SiO_2基有机—无机复合耐腐蚀薄膜的制备与性能研究
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摘要
随着复合耐腐蚀薄膜应用的拓展及使用环境的恶化,对薄膜技术及其性能也相应提出了更高的要求。作为一种优异的耐腐蚀材料,无机有机复合耐腐蚀薄膜在金属防腐上得到了广泛应用。但目前采用的制备方式大部分都是通过引入高分子物质或纳米级无机颗粒对薄膜进行改性,其制备过程复杂且不易控制。本文针对有机无机复合薄膜研究及应用中存在的问题开展研制工作,对有机无机复合薄膜的成膜过程及其结构性能进行理论分析与实验论证。
以正硅酸乙酯(TEOS)和γ-甲基丙烯酰氧丙基三甲氧基硅烷(KH570)为前驱体,以过氧化二苯甲酰(BPO)为引发剂,通过溶胶凝胶法制备SiO_2基有机无机复合溶胶,陈化后采用旋涂法在冷轧钢板表面成膜,制备有机无机复合防腐涂层。通过傅立叶红外光谱(FTIR)、扫描电镜(sEM)、溶胶凝胶色谱(GPC)等测试手段研究了复合防腐涂层的形貌及结构,通过盐雾腐蚀实验和电化学阻抗谱(EIS)测试对复合涂层的耐腐蚀性能进行研究。系统研究了加水量(R)、改性剂种类、添加量、pH值、反应温度等工艺条件对该溶胶体系下的分子结构及复合涂层性能的影响;同时考察了引发剂的种类、特性及添加方式对复合溶胶结构及最终涂层性能的影响。结果表明,在TEOS:KH570=1,R=3,pH=4.5的条件下,制备出的KH570改性SiO_2有机无机复合耐腐蚀涂层在铝板和冷轧钢板上分别能够耐盐雾腐蚀超过240小时和24小时,硬度大于8H,表面光泽度好,可直接应用到工业化生产;加入引发剂可以提高薄膜的韧性,增强其耐腐蚀性能:引发剂BPO的适宜用量为引发对象总质量的0.25%,反应前、后期的温度分别为75℃和65℃时,引发效率最佳,在R=2,TEOS:KH570=1:1条件下制备出的复合防腐涂层在冷轧钢板上能够耐盐雾腐蚀48小时以上,硬度大于8H。
本文初步研究了有机硅烷改性SiO_2-体系的薄膜制备及性能,为该薄膜的进一步应用奠定了一定理论和实验基础。
With the expansion in application of composite anti-corrosion thin-film and the deterioration of environment for its use, requirements for thin film technology and its performance are getting higher day by day. As an excellent anti-corrosion material, inorganic-organic composite anti-corrosion coating has been widely used on mesoporphyrin protection. However, the coating preparation method mostly used currently is adding polymer materials or inorganic nano-particles in to modify the coating, with the process complex and hard to control. The present paper aims to study the problems in research and application of organic-inorganic composite thin-film, and to testify and analyse the film-forming process, structure and properties of organic-inorganic composite coating and its structural properties.
With ethyl orthosilicate (TEOS) andγ-methacryloxypropyl trimethoxysilane (KH570) as precursor, dibenzoyl peroxide (BPO) as evocating agent, SiO_2-based organic-inorganic composite anti-corrosion sol was prepared by sol-gel method. After aging, the composite coating on the surface of cold-rolled steel sheet was obtained , using spin-coating method. After heat treatment, Fourier Transform Infrared Spectroscopy (FTIR), Scanning Electron Microscopy (SEM), Sol-gel Chromatography (GPC) were applied to characterized the morphology and structure of composite anti-corrosion coating, andthe anti-corrosion property of composite coatings was examined by Salt-spray Test and Electrochemical Impedance Spectroscopy (E1S). The paper systematically studied the influence on structure and properties of composite coatings under this sol system of process conditions including the amount of added water(R) and the modifier, pH, temperature etc..Meanwhile it investigated the influence on structure and properties of composite coatings of type, conditions of use and adding ways of evocating agent. The results show that, the best anti-corrosion performance is achieved at TEOS:KH570=1, R=3, pH=4.5, and the coating can endure salt-spray for over 240 hours on aluminum plate or over 24 hours on steel plate, the hardness is greater than 8H, surface gloss and can be applied to industrial production directly;initiator can improve the tenacity of coating, enhanced anti-corrosion performance of system at the same time:the appropriate dosage of BPO is 0.25% of the total mass of triggered object, when the temperature of prior and later period in reaction are 75℃and 65℃, the efficiency of initiation is best, and with the conditions of R=2, TEOS:KH570=1:1, the composite anti-corrosion coating can endure salt-spray for over 48 hours on steel plate, the hardness is greater than 8H.
The paper preliminarily studied the preparation and characterization of coating of SiO_2-organic-silane compound system, and thus provides some theoretical and experimental basis for the application of this the organic-inorganic anti-corrosion thin-film system.in the future.
以正硅酸乙酯(TEOS)和γ-甲基丙烯酰氧丙基三甲氧基硅烷(KH570)为前驱体,以过氧化二苯甲酰(BPO)为引发剂,通过溶胶凝胶法制备SiO_2基有机无机复合溶胶,陈化后采用旋涂法在冷轧钢板表面成膜,制备有机无机复合防腐涂层。通过傅立叶红外光谱(FTIR)、扫描电镜(sEM)、溶胶凝胶色谱(GPC)等测试手段研究了复合防腐涂层的形貌及结构,通过盐雾腐蚀实验和电化学阻抗谱(EIS)测试对复合涂层的耐腐蚀性能进行研究。系统研究了加水量(R)、改性剂种类、添加量、pH值、反应温度等工艺条件对该溶胶体系下的分子结构及复合涂层性能的影响;同时考察了引发剂的种类、特性及添加方式对复合溶胶结构及最终涂层性能的影响。结果表明,在TEOS:KH570=1,R=3,pH=4.5的条件下,制备出的KH570改性SiO_2有机无机复合耐腐蚀涂层在铝板和冷轧钢板上分别能够耐盐雾腐蚀超过240小时和24小时,硬度大于8H,表面光泽度好,可直接应用到工业化生产;加入引发剂可以提高薄膜的韧性,增强其耐腐蚀性能:引发剂BPO的适宜用量为引发对象总质量的0.25%,反应前、后期的温度分别为75℃和65℃时,引发效率最佳,在R=2,TEOS:KH570=1:1条件下制备出的复合防腐涂层在冷轧钢板上能够耐盐雾腐蚀48小时以上,硬度大于8H。
本文初步研究了有机硅烷改性SiO_2-体系的薄膜制备及性能,为该薄膜的进一步应用奠定了一定理论和实验基础。
With the expansion in application of composite anti-corrosion thin-film and the deterioration of environment for its use, requirements for thin film technology and its performance are getting higher day by day. As an excellent anti-corrosion material, inorganic-organic composite anti-corrosion coating has been widely used on mesoporphyrin protection. However, the coating preparation method mostly used currently is adding polymer materials or inorganic nano-particles in to modify the coating, with the process complex and hard to control. The present paper aims to study the problems in research and application of organic-inorganic composite thin-film, and to testify and analyse the film-forming process, structure and properties of organic-inorganic composite coating and its structural properties.
With ethyl orthosilicate (TEOS) andγ-methacryloxypropyl trimethoxysilane (KH570) as precursor, dibenzoyl peroxide (BPO) as evocating agent, SiO_2-based organic-inorganic composite anti-corrosion sol was prepared by sol-gel method. After aging, the composite coating on the surface of cold-rolled steel sheet was obtained , using spin-coating method. After heat treatment, Fourier Transform Infrared Spectroscopy (FTIR), Scanning Electron Microscopy (SEM), Sol-gel Chromatography (GPC) were applied to characterized the morphology and structure of composite anti-corrosion coating, andthe anti-corrosion property of composite coatings was examined by Salt-spray Test and Electrochemical Impedance Spectroscopy (E1S). The paper systematically studied the influence on structure and properties of composite coatings under this sol system of process conditions including the amount of added water(R) and the modifier, pH, temperature etc..Meanwhile it investigated the influence on structure and properties of composite coatings of type, conditions of use and adding ways of evocating agent. The results show that, the best anti-corrosion performance is achieved at TEOS:KH570=1, R=3, pH=4.5, and the coating can endure salt-spray for over 240 hours on aluminum plate or over 24 hours on steel plate, the hardness is greater than 8H, surface gloss and can be applied to industrial production directly;initiator can improve the tenacity of coating, enhanced anti-corrosion performance of system at the same time:the appropriate dosage of BPO is 0.25% of the total mass of triggered object, when the temperature of prior and later period in reaction are 75℃and 65℃, the efficiency of initiation is best, and with the conditions of R=2, TEOS:KH570=1:1, the composite anti-corrosion coating can endure salt-spray for over 48 hours on steel plate, the hardness is greater than 8H.
The paper preliminarily studied the preparation and characterization of coating of SiO_2-organic-silane compound system, and thus provides some theoretical and experimental basis for the application of this the organic-inorganic anti-corrosion thin-film system.in the future.
引文
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