Research on the preparation and hydration mechanism of the high-titanium blast furnace slag based cementitious material with low carbon emission
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摘要: 为实现混凝土中胶凝材料的低碳化，并促进高钛型高炉渣的进一步高效、高附加值利用，采用高钛型高炉渣-锂渣-硅灰复合掺合料替代部分水泥制备高钛型高炉渣基低碳胶凝材料，探讨复合掺合料配比、物理和化学激发方式对该低碳胶凝材料物理和力学性能的影响规律，并分析其水化机理。研究表明：机械活化和化学激发均可提高高钛型高炉渣基低碳胶凝材料的早期和后期强度，当m(水泥)：m(高钛型高炉渣粉)：m(锂渣粉)：m(硅灰)：m(Ca(OH)2)=70:21:6:3:2时，低碳胶凝材料7 d和28 d抗压强度比可分别达到82.01%和97.21%；机械活化可使机械能转化为表面能，增强锂渣粉的水化活性，同时，Ca(OH)2的碱激发协同锂渣粉的硫酸盐激发，进一步促进了复合掺合料的二次水化反应。Abstract: To achieve a lower carbon footprint for cementitious materials in concrete and promote the further efficient and high-value utilization of high-titanium blast furnace slag (HTBFS), a novel low-carbon HTBFS-based cementitious material was developed by using a composite mineral admixture of HTBFS powder (HTBFSP), lithium slag powder (LSP), and silica fume (SF) as a partial replacement for cement. Effects of mix proportions, along with mechanical and chemical activation methods on the physical and mechanical properties of this low-carbon HTBFS-based cementitious material were investigated, and its hydration mechanism was analyzed. The results showed that both mechanical activation and chemical excitation could increase the early and later-age strength of the low-carbon HTBFS-based cementitious material. At a mix proportion of 70% cement, 21% HTBFSP, 6% LSP, 3% SF, and 2% Ca(OH)2, the compressive strength ratios reached 82.01% at 7 days and 97.21% at 28 days. The hydration reactivity of LSP was enhanced through the mechanical activation, a process that converted mechanical energy into surface energy. Meanwhile, a synergistic effect was achieved between the alkaline activation from Ca(OH)2 and the sulfate activation from the LSP, which further stimulated the secondary hydration reaction of the composite mineral admixture.
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图 1 HTBFSP、LSP和SF的X射线衍射（XRD）分析结果
Figure 1. The results from the analysis of X-ray diffraction (XRD) pattern
（a）HTBFSP；（b）LSP；（c）SF
图 2 HTBFSP、LSP和SF的形貌
Figure 2. Appearance and microstructures of the HTBFSP, LSP and SF
（a1）（a2）HTBFSP；（b1）（b2）LSP；（c1）（c2）SF
图 4 LSP与SF的质量比对胶砂流动性和抗压强度的影响
Figure 4. Effects of the mass ratio of LSP to SF on the flowability and compressive strength of the mortars
图 5 不同球磨时间LSP的粒径分布
Figure 5. The particle size distribution of the LSPs with different ball-milling time
图 7 机械活化和化学激发对胶砂流动性和抗压强度的影响
Figure 7. Effects of the mechanical and chemical activation on the flowability and compressive strength of the mortars
图 8 不同配比胶砂试件XRD分析结果
Figure 8. The XRD analysis of different mortar samples
（a）7 d；（b）28 d
图 9 不同配比胶砂试件在7 d龄期时的微观形貌分析
Figure 9. Microstructure analysis of different mortar samples at 7 days
（a1）（a2）C0；（b1）（b2）L20S10；（c1）（c2）ML20S10；(d1）（d2) ML20S10Ca2
图 10 不同配比胶砂试件在28 d龄期时的微观形貌分析
Figure 10. Microstructure analysis of different mortar samples at 28 days
（a1）（a2）C0；（b1）（b2）L20S10；（c1）（c2）ML20S10；（d1）（d2）ML20S10Ca2
图 11 高钛型高炉渣基复合胶凝材料的水化机理示意
Figure 11. Hydration mechanism of HTBFS based composite binders
表 1 P·O 42.5水泥的主要物理力学性能
Table 1. The basic physical and mechanical properties of the P·O 42.5 cement
Properties Specific area /(m2·kg−1) Water requirement for
normal consistency/%Setting time/min Flexural strength /MPa Compressive strength /MPa Initial Final 3 d 28 d 3 d 28 d Testing value 410.76 27.6 292 410 5.08 8.89 26.10 45.77 
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表 2 HTBFSP、LSP和SF的主要物理力学性能
Table 2. The basic physical and mechanical properties of the HTBFSP, LSP and SF
Raw materials Density/(g·cm−3) Specific area/(m2·kg−1) Fluidity ratio/% Activity index/% 7 d 28 d HTBFSP 3.22 380.44 113.65 51.18 64.13 LSP 2.39 239.35 95.78 64.03 96.51 SF 2.21 79.37 106.15 110.48
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表 3 HTBFSP、LSP和SF的主要化学组成
Table 3. The main chemical compositions of the HTBFSP, LSP and SF
% Raw materials SiO2 Al2O3 Fe2O3 CaO SO3 MgO Na2O K2O MnO TiO2 Loss HTBFSP 23.10 13.56 1.87 28.43 1.56 6.98 0.83 0.74 1.87 21.80 7.55 LSP 46.49 20.61 1.66 10.32 11.65 0.39 0.22 0.58 0.18 7.35 SF 95.59 0.40 0.26 0.90 2.03 0.19 0.09 0.42 3.34
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表 4 试验配合比设计
Table 4. Mix proportions of mortar samples
% No. Cement HTBFSP LSP SF Ca(OH)2 Water Sand C0 1.00 0 0 0 0 0.50 3.00 L30S0 0.70 0.21 0.09 0 0 0.50 3.00 L20S10 0.70 0.21 0.06 0.03 0 0.50 3.00 L10S20 0.70 0.21 0.03 0.06 0 0.50 3.00 L0S30 0.70 0.21 0 0.09 0 0.50 3.00 ML20S10 0.70 0.21 0.06* 0.03 0 0.50 3.00 ML20S10Ca2 0.70 0.21 0.06* 0.03 0.02 0.50 3.00 ML20S10Ca4 0.70 0.21 0.06* 0.03 0.04 0.50 3.00 Note: An asterisk (*) denotes LSP prepared via mechanical activation.
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