Preparation and properties study of ternary composite admixture consisting of silica fume, yellow phosphorus slag, and high titanium blast furnace slag
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摘要: 高钛型高炉渣活性较低是限制其在混凝土中单独作为掺合料应用的主要因素之一。为解决这一问题，制备了硅灰-黄磷渣-高钛型高炉渣三元复合掺合料，研究其对水泥胶砂流动度比与活性指数的影响。结合XRD、SEM-EDS微观测试手段，分析了不同掺合料对水泥胶砂性能的影响机理。结果表明：随着硅灰-黄磷渣的掺入，水泥胶砂的流动度比会下降，且硅灰的影响大于黄磷渣。三元复合掺合料的活性指数较高钛型高炉渣单独作为掺合料时得到了明显的提升。高钛型高炉渣：硅灰：黄磷渣占比为5:2:3时7 d和28 d龄期的活性指数最优，分别达到了76.9%和100.2%，满足II级掺合料对活性指数的要求。微观测试表明，硅灰-黄磷渣的掺入能消耗片状Ca(OH)2，生成更多絮凝状胶体C-S(A)-H与针棒状AFt的水化产物，形成相互交错、致密的网状结构，从而增强水泥胶砂的强度。Abstract: The low reactivity of high titanium blast furnace slag is one of the main factors limiting its application as a sole admixture in concrete. To address this issue, a ternary composite admixture consisting of silica fume, yellow phosphorus slag, and high titanium blast furnace slag was prepared, and its effects on the flow ratio and activity index of cement mortar were investigated. Combined with microscopic testing methods such as XRD and SEM-EDS, the influence mechanism of different admixtures on the performance of cement mortar was analyzed. The results indicate that the incorporation of silica fume and yellow phosphorus slag leads to a decrease in the flow ratio of cement mortar, with the silica fume having a greater impact than the yellow phosphorus slag. The activity index of the ternary composite admixture is significantly improved compared to when high titanium blast furnace slag is used alone as an admixture. The optimal activity indices at 7 days and 28 days of curing are achieved when the ratio of high-titanium blast furnace slag: silica fume: yellow phosphorus slag is 5:2:3, reaching 76.9% and 100.2%, respectively, which meets the requirements for the activity index of Grade II admixtures. Microscopic testing reveals that the incorporation of silica fume and yellow phosphorus slag consumes flaky Ca(OH)2, generating more flocculent colloidal C-S(A)-H and needle-like AFt hydrates, which form an interlaced and dense network structure, thereby enhancing the strength of cement mortar.
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图 5 水泥胶砂7 d和28 d龄期的强度与活性指数
(a) 7 d龄期；(b) 28 d龄期
Figure 5. Strength and activity index of cement mortar after 7 days and 28 days of curing
图 6 水泥胶砂7 d和28 d龄期的XRD图谱
(a) 7 d龄期；(b) 28 d龄期
Figure 6. XRD patterns of cement mortar after 7 days and 28 days of curing
图 7 水泥胶砂7 d龄期的微观结构
(a) DB；(b) T；(c) T5S2H3
Figure 7. Microstructure products of cement mortar after 7 days of curing
图 8 水泥胶砂28 d龄期的微观结构和EDS图
(a) DB；(b) T；(c) T5S2H3；(a1) EDS点1；(b1) EDS点2；(c1) EDS点3
Figure 8. Microstructure products and EDS patterns of cement mortar after 28 days of curing
表 1 部分原材料主要化学成分及含量
Table 1. The main chemical compositions and content of some raw materials
% Some raw materials CaO SiO2 TiO2 Al2O3 MgO Fe2O3 SO3 K2O Na2O P2O5 F Other Cement 63.09 18.84 1.15 5.07 2.04 3.52 4.42 0.95 0.34 0.15 0.00 0.43 High titanium blast furnace slag 28.43 23.1 21.79 13.56 6.98 1.87 1.56 0.74 0.83 0.02 0.00 1.12 Silica fume 0.90 95.59 0.00 0.40 0.19 0.26 2.03 0.42 0.09 0.08 0.00 0.04 Yellow phosphorus slag 47.58 36.9 0.22 3.63 2.67 0.65 0.74 0.79 0.55 2.86 3.18 0.23 
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表 2 不同掺合料水泥胶砂样品配合比
Table 2. Mix proportions of cement mortar samples with different admixtures
Number Group Cement/g Admixture/g Standard sand/g Water/mL Admixture type Type of cement mortar High titanium blast furnace slag Silica fume Yellow phosphorus slag A DB 450 0 0 0 1350 225 Admixture-free Comparison mortar B T 315 135 0 0 1350 225 Single-blended admixture Test mortar C T7S1H2 315 94.5 13.5 27 1350 225 Ternary composite admixture D T7S1.5H1.5 315 94.5 20.25 20.25 1350 225 E T7S2H1 315 94.5 27 13.5 1350 225 F T6S1H3 315 81 13.5 40.5 1350 225 G T6S1.5H2.5 315 81 20.25 33.75 1350 225 H T6S2H2 315 81 27 27 1350 225 I T5S1H4 315 67.5 13.5 54 1350 225 J T5S1.5H3.5 315 67.5 20.25 47.25 1350 225 K T5S2H3 315 67.5 27 40.5 1350 225 Note: In the group designations, T represents high-titanium blast furnace slag, S denotes silica fume, and H indicates yellow phosphorus slag. T7S1H2 signifies the proportions of each material in the admixture (e.g., T:S:H = 7:1:2), and other groups follow the same naming convention.
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