Article(id=1319726461947327271, tenantId=1146029695717560320, journalId=1263187385517883426, issueId=1319726382268138030, articleNumber=null, orderNo=null, doi=10.14062/j.issn.0454-5648.20250427, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1748880000000, receivedDateStr=2025-06-03, revisedDate=1750089600000, revisedDateStr=2025-06-17, acceptedDate=null, acceptedDateStr=null, onlineDate=1792576907860, onlineDateStr=2026-10-21, pubDate=1763568000000, pubDateStr=2025-11-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1792576907860, onlineIssueDateStr=2026-10-21, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1792576907860, creator=13701087609, updateTime=1792576907860, updator=13701087609, issue=Issue{id=1319726382268138030, tenantId=1146029695717560320, journalId=1263187385517883426, year='2025', volume='53', issue='11', pageStart='3079', pageEnd='3432', issueExtLink='null', onlineDate='null', pubDate='1763568000000', pubDateStr='2025-11-20', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1792576888863, creator='13701087609', updateTime=1792577494231, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext={EN=IssueExt(id=1319728921399116056, tenantId=1146029695717560320, journalId=1263187385517883426, issueId=1319726382268138030, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1319728921403310361, tenantId=1146029695717560320, journalId=1263187385517883426, issueId=1319726382268138030, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null, downloadFileDto=null}, startPage=3239, endPage=3249, ext={EN=ArticleExt(id=1319726462173819688, articleId=1319726461947327271, tenantId=1146029695717560320, journalId=1263187385517883426, language=EN, title=Hydrophobicity Degradation of Silane-Impregnated Cement-Based Materials, columnId=1319726165087077079, journalTitle=Journal of the Chinese Ceramic Society, columnName=Research Article, runingTitle=null, highlight=null, articleAbstract=
Introduction

Silane-impregnation is one of the most used surface waterproofing treatments for concrete structures to improve the durability, but long-term engineering observations find that silane-impregnation will deteriorate during the service life of concrete structures. The deterioration of silane treatment undermines its effectiveness in protecting the concrete structures and improving their durability. However, the deterioration mechanism of silane-impregnated treatment has rarely been studied. To fill this gap, This paper studied the deterioration mechanism of surface hydrophobicity of silane-impregnated cement-based materials through laboratory accelerated tests. The accelerated tests include drying-wetting cycles by pure water and ultraviolet (UV) irradiation. Then, the silane-impregnated materials are characterized by infrared spectroscopy, pyrolysis gas chromatography-mass spectrometry, thermal analysis system, and dynamic water vapor desorption. The aim of this study is to provide a research basis for quantifying the usage life of surface silane impregnation treatment used in engineering.

Methods

Laboratory accelerated deterioration tests were conducted to study the deterioration mechanism of surface hydrophobicity of silane-impregnated cement-based materials. The accelerated tests include drying-wetting cycles by pure water and ultraviolet (UV) irradiation. For drying-wetting cycle tests, an experimental design of 4 h wetting time and 8 h drying time was adopted. The irradiance of ultraviolet (UV) irradiation tests is irradiance, and the irradiation cycle is 30 d. After accelerated deterioration tests, the silane-impregnated cementitious materials are characterized by infrared spectroscopy, pyrolysis gas chromatography-mass spectrometry, thermal analysis system, and dynamic water vapor desorption.

Infrared spectroscopy was conducted to study the silane molecular structural changes during accelerated deterioration tests; pyrolysis gas chromatography-mass spectrometry and thermal analysis system was conducted to characterize the silane content in cementitious materials; and dynamic water vapor desorption was conducted to characterize the hydrophobic performance of impregnated cementitious materials.

Results and discussion

Under the action of drying-wetting cycles: 1) infrared spectroscopy results of impregnated cementitious materials showed that the relative content of different alkyl groups had not changed, indicating that the molecular structure of silane was stable; 2) Both pyrolysis chromatography-mass spectrometry and thermal analysis system results showed that the silane content in impregnated cementitious materials was decreasing, combining with the analysis of infrared spectroscopy results, silane in impregnated cementitious materials was most likely underwent hydrolysis reaction, and the hydrolyzed silane continuously detached from impregnated particles under the action of drying-wetting cycles; 3) In addition, the water vapor adsorption capacity of cement paste powders, the water sorptivity and contact angle of mortar specimens had all increased.

Under the action of UVB-313 ultraviolet radiation: 1) the silane impregnated on the surface of cement-based material particles underwent chemical bond breakage. Based on the wavelength of the ultraviolet radiation, it is inferred that this likely caused the breaking and recombination of tertiary carbon bonds. Infrared spectroscopy, gas chromatography-mass spectrometry, thermal analysis system, and water vapor adsorption capacity results all indicate this aging process; 2) Due to the direct impact of ultraviolet irradiation on the surface of impregnated materials, the water sorptivity and contact angle of the impregnated mortar specimens had changed significantly. However, it should be noted that this significant aging effect depends on the UV wavelength and irradiation energy of UVB-313 lamps using in the laboratory. In the natural environment, the irradiance of sunlight is much lower than that of UVB-313. Therefore, the accelerated UV testing results are primarily suitable for mechanistic research and cannot not be directly applied to the aging behavior of silane impregnations in natural environment.

Conclusion

The stability of cement-based materials impregnated with high-purity silane (isobutyl triethoxysilane) was confirmed through drying-wetting cycles and ultraviolet irradiation. The stability is attributed to the condensation network between silane monomers and the condensation reaction with the surface of cement-based materials (Si—O—Si bonds); The wavelength distribution of natural light and the barrier effect of cement-based materials make the deterioration caused by ultraviolet irradiation less likely to occur in natural environment. The deterioration caused by hydrolysis of silane should be more related to the effect of environmental water. Based on the study of the drying-wetting cycles results and the mechanism of silane hydrolysis, it can be reasonably inferred that the hydrophobicity degradation of cement-based materials surface (layer) impregnated with silane in natural environments is related to the hydrolysis of silane and the migration of hydrolyzed silane.

For the four different cement pastes used in this study, OPC showed the greatest decrease in water vapor adsorption capacity after silane impregnation, indicating that the silane impregnation effect of OPC is better than that of OFA, OSG, and OFS. Combined with the chemical reaction mechanism of silane impregnation, alkaline conditions can catalyze the impregnation reaction of silane. However, pozzolanic reaction, occurred in the three cementitious materials mixed with fly ash or slag, consumes the alkali reserve of the pore solution. Therefore, the alkalinity of the pore solution of OPC is the highest, resulting in the best silane impregnation effect.

, authors=Xin ZHANG, Le LI, Siyu LIN, Kefei LI, authorsList=Xin ZHANG, Le LI, Siyu LIN, Kefei LI, authorCompany=null, correspAuthors=Kefei LI, authorNote=

ZHANG Xin (1998-), female, Master candidate. E-mail:

, correspAuthorsNote=
LI Kefei (1972-), male, Ph.D., Professor. E-mail:
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硅烷作为混凝土常用的耐久性防护材料,其憎水性劣化机理对评估防护效果至关重要。对硬化水泥浆体粉末进行硅烷浸渍,使用加速试验研究硅烷浸渍水泥基材料表面憎水性的劣化机理,加速试验方法包括纯水干湿循环和紫外辐照,采用红外光谱、裂解气相色谱质谱、热分析联用系统和动态水蒸气脱吸附等方法表征劣化后水泥浆体粉末表面硅烷状态以及憎水特性。结果表明:纯水干湿循环和紫外辐照之后硅烷浸渍水泥浆体粉末中硅烷占比有一定的下降,浸渍粉末的水蒸气吸附和浸渍砂浆试件质量吸水率均有增加的趋势;干湿循环极有可能是通过硅烷的水解与溢出导致憎水性的劣化,紫外辐照则是通过改变硅烷单体的结构而导致对憎水性的劣化作用。

, authors=张鑫, 李乐, 林思宇, 李克非, authorsList=张鑫, 李乐, 林思宇, 李克非, authorCompany=null, correspAuthors=李克非, authorNote=

张鑫(1998—),女,硕士研究生。

, correspAuthorsNote=
李克非(1972—),男,博士,教授。
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硅烷浸渍水泥基材料表面憎水性劣化
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张鑫 , 李乐 , 林思宇 , 李克非
硅酸盐学报 | 研究论文 2025,53(11): 3239-3249
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硅酸盐学报 |研究论文 2025 , 53 (11) : 3239 -3249
硅烷浸渍水泥基材料表面憎水性劣化
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张鑫 , 李乐, 林思宇, 李克非
作者信息
  • 清华大学土木工程系,教育部土木工程安全与耐久重点实验室,北京 100084
通讯作者:
李克非(1972—),男,博士,教授。
作者简介:

张鑫(1998—),女,硕士研究生。

Hydrophobicity Degradation of Silane-Impregnated Cement-Based Materials
Xin ZHANG , Le LI, Siyu LIN, Kefei LI
Affiliations
  • Key Laboratory of Civil Engineering Safety and Durability of China Education Ministry, Department of Civil Engineering, Tsinghua University, Beijing 100084, China
  • Corresponding Author:
    LI Kefei (1972-), male, Ph.D., Professor. E-mail:

    ZHANG Xin (1998-), female, Master candidate. E-mail:

出版时间: 2025-11-20 doi: 10.14062/j.issn.0454-5648.20250427
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硅烷作为混凝土常用的耐久性防护材料,其憎水性劣化机理对评估防护效果至关重要。对硬化水泥浆体粉末进行硅烷浸渍,使用加速试验研究硅烷浸渍水泥基材料表面憎水性的劣化机理,加速试验方法包括纯水干湿循环和紫外辐照,采用红外光谱、裂解气相色谱质谱、热分析联用系统和动态水蒸气脱吸附等方法表征劣化后水泥浆体粉末表面硅烷状态以及憎水特性。结果表明:纯水干湿循环和紫外辐照之后硅烷浸渍水泥浆体粉末中硅烷占比有一定的下降,浸渍粉末的水蒸气吸附和浸渍砂浆试件质量吸水率均有增加的趋势;干湿循环极有可能是通过硅烷的水解与溢出导致憎水性的劣化,紫外辐照则是通过改变硅烷单体的结构而导致对憎水性的劣化作用。

硅烷浸渍  /  水泥基材料  /  干湿循环  /  紫外辐照
Introduction

Silane-impregnation is one of the most used surface waterproofing treatments for concrete structures to improve the durability, but long-term engineering observations find that silane-impregnation will deteriorate during the service life of concrete structures. The deterioration of silane treatment undermines its effectiveness in protecting the concrete structures and improving their durability. However, the deterioration mechanism of silane-impregnated treatment has rarely been studied. To fill this gap, This paper studied the deterioration mechanism of surface hydrophobicity of silane-impregnated cement-based materials through laboratory accelerated tests. The accelerated tests include drying-wetting cycles by pure water and ultraviolet (UV) irradiation. Then, the silane-impregnated materials are characterized by infrared spectroscopy, pyrolysis gas chromatography-mass spectrometry, thermal analysis system, and dynamic water vapor desorption. The aim of this study is to provide a research basis for quantifying the usage life of surface silane impregnation treatment used in engineering.

Methods

Laboratory accelerated deterioration tests were conducted to study the deterioration mechanism of surface hydrophobicity of silane-impregnated cement-based materials. The accelerated tests include drying-wetting cycles by pure water and ultraviolet (UV) irradiation. For drying-wetting cycle tests, an experimental design of 4 h wetting time and 8 h drying time was adopted. The irradiance of ultraviolet (UV) irradiation tests is irradiance, and the irradiation cycle is 30 d. After accelerated deterioration tests, the silane-impregnated cementitious materials are characterized by infrared spectroscopy, pyrolysis gas chromatography-mass spectrometry, thermal analysis system, and dynamic water vapor desorption.

Infrared spectroscopy was conducted to study the silane molecular structural changes during accelerated deterioration tests; pyrolysis gas chromatography-mass spectrometry and thermal analysis system was conducted to characterize the silane content in cementitious materials; and dynamic water vapor desorption was conducted to characterize the hydrophobic performance of impregnated cementitious materials.

Results and discussion

Under the action of drying-wetting cycles: 1) infrared spectroscopy results of impregnated cementitious materials showed that the relative content of different alkyl groups had not changed, indicating that the molecular structure of silane was stable; 2) Both pyrolysis chromatography-mass spectrometry and thermal analysis system results showed that the silane content in impregnated cementitious materials was decreasing, combining with the analysis of infrared spectroscopy results, silane in impregnated cementitious materials was most likely underwent hydrolysis reaction, and the hydrolyzed silane continuously detached from impregnated particles under the action of drying-wetting cycles; 3) In addition, the water vapor adsorption capacity of cement paste powders, the water sorptivity and contact angle of mortar specimens had all increased.

Under the action of UVB-313 ultraviolet radiation: 1) the silane impregnated on the surface of cement-based material particles underwent chemical bond breakage. Based on the wavelength of the ultraviolet radiation, it is inferred that this likely caused the breaking and recombination of tertiary carbon bonds. Infrared spectroscopy, gas chromatography-mass spectrometry, thermal analysis system, and water vapor adsorption capacity results all indicate this aging process; 2) Due to the direct impact of ultraviolet irradiation on the surface of impregnated materials, the water sorptivity and contact angle of the impregnated mortar specimens had changed significantly. However, it should be noted that this significant aging effect depends on the UV wavelength and irradiation energy of UVB-313 lamps using in the laboratory. In the natural environment, the irradiance of sunlight is much lower than that of UVB-313. Therefore, the accelerated UV testing results are primarily suitable for mechanistic research and cannot not be directly applied to the aging behavior of silane impregnations in natural environment.

Conclusion

The stability of cement-based materials impregnated with high-purity silane (isobutyl triethoxysilane) was confirmed through drying-wetting cycles and ultraviolet irradiation. The stability is attributed to the condensation network between silane monomers and the condensation reaction with the surface of cement-based materials (Si—O—Si bonds); The wavelength distribution of natural light and the barrier effect of cement-based materials make the deterioration caused by ultraviolet irradiation less likely to occur in natural environment. The deterioration caused by hydrolysis of silane should be more related to the effect of environmental water. Based on the study of the drying-wetting cycles results and the mechanism of silane hydrolysis, it can be reasonably inferred that the hydrophobicity degradation of cement-based materials surface (layer) impregnated with silane in natural environments is related to the hydrolysis of silane and the migration of hydrolyzed silane.

For the four different cement pastes used in this study, OPC showed the greatest decrease in water vapor adsorption capacity after silane impregnation, indicating that the silane impregnation effect of OPC is better than that of OFA, OSG, and OFS. Combined with the chemical reaction mechanism of silane impregnation, alkaline conditions can catalyze the impregnation reaction of silane. However, pozzolanic reaction, occurred in the three cementitious materials mixed with fly ash or slag, consumes the alkali reserve of the pore solution. Therefore, the alkalinity of the pore solution of OPC is the highest, resulting in the best silane impregnation effect.

silane impregnation  /  cement-based materials  /  drying-wetting cycle  /  ultraviolet irradiation
张鑫, 李乐, 林思宇, 李克非. 硅烷浸渍水泥基材料表面憎水性劣化. 硅酸盐学报, 2025 , 53 (11) : 3239 -3249 . DOI: 10.14062/j.issn.0454-5648.20250427
Xin ZHANG, Le LI, Siyu LIN, Kefei LI. Hydrophobicity Degradation of Silane-Impregnated Cement-Based Materials[J]. Journal of the Chinese Ceramic Society, 2025 , 53 (11) : 3239 -3249 . DOI: 10.14062/j.issn.0454-5648.20250427
  • 国家自然科学基金重点项目(52038004)
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2025年第53卷第11期
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doi: 10.14062/j.issn.0454-5648.20250427
  • 接收时间:2025-06-03
  • 首发时间:2026-10-21
  • 出版时间:2025-11-20
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  • 收稿日期:2025-06-03
  • 修回日期:2025-06-17
基金
国家自然科学基金重点项目(52038004)
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    清华大学土木工程系,教育部土木工程安全与耐久重点实验室,北京 100084

通讯作者:

李克非(1972—),男,博士,教授。
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2种不同金属材料的力学参数
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种数
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species
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Percentage of total
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鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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