Effect of Epoxy-Cement-Based Permeable Crystalline Composite Coating on Chloride Salt Freeze-Thaw Protection Performance of Concrete

doi:10.16552/j.cnki.issn1001-1625.2025.0986

Abstract

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

CLC Number:

TU528

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.

Figures/Tables 24

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

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

Fig.1 Specimens for rapid freeze-thaw test

Fig.2 Failure modes of specimens

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

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

Fig.3 Specimens for chloride ion penetration resistance performance test

Fig.4 Color map of specimen section

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

Fig.5 Chloride ion diffusion coefficient

Fig.6 Reduction rate of chloride ion diffusion coefficient

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

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

Fig.8 Chloride ion diffusion coefficient and its reduction rate

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

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

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

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

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

Table 9 Concrete curing coefficient kc

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

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

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

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

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

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

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

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

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

References 22

[1]	HOLT E， FERREIRA M， KUOSA H， et al. Performance and durability of concrete under the effect of multi-deterioration mechanisms［C］. The 14th International Congress on the Chemistry of Cement （ICCC 2015）， China Building Materials Academy， 2015： 70.
[2]	WANG R J， ZHANG Q J， LI Y. Deterioration of concrete under the coupling effects of freeze-thaw cycles and other actions： a review［J］. Construction and Building Materials， 2022， 319： 126045.
[3]	肖阳，张亮，张宿峰，等. 涂层类型对混凝土抗盐冻性能的影响［J］. 材料导报， 2022， 36（增刊2）： 214-221.
	XIAO Y， ZHANG L， ZHANG S F， et al. Influence of coating type on salt freezing resistance of concrete［J］. Materials Reports， 2022， 36（supplement 2）： 214-221 （in Chinese）.
[4]	张铖，李维红，范金朋，等. 不同防护涂层提升混凝土耐久性能研究［J］. 混凝土， 2019（12）： 165-168.
	ZHANG C， LI W H， FAN J P， et al. Study on durability of concrete structures strengthened by different protective coatings［J］. Concrete， 2019（12）： 165-168 （in Chinese）.
[5]	马衍轩，高玉华，李美玉，等. 海工混凝土环氧涂层的改性设计与防护机制研究进展［J］.复合材料学报，2025， 42（11）： 6181-6200.
	MA Y X， GAO Y H， LI M Y， et al. Research progress of modified design and protection mechanism of epoxy based protective coating on marine concrete surface［J］. Acta Materiae Compositae Sinica， 2025， 42（11）： 6181-6200 （in Chinese）.
[6]	SHEN B H， SHENG Y P， ABDULAKEEM A， et al. An experimental characterization of the properties of graphene oxide： waterborne epoxy resin coating of concrete after chloride erosion［J］. Construction and Building Materials， 2024， 428： 136207.
[7]	张乙山. 寒区桥梁混凝土盖梁防腐涂层耐久性研究［D］. 沈阳：沈阳建筑大学， 2024.
	ZHANG Y S. Study on the durability of anticorrosive coating forconcrete cover beams of bridges in cold regions［D］. Shenyang： Shenyang Jianzhu University， 2024 （in Chinese）.
[8]	梁栋，孙静，申慧才. 桥梁结构耐久性病害处理措施研究［J］. 2014（1）： 31-34.
	LIANG D， SUN J， SHEN H C. Study on treatment measures of durability diseases of bridge structure［J］. Highway， 2014（1）： 31-34 （in Chinese）.
[9]	余概宁. 水性渗透防水剂的实际应用效果研究［J］. 中外公路， 2014， 34（1）： 286-289.
	YU G N. Practical application effect of water-based penetrating waterproofing agent［J］. Journal of China & Foreign Highway， 2014， 34（1）： 286-289 （in Chinese）.
[10]	SUN Q L， WANG W S， XU S Q， et al. Effect of modified nano silica on the protective effect of cement-based penetrating crystallization coating［J］. Integrated Ferroelectrics， 2023， 236（1）： 52-62.
[11]	ZHAO H B， WANG Q Z， SHANG R P， et al. Development， challenges， and applications of concrete coating technology： exploring paths to enhance durability and standardization［J］. Coatings， 2025， 15（4）： 409.
[12]	国家质量监督检验检疫总局，国家标准化管理委员会. 色漆、清漆和印刷油墨研磨细度的测定： GB/T 6753.1—2007 ［S］. 北京：中国标准出版社， 2008.
	General Administration of Quality Supervision， Inspection and Quarantine of the People’s Republic of China， National Standardization Management Committee. Determination of grinding fineness of paint， varnish and printing ink： GB/T 6753.1—2007 ［S］. Beijing ： China Standards Publishing House， 2008 （in Chinese）.
[13]	国家市场监督管理总局，国家标准化管理委员会. 漆膜、腻子膜干燥时间测定法： GB/T 1728—2020 ［S］. 北京：中国标准出版社， 2020.
	State Administration of Market Supervision and Administration of the People’s Republic of China， National Standardization Management Committee. Determination of drying time of paint film and putty film： GB/T 1728—2020 ［S］.Beijing ： China Standards Publishing House， 2020 （in Chinese）.
[14]	国家市场监督管理总局，国家标准化管理委员会. 漆膜耐冲击测定法： GB/T 1732—2020 ［S］. 北京：中国标准出版社， 2020.
	State Administration of Market Supervision and Administration， National Standardization Management Committee. Determination of impact resistance of paint film： GB/T 1732—2020 ［S］.Beijing： China Standards Publishing House， 2020 （in Chinese）.
[15]	国家质量监督检验检疫总局，国家标准化管理委员会. 色漆和清漆拉开法附着力试验： GB/T 5210—2006 ［S］. 北京：中国标准出版社， 2007.
	General Administration of Quality Supervision， Inspection and Quarantine of the People’s Republic of China， National Standardization Management Committee. Adhesion test of paint and varnish by pull-off method： GB/T 5210—2006 ［S］. Beijing： China Standards Publishing House， 2007 （in Chinese）.
[16]	国家质量监督检验检疫总局，国家标准化管理委员会. 水泥基渗透结晶型防水材料： GB 18445—2025 ［S］. 北京：中国标准出版社， 2025.
	General Administration of Quality Supervision， Inspection and Quarantine of the People’s Republic of China， National Standardization Management Committee. Cement-based permeable crystalline waterproofing material： GB 18445—2025 ［S］. Beijing： China Standards Publishing House， 2025 （in Chinese）.
[17]	国家市场监督管理总局，国家标准化管理委员会. 水泥胶砂强度检验方法（ISO法）： GB/T 17671—2021 ［S］. 北京：中国标准出版社， 2021.
	State Administration of Market Supervision and Administration， National Standardization Management Committee. Cement mortar strength test method （ISO method）： GB/T 17671—2021 ［S］. Beijing： China Standard Publishing House， 2021 （in Chinese）.
[18]	中华人民共和国住房和城乡建设部，国家市场监督管理总局. 混凝土长期性能和耐久性能试验方法标准： GB/T 50082—2024 ［S］. 北京：中国建筑工业出版社， 2024.
	Ministry of Housing and Urban-Rural Development of the People’s Republic of China， State Administration of Market Supervision and Administration. Standard for test methods of long-term performance and durability of concrete： GB/T 50082—2024 ［S］. Beijing： China Construction Industry Publishing House， 2024 （in Chinese）.
[19]	邓嘉辉. 氯盐冻融环境下混凝土多措施复合作用的耐久性研究［D］. 广州：广州大学， 2022.
	DENG J H. Research on the durability of concrete under chloride salt freeze-thaw environment with the composite action of multiple measures［D］. Guangzhou： Guangzhou University， 2022 （in Chinese）.
[20]	李金玉，彭小平，邓正刚，等. 混凝土抗冻性的定量化设计［J］. 混凝土， 2000（12）： 61-65.
	LI J Y， PENG X P， DENG Z G， et al. Quantitative design of frost resistance of concrete［J］. Concrete， 2000（12）： 61-65 （in Chinese）.
[21]	林宝玉. 我国港工混凝土抗冻耐久性指标的研究与实践［C］//混凝土结构耐久性设计与施工论文集. 北京：中国建筑工业出版社， 2004： 11.
	LIN B Y. Research and practice on freeze-thaw durability indices of harbor engineering concrete in China［C］// Collected Papers on Durability Design and Construction of Concrete Structures. Beijing： China Architecture and Building Press， 2004： 11 （in Chinese）.
[22]	钟小平，金伟良，张宝健. 氯盐环境下混凝土结构的耐久性设计方法［J］. 建筑材料学报， 2016， 19（3）： 544-549.
	ZHONG X P， JIN W L， ZHANG B J. Durability design method of concrete structures under chloride environment［J］. Journal of Building Materials， 2016， 19（3）： 544-549 （in Chinese）.