solutions in concrete and reactive non-crystalline SiO2 in aggregates, which leads to expansion and cracking of the concrete, and degradation of mechanical properties. In this study, based on the microbial induced calcium carbonate precipitation (MICP) technique of Bacillus pasteurus, various treatment frequencies and methods, including surface treatments of potentially active aggregates and mortar bars made by them, to comprehensively evaluate the inhibition law and mechanism of MICP on ASR. The results showed that the MICP treatment could form a dense CaCO3 layer with adhesive effect on the surface of aggregates and mortar bars, thus preventing the intrusion of alkaline ions and water, and the inhibiting effect became stronger with the treatment numbers. Compared with the control group, the maximum increase in mechanical properties of 13.8%, and the decrease in expansion rate of 35% were observed when the mortar bars were treated. When treating the aggregate, the mechanical properties were improved by 25.3% and the expansion rate was reduced by 59.6% with a better inhibition effect, as the surface CaCO3 layer could simultaneously block the alkaline ions and water existing in the pore solution and invading from outside. Microstructural and compositional analyses showed that the proportion of Si and Na atoms on the aggregate surface decreased by 69.6% and 88.9%, respectively, after treatment, indicating a significant reduction in the ASR gel.
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Key words:
- MICP /
- alkali-silica reaction /
- Jinping sandstone /
- mechanical properties /
- expansion rate
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图 1 试件制作、测试和分析步骤示意图
Figure 1. Schematic diagram of specimen preparing, testing and analysis procedure
图 2 微生物诱导碳酸钙沉淀(MICP)处理后砂浆棒表面的CaCO3沉积
Figure 2. CaCO3 deposition on the surface of mortar bars after microbial induced calcium carbonate precipitation (MICP) treatment
图 3 砂浆棒在MICP处理后的膨胀率及力学性能变化
Figure 3. Variations in expansion rate and mechanical properties of mortar bars after MICP treatment
图 4 MICP处理后骨料(锦屏砂岩)表面的CaCO3沉积
Figure 4. CaCO3 deposition on the aggregate (Jinping sandstone) surface after MICP treatment
图 5 使用MICP处理骨料的砂浆棒膨胀率及力学性能变化
Figure 5. Variations in expansion rate and mechanical properties of mortar bars with MICP-treated aggregates
图 6 不同处理方式及处理程度下MICP抑制碱-硅酸反应(ASR)的规律
R2—Coefficient of determination
Figure 6. Rules of alkali-silica reaction (ASR) inhibition by MICP under different treatment methods and degrees
图 7 碱激发28天时骨料表面SEM图像：(a)对照组；(b)骨料处理6次
Figure 7. SEM images of aggregate surface at 28 days of alkali activation: (a) Control group; (b) Aggregate treated 6 times
图 8 碱激发28天骨料表面XRD图谱：(a)对照组；(b)骨料处理6次
Figure 8. XRD patterns of aggregate surface at 28 days of alkali activation: (a) Control group; (b) Aggregate treated 6 times
图 9 MICP抑制ASR机制示意图：(a)对照组；(b)砂浆处理 (B方式)；(c)骨料处理 (A方式)
Figure 9. Schematic diagram of the mechanism of ASR inhibition by MICP: (a) Control group; (b) Mortar treatment (Method B); (c) Aggregate treatment (Method A)
表 1 骨料粒度级配表
Table 1. Grain size distribution of aggregates used
Size/mm 2.5-5 1.25-2.5 0.63-1.25 0.315-0.63 0.16-0.315 Mass/wt% 10 25 25 25 15 
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表 2 试件砂浆配合比
Table 2. Design of mortar proportion for specimen
Cement/g Water/g Aggregate/g
(Before MICP)Size/(mm3) Purpose 450 225 1350 40×40×160 Measuring mechanical properties 400 188 900 25.4×25.4×285 Measuring expansion rate Notes: The total CaCO3 deposition on the aggregate surface increased by approximately 1.9% per two treatments；MICP—Microbial induced calcium carbonate precipitation.
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表 3 试件参数
Table 3. Details of specimens
No. Number of processes MICP processing objects Processing time point Curing method Content of analysis Control 0 — — 80℃ in 1 mol/L
NaOH solutionMechanical properties,
expansion rate,
microanalysisB1 1 Mortar bars made from original
reactive aggregatesAfter pouring B2 2 B3 3 A2 2 Reactive aggregates Before pouring A4 4 A6 6 Notes: Control is the untreated standard group; B represents the MICP treatment of mortar bar surface; A represents the treatment of aggregate surface, and the number of processes represents the treatment times.
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表 4 锦屏砂岩的化学成分(wt%)
Table 4. Chemical composition of Jinping sandstone (wt%)
Materials SiO2 Al2O3 CaO Fe2O3 K2O Na2O Others Jinping sandstone 63.62 16.55 7.93 4.41 2.81 2.49 2.19
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表 5 CaCO3在砂浆棒表面的质量比
Table 5. Mass ratio of CaCO3 on the surface of mortar bar
No. Processing times S0/g S1/g S2/g S/% B1 1 601.86 617.45 15.59 2.59 B2 2 603.52 632.67 29.15 4.83 B3 3 601.31 644.84 43.53 7.24 Notes: S0—Initial mass of specimen; S1—Mass of specimen after treatment; S2—Calculated content of CaCO3; S—Percentage of CaCO3 deposits in mortar bars. The data in the table are the average values obtained from three parallel specimens.
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表 6 骨料表面CaCO3质量占比
Table 6. Mass proportion of CaCO3 on the aggregate surface
No. Processing times M0/g M1/g M2/g M/% A2 2 9.89 10.08 0.19 1.94 A4 4 9.70 10.06 0.36 3.80 A6 6 9.58 10.13 0.55 5.74 Notes: M0—Mass of aggregate after acid washing; M1—Mass of aggregate after MICP treatment; M2—Calculated content of CaCO3; M—Percentage of CaCO3 deposited in the aggregate. The data in the table are the average values obtained from three parallel samples.
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表 7 碱激发28天时骨料表面EDS元素的原子比例
Table 7. Atomic proportion of EDS elements on aggregate surface at 28 days of alkali activation
No. K/at% C/at% O/at% Na/at% Al/at% Si/at% Au/at% Ca/at% Control 1.52 — 44.34 9.35 3.24 34.49 3.03 4.03 A2 — 10.74 37.01 5.79 1.91 27.21 0.71 15.63 A4 — 13.54 42.93 3.04 0.97 18.24 1.99 19.29 A6 — 18.70 44.46 1.04 0.63 10.48 1.17 23.52
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