面向海工结构阴极防护用纳米水泥基热电复合材料制备及其温差自供能性

袁士柯; 罗健林; 高乙博; 滕飞; 张纪刚; 刘昂; 张立卿

doi:10.13801/j.cnki.fhclxb.20231103.003

面向海工结构阴极防护用纳米水泥基热电复合材料制备及其温差自供能性

doi: 10.13801/j.cnki.fhclxb.20231103.003

袁士柯¹,
罗健林^{1, 2, ,},
高乙博¹,
滕飞¹,
张纪刚^{1, 2},
刘昂^{1, 2},
张立卿³

1.
青岛理工大学　土木工程学院，青岛 266520
2.
海洋混凝土教育部工程研究中心，青岛 266520
3.
华东交通大学　土木工程学院，南昌 330013

基金项目: 国家自然科学基金 (51878364)；山东省自然科学基金(ZR2023ME011)；中建八局横向合作项目(JM20191030；B2-2022-0253；B2-2022-0048；B2-2023-0014)；国家111计划、省高峰学科资助

详细信息

通讯作者:
罗健林，博士，教授，博士生导师，研究方向为复合材料与结构　E-mail: lawjanelim@qut.edu.cn

中图分类号: TB332
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出版历程
- 收稿日期: 2023-07-31
- 修回日期: 2023-09-24
- 录用日期: 2023-10-26
- 网络出版日期: 2023-11-06
- 刊出日期: 2024-05-15

Preparation of nano-modified cement-based thermoelectric composite and its self-power supply behaviors engineered cathodic protection for offshore structure

YUAN Shike¹,
LUO Jianlin^{1, 2
, ,},
GAO Yibo¹,
TENG Fei¹,
ZHANG Jigang^{1, 2},
LIU Ang^{1, 2},
ZHANG Liqing³

1.
School of Civil Engineering, Qingdao University of Technology, Qingdao 266520, China
2.
Marine Environmental Concrete Technology Engineering Research Center of Ministry of Education, Qingdao 266520, China
3.
School of Civil Engineering, East China Jiaotong University, Nanchang 330013, China

Funds: National Natural Science Foundation of China (51878364); Natural Science Foundation of Shandong Province (ZR2023ME011); Cooperation Project of China Construction Eight Division (JM20191030; B2-2022-0253; B2-2022-0048; B2-2023-0014); National 111 Program, Provincial Peak Discipline Funding

摘要

摘要: 经略海洋及双碳背景下，用阴极防护(CP)技术提升海工结构服役寿命具有重要意义，然而需外加电源额外驱动。为此本文先用水热法合成纳米二氧化锰(nMnO₂)，然后与碳纳米管(CNTs)复掺水泥砂浆体系中，制备纳米水泥基热电复合材料(NTEC)；最后将20个NTEC串联成1套热电发电模块，并结合电化学方法综合评价基于温差发电的NTEC热电模块直接用作海工结构钢筋CP系统电流供给源的可行性。结果表明：复掺有0.2wt%CNTs与5.0wt%nMnO₂的NTEC试件的热电系数、热电功率因数可分别达3612 μV/℃和301.4 μW·m⁻¹·℃⁻²，本征力学强度与耐久抗渗性得到保障；施加基于NTEC温差发电的CP，钢筋的腐蚀电位正移，腐蚀概率显著降低；施加基于NTEC热电模块的CP后能使钢筋腐蚀电流密度降低3个数量级，腐蚀电荷转移得到了抑制，腐蚀速率大为降低，实现海工结构钢筋CP的自供能，同时保障了其用作保护层的强度与耐久性。
- 海工结构 /
- 阴极防护自供能 /
- 纳米水泥基热电复合材料 /
- 温差发电性能 /
- 电化学性能
Abstract: Under the background of strategic ocean and double-carbon, it is important to use cathodic protection (CP) technology to enhance the service life of offshore structures. However, it requires additional power supply for extra drive. Here, nano-size nMnO₂ was synthesized by hydrothermal method, and then was mixed into cement mortar along with carbon nanotubes (CNTs) to prepare nano-modified cement-based thermoelectric composites (NTEC). 20 NTECs were connected in series to form a set of thermoelectric power generation module, and combined with electrochemical methods to comprehensively evaluate the feasibility of NTEC thermoelectric module based on differential temperature power generation directly serving as a current supply source for the reinforcement CP system of offshore structure. Results show that: The thermoelectric coefficient and thermoelectric power factor of NTEC specimens doped with 0.2wt%CNTs and 5.0wt%nMnO₂ can be up to 3612 μV/℃, and 301.4 μW·m⁻¹·℃⁻², respectively. The intrinsic mechanical strength and anti-permeability are accordingly guaranteed. Applying the CP based on the temperature difference power generation of NTEC, the corrosion potential of the reinforcement bar positively shifts, and the probability of corrosion is significantly reduced. Applying the CP based on the NTEC thermoelectric module the corrosion current density of the reinforcement is reduced by 3 orders of magnitude, the corrosion charge transfer is suppressed, the corrosion rate is greatly reduced, the self-power supply of CP for reinforcement in offshore structures is realized, and its mechanical properties and durability are guaranteed when simultaneously serving as concrete cover.

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图 1 纳米水泥基热电复合材料(NTEC)试样的电极分布图(a)和热电系数(S)测试示意图(b)

ΔT—Change in temperature; ΔV—Change in voltage

Figure 1. Electrode distribution diagram (a) and schematic diagram of thermoelectric coefficient (S) test (b) for nano-modified cement-based thermoelectric composites (NTEC) specimen

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图 2 NTEC温差发电模块示意图

Figure 2. Schematic diagram of temperature gap power generationmodule of NTEC

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图 3 电化学测试示意图：(a)不设阴极防护(NP)；(b)设置阴极防护(CP)

NP—No cathodic protection; CP—Cathodic protection

Figure 3. Schematic diagram of electrochemical testing: (a) Testing without cathodic protection (NP); (b) Testing with cathodic protection (CP)

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图 4 nMnO₂的XRD图谱

Figure 4. XRD patterns of nMnO₂

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图 5 nMnO₂的SEM图像

Figure 5. SEM image of nMnO₂

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图 6 不同nMnO₂掺量下NTEC的温差电压随温差变化趋势

CNTs—Carbon nanotubes

Figure 6. Curves of thermoelectric voltage with temperature gap for NTEC with different doping of nMnO₂

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图 7 不同nMnO₂掺量下NTEC的S和热电功率因数(P_F)变化趋势

Figure 7. Trends of S and thermoelectric power factor (P_F) of NTEC with different nMnO₂ doping

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图 8 不同nMnO₂掺量下NTEC与nMnO₂水泥基复合材料(nMnO₂/CC)试样的28天抗压强度(f_c^{28 d})和抗折强度(f_t^{28 d})

Figure 8. 28 days compressive strength (f_c^{28 d}) and flexural strength (f_t^{28 d}) of NTEC and nMnO₂-cement-based composite (nMnO₂/CC) specimens with different nMnO₂ doping

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图 9 不同nMnO₂掺量下NTEC与nMnO₂/CC试样的迁移系数(λ)

Figure 9. Migration coefficient (λ) of NTEC and nMnO₂/CC specimens with different nMnO₂ doping

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图 10 两组钢筋的腐蚀电位变化曲线(a)和在腐蚀模拟孔隙液(CSF)中浸泡21天后的动电位极化曲线图(b)

E_corr—Corrosion potential

Figure 10. Corrosion potential change curves for two groups of steel rebars (a) and dynamic potential polarization plots for two groups of steel rebars after 21 d immersion in corrosion simulation of pore fluid (CSF) (b)

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图 11 两组钢筋不同腐蚀龄期下的Nyquist图((a₁)~(e₁))和Bode图((a₂)~(e₂))

Z'—Real part of impedance; –Z''—Negative of the imaginary part of the impedance; f—Frequency; |Z|—Impedance modulus

Figure 11. Nyquist ((a₁)-(e₁)) and Bode ((a₂)-(e₂)) diagrams for two groups of steel rebars at different ages of corrosion

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图 12 不同腐蚀龄期下的EIS模拟等效电路图

R_s—Resistance of the electrolyte solution; R_f—Film resistance of the conversion film on the surface of the steel rebars; R_ct—Resistance of the charge transfer during the corrosion of the steel rebars; CPE_f—Membrane capacitor; CPE_dl—Double layer capacitor

Figure 12. Equivalent circuit diagrams for EIS simulations at different corrosion ages

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表 1 碳纳米管(CNTs)的主要物理性能指标

Table 1. Main physical property indexes of carbon nanotubes (CNTs)

Diameter/nm	Length/μm	Purity/%	Amorphous carbon/%	Specific surface area/(m²·g⁻¹)	Thermal conductivity/(W·(m·K)⁻¹)	Resistivity/ (Ω·cm)
20-40	5-15	≥90%	≤3%	40-300	1.60	＜5

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表 2 两组钢筋的极化曲线拟合数据

Table 2. Fitting data of polarization curves for two groups of steel rebars

Group	E_corr/V	I_corr/(μA·cm⁻²)	Corrosion rate/(mm·a⁻¹)
CSF-NP	−0.762	1.56×10	1.83×10⁻¹
CSF-CP	−0.336	7.58×10⁻²	8.91×10⁻⁴
Note: I_corr—Corrosion current density.

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表 3 不同腐蚀龄期下钢筋的EIS拟合数据

Table 3. EIS fitting data for steel rebars at differentcorrosion ages

Group	Corrosion ages/d	R_s/(Ω·cm²)	R_f/(kΩ·cm²)	R_ct/(kΩ·cm²)
CSF-NP	0	3.24	101.38	–
	3	2.85	126.42	236.51
	7	2.88	154.36	180.04
	14	2.84	7.20	62.92
	21	3.07	1.07	29.26
CSF-CP	0	2.97	123.77	–
	3	2.95	253.70	302.64
	7	2.80	501.48	447.21
	14	2.83	245.73	3125.21
	21	2.95	102.31	3232.93

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