第二代磷酸盐防锈颜料腐蚀抑制性能的评价及防锈机理的研究
摘要
第二代低/无毒活性磷酸盐防锈颜料,是当前取代红丹和锌铬黄等传统有毒颜料的有效品种之一,以其突出的耐腐蚀性能日益受到重视。本文在简要论述第二代磷酸盐防锈颜料种类、制备技术、应用性能的基础上,重点考察了六种典型颜料的腐蚀抑制性能、可能的失效机制和两种新型颜料的防锈机理。主要研究工作及结论如下:
(1)对45#碳钢电极在不同pH值3.5 % NaCl磷酸盐颜料提取液电化学行为的考察结果显示:①掺钼的磷酸锌AlZnPO4MoO_4·4H_2O (以下简称35号颜料)、掺钼的聚磷酸铝AlZn_2P3O10(MoO_4)_2·2H_2O(以下简称36号颜料)在不同酸碱度条件下,均显示出异常优异的腐蚀抑制性能,且是以抑制阳极为主的防锈颜料;②ZPA、ZMP颜料在酸性和中性环境中性能优异,但碱性条件下效果不佳;③碱性体系下,传统磷酸盐颜料APW-I的结果较为理想。
(2)ZMP样品在酚醛树脂、松香改性酚醛树脂、氯化橡胶防腐涂料、环氧富锌树脂4种中性体系中均获得了理想的效果。尤其连同ZPA颜料在氯化橡胶和环氧富锌体系中显示出更好的稳定性和耐腐蚀性。此外,磷酸盐颜料在210#松香改性酚醛树脂与酚醛混合树脂中的应用探索达到了目的,尤其对于后期稳定性能的提高效果显著。
(3)钼酸盐与正磷酸盐的复配,能够形成氧化性能更佳的磷钼杂多酸离子;而与聚磷酸盐结合得到更为优异的钝化保护膜,有效阻碍侵蚀性介质的扩散。
The second-generation low/non-toxic active phosphate pigments, one of the efficient alternatives to the toxic red lead and zinc chromate, have received a great deal of recent attention because of their excellent anti-corrosive abilities. Corrosion inhibitions, possible abate mechanisms of six typical pigments, and antirust mechanisms of two new-engineered pigments are especially studied, based on the second-genenration phosphate antirust pigments in types, preparations, and applications are reviewed. The major studies and conclusions as follows:
(1)The electrochemical behaviors of 45# carbon steel electrode were observed in phosphate-doped water extracts with 3.5 % NaCl. The results show that: firstly, more-excelling corrosion inhibitions of Mo-doped zinc phosphate AlZnPO4MoO4?4H2O (shorted as No.35 ) and Mo-doped aluminou polyphosphate AlZn_2P_3O10(MoO_4)2·2H_2O (shorted as No.36), taking inhibite anode reactions as the principal things, were revealed in different pH values. Secondly, high-performances were also obtained in ZPA-doped and ZMP-doped acidic and neutral systems, but not in basic conditions. Finally, pefect results were indicated in basic systems with traditional pigments of APW-I.
(2)Good effects were acquired in four neutral conditions of phenolic resin, rosin-modified phenolic resin, Chlorinated rubber anti-corrosive topcoat, and epoxy zinc-rich compound coating with ZMP. Especially, more-excelling stabilizations and corrosion inhibitions were showed in chlorinated rubber and epoxy zinc-rich systems together with ZPA. Furthermore, the study of phosphate pigments applied in mixed resin, with 210# rosin-modified phenolic resin and phenolic resin, have achieved anticipate, particularly in later stabilizations.
(3)The P-Mo heteropolyanions with better oxidation behaviors were formed by molybdate-phosphate composite pigments. Combination with the polyphosph–ate to be more excellent passive protective film, effectively impeding the spread of aggressive media.
(1)对45#碳钢电极在不同pH值3.5 % NaCl磷酸盐颜料提取液电化学行为的考察结果显示:①掺钼的磷酸锌AlZnPO4MoO_4·4H_2O (以下简称35号颜料)、掺钼的聚磷酸铝AlZn_2P3O10(MoO_4)_2·2H_2O(以下简称36号颜料)在不同酸碱度条件下,均显示出异常优异的腐蚀抑制性能,且是以抑制阳极为主的防锈颜料;②ZPA、ZMP颜料在酸性和中性环境中性能优异,但碱性条件下效果不佳;③碱性体系下,传统磷酸盐颜料APW-I的结果较为理想。
(2)ZMP样品在酚醛树脂、松香改性酚醛树脂、氯化橡胶防腐涂料、环氧富锌树脂4种中性体系中均获得了理想的效果。尤其连同ZPA颜料在氯化橡胶和环氧富锌体系中显示出更好的稳定性和耐腐蚀性。此外,磷酸盐颜料在210#松香改性酚醛树脂与酚醛混合树脂中的应用探索达到了目的,尤其对于后期稳定性能的提高效果显著。
(3)钼酸盐与正磷酸盐的复配,能够形成氧化性能更佳的磷钼杂多酸离子;而与聚磷酸盐结合得到更为优异的钝化保护膜,有效阻碍侵蚀性介质的扩散。
The second-generation low/non-toxic active phosphate pigments, one of the efficient alternatives to the toxic red lead and zinc chromate, have received a great deal of recent attention because of their excellent anti-corrosive abilities. Corrosion inhibitions, possible abate mechanisms of six typical pigments, and antirust mechanisms of two new-engineered pigments are especially studied, based on the second-genenration phosphate antirust pigments in types, preparations, and applications are reviewed. The major studies and conclusions as follows:
(1)The electrochemical behaviors of 45# carbon steel electrode were observed in phosphate-doped water extracts with 3.5 % NaCl. The results show that: firstly, more-excelling corrosion inhibitions of Mo-doped zinc phosphate AlZnPO4MoO4?4H2O (shorted as No.35 ) and Mo-doped aluminou polyphosphate AlZn_2P_3O10(MoO_4)2·2H_2O (shorted as No.36), taking inhibite anode reactions as the principal things, were revealed in different pH values. Secondly, high-performances were also obtained in ZPA-doped and ZMP-doped acidic and neutral systems, but not in basic conditions. Finally, pefect results were indicated in basic systems with traditional pigments of APW-I.
(2)Good effects were acquired in four neutral conditions of phenolic resin, rosin-modified phenolic resin, Chlorinated rubber anti-corrosive topcoat, and epoxy zinc-rich compound coating with ZMP. Especially, more-excelling stabilizations and corrosion inhibitions were showed in chlorinated rubber and epoxy zinc-rich systems together with ZPA. Furthermore, the study of phosphate pigments applied in mixed resin, with 210# rosin-modified phenolic resin and phenolic resin, have achieved anticipate, particularly in later stabilizations.
(3)The P-Mo heteropolyanions with better oxidation behaviors were formed by molybdate-phosphate composite pigments. Combination with the polyphosph–ate to be more excellent passive protective film, effectively impeding the spread of aggressive media.
引文
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