水泥基材料离子热电效应与机制

崔一纬; 王亚琼; 魏亚

doi:10.13801/j.cnki.fhclxb.20210311.001

水泥基材料离子热电效应与机制

doi: 10.13801/j.cnki.fhclxb.20210311.001

崔一纬^{1, 2,},
王亚琼^2,,
魏亚^1, ,

1.
清华大学　土木工程系土木工程安全与耐久教育部重点实验室，北京 100084
2.
长安大学　公路学院，西安 710064

基金项目: 国家重点研发计划(2018YFB1600200)

详细信息

通讯作者:
魏亚，博士，副教授，博士生导师，研究方向为水泥基材料变形力学性能多尺度模拟表征、长寿命道路材料与结构、结构新材料研发　E-mail：yawei@tsinghua.edu.cn

中图分类号: TB332
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- 被引次数: 0
出版历程
- 收稿日期: 2021-01-27
- 修回日期: 2021-02-24
- 录用日期: 2021-03-03
- 网络出版日期: 2021-03-11
- 刊出日期: 2022-01-15

Ionic thermoelectric effect and mechanism of cement-based materials

CUI Yiwei^{1, 2
,},
WANG Yaqiong^2
,,
WEI Ya^{1
, ,}

1.
Key Laboratory of Civil Engineering Safety and Durability of China Education Ministry, Department of Civil Engineering, Tsinghua University, Beijing 100084, China
2.
School of Highway, Chang’an University, 710046 Xi’an, Shaanxi Province, China

摘要

摘要: 当前水泥基材料热电效应主要通过掺入大量功能填料来增强。但掺量过高的功能填料提高了水泥基复合材料的成本，劣化了其力学性能，阻碍其大范围的应用。本研究发现，由于孔隙溶液中存在大量自由移动的离子，不掺任何功能填料的水泥净浆表现出显著的离子热电效应。本研究通过对比水泥净浆干燥前后的热电压，研究了水泥基材料的离子热电效应，并通过离子浸出与饱和碱溶液实验对水泥净浆的离子热电效应机制进行了探究。结果表明，由于孔隙溶液中OH⁻的热扩散，干燥前水泥净浆表现出显著的n-type离子热电效应。离子浸出过程中OH⁻浓度的降低导致水泥净浆的离子热电特性由n-type转变为p-type。饱和碱溶液后，在OH⁻浓度较大时，阳离子种类亦会对离子热电特性产生显著影响。此外，未添加功能性填料的水泥净浆的Seebeck系数可达1.133 mV·℃⁻¹，功率因数(P_F)可达0.042 μW·m⁻¹·℃⁻²，高于文献中一些功能性填料掺量达5%的水泥基复合材料，具有显著的热电转换效率。
- 离子热电效应 /
- 水泥基材料 /
- 离子浓度 /
- Seebeck系数 /
- 离子浸出
Abstract: At present, the thermoelectric effect of cement-based materials is mainly enhanced by adding a large amount of functional fillers. However, the high content of the functional filler increases the cost, degrades their mechanical properties and hinders their wide application. It is found in this study that the pure cement paste without any functional fillers shows a significant ionic thermoelectric effect due to the freely moving ions in the pore solution of the cement-based materials. The ionic thermoelectric effect of the cement-based materials was studied by comparing the thermoelectric voltage of pure cement paste before and after drying, and the mechanism of the ionic thermoelectric effect of pure cement paste was further explored through ion leaching and saturated alkali solution experiments. Results show that the pure cement paste before dry shows a significant n-type ionic thermoelectric effect due to the thermal diffusion of OH⁻. The decrease of the concentration of OH⁻ in the leaching process leads to the change of ionic thermoelectric voltage from n-type to p-type. After saturated in NaOH solution, the type of cations has a significant effect on the ionic thermoelectric properties even under the condition of high OH⁻ concentration. In addition, the Seebeck coefficient of cement paste without any functional filler can reach 1.133 mV·℃⁻¹, and the power factor P_F can reach 0.042 μW·m⁻¹·℃⁻², which is higher than that of some cement-based composites with 5% functional filler in the literature.
- ionic thermoelectric effect /
- cement-based material /
- ion concentration /
- Seebeck coefficient /
- ion leaching

HTML全文

图 1 实验方法与装置((a)两电极法示意图；(b)Seebeck系数测量装置示意图)

Figure 1. Experimental method and test set up (a) Schematic diagram of two electrode method; (b) Schematic diagram of the set-up for Seebeck coefficient measurements)

R—Direct current resistance; ΔT—Temperature difference; ΔV—Potential difference

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图 2 饱水后的水泥净浆电导率随离子浸出时间的变化

Figure 2. Electrical conductivity of saturated cement paste versus leaching time

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图 3 饱和NaOH后水泥净浆电导率与NaOH浓度的关系

Figure 3. Electrical conductivity of cement paste saturated with NaOH versus NaOH concentration

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图 4 干燥前水泥净浆热电压随温差的变化

Figure 4. Thermoelectric voltage of cement paste before drying versus temperature difference

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图 5 不同浸出时间水泥净浆热电压随温差的变化

Figure 5. Thermoelectric voltage of cement paste at different leaching time versus temperature difference

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图 6 饱和NaOH溶液后水泥净浆热电压随温差的变化

Figure 6. Thermoelectric voltage of cement paste saturated with NaOH solution versus temperature difference

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图 7 水泥净浆随离子浸出时间变化的峰值热电压

Figure 7. Maximum thermoelectric voltage of pure cement paste versus leaching time

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图 8 水泥净浆离子热电效应机制示意图((a)干燥前与离子浸出0 h；(b)离子浸出24 h后)

Figure 8. Mechanism of ionic thermoelectric effect of cement paste((a) Before drying and leaching for 0 h; (b) After leaching for 24 h)

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图 9 (a)浸出液pH值与OH⁻浓度与浸出时间的关系; (b) 浸出液K⁺、Ca²⁺、Na⁺浓度与浸出时间的关系

Figure 9. (a) pH-value and OH⁻ concentration of leachant versus leaching time; (b) Concentration of K⁺, Ca²⁺, Na⁺ of leachant versus leaching time

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图 10 饱和NaOH后水泥净浆热电压峰值随NaOH浓度的变化

Figure 10. Variation of peak value of thermoelectric voltage of cement paste with NaOH concentration

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图 11 不同状态下水泥净浆Seebeck系数随温差的变化

Figure 11. Seebeck coefficient of cement paste versus temperature difference in different states

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图 12 水泥净浆随离子浸出时间变化的Seebeck系数 (S) 与功率因数(P_F)的峰值

Figure 12. Maximum value of Seebeck coefficient (S ) and power factor (P_F) of cement paste versus leaching time

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图 13 水泥基材料功率因数研究进展

Figure 13. Advances in power factor for cement composites

EG—Expanded graphite; GNP—Graphene nanoplate; CNT—Carbon nanotube; CF—Carbon fiber; PC—Pure cement paste

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表 1 采用的普通硅酸盐水泥化学成分和物理性能

Table 1. Chemical compositions and physical properties of ordinary Portland cement

SiO₂/%	Al₂O₃/%	Fe₂O₃/%	CaO/%	MgO/%	SO₃/%	Na₂O/%	Ignition loss/%	Specific gravity	Blaine fineness/(cm²·g⁻¹)
22.00	4.40	3.43	61.75	2.49	2.83	0.56	1.77	3.14	3500

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表 2 试件饱和面干质量随真空饱水时间的变化

Table 2. Saturated surface dry mass versus vacuum saturation time

t_s/h	m/g	W/wt%
0	73.715±0.438	—
1	79.968±0.385	8.48%
2	80.120±0.381	0.19%
3	80.168±0.384	0.06%
4	80.193±0.382	0.03%
Notes: t_s—Vacuum saturation time; m—Saturated surface dry mass; W—Mass variation.

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