环氧-水泥基渗透结晶型复合涂层对混凝土氯盐冻融防护性能的影响

doi:10.16552/j.cnki.issn1001-1625.2025.0986

摘要/Abstract

摘要：

本文研究了氯盐冻融环境下环氧-水泥基渗透结晶型复合涂层对混凝土结构的防护效果，通过开展快速冻融试验、抗氯离子渗透性能试验及氯盐冻融复合环境下耐久性试验，测定了混凝土试件相对动弹性模量、质量损失率及氯离子扩散系数等参数的变化规律。结果表明：相较于环氧防腐涂层和水泥基渗透结晶材料两类单一涂层，环氧-水泥基渗透结晶型复合涂层能够显著降低混凝土试件的氯离子扩散系数，有效延缓混凝土试件相对动弹性模量和质量损失率的下降速度，有效延缓冻融破坏发生时间。基于修正的Duracrete模型，预测了氯盐冻融环境下涂覆不同涂层混凝土结构的使用寿命，在水下区、潮汐区和大气区环境，涂覆环氧-水泥基渗透结晶型复合涂层的混凝土结构的使用寿命相较于涂覆环氧防腐涂层单一涂层结构的使用寿命分别延长了90.6%、92.9%、90.7%，相较于水泥基渗透结晶材料单一涂层结构的使用寿命分别延长了55.6%、74.4%和66.4%，表明环氧-水泥基渗透结晶型复合涂层可有效延长氯盐冻融环境下混凝土结构的使用寿命。

关键词: 混凝土结构, 环氧防腐涂层, 水泥基渗透结晶材料, 复合涂层, 冻融损伤, 抗氯离子渗透性能

Abstract:

This study investigated the protective effect of epoxy-cement-based permeable crystalline composite coating on concrete structures in a chloride freeze-thaw environment. Rapid freeze-thaw tests， chloride ion penetration resistance performance tests， and durability tests under combined chloride and freeze-thaw environment were conducted. The variations in key parameters， including the relative dynamic elastic modulus， mass loss rate， and chloride ion diffusion coefficient of concrete specimens were measured. The results indicate that， compared to the two single coatings （epoxy anti-corrosion coating and cement-based permeable crystalline material）， the composite coating significantly reduces the chloride ion diffusion coefficient of concrete specimens， effectively slows the decline in relative dynamic elastic modulus and mass loss rate， and delays the onset of freeze-thaw damage. Based on the modified Duracrete model， the service life of concrete structures with different coatings under chloride freeze-thaw environment was predicted. In submerged， tidal， and atmospheric zones， the service life of concrete structures coated with the composite coating increases by approximately 90.6%， 92.9%， and 90.7%， respectively， compared to those with a single epoxy coating， and by approximately 55.6%， 74.4%， and 66.4%， respectively， compared to those with a single cement-based permeable crystalline coating. These findings demonstrate that the epoxy-cement-based permeable crystalline composite coating can effectively extend the service life of concrete structures in chloride salt freeze-thaw environment.

Key words: concrete structure, epoxy anti-corrosion coating, cement-based permeable crystalline material, composite coating, freeze-thaw damage, chloride ion penetration resistance performance

中图分类号:

TU528

付涛, 耿琳, 任宪富, 李燕, 杨波, 李伟华. 环氧-水泥基渗透结晶型复合涂层对混凝土氯盐冻融防护性能的影响[J]. 硅酸盐通报, 2026, 45(4): 1160-1174.

FU Tao, GENG Lin, REN Xianfu, LI Yan, YANG Bo, LI Weihua. Effect of Epoxy-Cement-Based Permeable Crystalline Composite Coating on Chloride Salt Freeze-Thaw Protection Performance of Concrete[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2026, 45(4): 1160-1174.

图/表 24

表1 混凝土配合比

Table 1 Mix proportion of concrete

Composition	Cement	Fly ash	Sand	Stone	Water-reducing agent	Water
Mix proportion/（kg·m^-3）	432.42	116.17	558.00	1 242.00	3.40	168.19

表2 环氧防腐涂层的基本性能

Table 2 Basic properties of epoxy anti-corrosion coatings

Paint fineness/μm	Drying time/min		Impact resistanceheight/cm	Adhesion/MPa
Paint fineness/μm	Surface drying time	Actual drying time	Impact resistanceheight/cm	Adhesion/MPa
35	8	60	40	7

图1 快速冻融试验试件

Fig.1 Specimens for rapid freeze-thaw test

图2 试件破坏形态

Fig.2 Failure modes of specimens

表3 混凝土相对动弹性模量变化

Table 3 Changes in relative dynamic elastic modulus of concrete

Number of freeze-thaw cycles	Relative dynamic elastic modulus/%
Number of freeze-thaw cycles	Ft-Bs	Ft-Er	Ft-Cb	Ft-Er+Cb
0	100.0	100.0	100.0	100.0
25	99.3	99.8	99.9	99.9
50	98.1	98.9	99.1	99.8
75	95.7	97.3	98.8	99.6
100	90.3	95.6	98.2	99.1
125	82.3	93.4	96.7	98.4
150	75.1	89.0	94.8	97.7
175	66.2	83.9	90.1	95.1
200	59.8	75.2	84.9	91.6
225		68.8	79.4	87.5
250		59.9	75.7	81.9
275				76.6
300				67.3

表4 混凝土质量损失率变化

Table 4 Changes in mass loss rate of concrete

Number of freeze-thaw cycles	Mass loss rate/%
Number of freeze-thaw cycles	Ft-Bs	Ft-Er	Ft-Cb	Ft-Er+Cb
0	0	0	0	0
25	-0.10	-0.07	-0.03	0
50	0.80	0.09	0.07	-0.01
75	1.70	0.20	0.80	-0.02
100	1.75	0.53	1.30	0.03
125	2.10	1.11	1.51	0.30
150	2.51	1.56	2.17	0.57
175	3.20	2.00	2.56	0.94
200	4.89	2.34	3.17	1.16
225		2.96	3.58	1.72
250		3.87	4.98	2.56
275				3.30
300				4.06

图3 抗氯离子渗透性能试验试件

Fig.3 Specimens for chloride ion penetration resistance performance test

图4 试件截面显色图

Fig.4 Color map of specimen section

表5 氯离子扩散系数测定值

Table 5 Measured values of chloride ion diffusion coefficient

Specimen number	Voltage/V	Duration/h	Average penetrationdepth/mm	Calculated value ofchloride ion diffusioncoefficient/（10^-12 m²·s^-1）	Measured value of chloride ion diffusion coefficient/（10^-12 m²·s^-1）
Cl-Bs-1	30.31	24	16.47	7.49	8.34
Cl-Bs-2	29.60	24	17.75	8.25
Cl-Bs-3	29.48	24	19.46	9.27
Cl-Er-1	50.32	24	16.10	4.55	4.96
Cl-Er-2	50.28	24	15.76	4.40
Cl-Er-3	39.42	24	16.30	5.92
Cl-Cb-1	59.67	24	17.46	4.18	3.37
Cl-Cb-2	59.65	24	11.76	2.84
Cl-Cb-3	59.62	24	13.60	3.34
Cl-Er+Cb-1	50.30	24	10.40	2.61	2.59
Cl-Er+Cb-2	59.92	24	11.20	2.63
Cl-Er+Cb-3	59.90	24	9.50	2.53

图5 氯离子扩散系数

Fig.5 Chloride ion diffusion coefficient

图6 氯离子扩散系数降低率

Fig.6 Reduction rate of chloride ion diffusion coefficient

图7 氯盐冻融复合试验试件

Fig.7 Specimens for chloride salt freeze-thaw composite test

表6 氯离子扩散系数测定值

Table 6 Measured values of chloride ion diffusion coefficient

Number of freeze-thaw cycles	Specimennumber	Averagevoltage/V	Duration/h	Average penetrationdepth/mm	Measured value of chloride ion diffusioncoefficient/（10^-12 m²·s^-1）
50	Ft+Cl-Bs	31.67	24	21.53	10.30
	Ft+Cl-Er	46.67	24	17.17	5.87
	Ft+Cl-Cb	30.00	24	14.77	4.59
	Ft+Cl-Er+Cb	28.33	24	11.73	3.78
100	Ft+Cl-Bs	26.67	24	27.33	13.10
	Ft+Cl-Er	40.00	24	19.03	7.34
	Ft+Cl-Cb	33.33	24	16.30	6.52
	Ft+Cl-Er+Cb	26.67	24	12.63	4.92
150	Ft+Cl-Bs	26.67	24	30.50	17.70
	Ft+Cl-Er	53.33	24	21.67	9.07
	Ft+Cl-Cb	35.00	24	20.83	8.59
	Ft+Cl-Er+Cb	28.33	24	15.33	6.85
200	Ft+Cl-Bs	25.00	24	43.20	24.32
	Ft+Cl-Er	38.33	24	25.17	12.59
	Ft+Cl-Cb	35.00	24	23.57	12.27
	Ft+Cl-Er+Cb	30.00	24	18.50	9.57
250	Ft+Cl-Er+Cb	32.50	24	21.50	13.22

图8 氯离子扩散系数及降低率

Fig.8 Chloride ion diffusion coefficient and its reduction rate

图9 非稳态氯离子迁移系数变化规律

Fig.9 Variation law of non-steady-state chloride ion migration coefficient

表7 非稳态氯离子迁移系数与冻融循环次数的关系

Table 7 Relationship between non-steady-state chloride ion migration coefficient and freeze-thaw cycles

Specimen number	$λ$	$D R C M, 0$	Fitting formula	$R 2$
Bs	0.006 52	8.34	$D R C M (n) = 8.34 ⋅ e 0.006 52 n$	0.908
Er	0.006 42	4.96	$D R C M (n) = 4.96 ⋅ e 0.006 42 n$	0.899
Cb	0.005 22	3.37	$D R C M (n) = 3.37 ⋅ e 0.005 22 n$	0.978
Er+Cb	0.004 45	2.59	$D R C M (n) = 2.59 ⋅ e 0.004 45 n$	0.977

表7 非稳态氯离子迁移系数与冻融循环次数的关系

Table 7 Relationship between non-steady-state chloride ion migration coefficient and freeze-thaw cycles

Specimen number	$λ$	$D R C M, 0$	Fitting formula	$R 2$
Bs	0.006 52	8.34	$D R C M (n) = 8.34 ⋅ e 0.006 52 n$	0.908
Er	0.006 42	4.96	$D R C M (n) = 4.96 ⋅ e 0.006 42 n$	0.899
Cb	0.005 22	3.37	$D R C M (n) = 3.37 ⋅ e 0.005 22 n$	0.978
Er+Cb	0.004 45	2.59	$D R C M (n) = 2.59 ⋅ e 0.004 45 n$	0.977

图10 非稳态氯离子迁移系数与冻融循环次数拟合曲线

Fig.10 Fitting curves of non-steady-state chloride migration coefficient and freeze-thaw cycles

表8 环境影响系数ke

Table 8 Environmental impact coefficient ke

Cementing material	Portland cement	Mineral powder
Submerged zone	1.32	3.88
Tidal splash zone	0.92	2.70
Atmospheric zone	0.65	1.98

表9 混凝土养护系数kc

Table 9 Concrete curing coefficient kc

Curing time/d	1	3	7	28
Curing coefficient	2.08	1.50	1.00	0.79

表10 龄期指数n

Table 10 Age index n

Cementing material	Portland cement	Fly ash	Mineral powder	Silica fume
Submerged zone	0.30	0.69	0.71	0.62
Tidal splash zone	0.37	0.93	0.60	0.39
Atmospheric zone	0.65	0.66	0.85	0.79

表11 表面氯离子浓度拟合回归系数Ac

Table 11 Fitting regression coefficient of surface chloride ion concentration Ac

Area	A_c
Area	Portland cement	Fly ash	Mineral powder	Silica fume
Submerged zone	10.30	10.80	5.06	12.50
Tidal splash zone	7.76	7.45	6.77	8.96
Atmospheric zone	2.57	4.42	3.05	3.23

表12 临界氯离子浓度

Table 12 Critical chloride ion concentration

Area	$C c$
Area	Water-cement ratio 0.3	Water-cement ratio 0.4	Water-cement ratio 0.5
Submerged zone	2.3	2.1	1.6
Tidal splash zone	0.9	0.8	0.5
Atmospheric zone	0.3	0.2	0.1

表12 临界氯离子浓度

Table 12 Critical chloride ion concentration

Area	$C c$
Area	Water-cement ratio 0.3	Water-cement ratio 0.4	Water-cement ratio 0.5
Submerged zone	2.3	2.1	1.6
Tidal splash zone	0.9	0.8	0.5
Atmospheric zone	0.3	0.2	0.1

表13 与维修成本有关的参数

Table 13 Parameters related to maintenance costs

Parameter	Cost of maintenance for risk reduction
Parameter	High	Medium	Low
$Δ x$ /mm	20	14	8
$γ c$	1.20	1.06	1.03
$γ s$	1.70	1.40	1.20
$γ R$	3.25	2.35	1.50

表13 与维修成本有关的参数

Table 13 Parameters related to maintenance costs

Parameter	Cost of maintenance for risk reduction
Parameter	High	Medium	Low
$Δ x$ /mm	20	14	8
$γ c$	1.20	1.06	1.03
$γ s$	1.70	1.40	1.20
$γ R$	3.25	2.35	1.50

表14 考虑冻融损伤破坏的混凝土结构预测寿命

Table 14 Predicted service life of concrete structures considering freeze-thaw damage and destruction

Coating specimen group	Environmental type	$A c$	$C c d$ /%	$C s d$ /%	n	Predicted lifespan/a
Bs group	Submerged zone	10.30	1.98	6.06	0.30	20.0
	Tidal splash zone	7.76	0.75	4.56	0.37	17.9
	Atmospheric zone	2.57	0.19	1.51	0.65	32.1
Er group	Submerged zone	10.30	1.98	6.06	0.30	45.8
	Tidal splash zone	7.76	0.75	4.56	0.37	33.9
	Atmospheric zone	2.57	0.19	1.51	0.65	110.2
Cb group	Submerged zone	10.30	1.98	6.06	0.30	56.1
	Tidal splash zone	7.76	0.75	4.56	0.37	37.5
	Atmospheric zone	2.57	0.19	1.51	0.65	126.3
Er+Cb group	Submerged zone	10.30	1.98	6.06	0.30	87.3
	Tidal splash zone	7.76	0.75	4.56	0.37	65.4
	Atmospheric zone	2.57	0.19	1.51	0.65	210.2

表14 考虑冻融损伤破坏的混凝土结构预测寿命

Table 14 Predicted service life of concrete structures considering freeze-thaw damage and destruction

Coating specimen group	Environmental type	$A c$	$C c d$ /%	$C s d$ /%	n	Predicted lifespan/a
Bs group	Submerged zone	10.30	1.98	6.06	0.30	20.0
	Tidal splash zone	7.76	0.75	4.56	0.37	17.9
	Atmospheric zone	2.57	0.19	1.51	0.65	32.1
Er group	Submerged zone	10.30	1.98	6.06	0.30	45.8
	Tidal splash zone	7.76	0.75	4.56	0.37	33.9
	Atmospheric zone	2.57	0.19	1.51	0.65	110.2
Cb group	Submerged zone	10.30	1.98	6.06	0.30	56.1
	Tidal splash zone	7.76	0.75	4.56	0.37	37.5
	Atmospheric zone	2.57	0.19	1.51	0.65	126.3
Er+Cb group	Submerged zone	10.30	1.98	6.06	0.30	87.3
	Tidal splash zone	7.76	0.75	4.56	0.37	65.4
	Atmospheric zone	2.57	0.19	1.51	0.65	210.2

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