颗粒负载氧化石墨烯复合水泥基材料的微观结构及自修复性能

胡德鑫; 单玉玺; 王海亮; 李东旭; 张毅

doi:10.13801/j.cnki.fhclxb.20231025.002

颗粒负载氧化石墨烯复合水泥基材料的微观结构及自修复性能

doi: 10.13801/j.cnki.fhclxb.20231025.002

1.
安徽工业大学　材料科学与工程学院，马鞍山 243002
2.
南京工业大学　材料科学与工程学院，南京 210009

基金项目: 国家自然科学基金(51872137)

详细信息

通讯作者:
张毅，博士，副教授，硕士生导师，研究方向为水泥基复合材料　E-mail: zhy1987@ahut.edu.cn

中图分类号: TU528.01；TB332
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- 被引次数: 0
出版历程
- 收稿日期: 2023-08-28
- 修回日期: 2023-10-01
- 录用日期: 2023-10-20
- 网络出版日期: 2023-10-25
- 刊出日期: 2024-06-15

Microstructure and self-repairing performance of granular loaded graphene oxide composite cement-based materials

1.
School of Materials Science and Engineering, Anhui University of Technology, Maanshan 243002, China
2.
School of Materials Science and Engineering, Nanjing University of Technology, Nanjing 210009, China

Funds: Natural Science Foundation of China (51872137)

摘要

摘要: 以纳米SiO₂、CaCO₃粉体为氧化石墨烯(GO)载体得到SiO₂-GO (SG)，SiO₂-CaCO₃-GO (SCG)，并将其掺入水泥基材料中，实现GO在水泥基材料中的分散，并研究其掺入对水泥基材料力学和自修复性能、水化产物和微观结构等方面的影响。研究表明，SG和SCG掺入进一步提高了水泥基材料的力学性能，SCG掺入水泥28天抗折和抗压强度较空白试样分别提高了7.3%和18.7%，高于掺入SiO₂和SG试样。SCG掺入使水泥石具有良好的自修复性能，其中抗压强度修复率达到110.6%，28天抗渗性能修复率达到100%，裂缝面积测试表明SCG对于水泥基材料裂缝具有更为明显的修复效果。XRD分析显示SiO₂、SG和SCG掺入均有助于促进水泥早期水化。TG分析表明，随着水化龄期的延长，SCG复合水泥试样中Ca(OH)₂和SiO₂之间的反应程度较高，与早期水化3天相比，SCG复合水泥基材料28天Ca(OH)₂含量降低至14.90%。微观结构分析表明SCG与水泥石界面具有更好的相容性，能够促进水泥水化后期生成较多水化硅酸钙(C-S-H)凝胶，有效填充水泥石微观裂缝，SCG复合水泥基材料具有优良的自修复性能。
- 氧化石墨烯 /
- 纳米SiO₂ /
- 力学性能 /
- 微观结构 /
- 自修复
Abstract: To improve the dispersion performance of graphene oxide (GO) in the cement materials, nano SiO₂ and CaCO₃ powder were used as support of the GO and the SiO₂-GO (SG) and SiO₂-CaCO₃-GO (SCG) were prepared. The effects of the SG and SCG on the mechanical strength, self-repairing performance, hydration products and microstructure of the cement materials were studied. The results show that the mechanical strength of the cement material is improved as the addition of SG and SCG, the flexural strength and compressive strength of the cement-based materials with SCG at 28 days are improved by 7.3% and 18.7%, respectively. The self-repairing performance of SCG composite cement is also improved which shows a higher compressive strength repairing rate of about 110.6% and a higher water permeability repairing rate of 100%. The crack area testing shows that SCG has a more significant repair effect on cracks in the cement materials. XRD analysis shows that the early stage cement hydration is accelerated as the addition of SG and SCG, especially for the SCG, the hydration degree at 3 days is obviously improved. TG analysis shows that with the extension of hydration age, a higher reaction degree of Ca(OH)₂ and SiO₂ is achieved in the SCG composite cement, compared with the early 3 days hydration stage, the Ca(OH)₂ content of SCG composite cement at 28 days reduces to 14.90%. Microstructure analysis shows that the SCG has better compatibility with the cement, more hydrate calcium silicate (C-S-H) gels in the late hydration stage is generated and the microcracks of cement could be filled, which makes the excellent self-repairing performance of the SCG composite cement.
- graphene oxide /
- nano-SiO₂ /
- mechanical strength /
- microstructure /
- self-repairing

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图 1 氧化石墨烯(GO)的拉曼光谱

Figure 1. Raman spectrum of graphene oxide (GO)

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图 2 GO (a)、SiO₂ (b)和制备SiO₂-GO (SG) (c)、SiO₂-CaCO₃ (SC) (d)及SiO₂-CaCO₃-GO (SCG) (e)颗粒的SEM图像

Figure 2. SEM images of the GO (a), SiO₂ (b) and prepared SG (c), SC (d), SCG particles (e)

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图 3 自制透水装置示意图

Figure 3. Schematic diagram of self-made water permeability device

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图 4 GO、SiO₂、SG、SC、SCG的FTIR图谱

Figure 4. FTIR spectra of GO, SiO₂, SG, SC and SCG

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图 5 GO、SiO₂、SG、SC及 SCG的XRD图谱

Figure 5. XRD patterns of GO, SiO₂, SG, SC and SCG

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图 6 水泥基材料试样各龄期力学性能

Figure 6. Mechanical properties of the cement specimens at each curing age

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图 7 修复前后硬化水泥石抗压强度

Figure 7. Compressive strength of the hardened cement before and after repairing

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图 8 空白和3wt%SiO₂/CE、3wt%SG/CE、3wt% SCG/CE试样的渗水修复率

Figure 8. Water permeability repairing rate of blank, 3wt%SiO₂/CE, 3wt%SG/CE and 3wt%SCG/CE

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图 9 空白试样修复前后照片：(a) 0天；(b) 3天；(c) 7天；(d) 14天；(e) 28天

Figure 9. Photos of blank samples before and after repairing: (a) 0 day; (b) 3 days; (c) 7 days; (d) 14 days; (e) 28 days

C-S-H—Hydrate calcium silicate; S—Crack area

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图 10 3wt%SiO₂/CE试样修复前后照片：(a) 0天；(b) 3天；(c) 7天；(d) 14天；(e) 28天

Figure 10. Photos of 3wt%SiO₂/CE samples before and after repairing: (a) 0 day; (b) 3 days; (c) 7 days; (d) 14 days; (e) 28 days

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图 11 3wt%SG/CE试样修复前后照片：(a) 0天；(b) 3天；(c) 7天；(d) 14天；(e) 28天

Figure 11. Photos of 3wt%SG/CE samples before and after repairing: (a) 0 day; (b) 3 days; (c) 7 days; (d) 14 days; (e) 28 days

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图 12 3wt%SCG/CE试样修复前后照片：(a) 0天；(b) 3天；(c) 7天；(d) 14天；(e) 28天

Figure 12. Photos of 3wt%SCG/CE samples before and after repairing: (a) 0 day; (b) 3 days; (c) 7 days; (d) 14 days; (e) 28 days

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图 13 各水泥基材料试样裂缝修复率

Figure 13. Crack repairing rate of each cement-based material sample

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图 14 水泥基材料试样各龄期水化产物 XRD图谱：(a) 空白试样；(b) 3wt%SiO₂/CE；(c) 3wt%SG/CE；(d) 3wt%SCG/CE

Figure 14. XRD patterns of the hydration products at each age: (a) Blank; (b) 3wt%SiO₂/CE; (c) 3wt%SG/CE; (d) 3wt%SCG/CE

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图 15 空白、3wt%SiO₂/CE、3wt%SG/CE及3wt%SCG/CE硬化水泥浆体TG-DTG曲线：(a) 3天；(b) 28天

Figure 15. TG-DTG curves of blank, 3wt%SiO₂/CE, 3wt%SG/CE and 3wt%SCG/CE hardened cement paste: (a) 3 days; (b) 28 days

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图 16 不同水化龄期水泥浆体SEM-EDS微观结构：(a) 空白3天；(b) 空白28天；(c) 3wt%SiO₂/CE 3天；(d) 3wt%SiO₂/CE 28天；(e) 3wt%SG/CE 3天；(f) 3wt%SG/CE 28天；(g) 3wt%SCG/CE 3天；(h) 3wt%SCG/CE 28天

Figure 16. SEM-EDS images of the cement paste at different curing ages: (a) Blank 3 days; (b) Blank 28 days; (c) 3wt%SiO₂/CE 3 days; (d) 3wt%SiO₂/CE 28 days; (e) 3wt%SG/CE 3 days; (f) 3wt%SG/CE 28 days; (g) 3wt%SCG/CE 3 days; (h) 3wt%SCG/CE 28 days

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图 17 水泥基材料试样水化反应示意图：(a) 3wt%SiO₂/CE；(b) 3wt%SG/CE；(c) 3wt%SCG/CE

Figure 17. Schematic diagram of hydration reaction of cement-based material samples: (a) 3wt%SiO₂/CE; (b) 3wt%SG/CE; (c) 3wt%SCG/CE

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表 1 水泥的化学成分

Table 1. Chemical composition of cement

CaO/wt%	SiO₂/wt%	Al₂O₃/wt%	SO₃/wt%	Fe₂O₃/wt%	MgO/wt%	TiO₂/wt%	P₂O₅/wt%	K₂O/wt%	LOI/wt%
64.51	20.20	4.83	2.25	3.75	2.67	0.375	0.071	0.80	0.54
Note: LOI—Loss on ignition.

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表 2 颗粒配比

Table 2. Proportion of the prepared particles

Sample	SiO₂/wt%	CaCO₃/wt%	GO/wt%
SiO₂	100	0	0
SG	33.4	0	66.6
SC	50	50	0
SCG	16.7	16.7	66.6
Notes: SG—SiO₂-GO; SC—SiO₂-CaCO₃; SCG—SiO₂-CaCO₃-GO.

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表 3 不同水泥基材料试样3天和28天龄期Ca(OH)₂含量(wt%)

Table 3. Ca(OH)₂ content of the cement-based material samples at 3 days and 28 days (wt%)

Sample	Blank	3wt%SiO₂/CE	3wt%SG/CE	3wt%SCG/CE
3 days	11.71	16.49	17.16	15.77
28 days	17.14	17.55	17.63	14.90

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