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材料研究学报  2026, Vol. 40 Issue (8): 631-640    DOI: 10.11901/1005.3093.2025.287
  研究论文 本期目录 | 过刊浏览 |
镀锌紧固件表面有机-无机复合转化膜的制备和性能
李庆鹏1,2(), 安晓云1, 尚颖3, 刘佳兴1,4, 栾钧涵1, 李永智5, 王娜1,2
1.沈阳化工大学材料科学与工程学院 沈阳 110142
2.沈阳市新型功能涂层材料重点实验室 沈阳 110142
3.沈阳胜科水务有限公司 沈阳 110141
4.孚迪斯石油化工科技(葫芦岛)股份有限公司 葫芦岛 125000
5.沈阳市航达科技有限责任公司 沈阳 110034
Preparation and Property of High-performance Organic-inorganic Composite Conversion Film for Galvanized Fasteners
LI Qingpeng1,2(), AN Xiaoyun1, SHANG Ying3, LIU Jiaxing1,4, LUAN Junhan1, LI Yongzhi5, WANG Na1,2
1.School of Materials Science and Engineering, Shenyang University of Chemical Technology, Shenyang 110142, China
2.Shenyang Research Institute of Industrial Technology for Advanced Coating Materials, Shenyang 110142, China
3.Sembcorp Shenyang Water Co., Ltd., Shenyang 110141, China
4.Fudis Petrochemical Technology (Huludao) Co., Ltd., Huludao 125000, China
5.Shenyang Hangda Technology Co., Ltd., Shenyang 110034, China
引用本文:

李庆鹏, 安晓云, 尚颖, 刘佳兴, 栾钧涵, 李永智, 王娜. 镀锌紧固件表面有机-无机复合转化膜的制备和性能[J]. 材料研究学报, 2026, 40(8): 631-640.
Qingpeng LI, Xiaoyun AN, Ying SHANG, Jiaxing LIU, Junhan LUAN, Yongzhi LI, Na WANG. Preparation and Property of High-performance Organic-inorganic Composite Conversion Film for Galvanized Fasteners[J]. Chinese Journal of Materials Research, 2026, 40(8): 631-640.

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摘要: 

将KH-550 (3-氨丙基三乙氧基硅烷)和KH-560 (3-(2,3-环氧丙氧)丙基三甲氧基硅烷)按1∶1混合水解成有机组分,使KOH/NaOH与SiO2反应生成无机组分K2SiO3/Na2SiO3溶液(并改变较优硅酸盐含量调整无机组分模数),将有机组分与无机组分按9∶1~1∶9复配成一种有机-无机转化液并将镀锌紧固件浸入其中,转化液粘附在紧固件的表面固化后形成有机-无机转化膜。使用扫描电子显微镜(SEM)、能谱(EDS)、铅笔硬度测试、极化曲线测试等手段表征其形貌、成分、机械性能和耐蚀性能。结果表明:M3(9∶1)转化膜表面清洁完整,机械性能良好、耐腐蚀性能优异。膜层结构致密均匀与基体结合紧密,具有优异的物理屏蔽性能。

关键词 材料表面与界面硅烷偶联剂转化膜镀锌层电化学测试耐蚀性    
Abstract

Novel organic-inorganic composite conversion liquids were designed and prepared, aiming to address troubles related with the yellowing and inadequate corrosion resistance of the silane film for galvanized fasteners. First, KH-550 (3-amino propyl triethoxy silane) and KH-560 (3-(2,3-epoxy propoxyoxy) propyl trimethoxy silane) were mixed and hydrolyzed to get organic component, and two series liquid silicates K2SiO3 and Na2SiO3 were prepared by reaction of KOH and NaOH with SiO2 of varying proportion to get silicates of different modulus respectively as inorganic component. Next the novel composite organic-inorganic conversion liquids were obtained by compounding the organic component with the two series inorganic components at 9:1-1:9 respectively. Further, galvanized fasteners were immersed in the liquids for 30-60 s, subsequent dried, and cured at 80-120 oC for 10 min and followed at 180-200 oC for 30 min, thereby, an organic-inorganic conversion film is formed on the galvanized fasteners. The storage stability of the conversion solution and the yellowing resistance of the conversion film were evaluated by macroscopic observation. Results of neutral salt spray testing and copper sulfate titration testing reveal that the corrosion resistance of the potassium silicate containing conversion films was superior to the sodium silicate containing conversion films. The corrosion resistance of conversion films with varying proportion of organic component was assessed by the forementioned way (note, by taking M1(9:1) as an example, herewith M1 presents modulus 1 and 9:1 presents the ratio of the two components). Besides, the corrosion resistance of conversion films prepared with conversion liquids composed of varying proportion of organic component to potassium silicate series of different modulus was assessed by the forementioned way. Meanwhile, the morphology, composition, mechanical properties and corrosion resistance of the conversion film, which presents the best corrosion resistance were characterized by means of scanning electron microscopy, energy spectroscopy, pencil hardness tester, and polarization curve test. The results showed that the prepared films M1(9:1), M1(8:2), M1(7:3), M1(1:9), M2(9:1), M2(8:2) and M3(9:1) all showed a clear and transparent state, without delamination or gel, showing good storage stability. After 72 h salt spray test, the surface of the M3(9:1) conversion film remained intact and clean, without any white rust or red rust, showing the best corrosion resistance. The film is transparent, eliminating the yellowing phenomenon of traditional silane films. SEM observation showed that the film was compact and uniform, tightly bound to the matrix, and had excellent physical shielding performance. The results of the pencil hardness test and adhesion test further confirm that the film has good mechanical properties.

Key wordssurface and interface in the materials    silane coupling agent    conversion coatings    galvanized layer    electrochemical test    corrosion resistance
收稿日期: 2025-09-16     
ZTFLH:  TG174.4  
通讯作者: 李庆鹏,讲师,qpli001@163.com,研究方向为环保化防护技术
Corresponding author: LI Qingpeng, Tel: (024)83988092, E-mail: qpli001@163.com
作者简介: 李庆鹏,男,1984年生,博士
图1  不同比例的K2SiO3溶液/硅烷水解液制备的复合转化液贮存180 d后的照片
图2  不同比例的Na2SiO3溶液/硅烷水解液制备的复合转化液贮存180 d后的照片
图3  不同比例的K2SiO3溶液/硅烷水解液制备的复合转化膜的宏观形貌
图4  不同比例的Na2SiO3溶液/硅烷水解液制备的复合转化膜的宏观形貌
Na2SiO3-type composite silane filmK2SiO3-type composite silane film
Bits of time / sAverage time / sBits of time / sAverage time / s
9:154.51010
513
48
49
8:2981515
816
714
815
7:31514.752021.25
1722
1422
1321
表1  不同比例/不同硅酸盐制备的有机-无机复合转化膜的耐硫酸铜滴定时间
图5  紧固件空白样与不同硅酸盐/硅烷水解液比例制备的复合转化膜在5%NaCl中性盐雾中72 h试验图
图6  不同比例的M2/硅烷水解液制备的复合转化液贮存180 d后的照片
图7  不同比例的M3/硅烷水解液制备的复合转化液贮存180 d后的照片
图8  紧固件空白样和不同复合转化膜在5%NaCl中性盐雾中72 h试验图
图9  硅烷转化膜与M3(9:1)复合转化膜的宏观形貌对比
图10  镀锌板空白样和M3(9∶1)复合转化膜的表面SEM形貌
图11  M3(9∶1)复合转化膜的截面SEM形貌和EDS图像
图12  M3(9∶1)复合转化膜的附着力测试
图13  镀锌板空白样和M3(9∶1)复合转化膜的Tafel极化曲线
Sampleφcorr / Vjcorr /A·cm-2Rp / Ω·cm2
Blank sample-1.0956.227 × 10-59.542 × 103
M3(9:1)-0.9808.639 × 10-58.419 × 103
表2  镀锌板空白样和M3(9∶1)复合转化膜的动电位极化曲线拟合数据
图14  复合转化膜的黄变及其抑制机理示意图
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