不同壳材相变微胶囊对深水固井水泥浆水化及孔隙结构演化的调控机理

doi:10.3969/j.issn.2096-1693.2026.03.002

石油科学通报 ›› 2026, Vol. 11 ›› Issue (1): 226-238. doi: 10.3969/j.issn.2096-1693.2026.03.002

不同壳材相变微胶囊对深水固井水泥浆水化及孔隙结构演化的调控机理

吴祖锐¹(), 郑明明¹^,^*(), 张亚伟¹, 杜奕辰¹, 李可赛², 胡云鹏¹

1 成都理工大学地质灾害防治与地质环境保护全国重点实验室，成都 610059
2 成都理工大学油气藏地质及开发工程全国重点实验室，成都 610059

收稿日期:2025-10-29 修回日期:2025-12-04 出版日期:2026-02-15 发布日期:2026-02-12
通讯作者: * 郑明明(1988年—)，博士，教授，博士生导师，主要从事地质工程方面的教学与科研工作，mingming_zheng513@163.com。
作者简介:吴祖锐(2000年—)，博士研究生，主要从事油气井固井与功能性水泥基材料的研究，wuzurui0106@163.com。
基金资助:
国家自然科学基金(42272363);四川省科技计划项目(2023NSFSC0432);地质灾害防治与地质环境保护全国重点实验室自主研究项目(SKLGP2023Z019)

Regulation mechanisms of phase change microcapsules with different shell materials on hydration and pore structure evolution in deepwater well cementing slurry

WU Zurui¹(), ZHENG Mingming¹^,^*(), ZHANG Yawei¹, DU Yichen¹, LI Kesai², HU Yunpeng¹

1 State Key Laboratory of Geohazard Prevention and Geoenvironment Protection, Chengdu University of Technology, Chengdu 610059, China
2 State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation, Chengdu University of Technology, Chengdu 610059, China

Received:2025-10-29 Revised:2025-12-04 Online:2026-02-15 Published:2026-02-12
Contact: *mingming_zheng513@163.com

摘要/Abstract

摘要：

为调控深水固井水泥浆水化热，本研究制备了有机(PMMA)和无机(SiO₂)壳材的相变微胶囊(m-PCM)，探究了壳材性质对水泥基体性能的影响机制。结果表明，两种m-PCM均具有优异的剪切稳定性和相近的相变峰值温度(25.6 ℃)，能有效降低水化放热。关键差异在于：PMMA@m-PCM呈疏水性(116.5°)，而SiO₂@m-PCM呈强亲水性(27.3°)。Micro-CT证实，6 wt%掺量的m-PCM有效减少了大孔隙占比，优化了孔结构。力学测试显示，SiO₂@m-PCM在3天和7天龄期均表现出显著的强度增强效果，而PMMA@m-PCM则严重削弱了基体强度。SEM分析揭示，性能差异的核心在于界面相容性：亲水的SiO₂壳材与基体形成了致密的界面过渡区(ITZ)，而疏水的PMMA壳材导致了严重的界面脱粘，构成了力学薄弱点。研究表明，采用亲水性无机壳材是实现m-PCM水化热调控与力学性能增强相统一的关键。这些结果为设计低热水泥浆提供了新方法，为安全、可持续的深海油气开采提供了理论和技术见解，减少了生态影响。

关键词: 微胶囊相变材料, 固井水泥浆, 水化热致裂缝, 孔隙分布, Micro-CT

Abstract:

To regulate the hydration heat of deep-water well cementing slurry, phase change microcapsules (m-PCMs) with organic (PMMA) and inorganic (SiO₂) shells were prepared in this study to investigate the influence mechanism of shell properties on the cement matrix performance. The results indicated that both types of m-PCMs exhibited excellent shear stability and similar peak phase change temperatures (25.6 °C), effectively reducing hydration exotherms. The critical difference lay in their wettability: PMMA@m-PCM was hydrophobic (116.5°), whereas SiO₂@m-PCM was strongly hydrophilic (27.3°). Micro-CT confirmed that m-PCMs at a 6 wt% dosage effectively reduced the proportion of large pores, optimizing the pore structure. Mechanical tests revealed that SiO₂@m-PCM demonstrated a significant strength enhancement effect at 3 and 7 days, while PMMA@m-PCM severely weakened the matrix strength. SEM analysis revealed that the core of this performance disparity was interfacial compatibility: the hydrophilic SiO₂ shell formed a dense interfacial transition zone (ITZ) with the matrix, whereas the hydrophobic PMMA shell caused severe interfacial debonding, creating mechanical weak points. This study demonstrates that using hydrophilic inorganic shells is key to achieving the unification of m-PCM hydration heat regulation and mechanical performance enhancement. These findings provide a new methodology for designing low-heat cement slurries, offering theoretical and technical insights for safe and sustainable deep-sea oil and gas exploitation and reducing ecological impact.

Key words: microencapsulated phase change materials, cementing slurry, fracture caused by hydration heat, pore distribution, Micro-CT

中图分类号:

TE256

吴祖锐, 郑明明, 张亚伟, 杜奕辰, 李可赛, 胡云鹏. 不同壳材相变微胶囊对深水固井水泥浆水化及孔隙结构演化的调控机理[J]. 石油科学通报, 2026, 11(1): 226-238.

WU Zurui, ZHENG Mingming, ZHANG Yawei, DU Yichen, LI Kesai, HU Yunpeng. Regulation mechanisms of phase change microcapsules with different shell materials on hydration and pore structure evolution in deepwater well cementing slurry[J]. Petroleum Science Bulletin, 2026, 11(1): 226-238.

https://sykxtb.cup.edu.cn/CN/Y2026/V11/I1/226

图/表 12

图1 m-PCM的合成流程示意图^[39]
(a) PMMA@m-PCM(有机壳材)；(b) SiO₂@m-PCM(无机壳材)

Fig. 1 Schematic diagram of the synthesis process of m-PCM^[39]

表1 人工海水主要离子浓度

Table 1 Concentrations of major ions in artificial seawater

离子	浓度/(mg/L)
镁离子(Mg²⁺)	1270
钙离子(Ca²⁺)	405
钠离子(Na⁺)	10 770
氯离子(Cl^-)	18 980
硫酸根离子(SO₄^2-)	2580

表2 水泥浆配方的标准化设计

Table 2 Standardized mix design of cement paste

测试组	水泥/g	拌合水/g	PMMA@m-PCM含量/wt%	SiO₂@m-PCM含量/wt%	Ⅰ/g	Ⅱ/g	Ⅲ/g	Ⅳ/g	天数/d
对照组	100	50	None	None	2	1	0.55	0.5	3/7
PMMA@m-PCM	100	50	3, 6, 9, 12	None	2	1	0.55	0.5	3/7
SiO₂@m-PCM	100	50	None	3, 6, 9, 12	2	1	0.55	0.5	3/7

图2 nanoVoxel 3000工业CT设备及扫描原理

Fig. 2 NanoVoxel 3000 industrial CT equipment and scanning principle

图3 m-PCM的DSC曲线

Fig. 3 DSC curves of m-PCM

图4 m-PCM的剪切稳定性及循环6次后的微观形貌变化

Fig. 4 The shear stability of m-PCM and the microscopic morphological changes after 6 cycles

图5 (a) PMMA@m-PCM和 (b) SiO₂@m-PCM剪切6次前后的FTIR图谱

Fig. 5 FTIR spectra of (a) PMMA@m-PCM and (b) SiO₂@m-PCM before and after 6 shear cycles

图6 两种m-PCM的粒径分布与润湿性分析

Fig. 6 Particle size distribution and wettability analysis of the two types of m-PCM

图7 (a) PMMA@m-PCM和 (b) SiO₂@m-PCM对水泥浆水化放热量的影响

Fig. 7 The influence of PMMA@m-PCM and (b) SiO₂@m-PCM on the heat of hydration of cement paste

图8 (a) PMMA@m-PCM和 (b) SiO₂@m-PCM掺量对3天、7天抗压强度的影响

Fig. 8 (a) The influence of the content of PMMA@m-PCM and (b) the influence of the content of SiO₂@m-PCM on the compressive strength at 3 days and 7 days

图9 掺量为6 wt%时(a) PMMA@m-PCM和(b) SiO₂@m-PCM微胶囊与基体界面的SEM及二值化图像

Fig. 9 SEM images and corresponding binarized images of the interface between the matrix and microcapsules at a loading of 6 wt%: (a) PMMA@m-PCM and (b) SiO₂@m-PCM

图10 不同样品的孔隙结构Micro-CT分析结果：(a) 空白对照组，(b) PMMA@m-PCM 6 wt%，(c) SiO₂@m-PCM 6 wt%

Fig. 10 Analysis results of pore structure of different samples by Micro-CT: (a) Blank control group, (b) PMMA@m-PCM 6 wt%, (c) SiO₂@m-PCM 6 wt%

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不同壳材相变微胶囊对深水固井水泥浆水化及孔隙结构演化的调控机理

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不同壳材相变微胶囊对深水固井水泥浆水化及孔隙结构演化的调控机理

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