金属表面新型无铬化学转化膜的研究
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摘要
本论文研究了金属表面无铬化学处理的几种新方法,主要分为三个部分:Ⅰ.镁合金AM60上的一种硅酸盐/钨酸盐复合转化膜;Ⅱ.镀锌钢板上有机-无机复合钝化膜;Ⅲ.二氧化硅溶胶对磷化膜的改性。
Ⅰ.研究了一种镁合金AM60上的硅酸盐/钨酸盐复合转化膜处理的方法。扫描电子显微镜(SEM)观察表明该膜层是一种干涸河床状的的微观膜层结构,电化学极化曲线测试表明该转化膜具有良好的耐腐蚀性能。X射线衍射谱(XRD)表明膜层是一种非晶相结构,能谱(EDX)对膜的成分分析,结果表明膜层主要成分为钨的化合物,镁、铝以及锰的氧化物。得出的最佳配方和成膜工艺是:Na2SiO3:4g/L,Na2WO4:10g/L,KClO4:4 g/L,KMnO4:2g/L;pH 4,温度50℃,浸渍时间10分钟。
Ⅱ.研究了一种有机-无机膜处理热镀锌板的方法,采用水溶性丙烯酸树脂作为成膜剂,加入有缓蚀作用的钒酸盐和钨酸盐,形成了这种复合膜层体系。重点研究了不同纳米二氧化硅对其的改性作用,通过SEM观察、盐水浸泡及塔菲尔极化曲线方法对比了纳米SiO2溶胶和纳米SiO2粉体的加入对膜层外观及耐蚀性的影响,发现这两种纳米材料的加入都可以改善膜层干燥过程中易干裂的情况,提高了膜层的致密性,尤其是以胶体二氧化硅改性的效果较好,红外光谱结果表明纳米二氧化硅与树脂之间发生了一定程度的化学键合,且纳米颗粒附着在膜层表面起到一定的保护作用。钒酸盐和钨酸盐加入该体系进一步提高了膜层的耐蚀性,钝化膜最佳干燥温度是140℃,其钝化机理及优化配方还在进一步研究中。
Ⅲ.研究了一种二氧化硅溶胶对磷化膜的改性方法,在磷化之前采用二氧化硅溶胶液对金属进行处理,发现这种溶胶液处理具有有类似表面调整的作用,细化了磷化膜晶粒,提高了膜层的致密性,塔菲尔极化曲线结果表明SiO2溶胶处理后磷化膜的耐蚀性得到了提高。这种结晶细化作用对于多种金属底材都适用。这可能是因为SiO2溶胶粒子吸附在金属的表面提供了大量的活性点,有利于形成更致密的磷化膜结晶。
In this paper, the novel methods of chrome-free surface treatments on metal substrates were studied.The thesis was composed of three major parts:Ⅰ. Silicate and tungstate conversion coating on magnesium alloy ;Ⅱ.Organic-inorganic composite passivation films modified by nano-SiO2;Ⅲ. Silica Sol modified phosphate coating.
Ⅰ.The conversion coating based on silicate and tungstate composite on magnesium alloy surface were investigated. SEM ,XRD and EDX showed that the composite coating was composed of W, Mg, Al and Mn with a uniform dry riverbed structure.The anticorrosion was detected by electrochemical measure- ments. X-ray diffraction indicated that the film was amorphous. The reasonable technics parameters was that:Na2SiO3:4g/L,Na2WO4:10g/L,KClO4:4g/ L,KMnO4: 2g /L; pH=4, temperature: 50℃, dipping time: 10 mins.
Ⅱ.The anticorrosion organic/ inorganic composite coating based on acrylic resin film modified by nano-SiO2 was prepared on the hot dipped galvanized steel surface and inhibitor vanadate and tungstate were used as the pigments.The morphology of the composite film was observed using a scanning electron microscope,while the corrosion resistance were investigated by electrochemical measurement and immersion test.The result indicated the organic films including colloidal silica and Silica powders showed better corrosion resistance than which added without nano-SiO2 particles, and colloidal silica modified resin film provided superior corrosion inhibition for galvanizing coating.Infrared spectrum showed that nano-SiO2 were cross linkaged with the resin. Nano-SiO2 could limit the crack in the resin coatings and protect the films with deposition.The pigments improved the anticorrosion of the passivation films; the best heating temperature was 140℃. The mechanisms of passivation and optimal proportion were to be further studied.
Ⅲ.We also made research on the function of silica sol before phosphori- zation .SEM showed the crystal size of zinc phosphate coating can be refined by the silica sol pretreatment before phosphorization. The role of the silica sol was similar as activation of traditional conditioner before phosphorization.The electrochemical measurement indicated that the corrosion resistance of phosphate coating was improved by treating with silica sol before phosphorization. The effect could be found in several metals and alloys,such as steel,Zn as well as Mg. The possible mechanism was that the colloidal silica was sorbed on the metal surfaces and acted as nucleation agents when phosphorization, which was helpful to form compact and tiny phosphate crystal.
Ⅰ.研究了一种镁合金AM60上的硅酸盐/钨酸盐复合转化膜处理的方法。扫描电子显微镜(SEM)观察表明该膜层是一种干涸河床状的的微观膜层结构,电化学极化曲线测试表明该转化膜具有良好的耐腐蚀性能。X射线衍射谱(XRD)表明膜层是一种非晶相结构,能谱(EDX)对膜的成分分析,结果表明膜层主要成分为钨的化合物,镁、铝以及锰的氧化物。得出的最佳配方和成膜工艺是:Na2SiO3:4g/L,Na2WO4:10g/L,KClO4:4 g/L,KMnO4:2g/L;pH 4,温度50℃,浸渍时间10分钟。
Ⅱ.研究了一种有机-无机膜处理热镀锌板的方法,采用水溶性丙烯酸树脂作为成膜剂,加入有缓蚀作用的钒酸盐和钨酸盐,形成了这种复合膜层体系。重点研究了不同纳米二氧化硅对其的改性作用,通过SEM观察、盐水浸泡及塔菲尔极化曲线方法对比了纳米SiO2溶胶和纳米SiO2粉体的加入对膜层外观及耐蚀性的影响,发现这两种纳米材料的加入都可以改善膜层干燥过程中易干裂的情况,提高了膜层的致密性,尤其是以胶体二氧化硅改性的效果较好,红外光谱结果表明纳米二氧化硅与树脂之间发生了一定程度的化学键合,且纳米颗粒附着在膜层表面起到一定的保护作用。钒酸盐和钨酸盐加入该体系进一步提高了膜层的耐蚀性,钝化膜最佳干燥温度是140℃,其钝化机理及优化配方还在进一步研究中。
Ⅲ.研究了一种二氧化硅溶胶对磷化膜的改性方法,在磷化之前采用二氧化硅溶胶液对金属进行处理,发现这种溶胶液处理具有有类似表面调整的作用,细化了磷化膜晶粒,提高了膜层的致密性,塔菲尔极化曲线结果表明SiO2溶胶处理后磷化膜的耐蚀性得到了提高。这种结晶细化作用对于多种金属底材都适用。这可能是因为SiO2溶胶粒子吸附在金属的表面提供了大量的活性点,有利于形成更致密的磷化膜结晶。
In this paper, the novel methods of chrome-free surface treatments on metal substrates were studied.The thesis was composed of three major parts:Ⅰ. Silicate and tungstate conversion coating on magnesium alloy ;Ⅱ.Organic-inorganic composite passivation films modified by nano-SiO2;Ⅲ. Silica Sol modified phosphate coating.
Ⅰ.The conversion coating based on silicate and tungstate composite on magnesium alloy surface were investigated. SEM ,XRD and EDX showed that the composite coating was composed of W, Mg, Al and Mn with a uniform dry riverbed structure.The anticorrosion was detected by electrochemical measure- ments. X-ray diffraction indicated that the film was amorphous. The reasonable technics parameters was that:Na2SiO3:4g/L,Na2WO4:10g/L,KClO4:4g/ L,KMnO4: 2g /L; pH=4, temperature: 50℃, dipping time: 10 mins.
Ⅱ.The anticorrosion organic/ inorganic composite coating based on acrylic resin film modified by nano-SiO2 was prepared on the hot dipped galvanized steel surface and inhibitor vanadate and tungstate were used as the pigments.The morphology of the composite film was observed using a scanning electron microscope,while the corrosion resistance were investigated by electrochemical measurement and immersion test.The result indicated the organic films including colloidal silica and Silica powders showed better corrosion resistance than which added without nano-SiO2 particles, and colloidal silica modified resin film provided superior corrosion inhibition for galvanizing coating.Infrared spectrum showed that nano-SiO2 were cross linkaged with the resin. Nano-SiO2 could limit the crack in the resin coatings and protect the films with deposition.The pigments improved the anticorrosion of the passivation films; the best heating temperature was 140℃. The mechanisms of passivation and optimal proportion were to be further studied.
Ⅲ.We also made research on the function of silica sol before phosphori- zation .SEM showed the crystal size of zinc phosphate coating can be refined by the silica sol pretreatment before phosphorization. The role of the silica sol was similar as activation of traditional conditioner before phosphorization.The electrochemical measurement indicated that the corrosion resistance of phosphate coating was improved by treating with silica sol before phosphorization. The effect could be found in several metals and alloys,such as steel,Zn as well as Mg. The possible mechanism was that the colloidal silica was sorbed on the metal surfaces and acted as nucleation agents when phosphorization, which was helpful to form compact and tiny phosphate crystal.
引文
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[3] Magalhaes A A O,Margarit I C P,Mattos O R.Molybdate conversion coatings on zinc surfaces.Journal of Electroanalytical Chemistry,2004,572(2):433-440
[4] Konno H,Narumi K,Habazaki H.Molybdate/Al(III) composite films on steel and zinc-plated steel by chemical conversion.Corrosion Science,2002,44(8):1889- 1900
[5] 刘娅莉,雍止一,朱婧等.一种镁合金表面钼酸盐复合转化膜的制备方法.专利申请号:200710034700.9
[6] Hinton B R W,Arnott D R,Ryan N E.Cerium conversion coatings for the corrosion protection of aluminum.Materials Forum,1986,9(3):162-173
[7] Scholes F H,Soste C,Hughes A E,et al.The role of hydrogen peroxide in the deposition of cerium-based conversion coatings.Applied Surface Science,2007, 253(4):1770-1780
[8] 杨宁,龙晋明.稀土钝化—金属防腐蚀表面处理新技术.稀土,2002,23 (2):55-62
[9] Arenas M A,Damborenea J J.Surface characterisation of cerium layers on galvanised steel. Surface and Coatings Technology,2004,187 (2-3):320-325
[10] Lu J T,Wu H J,Kong G.Growth and corrosion behavior of rare earth film on hot-dip galvanized steel.Transactions of Nonferrous Metals Society of China,2007,16(6):1397-1401
[11] Rudd A L,Breslin C B.The corrosion protection afforded by rare earth conversion coatings applied to magnesium.Corrosion Science,2000,42(2): 275-288
[12] Montemor M F,Ferreira M G S.Electrochemical study of modified bis- [triethoxysilylpropyl] tetrasulfide silane films applied on the AZ31 Mg alloy.Electrochimica Acta,2007,7(2):123-129
[13] Gray J E,Luan B.Protective coatings on magnesium and its alloys a critical review.Journal of Alloys and Compounds,2002,36(1-2):88-113
[14] Huo H W,Li Y.Corrosion of AZ91D magnesium alloy with a chemical conversion coating and electroless nickel layer.Corrosion Science,2004,46 (6):1467-1477
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