Hardening Properties and Enhancement Mechanisms of Modified Alumina Cement at Minus Temperature
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摘要: 针对负温环境下固井水泥浆水化反应减缓甚至停滞，导致固井施工难以进行的问题，开展了改性高铝水泥浆的硬化特性优化和早期强度的增强机制研究。在0，–10和–18 ℃温度下，进行了改性高铝水泥浆的凝结时间、流动度及抗压强度等性能对比试验，研究了负温环境下水泥浆关键性能的变化规律及与凝结时间调节剂SCEG之间的关系；在分析水化产物物相组成和微观结构的基础上，研究了水泥浆负温硬化机制，并通过添加石膏促进AFt生成来提高水泥石的抗压强度。试验表明：–18～0 ℃温度下，改性高铝水泥浆中添加占水泥质量0～3%的SCEG，该水泥浆可在0.3～6.0 h内硬化；该水泥浆24 h抗压强度达9.7～11.2 MPa，添加占水泥质量10%～15%的石膏后，水泥石抗压强度可提高30%左右。XRD测试发现，负温环境下水泥水化矿物主要为铝酸盐熟料而非硅酸盐熟料，产物主要为Ca2Al(Al,Si)2O7、AFm、AFt及少量硅酸盐水化产物C–S–H，且AFt含量越高，水泥石抗压强度越高。研究表明，改性高铝水泥具有良好的负温硬化能力，添加适量的石膏可提高水泥水化产物中AFt的含量，有助于提高水泥石的抗压强度。Abstract: Because the hydration reaction of cement is unable to proceed below the freezing point and hinders cementing, a research on the hardening properties optimization and enhancement mechanism for early strength of modified alumina cement was conducted. Changes in setting time, fluidity and compressive strength of cement at different temperatures of 0, −10, and −18 °C were compared, and the relationship between these changes at different temperatures and the setting time modifier SCEG was studied. Based on the analysis of phase compositions and microstructures of hydration products, the mechanism of hardening of cement at minus temperature was studied, and gypsum was added to promote the formation of AFt so as to enhance the compressive strength of hardened cement paste. The experiment demonstrated that the cement can be hardened within 0.3–6.0 hour when SCEG about 0–3% cement mass is added to the modified alumina cement from 0 °C to −18 °C. In that case, its compressive strength can reach 9.7–11.2 MPa within 24 hours and even rise 30% after gypsum about 10%–15% cement mass is added. X-ray diffraction (XRD) analysis indicates that the main hydrated mineral in the cement is aluminate clinker instead of silicate clinker at minus temperature, with Ca2Al(Al,Si)2O7, AFm, AFt, and a few C－S－H as the main products. To be specific, a higher content of AFt can bring higher compressive strength of hardened cement paste. The results show that modified alumina cement possesses optimized hardening properties at minus temperatures, and appropriate amount of gypsum can increase the content of AFt in hydration products, improving the compressive strength of hardened cement paste.
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Keywords:
- minus temperature /
- cementing /
- modified alumina cement /
- hydration /
- ettringite /
- early strength
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图 1 不同温度下改性高铝水泥的抗压强度（养护24 h）
Figure 1. Compressive strength of modified alumina cement at different temperatures (24 h)
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图 2 不同石膏加量改性高铝水泥石的负温抗压强度（–18 ℃/24 h）
Figure 2. Compressive strength of modified alumina cement containing different amount of gypsum at minus temperature (–18 ℃/24 h)
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图 3 –18 ℃下改性高铝水泥水化产物XRD图谱
Figure 3. XRD of hydration products of modified alumina cement at –18 ℃
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图 4 改性高铝水泥在–18 ℃养护下水化7 d的水化产物及能谱分析结果（石膏加量15%）
Figure 4. SEM and EDX of hydration products of modified alumina cement containing 15% gypsum at –18 ℃ (7 d hydration)
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图 5 –18 ℃养护下水化7 d 的改性高铝水泥水化产物不同断面位置形貌（石膏加量15%）
Figure 5. Morphologies of different sections of hydration products of modified alumina cement containing 15% gypsum at –18 ℃ (7 d hydration)
表 1 改性高铝水泥浆负温凝结时间试验结果
Table 1 Setting time of modified alumina cement at minus temperature
试验温度/℃ SCEG加量，% 初凝时间/min 终凝时间/ min 0 0 20 35 3.0 85 204 9.0 205 258 15.0 275 453 25.0 — — –10 0 23 87 3.0 130 245 6.0 279 497 10.0 507 1400 15.0 — — –18 0 26 46 1.0 107 162 1.5 141 235 2.0 265 547 3.0 397 719 注：基浆为220 mL SCLC-1溶液+2.5 g TEL+500 g改性高铝水泥，其中SCLC-1溶液中溶质含量为20%，下同；如未特殊说明，本文所有外加剂加量均为与水泥的质量比；“—”表示未测出，即7 d未凝。 
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表 2 改性高铝水泥浆负温流动度试验结果
Table 2 Fluidity of modified alumina cement at minus temperatures
试验温度/℃ SCEG加量，% 流动度/cm 0 0 13 1.0 14 1.5 16 2.0 16 3.0 17 3.5 18 –10 0 16 1.0 16 1.5 17 2.0 17 3.0 18 3.5 18 –18 0 16 1.0 17 1.5 16 2.0 17 3.0 18 3.5 19
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表 3 石膏加量对改性高铝水泥浆性能的影响（–18 ℃）
Table 3 Influence of amount of gypsum on modified alumina cement performance (–18 ℃)
试验编号 石膏加量，% 流动度/cm 凝结时间/min 初凝 终凝 1 0 16 141 235 2 5 17 170 253 3 10 17 182 265 4 15 18 175 242 5 20 16 142 230 6 30 14 113 210
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表 4 光标处水泥水化产物能谱分析结果
Table 4 EDX analysis result on the cursor of hydration products of modified alumina cement
原子序数 元素符号 原子个数比，% 质量比，% 8 O 75.81 59.01 20 Ca 12.52 24.42 14 Si 7.90 10.80 17 Cl 2.00 3.45 13 Al 1.77 2.32
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