Effect of red mud substitution rate on the properties of ternary solid waste geopolymers
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摘要: 为进一步提升赤泥(Red mud，RM)综合利用率，本文将赤泥掺入矿渣-粉煤灰基地聚物中制备了三元全固废地聚物(Ternary solid waste geopolymer，TSWG)材料，研究了不同赤泥取代率对TSWG的力学性能及和易性的影响，结合X射线衍射(XRD)和扫描电子显微镜(SEM)测试，重点探讨了不同取代率赤泥对TSWG性能影响机制，并对TSWG砂浆的成本效益和环境影响进行了评估。结果表明，高掺量的赤泥能够促进铝硅酸盐材料的解聚过程，与基准组(赤泥掺量为0wt%)相比，40wt%赤泥掺量的TSWG的初凝时间缩短了113 min；随着赤泥取代率的增加，提高了地聚物的聚合反应程度，体系中出现了越来越多的硅酸二钙、石英等晶体，破坏地聚物材料的原有结构，导致抗压强度逐渐下降；20wt%赤泥取代率下TSWG28 d抗压强度达34.2 MPa，浆液初始流动度为254 mm，与普通波特兰水泥砂浆相比，具有更好的经济效益和环境效益，以及更方便的制备方法。Abstract: In order to further enhance the comprehensive utilization rate of red mud (RM), ternary solid waste geopolymer (TSWG) materials were prepared by incorporating red mud into slag-fly ash-based polymers. The effects of varying red mud substitution rates on the mechanical properties and workability of these TSWG materials were investigated. Combining X-ray diffraction (XRD) and scanning electron microscopy (SEM) tests, the influence mechanism of red mud with different substitution rates on the properties of TSWG was discussed. Furthermore, the cost-effectiveness and environmental impact of TSWG mortars were evaluated. The results indicate that a high content of red mud can stimulate the depolymerization process of aluminosilicate materials. Compared to the reference group (with 0wt% red mud content), the initial setting time of the TSWG containing 40wt% red mud is shortened by 113 minutes. As the red mud substitution rate increases, the degree of polymerization reaction in the geopolymer is improved, but an increasing number of crystals, such as dicalcium silicate and quartz, emerge in the system, disrupting the original structure of the geopolymer material and resulting in a gradual decrease in compressive strength. At a 20wt% red mud replacement rate, the compressive strength of the TSWG after 28 days reaches 34.2 MPa, and the initial fluidity of the slurry is 254 mm. Compared to ordinary Portland cement mortar, this TSWG exhibits superior economic and environmental benefits, as well as a more convenient preparation method.
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图 3 原材料的SEM图像：(a)赤泥；(b)矿渣；(c)粉煤灰
Figure 3. SEM images of materials：(a)Red mud;(b)Slag;(c)Fly ash
图 4 不同赤泥取代率对TSWG凝结时间的影响
Figure 4. Effect of different red mud substitution rates on the setting time of TSWG
图 5 不同赤泥取代率对TSWG流动度的影响
Figure 5. Effect of different red mud substitution rates on TSWG flowability
图 6 赤泥取代率对TSWG抗压强度的影响
Figure 6. Effect of red mud substitution rate on the compressive strength of TSWG
图 7 赤泥取代率对TSWG抗折强度的影响
Figure 7. Effect of red mud substitution rate on the flexural strength of TSWG
图 8 不同赤泥取代率的TSWG在3 d、7 d时的XRD图谱：(a)3 d；(b)7 d
Figure 8. XRD patterns of TSWG with different red mud substitution rates at 3 and 7 days：(a)3 d;(b)7 d
图 9 不同龄期不同赤泥取代率下TSWG中各种矿物相含量：(a) 3 d；(b) 7 d
Figure 9. Content of various mineral phases in TSWG under different red mud replacement rates at different ages: (a) 3 d; (b) 7 d
图 10 养护3 d时TSWG的SEM图像：(a) 0 wt%RM，养护3 d；(b) 10 wt%RM，养护3 d；(c) 20 wt%RM，养护3 d；(d) 30 wt%RM，养护3 d；(e) 40 wt%RM，养护3 d
Figure 10. SEM images of TSWG curing for 3 d: (a) 0 wt%RM，curing for 3 d; (b) 10 wt%RM，curing for 3 d; (c) 20 wt%RM，curing for 3 d; (d) 30 wt%RM，curing for 3 d; (e) 40 wt%RM，curing for 3 d
图 11 养护7 d时TSWG的SEM图像：(a) 0 wt%RM，养护7 d；(b) 10 wt%RM，养护7 d；(c) 20 wt%RM，养护7 d；(d) 30 wt%RM，养护7 d；(e) 40 wt%RM，养护7 d
Figure 11. SEM images of TSWG curing for 7 d: (a) 0 wt%RM，curing for 7 d; (b) 10 wt%RM，curing for 7 d; (c) 20 wt%RM，curing for 7 d;(d) 30 wt%RM，curing for 7 d; (e) 40 wt%RM，curing for 7 d
表 1 赤泥、矿渣和粉煤灰的化学成分(wt%)
Table 1. Chemical composition of red mud, slag, and fly ash (wt%)
Material Na2O MgO Al2O3 SiO2 P2O5 SO3 K2O CaO TiO2 MnO Fe2O3 ZrO2 Slag 0.47 8.58 15.24 30.54 0.01 2.08 0.45 40.75 0.73 0.58 0.31 0.04 Red mud 2.02 1.46 9.39 22.12 0.23 1.84 0.51 45.43 3.46 0.06 12.79 0.16 Fly ash 0.50 0.48 38.26 48.72 0.41 1.68 1.20 2.99 1.51 0.04 3.76 0.09 
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表 2 三元全固废地聚物(TSWG)浆液配合比
Table 2. Mix ratio of ternary solid waste geopolymer(TSWG) slurry
Group Slag content/wt% Fly ash content/wt% Red mud dosage/wt% Sodium silicate content
(relative to cementitious materials)/wt%Water-glue ratio 0 wt%RM 60 40 0 8.54 0.5 10 wt%RM 60 30 10 20 wt%RM 60 20 20 30 wt%RM 60 10 30 40 wt%RM 60 0 40
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表 3 3 d不同赤泥取代率下TSWG中各种矿物相含量(wt%)
Table 3. Content of various mineral phases in TSWG under different red mud replacement rates for three days (wt%)
Group Mullite Calcite Clinotobermorite Quartz Hematite Calcio 0 wt%RM 44.4 15.8 38 1.8 — — 10 wt%RM 37.5 24.9 33.6 4 — — 20 wt%RM 21.5 26.7 38.1 2.1 3 8.6 30 wt%RM 10.1 39 32.7 4.2 4.4 9.6 40 wt%RM 1.6 33.7 43 0.5 3.9 17.3
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表 4 7 d不同赤泥取代率下TSWG中各种矿物相含量(wt%)
Table 4. Content of various mineral phases in TSWG under different red mud replacement rates for seven days (wt%)
Group Mullite Calcite Clinotobermorite Quartz Hematite Calcio 0 wt%RM 50.5 24.4 19.8 5.3 — — 10 wt%RM 40 26.4 25.1 4.2 — 4.3 20 wt%RM 20.2 27.2 38.2 2.4 7.6 4.4 30 wt%RM 10.9 27.3 45.4 2.5 2.8 11.1 40 wt%RM 3.3 30.4 41.8 0.4 3.6 20.5
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表 5 原材料的成本和二氧化碳当量E
Table 5. Cost of raw materials and E
Materials Cost/(CNY·kg−1) E/(kgCO2·kg−1) Fly ash 0.25 0.027 Instant Na2SiO3 powder 2.50 1.530 Water 0.002 0.0006 Red mud 0.01 0.00518 Slag 0.09 0.143
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表 6 TSWG成本效益和环境影响
Table 6. Cost effectiveness and environmental impact of TSWG
Group Compressive strength/MPa ${C}_{\mathrm{p}} $/(CNY·
MPa−1·m−3)$ {E}_{\mathrm{p}} $/(kgCO2·
MPa−1·m−3)0 wt%RM 44.2 11.72 7.24 10 wt%RM 32.2 15.05 9.84 20 wt%RM 34.2 13.18 9.18 30 wt%RM 26.2 15.91 11.86 40 wt%RM 25.1 15.27 12.26 Control group 30 16.29 13.54 Notes: Control group refers to ordinary Portland cement mortar.
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