高耐蚀锌基涂料制备工艺及其性能研究
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摘要
高耐蚀锌基涂料技术是近年来发展起来的一种金属防腐蚀新技术，因其具有无污染、高耐蚀性、无氢脆等优点，故在许多工业领域中得到了日益广泛的应用。本文介绍了高耐蚀锌基涂料技术的历史及其在国内外的研究和应用情况，以及涂层性能特点。阐述了镀锌钝化膜的成膜及其耐蚀机理，高耐蚀锌基涂层的成膜机理及其防腐机理，并将锌基涂层和镀锌钝化膜进行比较，突出了锌基涂层耐蚀性的优越性。
本文研究了采用自制的片状锌粉，铬酸和重铬酸钾按一定的比例混合而成的铬酸组分，由溶剂、乳化剂和表面活性剂等有机物混合而成得到有机物组分，三者混合搅拌均匀得到高耐蚀锌基涂料。采用离心浸涂的处理方式，经烘烤固化得到高耐蚀锌基涂层。
研究了不同工艺条件对锌基涂层耐蚀性的影响，从中筛选出的最佳工艺条件为：搅拌时间1h为宜，甩液时电压控制在120V，甩液时间30s左右即可。烘干温度80±5℃，时间为10-20min，烧结温度为280-300℃，时间为20-30min时，所形成的高耐蚀锌基涂层的综合性能最佳。含铬组分的pH值以0.8-2.8为宜，最终涂料的pH值在4.5-6.0之间。
采用万能金相显微镜，分析涂层的表面形貌和断面形貌，结果表明：整个涂层很均匀，涂层和基体结合紧密，涂层的厚度也比较均匀。
各种耐蚀性试验证明：锌粉粒度越细，所得锌基涂层耐蚀性越好，当锌粉粒度小于300目时，所得高耐蚀锌基涂层的耐蚀性明显优于镀锌层。本试验中，采用自制的片状锌粉，锌粉的粒径大于5μm小于10μm，其厚度小于0.5μm。锌粉含量控制在280-320g／L为佳。
试验证明：铬酸组分采用混合铬酸(CrO_3：K_2Cr_2O_4=7：3)比采用单一铬酸所得涂层性能要好，铬酸含量过高，在烧结过程中涂层可能析出黄色的CrO_3，涂层耐蚀性下降，表面质量差，涂层呈现黄绿色；涂层有锌粉脱落，结合力不够。铬酸不足，锌粉之间，锌粉和基体之间粘结不牢，高耐蚀锌基涂层结合力不理想，有脱落现象，膜层发黑、粉化，本试验控制在40-44g／L。
昆明理工大学硕士学位论文摘要
本研究选用的溶剂3是一种芳香族烃类溶剂，同时加一种潜溶剂(有机醇)
后涂料分散得很好，涂层光滑、平整，颜色为亚银光色。所加溶剂的量越高，所
得高耐蚀锌基涂层耐蚀性越好，当加到120目L时，所得高耐蚀锌基涂层的耐蚀性
明显提高很多，不需再继续增加，故本试验控制在1209/L。
还原剂对提高锌基涂层的质量有着重要的意义，它的加入很大程度上改善了
涂层的外观，又不影响涂层的性能，还能防止析出而导致脱层现象，本试验选609/L
为佳。
试验表明:涂层的表面粗糙度随着乳化剂量的增加而逐渐变得平滑，细腻。
乳化剂的加入，直接影响到涂料是否能够充分混合，使涂料分散均匀，也影响到
涂料的流平性和粘稠度，但它对涂层的耐蚀性影响不大，本试验控制在26叨J。
腐蚀试验表明，.表面活性剂的量对所得高耐蚀锌基涂层耐蚀性影响不大，当
加到305几时，所得高耐蚀锌基涂层的耐蚀性很好，若继续增加，涂层的耐蚀性变
化不大，反而有所降低，故在保证涂层的均匀和良好的结合力的情况下，表面活
性剂的含量不宜太高，含量低一点涂层的耐蚀性更好。本试验控制在30乡毛。
结果表明，采用自制的片状锌粉，在优化工艺条件下制备的高耐蚀锌基涂层
均匀致密，对钢材具有优良的防腐蚀效果，盐雾试验的出红锈时间大于80oh，耐
腐蚀性远高于普通镀锌层。
The zinc-basic paint with high corrosion resistance technology was a new metal anticorrosion technology for iron and steel. Its applications in some fields such as automobile industry were getting increasingly common because of the advantages of less pollution, excellent anticorrosion property and non-hydrogen embrittlement. In this paper, the progress and current situation in research of the zinc-basic paint with high corrosion resistance technique and the specialty of the properties of the coating are introduced. The mechanism of formation of the passive zinc deposits and the zinc-basic coating with high corrosion resistance and the corrosion resistance mechanism were discussed. Moreover, zinc-basic coating was compared with the passive zinc deposits, so the superiority of corrosion resistance of the zinc-basic coating stood out.
In this thesis, the flake zinc powder made by ourselves was adopted. CrO3 and K2Cr2O4 were blended in definite proportion to form the chromium acid component. The solvent, the emulsification agent, and the surfactants were blended to form the organic matter component. Then, flake zinc powder, the chromium acid component and the organic matter component were blended and mixed to receive zinc-basic paint with high corrosion-resistance. The Dip-spin processing was adopted and by drying and solidification gained the zinc-basic coating with high corrosion-resistance.
The effects of different conditions on the corrosion resistance of zinc-basic coating were examined. The optimal conditions screened out were as follows: the time of mixing was one hour, the voltage of paint throwing off was 120V, the time of paint throwing off was about 30S, the temperature of drying was 805, the time of drying was 10-20min, the temperature of sintering was 280-300*C, and time of sintering was 20-30min. Under such conditions the syntheses properties of zinc-basic coating with high corrosion-resistance were the best. Additional, the pH of the chromium acid component was better during 0.8 and 2.8, and the pH of the finally paint during 4.5 and 6.0.
By omnipotence metallography microscope, the surface and cross section morphologies .were analyzed. The result showed that: the whole coating was equality, the coating combined with metal substrates tightly, and the thickness of coating was equality.
By different means of corrosion tester showed that: the thinner the zinc powder, the better the corrosion resistance of zinc-basic coating. The corrosion resistance of the zinc-basic coating was much better than the passive zinc deposits. In this experiment, the diameter of zinc powder was more than 5m but less than 10m, and the thickness was less than 0.5m. The content of zinc was controlled between 280 and 320g/L.
By experiment, the mixture of CrO3 and K2Cr2O4 was much better than the pure CrO3 for the properties of zinc-basic coating. If the content was too high, the coating would separate out yellow CrO3 during the course of sintering, the corrosion resistance of the coating and the quality of surface became worse, the coating turned out green-yellow color, some zinc powder was brushed off from the coating, and the binding was inadequate. If the content of was lack, the adhesion among zinc powder and between zinc powder and the substrate were inadequate, some zinc powder was brushed off from the coating, and the color of the coating became black, pulverized. The content of zinc powder was controlled between 40 and 44g/L.
The No. 3 solvent chose in this research was an aroma hydrocarbon solvent, and a latent solvent (an organic alcohol) was used meanwhile. Consequently, the paint dispersed very well, the coating was sleek, smooth, and sub-silver color. The more the content of the solvent, the more fine the corrosion resistance of the zinc-basic coating. The property of corrosion resistance of the coating was obviously improved when the content of solvent was up to 120g/L. So the content wasn't needed to increase, and it was 120g/L in this experiment.
The reducing agent was vital to increase the corrosion resistance
本文研究了采用自制的片状锌粉，铬酸和重铬酸钾按一定的比例混合而成的铬酸组分，由溶剂、乳化剂和表面活性剂等有机物混合而成得到有机物组分，三者混合搅拌均匀得到高耐蚀锌基涂料。采用离心浸涂的处理方式，经烘烤固化得到高耐蚀锌基涂层。
研究了不同工艺条件对锌基涂层耐蚀性的影响，从中筛选出的最佳工艺条件为：搅拌时间1h为宜，甩液时电压控制在120V，甩液时间30s左右即可。烘干温度80±5℃，时间为10-20min，烧结温度为280-300℃，时间为20-30min时，所形成的高耐蚀锌基涂层的综合性能最佳。含铬组分的pH值以0.8-2.8为宜，最终涂料的pH值在4.5-6.0之间。
采用万能金相显微镜，分析涂层的表面形貌和断面形貌，结果表明：整个涂层很均匀，涂层和基体结合紧密，涂层的厚度也比较均匀。
各种耐蚀性试验证明：锌粉粒度越细，所得锌基涂层耐蚀性越好，当锌粉粒度小于300目时，所得高耐蚀锌基涂层的耐蚀性明显优于镀锌层。本试验中，采用自制的片状锌粉，锌粉的粒径大于5μm小于10μm，其厚度小于0.5μm。锌粉含量控制在280-320g／L为佳。
试验证明：铬酸组分采用混合铬酸(CrO_3：K_2Cr_2O_4=7：3)比采用单一铬酸所得涂层性能要好，铬酸含量过高，在烧结过程中涂层可能析出黄色的CrO_3，涂层耐蚀性下降，表面质量差，涂层呈现黄绿色；涂层有锌粉脱落，结合力不够。铬酸不足，锌粉之间，锌粉和基体之间粘结不牢，高耐蚀锌基涂层结合力不理想，有脱落现象，膜层发黑、粉化，本试验控制在40-44g／L。
昆明理工大学硕士学位论文摘要
本研究选用的溶剂3是一种芳香族烃类溶剂，同时加一种潜溶剂(有机醇)
后涂料分散得很好，涂层光滑、平整，颜色为亚银光色。所加溶剂的量越高，所
得高耐蚀锌基涂层耐蚀性越好，当加到120目L时，所得高耐蚀锌基涂层的耐蚀性
明显提高很多，不需再继续增加，故本试验控制在1209/L。
还原剂对提高锌基涂层的质量有着重要的意义，它的加入很大程度上改善了
涂层的外观，又不影响涂层的性能，还能防止析出而导致脱层现象，本试验选609/L
为佳。
试验表明:涂层的表面粗糙度随着乳化剂量的增加而逐渐变得平滑，细腻。
乳化剂的加入，直接影响到涂料是否能够充分混合，使涂料分散均匀，也影响到
涂料的流平性和粘稠度，但它对涂层的耐蚀性影响不大，本试验控制在26叨J。
腐蚀试验表明，.表面活性剂的量对所得高耐蚀锌基涂层耐蚀性影响不大，当
加到305几时，所得高耐蚀锌基涂层的耐蚀性很好，若继续增加，涂层的耐蚀性变
化不大，反而有所降低，故在保证涂层的均匀和良好的结合力的情况下，表面活
性剂的含量不宜太高，含量低一点涂层的耐蚀性更好。本试验控制在30乡毛。
结果表明，采用自制的片状锌粉，在优化工艺条件下制备的高耐蚀锌基涂层
均匀致密，对钢材具有优良的防腐蚀效果，盐雾试验的出红锈时间大于80oh，耐
腐蚀性远高于普通镀锌层。
The zinc-basic paint with high corrosion resistance technology was a new metal anticorrosion technology for iron and steel. Its applications in some fields such as automobile industry were getting increasingly common because of the advantages of less pollution, excellent anticorrosion property and non-hydrogen embrittlement. In this paper, the progress and current situation in research of the zinc-basic paint with high corrosion resistance technique and the specialty of the properties of the coating are introduced. The mechanism of formation of the passive zinc deposits and the zinc-basic coating with high corrosion resistance and the corrosion resistance mechanism were discussed. Moreover, zinc-basic coating was compared with the passive zinc deposits, so the superiority of corrosion resistance of the zinc-basic coating stood out.
In this thesis, the flake zinc powder made by ourselves was adopted. CrO3 and K2Cr2O4 were blended in definite proportion to form the chromium acid component. The solvent, the emulsification agent, and the surfactants were blended to form the organic matter component. Then, flake zinc powder, the chromium acid component and the organic matter component were blended and mixed to receive zinc-basic paint with high corrosion-resistance. The Dip-spin processing was adopted and by drying and solidification gained the zinc-basic coating with high corrosion-resistance.
The effects of different conditions on the corrosion resistance of zinc-basic coating were examined. The optimal conditions screened out were as follows: the time of mixing was one hour, the voltage of paint throwing off was 120V, the time of paint throwing off was about 30S, the temperature of drying was 805, the time of drying was 10-20min, the temperature of sintering was 280-300*C, and time of sintering was 20-30min. Under such conditions the syntheses properties of zinc-basic coating with high corrosion-resistance were the best. Additional, the pH of the chromium acid component was better during 0.8 and 2.8, and the pH of the finally paint during 4.5 and 6.0.
By omnipotence metallography microscope, the surface and cross section morphologies .were analyzed. The result showed that: the whole coating was equality, the coating combined with metal substrates tightly, and the thickness of coating was equality.
By different means of corrosion tester showed that: the thinner the zinc powder, the better the corrosion resistance of zinc-basic coating. The corrosion resistance of the zinc-basic coating was much better than the passive zinc deposits. In this experiment, the diameter of zinc powder was more than 5m but less than 10m, and the thickness was less than 0.5m. The content of zinc was controlled between 280 and 320g/L.
By experiment, the mixture of CrO3 and K2Cr2O4 was much better than the pure CrO3 for the properties of zinc-basic coating. If the content was too high, the coating would separate out yellow CrO3 during the course of sintering, the corrosion resistance of the coating and the quality of surface became worse, the coating turned out green-yellow color, some zinc powder was brushed off from the coating, and the binding was inadequate. If the content of was lack, the adhesion among zinc powder and between zinc powder and the substrate were inadequate, some zinc powder was brushed off from the coating, and the color of the coating became black, pulverized. The content of zinc powder was controlled between 40 and 44g/L.
The No. 3 solvent chose in this research was an aroma hydrocarbon solvent, and a latent solvent (an organic alcohol) was used meanwhile. Consequently, the paint dispersed very well, the coating was sleek, smooth, and sub-silver color. The more the content of the solvent, the more fine the corrosion resistance of the zinc-basic coating. The property of corrosion resistance of the coating was obviously improved when the content of solvent was up to 120g/L. So the content wasn't needed to increase, and it was 120g/L in this experiment.
The reducing agent was vital to increase the corrosion resistance
引文
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