Design, Preparation and Property Study of Hydrocarbon-Triggered Self-Healing Materials
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摘要: 油井水泥环在长期服役过程中，受地层应力变化及井下复杂化学环境的影响，易产生微环隙与微裂缝，导致环空带压与层间封隔失效。使用遇烃自愈合材料解决这一问题是领域内的有效途径。在水泥浆环境与甲烷环境下，对自主开发的遇烃自愈合材料硼酸酯交联环糊精-丙烯酸酯复合树脂（DBC-CA）与氢化苯乙烯-丁二烯嵌段共聚物（SEBS）的吸烃膨胀比例进行了比较。通过三维断层扫描（CT）、电子显微镜（SEM）及傅里叶红外光谱（FTIR）和热重分析（TG），对2种遇烃自愈合材料的膨胀机理及热稳定性进行了探究。研究结果表明，DBC-CA在不同环境中的综合膨胀表现优于SEBS，并具有良好的热稳定性。DBC-CA在甲烷环境中最高膨胀比例达37%，且对环境响应灵敏，在水泥浆环境中的最大膨胀比例小于8%。DBC-CA掺量为10%的水泥基体在减少裂缝宽度和消除连通渗流通道方面表现最优。形貌分析表明，DBC-CA的弹性耗散特性通过刚性骨架-动态键重组-纳米空腔三重防护机制实现。DBC-CA会小幅度降低水泥石28 d抗压强度。为深部油气田井下自愈合密封材料的设计提供了新的思路。Abstract: In the long-time service life of a cement sheath, micro-annuli and microfractures are easy to be generated therein due to the formation stress variations and the complex chemical environment, resulting in sustained casing pressure and loss of interlayer isolation. The use of hydrocarbon-triggered self-healing materials is an effective means of addressing this problem. Under an environment with both cement slurry and methane, a comparison was made of the expansion ratios by hydrocarbon absorption of a self-developed hydrocarbon-triggered self-healing material DBC-CA, namely, borate-crosslinked cyclodextrin-acrylate compounded resin, and a hydrogenated styrene-butadiene block copolymer (SEBS). The expansion mechanisms and thermal stability of these two hydrocarbon-triggered self-healing materials were investigated through 3D computed tomography (CT), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR) and thermogravimetric analysis (TGA). The results of the research show that the expansion performance of DBC-CA in different environments is superior to that of SEBS, and DBC-CA also shows good thermal stability. In a methane environment, the highest expansion rate of DBC-CA is 37%, and DBC-CA is quite responsive to the environment, with its maximum expansion ratio in a cement slurry being less than 8%. A cement slurry containing 10% DBC-CA shows the best performance in minimizing the widths of the microfractures and in eliminating connected seepage channels. Morphological analysis demonstrates that the elastic energy dissipation characteristics of DBC-CA results from a triple protection mechanism involving rigid framework, dynamic bond rearrangement and nanocavities. DBC-CA can slightly reduce the 28-day compressive strength of a set cement. The achievements of this research provide a new idea for the design of downhole self-healing sealing materials for deep gas well application.
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Key words:
- Self-expansion /
- Self-healing /
- Hydrocarbon absorption /
- Cement sheath /
- Resin
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