电镀锌硅酸盐钝化工艺及机理研究
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摘要
金属的腐蚀给人类带来巨大的经济损失和社会危害。电镀锌是提高钢铁抗腐蚀能力的有效途径,但是锌镀层在潮湿的环境中,镀层极易发生腐蚀,从而失去防护作用。为进一步提高镀锌层的耐蚀性,提高其表面质量,延长其使用寿命,需对其进行钝化处理。传统铬酸盐钝化处理毒性大,污染环境和危害人体健康。本论文对无毒、无污染的硅酸盐(Na_2SiO_3)工艺进行了深入研究,并探讨了镀锌层硅酸盐钝化膜的耐蚀机理与成膜机理,主要内容包括:
采用正交试验及单因素试验确定了硅酸盐钝化最佳钝化液组成:Na_2SiO_3·9H_2O15g/L,H_2SO_4 5ml/L,H_2O_2 10ml/L,HNO_3 5ml/L,添加剂3g/L。该钝化液稳定性好,使用寿命长,适应性强。采用正交试验确定了影响钝化膜耐蚀性的三个主要因素为:钝化温度、pH值、钝化时间;并用单因素试验法研究了各因素对钝化膜耐蚀性的影响,最终确定其最佳工艺条件为:钝化温度15～40℃,pH值2.0～2.8,钝化时间90s左右。
对钝化及未钝化镀锌层进行中性盐雾试验(NSS)、盐水浸泡试验及CuSO_4点滴试验。试验结果表明,硅酸盐钝化膜能显著提高镀锌层的耐腐蚀性能及抗白锈能力,其耐蚀性优于低铬酸盐钝化膜。
通过电化学测试等手段研究了钝化及未钝化镀锌钢板在5mass%NaCl溶液中的Tafel曲线、交流阻抗谱和开路电位—时间曲线,并运用计算机拟合方法求解腐蚀电化学参数。其中,硅酸盐钝化膜的电化学参数E_(corr)为-0.85736 V,I_(corr)为0.00012623Amp/cm~2,R_t值为580Ω·cm~2;而低铬酸盐钝化膜的电化学参数为:E_(corr)-0.9456V,I_(corr)0.00034980 Amp/cm~2,R_t 150Ω·cm~2。并结合试验结果,分析了硅酸盐钝化膜耐蚀机理,认为硅酸盐钝化膜提高镀锌层耐蚀性表现为三方面作用:(1)电化学作用;(2)隔离作用;(3)缓蚀作用。
采用SEM、EDAX及XPS等测试技术对硅酸盐钝化膜表面形貌进行了微观观察及成分分析,并采用电化学方法研究了镀锌层在硅酸盐钝化液中的钝化过程,对硅酸盐钝化膜成膜机理进行了探讨,认为硅酸盐钝化膜形成的过程包括:1)镀锌层的溶解;2)聚合物成膜沉积过程。
将硅酸盐钝化工艺进行工业扩大试验,研究了扩大规模后钝化液的稳定性及耐蚀性,结果表明,硅酸盐钝化工艺扩大试验后稳定性好,成膜均匀,耐蚀性良好。考察了硅酸盐钝化工艺应用于低铁Zn—Fe合金镀层所形成钝化膜的耐蚀性能,试验结果表明,Zn—Fe合金钝化膜耐蚀性良好,并优于镀锌钝化膜。
综上所述,镀锌硅酸盐钝化工艺稳定性能好,耐蚀性优于传统低铬钝化工艺,操作简单,成本低,无毒、无污染,可改善电镀锌行业环境污染的现状。因此,硅酸盐钝化工艺在代替传统含铬钝化、促进电镀行业实现绿色生产方面,具有广阔的应用前景。
Enormous economic loss and society hazard are caused by metal corrosion.Even though electroplating zinc coating is an efficient means to improve the corrosion resistance ability of steel and iron,the corrosion is extremely easy to take place when the galvanized zinc coating is in the moist environment,thus the coating loses the protection effect.In order to enhance the corrosion resistance,improve the surface quality and extend the service life, the galvanized film must be carried on passivation processing.The traditional passivation processed by chromate is high toxicity,and it can easily cause the environment pollution and harm people's health.So,in this thesis,the non-toxic and non-pollution silicate (Na_2SiO_3)passivation technique was well studied.The passive film's anticorrosion mechanism and forming mechanism has been preliminary discussed.Therefore,the primary coverage of this thesis as follows:
The optimum composition of the passivation solution was gained by the orthogonal experiment and the single factor test as follows:Na_2SiO_3·9H_2O 15g/L,H_2SO_4 5ml/L, H_2O_2 10ml/L,HNO_3 5 ml/L,additive 3 g/L.Three primary factors,which influence the corrosion resistance of the silicate films determined by the orthogonal experiment,were the solution temperature,the pH value and the immersion time.And their effects on the corrosion resistance of silicate films were studied by the single factor test.Finally,the best technological conditions were gained as follows:the solution temperature 15～40℃,the pH value 2.0～2.8,the immersion time 90s around.
The corrosion resistances of passive film and galvanized film were studied by the neutral salt spray test(NSS)、dipping in salt solution and CuSO_4 solution drop test.The test results indicat that the silicate passive films can obviously improve the anti-corrosive performance and anti-white rust ability.Compared with the low chromate passive film,the silicate passive film's corrosion resistance is better.
Tafel polarization curve、EIS and Open circuit potential-time curve on passive film and galvanized film were investigated.The electrochemical parameters of electrochemistry were gained by computer fitting.And,the electrochemistry parameters of silicate passive films are:E_(corr)-0.85736 V,I_(corr)0.00012623 Amp/cm~2,R_t 580Ω·cm~2.But the low chromate passive film's electrochemistry parameters are:E_(corr)-0.9456 V,I_(corr)0.00034980 Amp/cm~2,R_t 150Ω·cm~2.According to the results from experiments,the silicate passive film's anticorrosion mechanism has been analyzed.It is thought that the silicate passive film has three aspects affects to enhance the corrosion resistance performance of galvanized Zinc coating,which are electrochemical effect,isolation effect and corrosion inhibitive effect.
The microscopic appearance and the component analysis of the silicate passive film have been investigated by SEM,EDAX and XPS techniques.The passivation process in silicate passivation solution has been investigated by electrochemistry methods.So the mechanism of forming the silicate passive film has been discussed.It is considered that the process of forming passive film has two steps:1)dissolved Zinc coating;2)the process of forming the membrane by polymer deposition.
After scale-up experiment,the stability and corrosion resistance of silicate passivation solution have been investigated.The results show that the stability of the solution is good, the film is even,and the corrosion resistance is good.When the silicate applies in the low-iron galvanized iron alloy coating,the anticorrosion performance of the formed silicate passive film has been studied.The results indicate that the silicate passive film can improve the corrosion resistance of the Zn-Fe alloy coating effectively.Compared with the Zn coating,the corrosion resistance silicate passive film on Zn-Fe coating is better.
In conclusion,the silicate passivation technique of electrogalvanized coating has many advantages,for example:Good stability,better corrosion resistance than the low chromate passivation,simple operation,low cost,non-toxic and non pollution,etc.The present situation of the environment pollution can be improved if the silicate passivition technique can be used in electro-plating industry.The silicate passivition technique has broad application prospect,because it can replace the traditional chromate passivation and promote a realization of green production in electro-plating industry.
采用正交试验及单因素试验确定了硅酸盐钝化最佳钝化液组成:Na_2SiO_3·9H_2O15g/L,H_2SO_4 5ml/L,H_2O_2 10ml/L,HNO_3 5ml/L,添加剂3g/L。该钝化液稳定性好,使用寿命长,适应性强。采用正交试验确定了影响钝化膜耐蚀性的三个主要因素为:钝化温度、pH值、钝化时间;并用单因素试验法研究了各因素对钝化膜耐蚀性的影响,最终确定其最佳工艺条件为:钝化温度15～40℃,pH值2.0～2.8,钝化时间90s左右。
对钝化及未钝化镀锌层进行中性盐雾试验(NSS)、盐水浸泡试验及CuSO_4点滴试验。试验结果表明,硅酸盐钝化膜能显著提高镀锌层的耐腐蚀性能及抗白锈能力,其耐蚀性优于低铬酸盐钝化膜。
通过电化学测试等手段研究了钝化及未钝化镀锌钢板在5mass%NaCl溶液中的Tafel曲线、交流阻抗谱和开路电位—时间曲线,并运用计算机拟合方法求解腐蚀电化学参数。其中,硅酸盐钝化膜的电化学参数E_(corr)为-0.85736 V,I_(corr)为0.00012623Amp/cm~2,R_t值为580Ω·cm~2;而低铬酸盐钝化膜的电化学参数为:E_(corr)-0.9456V,I_(corr)0.00034980 Amp/cm~2,R_t 150Ω·cm~2。并结合试验结果,分析了硅酸盐钝化膜耐蚀机理,认为硅酸盐钝化膜提高镀锌层耐蚀性表现为三方面作用:(1)电化学作用;(2)隔离作用;(3)缓蚀作用。
采用SEM、EDAX及XPS等测试技术对硅酸盐钝化膜表面形貌进行了微观观察及成分分析,并采用电化学方法研究了镀锌层在硅酸盐钝化液中的钝化过程,对硅酸盐钝化膜成膜机理进行了探讨,认为硅酸盐钝化膜形成的过程包括:1)镀锌层的溶解;2)聚合物成膜沉积过程。
将硅酸盐钝化工艺进行工业扩大试验,研究了扩大规模后钝化液的稳定性及耐蚀性,结果表明,硅酸盐钝化工艺扩大试验后稳定性好,成膜均匀,耐蚀性良好。考察了硅酸盐钝化工艺应用于低铁Zn—Fe合金镀层所形成钝化膜的耐蚀性能,试验结果表明,Zn—Fe合金钝化膜耐蚀性良好,并优于镀锌钝化膜。
综上所述,镀锌硅酸盐钝化工艺稳定性能好,耐蚀性优于传统低铬钝化工艺,操作简单,成本低,无毒、无污染,可改善电镀锌行业环境污染的现状。因此,硅酸盐钝化工艺在代替传统含铬钝化、促进电镀行业实现绿色生产方面,具有广阔的应用前景。
Enormous economic loss and society hazard are caused by metal corrosion.Even though electroplating zinc coating is an efficient means to improve the corrosion resistance ability of steel and iron,the corrosion is extremely easy to take place when the galvanized zinc coating is in the moist environment,thus the coating loses the protection effect.In order to enhance the corrosion resistance,improve the surface quality and extend the service life, the galvanized film must be carried on passivation processing.The traditional passivation processed by chromate is high toxicity,and it can easily cause the environment pollution and harm people's health.So,in this thesis,the non-toxic and non-pollution silicate (Na_2SiO_3)passivation technique was well studied.The passive film's anticorrosion mechanism and forming mechanism has been preliminary discussed.Therefore,the primary coverage of this thesis as follows:
The optimum composition of the passivation solution was gained by the orthogonal experiment and the single factor test as follows:Na_2SiO_3·9H_2O 15g/L,H_2SO_4 5ml/L, H_2O_2 10ml/L,HNO_3 5 ml/L,additive 3 g/L.Three primary factors,which influence the corrosion resistance of the silicate films determined by the orthogonal experiment,were the solution temperature,the pH value and the immersion time.And their effects on the corrosion resistance of silicate films were studied by the single factor test.Finally,the best technological conditions were gained as follows:the solution temperature 15～40℃,the pH value 2.0～2.8,the immersion time 90s around.
The corrosion resistances of passive film and galvanized film were studied by the neutral salt spray test(NSS)、dipping in salt solution and CuSO_4 solution drop test.The test results indicat that the silicate passive films can obviously improve the anti-corrosive performance and anti-white rust ability.Compared with the low chromate passive film,the silicate passive film's corrosion resistance is better.
Tafel polarization curve、EIS and Open circuit potential-time curve on passive film and galvanized film were investigated.The electrochemical parameters of electrochemistry were gained by computer fitting.And,the electrochemistry parameters of silicate passive films are:E_(corr)-0.85736 V,I_(corr)0.00012623 Amp/cm~2,R_t 580Ω·cm~2.But the low chromate passive film's electrochemistry parameters are:E_(corr)-0.9456 V,I_(corr)0.00034980 Amp/cm~2,R_t 150Ω·cm~2.According to the results from experiments,the silicate passive film's anticorrosion mechanism has been analyzed.It is thought that the silicate passive film has three aspects affects to enhance the corrosion resistance performance of galvanized Zinc coating,which are electrochemical effect,isolation effect and corrosion inhibitive effect.
The microscopic appearance and the component analysis of the silicate passive film have been investigated by SEM,EDAX and XPS techniques.The passivation process in silicate passivation solution has been investigated by electrochemistry methods.So the mechanism of forming the silicate passive film has been discussed.It is considered that the process of forming passive film has two steps:1)dissolved Zinc coating;2)the process of forming the membrane by polymer deposition.
After scale-up experiment,the stability and corrosion resistance of silicate passivation solution have been investigated.The results show that the stability of the solution is good, the film is even,and the corrosion resistance is good.When the silicate applies in the low-iron galvanized iron alloy coating,the anticorrosion performance of the formed silicate passive film has been studied.The results indicate that the silicate passive film can improve the corrosion resistance of the Zn-Fe alloy coating effectively.Compared with the Zn coating,the corrosion resistance silicate passive film on Zn-Fe coating is better.
In conclusion,the silicate passivation technique of electrogalvanized coating has many advantages,for example:Good stability,better corrosion resistance than the low chromate passivation,simple operation,low cost,non-toxic and non pollution,etc.The present situation of the environment pollution can be improved if the silicate passivition technique can be used in electro-plating industry.The silicate passivition technique has broad application prospect,because it can replace the traditional chromate passivation and promote a realization of green production in electro-plating industry.
引文
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