Effects of slag powder/metakaolin on the early performance of natural hydraulic lime
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摘要: 天然水硬性石灰(NHL) 在古建筑修缮工程中的应用效果是水泥和传统气硬性石灰所无法比拟的，但早期性能发展偏慢的特性使其应用受限。本文研究了矿粉/偏高岭土改性NHL早期硬化过程中物理力学性能、水化放热特性、物相组成和转变以及微观结构演变过程，系统地评估了矿粉/偏高岭土对NHL基材料早期性能发展的影响。结果表明：矿粉可以改善NHL基砂浆的流动性；矿粉/偏高岭土通过火山灰反应生成水化铝酸钙(C3AH6)、水化碳铝酸钙(C4AĈH11) 以及水化硅酸钙(C—S—H)，可促进NHL基材料凝结硬化、显著提高其抗压及抗折强度。本研究为推动火山灰质材料复合NHL在古建筑修复工程中的应用提供参考。Abstract: Natural Hydraulic Lime (NHL) has exceptional application in restoring ancient buildings compared to Portland cement and conventional air-hardening lime, but the characteristic of slow early performance development limits its fields of application. This paper studied the physical and mechanical properties, hydration exothermic properties, phase composition and transformation, and microstructure evolution of slag powder/metakaolin composite NHL during the early hardening process. The influence of slag powder/metakaolin on the hardening process and performance development of NHL are systematically evaluated. Results show that slag powder can improve the fluidity of NHL-based mortar; slag powder/metakaolin generates calcium aluminate hydrate (C3AH6), calcium carboaluminate hydrate (C4AĈH11) and calcium silicate hydrate (C—S—H) through pozzolanic reaction to promote the setting and hardening of NHL-based materials and significantly improve their compressive and flexural strength. This study provides reference for promoting the application of pozzolanic material composite NHL in the restoration of ancient buildings.
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Key words:
- natural hydraulic lime /
- slag powder /
- metakaolin /
- pozzolanic reaction /
- early performance
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图 2 天然水硬性石灰、矿粉和偏高岭土的粒径分布
Figure 2. Particle size distributions of NHL2, slag powder and metakaolin
图 4 不同养护龄期下NHL基砂浆的抗压强度和抗折强度
Figure 4. Compressive and flexural strengths of NHL-based mortars after various curing ages
图 5 各NHL基浆体的水化放热速率和累积放热量
Figure 5. Hydration heat release rate and total heat release of NHL-based pastes
图 6 不同养护龄期下NHL基硬化浆体的XRD图谱
Figure 6. XRD patterns of NHL-based hardened pastes cured at different ages
图 7 NHL基硬化浆体在7 d和28 d时的热分析
Figure 7. Thermal analysis of NHL-based pastes hydrated for 7 d and 28 d
图 8 不同养护龄期下NHL基硬化浆体中化学结合水含量、氢氧化钙含量和碳酸钙含量
Figure 8. The content of hydrate water, Ca(OH)2 and CaCO3 in NHL-based pastes at different curing ages
图 9 NHL基硬化浆体分别养护至3 d和28 d时的SEM图
Figure 9. SEM images of NHL-based pastes at 3 d and 28 d
表 1 原材料的化学组成
Table 1. Chemical composition of raw materials
原材料 化学组成质量分数/% 堆积密度/(g·cm-3) CaO SiO2 Fe2O3 Al2O3 MgO K2O SO3 Na2O 天然水硬性石灰 80.13 7.90 1.52 2.56 6.18 0.71 0.92 0.08 0.56 矿粉 38.45 35.03 0.63 14.95 9.31 0.38 1.13 0.12 0.92 偏高岭土 0.38 58.86 1.12 38.81 0.21 0.54 0.02 0.06 1.28 
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表 2 天然水硬性NHL基净浆配合比
Table 2. Mix proportions of NHL-based pastes
样品 水灰比 质量组分配合比/% 天然水硬性石灰 矿粉 偏高岭土 NHL 0.55 100 0 0 S10NHL 90 10 0 S20NHL 80 20 0 M10NHL 90 0 10 M20NHL 80 0 20
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表 3 各NHL基浆体的水化放热特征值
Table 3. Characteristic values of the hydration heat for NHL-based pastes
样品 NHL S10NHL S20NHL M10NHL M20NHL 水化加速期出现的时间/h 4.74 4.53 3.20 1.96 1.52 第1个放热峰峰值/(mW·g-1) 26.21 24.90 19.36 19.19 20.95 第2个放热峰出现的时间/h 7.47 10.12 12.39 4.43 2.72 第2个放热峰峰值/(mW·g-1) 0.27 0.35 0.39 0.41 0.46 第3个放热峰出现的时间/h — — — 23.68 8.86 第3个放热峰峰值/(mW·g-1) — — — 0.29 0.43 累积放热量/(J·g-1) 0~1 h 13.71 13.63 9.37 10.81 11.36 0~12 h 23.82 24.97 24.45 24.41 28.23 0~72 h 40.85 56.85 67.99 69.73 83.53 0~168 h 45.74 71.52 82.90 87.39 104.67
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表 4 NHL基硬化浆体28 d时的孔结构参数
Table 4. Pore structure parameter of NHL-based pastes at 28 d
样品 最可几孔径/nm 孔隙率/% 孔径分布/% 小于20 nm 20~100 nm 100~200 nm 大于200 nm NHL 927.21 48.06 2.07 5.27 3.14 89.52 S10NHL 934.28 47.08 2.74 11.20 2.60 83.46 S20NHL 879.53 46.69 5.18 14.61 3.94 76.27 M10NHL 645.17 46.52 2.86 19.47 4.89 72.78 M20NHL 352.83 46.13 5.89 32.25 6.72 55.14
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