<i>γ</i>-APS接枝环氧树脂分子对环氧涂层/金属界面化学键合的研究

doi:10.11900/0412.1961.2018.00121

金属学报

2019, Vol. 55

Issue (2): 238-248 DOI: 10.11900/0412.1961.2018.00121

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γ-APS接枝环氧树脂分子对环氧涂层/金属界面化学键合的研究

操发春^1,², 吴航³(

), 杨延格^1,⁴(

), 曹京宜⁴, 张涛^1,³, 王福会³

1 中国科学院金属研究所沈阳 110016
2 中国科学技术大学材料科学与工程学院沈阳 110016
3 东北大学材料科学与工程学院沈阳 110819
4 海军涂料分析检测中心北京 102442

Study on Chemical Bonding Between Epoxy Coating and Metal Substrate Using γ-Aminopropyltrimethoxysilaneto Modify Epoxy Resin Molecule

Fachun CAO^1,², Hang WU³(

), Yange YANG^1,⁴(

), Jingyi CAO⁴, Tao ZHANG^1,³, Fuhui WANG³

1 Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China
2 School of Materials Science and Engineering, University of Science and Technology of China, Shenyang 110016, China
3 School of Materials Science and Engineering, Northeastern University, Shenyang 110819, China
4 Navy Coating Analysis and Test Center, Beijing 102442, China

引用本文:

操发春, 吴航, 杨延格, 曹京宜, 张涛, 王福会. γ-APS接枝环氧树脂分子对环氧涂层/金属界面化学键合的研究[J]. 金属学报, 2019, 55(2): 238-248.
Fachun CAO, Hang WU, Yange YANG, Jingyi CAO, Tao ZHANG, Fuhui WANG. Study on Chemical Bonding Between Epoxy Coating and Metal Substrate Using γ-Aminopropyltrimethoxysilaneto Modify Epoxy Resin Molecule[J]. Acta Metall Sin, 2019, 55(2): 238-248.

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摘要:

利用γ-氨基丙基三甲氧基硅烷(γ-APS)对环氧树脂分子进行改性合成了具有键合特性的活性树脂(γ-APS/EP),将活性树脂作为液态添加剂加入到环氧涂层中,利用活性树脂与金属表面羟基反应生成耐水解的噁烷键的特点,实现了环氧涂层/金属界面的化学键合。研究表明,活性树脂添加量为3% (质量分数)时,环氧涂层与金属基体的界面结合力和对腐蚀介质的抗渗透性能达到最佳。根据活性树脂含量的影响,提出了活性树脂在环氧涂层/金属界面的键合机理。

关键词 ：环氧涂层, γ-氨基丙基三甲氧基硅烷;, 化学键合

Abstract：

Epoxy coatings are widely used to protect metals from corrosion in ocean engineering and process industries. It has been proved that the adhesion between epoxy coating and metal is a key factor that affects their service life of the coating. However, interface between epoxy coating and metal substrate is usually combined by weak van der Waals force or secondary bond, which limits the protective performance of coatings. This work aims to translate the interface state from the physical adsorption to chemical bonding so as to increase the service life of epoxy coating. A kind of reactive resin γ-APS/EP with hydrolysis characteristic was prepared using γ-aminopropyltrimethoxysilane (γ-APS), and used as a coating filler with different contents of 0.5%~10%. Both dry and wet adhesion strength of epoxy coatings with different contents of γ-APS/EP were examined, the resistance to aggressive medium of epoxy varied with the contents of γ-APS/EP was evaluated by water absorption measurement, and the structure and composition of the coating/metal systems were characterized by using SEM, XPS, DSC and FTIR. The results showed that amino groups in γ-APS/EP disappeared and methoxysilyl groups (Si—O—CH₃) were remained after the synthesis process. Adhesion strength of the epoxy coating with metal substrate was significantly enhanced by introducing γ-APS/EP. Moreover, the dry adhesion strength of epoxy coating with 3%γ-APS/EP reached the maximum value of 12.4 MPa, which was twice the strength of pure epoxy, and was decreased with the content of γ-APS/EP further increasing. Meanwhile, wet interface adhesion strength of epoxy coating with 3%γ-APS/EP was still kept about 7.4 MPa after 900 h immersion in 3.5%NaCl, more than three times of pure epoxy coating. And also, epoxy coating with 3%γ-APS/EP showed the best performance with lower saturated water absorption. The chemical bonding can be obtained by the generation of oxane on the interface resulting from the reaction between the synthesized reactive resin and the hydroxyl on the metal surface after the reactive resin was added in the epoxy resin. Furthermore, the content of γ-APS/EP affected the number of chemical bonds at the interface, the hydrophilicity and the bulk density of coating. Finally, an interfacial chemical bonding mechanism was proposed.

Key words： epoxy coating γ-aminopropyltrimethoxysilane; chemical bonding

收稿日期: 2018-03-30

ZTFLH:

TQ632.4

基金资助:资助项目国家自然科学基金项目No.51401217和中国博士后科学基金项目No.2017M613383

作者简介:

作者简介操发春,男,1994年生,硕士生

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https://www.ams.org.cn/CN/10.11900/0412.1961.2018.00121 或 https://www.ams.org.cn/CN/Y2019/V55/I2/238

图1 环氧树脂E51、硅烷KH540和活性树脂γ-APS/EP的FTIR谱

图2 活性树脂的合成反应机理示意图

图3 涂层干态附着力和剥离率随活性树脂含量的变化

图4 附着力测试后断口金属裸露区域背散射模式下的SEM像

图5 清漆和3%γ-APS/EP涂层试样附着力测试后金属裸露处的XPS谱

表1 元素结合能和半峰宽

图6 清漆、3%γ-APS/EP和10%γ-APS/EP涂层的湿态附着力随浸泡时间的变化

图7 Q235钢试样经900 h浸泡湿态附着力测试后的形貌

图8 涂层试样的吸水动力学曲线

表2 涂层在不同浸泡时间的吸水率

图9 涂层DSC热流-温度曲线及玻璃化转变温度(Tg)

图10 清漆、3%γ-APS/EP和10%γ-APS/EP涂层浸泡900 h前后纵截面SEM像

图11 10%γ-APS/EP涂层纵截面EDS结果

图12 10% g-APS/EP涂层纵截面形貌及对应EDS面分析结果

图13 活性树脂的作用机理示意图

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