Analysis of the strength mechanism of lime-base activated titanium gypsum composite cementitious material
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摘要: 以钛石膏、脱硫石膏和钛矿渣三种钛工业固体废弃物为主要原料，石灰作碱性激发剂制作钛石膏复合胶凝材料。采用正交试验，结合XRD、SEM等分析测试方法，对石灰碱激发钛石膏复合胶凝材料强度机理进行分析。结果表明：钛石膏的掺量在42.9%～50.3%，可以制作出强度达到《建筑石膏》（GB/T 9776—2008）2.0强度等级的钛石膏复合胶凝材料。石灰碱激发钛石膏复合胶凝材料的前期强度主要来自钛石膏和脱硫石膏水化产生的二水石膏，后期强度主要来自水泥、石灰和石膏进一步反应产生钙矾石。其水化机理为：第一，CaSO4·0.5H2O水化产生CaSO4·2H2O；第二，水泥中的3CaO·Al2O3与CaSO4·2H2O反应生成钙矾石，石灰与水反应产生Ca(OH)2，结合CaSO4·2H2O和CaO·Al2O3反应产生钙矾石，进一步提升钛石膏复合胶凝材料的强度。Abstract: Titanium gypsum, flue gas desulphurization gypsum and titanium slag are used as main raw materials of titanium industrial solid wastes, and lime is used as an alkaline activator to make titanium gypsum composite cementing materials. Orthogonal experiments, combined with XRD, SEM and other analytical testing methods, are used to analyze the strength mechanism of lime-base activated titanium gypsum composite cementing materials. The experimental results show that the content of titanium gypsum is between 42.9% and 50.3%, which can produce a titanium gypsum composite cementing material with strength of 2.0 in “Building Gypsum” (GB/T 9776—2008). The initial strength contribution of the lime-based titanium gypsum composite cementing material mainly comes from the dihydrate gypsum produced by the hydration of titanium gypsum and flue gas desulphurization gypsum, and the later strength contribution mainly comes from the further reaction of cement, lime and gypsum to produce ettringite. The hydration mechanism is as follows: First, CaSO4·0.5H2O hydrates to produce CaSO4·2H2O; Second, the 3CaO·Al2O3 in the cement reacts with CaSO4·2H2O to produce ettringite, the lime reacts with water to produce Ca(OH)2, and the combination of CaSO4·2H2O and CaO·Al2O3 react to produce ettringite. Therefore, the strength of the titanium gypsum composite cementitious material is further improved.
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图 3 石灰碱激发下钛石膏复合胶凝材料水化产物SEM形貌
Figure 3. SEM image of hydration product of TG composite cementitious material excited by lime base
图 5 TG、TG -FGD和钛石膏复合胶凝材料强度随时间的变化
Figure 5. Changes in the strength of TG, TG -FGD and titanium gypsum composite cementitious materials with time
表 1 原材料主要化学组成
Table 1. Main chemical compositions of raw materials
% SiO2 CaO TiO2 Al2O3 MgO SO3 Fe2O3 TFe 钛石膏 1.83 30.66 3.46 0.68 5.21 26.53 17.78 钛矿渣粉 43.82 7.70 3.90 9.40 7.57 0.46 8.79 脱硫石膏 0.58 32.28 0.015 0.34 0.63 41.91 0.35 
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表 2 正交试验因素及水平
Table 2. Factors and levels of orthogonal experiment
水平 TG FGD（A） TSP（B） 水泥（C） 石灰（D） 1 0.315 0.375（A1） 0.20（B1） 0.09（C1） 0.020（D1） 2 0.394 0.350（A2） 0.17（B2） 0.07（C2） 0.016（D2） 3 0.473 0.325（A3） 0.14（B3） 0.05（C3） 0.012（D3） 4 0.552 0.300（A4） 0.11（B4） 0.03（C4） 0.008（D4） 5 0.631 0.275（A5） 0.08（B5） 0.01（C5） 0.004（D5） 注：表中数值为总质量4 kg前提下，各物料加入量所占质量分数。
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表 3 抗折强度正交试验结果
Table 3. Flexural strength results from orthogonal experiments
组号 水/kg TG/% FGD（A） TSP（B） 水泥（C） 石灰（D） 抗折强度/MPa 2 h 7 d 28 d F1 1.19 31.5 A1 B1 C1 D1 1.93 2.44 3.70 F2 1.21 39.4 A2 B2 C2 D2 1.99 2.10 4.18 F3 1.24 47.3 A3 B3 C3 D3 2.27 2.00 3.93 F4 1.27 55.2 A4 B4 C4 D4 2.24 2.05 3.60 F5 1.30 63.1 A5 B5 C5 D5 2.13 2.16 3.60 F6 1.21 39.7 A1 B2 C3 D4 2.24 2.48 4.06 F7 1.24 47.6 A2 B3 C4 D5 2.39 2.29 3.50 F8 1.27 53.5 A3 B4 C5 D1 2.12 2.47 3.72 F9 1.30 51.4 A4 B5 C1 D2 2.08 2.11 3.56 F10 1.19 44.3 A5 B1 C2 D3 1.98 2.01 3.86 F11 1.24 45.9 A1 B3 C5 D2 2.42 2.06 3.47 F12 127 43.8 A2 B4 C1 D3 2.16 2.30 3.67 F13 1.30 51.7 A3 B5 C2 D4 2.30 2.21 3.65 F14 1.19 44.6 A4 B1 C3 D5 2.22 2.00 3.81 F15 1.21 50.5 A5 B2 C4 D1 1.97 1.97 3.62 F16 1.27 44.1 A1 B4 C2 D5 2.26 2.32 4.25 F17 1.30 50.0 A2 B5 C3 D1 2.28 2.70 3.64 F18 1.19 42.9 A3 B1 C4 D2 2.40 2.29 3.53 F19 1.21 50.8 A4 B2 C5 D3 2.02 1.93 3.84 F20 1.24 48.7 A5 B3 C1 D4 1.97 1.90 4.02 F21 1.30 50.3 A1 B5 C4 D3 2.56 2.30 3.69 F22 1.19 43.2 A2 B1 C5 D4 2.30 2.10 3.91 F23 1.21 41.1 A3 B2 C1 D5 2.17 2.21 4.23 F24 1.24 47.0 A4 B3 C2 D1 2.07 2.18 3.29 F25 1.27 54.9 A5 B4 C3 D2 2.21 2.38 3.56 2 h抗折强度极差Rf2 0.150 0.230 0.192 0.250 0.160 7 d抗折强度极差Rf7 0.164 0.266 0.218 0.168 0.244 28 d抗折强度极差Rf28 0.212 0.214 0.358 0.258 0.284
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表 4 抗压强度正交试验结果
Table 4. Compressive strength results from orthogonal experiments
组号 水/kg TG/% FGD（A） TSP（B） 水泥（C） 石灰（D） 抗压强度/MPa 2 h 7 d 28 d F1 1.19 31.5 A1 B1 C1 D1 5.50 7.79 16.32 F2 1.21 39.4 A2 B2 C2 D2 5.41 6.86 15.62 F3 1.24 47.3 A3 B3 C3 D3 6.17 8.11 17.65 F4 1.27 55.2 A4 B4 C4 D4 5.89 6.57 16.35 F5 1.30 63.1 A5 B5 C5 D5 5.93 6.04 15.90 F6 1.21 39.7 A1 B2 C3 D4 6.61 6.86 17.42 F7 1.24 47.6 A2 B3 C4 D5 6.53 6.53 17.61 F8 1.27 53.5 A3 B4 C5 D1 6.30 7.32 16.30 F9 1.30 51.4 A4 B5 C1 D2 5.74 6.72 16.12 F10 1.19 44.3 A5 B1 C2 D3 5.15 5.69 14.80 F11 1.24 45.9 A1 B3 C5 D2 6.45 5.69 16.55 F12 127 43.8 A2 B4 C1 D3 5.67 6.46 17.34 F13 1.30 51.7 A3 B5 C2 D4 5.88 5.88 17.34 F14 1.19 44.6 A4 B1 C3 D5 5.34 5.59 17.04 F15 1.21 50.5 A5 B2 C4 D1 5.08 5.39 15.16 F16 1.27 44.1 A1 B4 C2 D5 5.74 6.67 17.92 F17 1.30 50.0 A2 B5 C3 D1 5.75 7.51 16.98 F18 1.19 42.9 A3 B1 C4 D2 5.79 6.27 15.47 F19 1.21 50.8 A4 B2 C5 D3 6.18 5.31 16.38 F20 1.24 48.7 A5 B3 C1 D4 5.42 5.78 16.26 F21 1.30 50.3 A1 B5 C4 D3 6.68 5.86 17.60 F22 1.19 43.2 A2 B1 C5 D4 6.13 5.45 16.03 F23 1.21 41.1 A3 B2 C1 D5 5.66 6.62 16.42 F24 1.24 47.0 A4 B3 C2 D1 5.78 6.14 15.59 F25 1.27 54.9 A5 B4 C3 D2 5.99 7.66 15.75 2 h抗压强度极差Rc2 0.382 0.682 0.488 0.606 0.304 7 d抗压强度极差Rc7 1.272 0.774 0.778 1.184 0.722 28 d抗压强度极差Rc28 0.408 1.584 0.856 0.736 1.076
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