水基硅烷化处理剂的制备及应用研究
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摘要
金属材料经硅烷化处理后可显著增强其抗腐蚀性能及其与有机涂层的粘结力,硅烷化处理可有效替代环境污染严重的铬酸盐转化处理及磷化处理工艺。常规的硅烷化处理液大多含高浓度易挥发的甲醇或乙醇,从而导致该表面处理技术难以推广应用。本文制备了一种水基硅烷化处理剂(水基硅醇溶液),并利用该处理剂实现了铝及碳钢的硅烷化处理,比较了处理前后铝及碳钢的耐腐蚀性能。
1、水基硅烷化处理剂的制备与表征。充分利用非极性的硅烷单体不溶于水而水解产物极性较强的特点,构建了以硅烷/正庚烷混合物为油相、预先调节好pH值的去离子水为水相的复相水解体系,经水解反应后,得到了水基硅烷化处理剂。研究了双-[γ-(三乙氧基)硅丙基]-四硫化物(BTESPT)水解过程中与硅醇浓度相关的电导率变化趋势和水解完成后处理剂的红外(FT-IR)及质谱(ESI-MS)特征。同时,采用正交实验法研究了乙烯基三乙氧基硅烷(VTES)的水解时间、水解温度及pH值对硅烷化处理效果的影响。结果表明,BTESPT在复相体系中水解3小时后,生成了大量带2-3个羟基的BTESPT硅醇,水解时间增加,水相中的硅醇浓度基本不发生变化。VTES的最佳水解条件为：水解温度为35℃左右,水相pH值为7,水解时间不超过10小时。经此硅烷化试剂处理后的铝试样自腐蚀电流密度最小。
2、水基硅烷化处理剂中铝表面BTESPT硅烷膜的制备与表征。采用浸涂法或电化学辅助沉积技术在铝表面制备得到了BTESPT硅烷膜,并通过扫描电子显微镜/X-射线能量衍射谱(SEM/EDS)技术和电化学方法分析了膜层的微观形貌及防腐蚀能力。结果表明,经水基BTESPT处理剂处理后,金属铝表面覆盖了一层平均厚度为188 nm左右的致密硅烷膜。电化学阻抗谱(EIS)及Tafel曲线测试结果表明,硅烷化处理后铝基体的耐腐蚀能力增加了近两个数量级。72小时盐水浸泡实验结果表明,BTESPT膜具有与铬酸盐转化膜相当的保护效果。不同沉积电位下制备的BTESPT硅烷膜SEM和EIS分析结果表明,-1.0 VSCE条件下沉积的硅烷膜最为均匀、致密,膜层的低频区阻抗值|ZLF|达到60000Ω·cm-2，相比空白铝试样增加了近两个数量级。-1.0 VSCE为水基硅烷化处理剂中电化学辅助沉积法制备硅烷膜的临界电位。
3、碳钢表面硅烷化处理替代磷化工艺的研究。应用正交实验优化了常规磷化液配方,并在碳钢表面制备了高耐蚀性锌锰系磷化膜。磷化处理15分钟后的碳钢试片的EIS和Tafel曲线表明,磷化膜覆盖后碳钢的耐腐蚀性能显著提高,腐蚀电流密度下降至未磷化前的1/30左右。为替代能耗高的磷化工艺,采用浸涂法在碳钢表面制备了BTESPT、VTES及γ-环氧基硅丙基三甲氧基硅烷(GPTMS)膜层,并利用EIS和Tafel曲线外推法分析了膜层的防腐蚀性能。结果表明,孔隙率为0.95%的VTES硅烷膜保护效率为近90%左右；WB-GPTMS硅烷膜的孔隙率为7.52%,保护效率为87.21%。BTESPT最为均匀致密,其孔隙率小于1%,保护效率超过95%。表面和截面的SEM分析结果表明,其膜层厚度为260 nm左右。综上所述,经硅烷化处理后的碳钢的腐蚀电流密度平均下降了约90%,厚度为几百纳米的硅烷膜具有与磷化膜相近的防腐蚀能力。
Silanization of metal surface could significantly improve the corrosion resistance of materials and adhesion of paints upon substrates. And it has been studied as environmentally friendly surface treatment technology for replacing the pollutive chromate conversion chromating and phosphating treatments. But the traditional treatment chemicals are methanol or ethanol rich solutions which results in the waste of alcohol. So, the application of silane treatment is limited. In this paper the water based silanization solutions were prepared and the corrosion protection performance of silane treated aluminum and carbone steel were studied.
1. Preparation and characterization of water based silanization solutions. According to the polarity change of hydrophobic silane monomers and hydrolysis products, water based silanization solutions were prepared by a multiphase which was conposed of silane/n-heptane oil mixture and deionized water with adjusted pH value. In the meanwhile, bis-[triethoxysilylpropyl] tetrasulfide (BTESPT) silanol concentration was monitored by conductivity and the parameters of vinyltriethoxysilane (VTES) hydrolysis process were optimized by orthogonal experiments. Fourier transform infrared (FT-IR) and electrospray ionization mass spectrometry (ESI-MS) were used to analysis the chemical composition of silanization solutions. The reasons indicate that numerous BTESPT silanol with two or three hydroxyl groups are generated after about 3 hrs reaction in this multiphase. The concentration of silanol will not change much when the hydrolysis time continue to increase. The optimum hydrolysis parameters of VTES are depicted as:temperature is about 35℃, pH value is 7 and hydrolysis time is below 10 hrs. Aluminum samples treated by water based silanization solution synthesized under this condition show the best anticorrosive performance.
2. Preparation and characterization of BTESPT layer upon aluminum in water based silanization solution. BTESPT layers upon aluminum were prepared by using of dip-coating and electrodeposition techniques. Scanning electron microscopy with X-ray microanalysis (SEM/EDS) were used to characterize surface topography and chemical composition of aluminum samples. They electrochemical behavior in 0.1 mol/L NaCl solution were measured using electrochemical impedance spectra (EIS) and tafel polarization curves. The results demonstrate that aluminum samples coated with BTESPT layers, which is about 188 nm in thickness, show chromate alternative corrosive resistance after 72 hrs dipping in salty water. SEM and EIS observation of BTESPT layers deposited at different potentials indicate that BTESPT layer deposited at -1.0 VSCE was dense and uniform. Compared with the blank control samples, low frequency impedance (|ZLF|) value of silane layers covered aluminum was increased by two order of magnitude that attained 60000Ω·cm-2. And the potential -1.0 VSCE is a critical value for electrodeposition BTESPT layers upon aluminum in water based silanization solution.
3. Silane treatment as alternative to phosphating of carbon steel.Traditional phosphating bath were optimized by orthogonal experiments and zinc-manganese phosphating film with additional corrosion resistance was achieved. EIS and Tafel results indicate that carbon steel show superior corrosion resistance after phosphating for 15 minitures. Its corrosion current density is reduced to about 1/30 in comparison with bare carbon. In order to replace the heavy-polluting phosphating technology and assure the protection performance, silane layers of BTESPT, VTES and y-glycidoxypropyltrimethoxysilane (GPTMS) were prepared upon carbon steel. In the meanwhile, EIS and tafel curves were used to verify their protection efficiency. The results demonstrate that VTES and BTESPT layers with about 0.95% porosity could provide at least 90% corrosion inhibition for carbon steel. The porosity of GPTMS layer is slightly more,7.52%, and its protection efficiency is about 87.5%. SEM images of BTESPT coated sample show 260 nm of organic layer with dense and uniform surface. Overall, current densities of silane treated carbon steel decreased almost 90% and the thin silane layers exhibit phosphatic film alternative corrosion resistance.
1、水基硅烷化处理剂的制备与表征。充分利用非极性的硅烷单体不溶于水而水解产物极性较强的特点,构建了以硅烷/正庚烷混合物为油相、预先调节好pH值的去离子水为水相的复相水解体系,经水解反应后,得到了水基硅烷化处理剂。研究了双-[γ-(三乙氧基)硅丙基]-四硫化物(BTESPT)水解过程中与硅醇浓度相关的电导率变化趋势和水解完成后处理剂的红外(FT-IR)及质谱(ESI-MS)特征。同时,采用正交实验法研究了乙烯基三乙氧基硅烷(VTES)的水解时间、水解温度及pH值对硅烷化处理效果的影响。结果表明,BTESPT在复相体系中水解3小时后,生成了大量带2-3个羟基的BTESPT硅醇,水解时间增加,水相中的硅醇浓度基本不发生变化。VTES的最佳水解条件为：水解温度为35℃左右,水相pH值为7,水解时间不超过10小时。经此硅烷化试剂处理后的铝试样自腐蚀电流密度最小。
2、水基硅烷化处理剂中铝表面BTESPT硅烷膜的制备与表征。采用浸涂法或电化学辅助沉积技术在铝表面制备得到了BTESPT硅烷膜,并通过扫描电子显微镜/X-射线能量衍射谱(SEM/EDS)技术和电化学方法分析了膜层的微观形貌及防腐蚀能力。结果表明,经水基BTESPT处理剂处理后,金属铝表面覆盖了一层平均厚度为188 nm左右的致密硅烷膜。电化学阻抗谱(EIS)及Tafel曲线测试结果表明,硅烷化处理后铝基体的耐腐蚀能力增加了近两个数量级。72小时盐水浸泡实验结果表明,BTESPT膜具有与铬酸盐转化膜相当的保护效果。不同沉积电位下制备的BTESPT硅烷膜SEM和EIS分析结果表明,-1.0 VSCE条件下沉积的硅烷膜最为均匀、致密,膜层的低频区阻抗值|ZLF|达到60000Ω·cm-2，相比空白铝试样增加了近两个数量级。-1.0 VSCE为水基硅烷化处理剂中电化学辅助沉积法制备硅烷膜的临界电位。
3、碳钢表面硅烷化处理替代磷化工艺的研究。应用正交实验优化了常规磷化液配方,并在碳钢表面制备了高耐蚀性锌锰系磷化膜。磷化处理15分钟后的碳钢试片的EIS和Tafel曲线表明,磷化膜覆盖后碳钢的耐腐蚀性能显著提高,腐蚀电流密度下降至未磷化前的1/30左右。为替代能耗高的磷化工艺,采用浸涂法在碳钢表面制备了BTESPT、VTES及γ-环氧基硅丙基三甲氧基硅烷(GPTMS)膜层,并利用EIS和Tafel曲线外推法分析了膜层的防腐蚀性能。结果表明,孔隙率为0.95%的VTES硅烷膜保护效率为近90%左右；WB-GPTMS硅烷膜的孔隙率为7.52%,保护效率为87.21%。BTESPT最为均匀致密,其孔隙率小于1%,保护效率超过95%。表面和截面的SEM分析结果表明,其膜层厚度为260 nm左右。综上所述,经硅烷化处理后的碳钢的腐蚀电流密度平均下降了约90%,厚度为几百纳米的硅烷膜具有与磷化膜相近的防腐蚀能力。
Silanization of metal surface could significantly improve the corrosion resistance of materials and adhesion of paints upon substrates. And it has been studied as environmentally friendly surface treatment technology for replacing the pollutive chromate conversion chromating and phosphating treatments. But the traditional treatment chemicals are methanol or ethanol rich solutions which results in the waste of alcohol. So, the application of silane treatment is limited. In this paper the water based silanization solutions were prepared and the corrosion protection performance of silane treated aluminum and carbone steel were studied.
1. Preparation and characterization of water based silanization solutions. According to the polarity change of hydrophobic silane monomers and hydrolysis products, water based silanization solutions were prepared by a multiphase which was conposed of silane/n-heptane oil mixture and deionized water with adjusted pH value. In the meanwhile, bis-[triethoxysilylpropyl] tetrasulfide (BTESPT) silanol concentration was monitored by conductivity and the parameters of vinyltriethoxysilane (VTES) hydrolysis process were optimized by orthogonal experiments. Fourier transform infrared (FT-IR) and electrospray ionization mass spectrometry (ESI-MS) were used to analysis the chemical composition of silanization solutions. The reasons indicate that numerous BTESPT silanol with two or three hydroxyl groups are generated after about 3 hrs reaction in this multiphase. The concentration of silanol will not change much when the hydrolysis time continue to increase. The optimum hydrolysis parameters of VTES are depicted as:temperature is about 35℃, pH value is 7 and hydrolysis time is below 10 hrs. Aluminum samples treated by water based silanization solution synthesized under this condition show the best anticorrosive performance.
2. Preparation and characterization of BTESPT layer upon aluminum in water based silanization solution. BTESPT layers upon aluminum were prepared by using of dip-coating and electrodeposition techniques. Scanning electron microscopy with X-ray microanalysis (SEM/EDS) were used to characterize surface topography and chemical composition of aluminum samples. They electrochemical behavior in 0.1 mol/L NaCl solution were measured using electrochemical impedance spectra (EIS) and tafel polarization curves. The results demonstrate that aluminum samples coated with BTESPT layers, which is about 188 nm in thickness, show chromate alternative corrosive resistance after 72 hrs dipping in salty water. SEM and EIS observation of BTESPT layers deposited at different potentials indicate that BTESPT layer deposited at -1.0 VSCE was dense and uniform. Compared with the blank control samples, low frequency impedance (|ZLF|) value of silane layers covered aluminum was increased by two order of magnitude that attained 60000Ω·cm-2. And the potential -1.0 VSCE is a critical value for electrodeposition BTESPT layers upon aluminum in water based silanization solution.
3. Silane treatment as alternative to phosphating of carbon steel.Traditional phosphating bath were optimized by orthogonal experiments and zinc-manganese phosphating film with additional corrosion resistance was achieved. EIS and Tafel results indicate that carbon steel show superior corrosion resistance after phosphating for 15 minitures. Its corrosion current density is reduced to about 1/30 in comparison with bare carbon. In order to replace the heavy-polluting phosphating technology and assure the protection performance, silane layers of BTESPT, VTES and y-glycidoxypropyltrimethoxysilane (GPTMS) were prepared upon carbon steel. In the meanwhile, EIS and tafel curves were used to verify their protection efficiency. The results demonstrate that VTES and BTESPT layers with about 0.95% porosity could provide at least 90% corrosion inhibition for carbon steel. The porosity of GPTMS layer is slightly more,7.52%, and its protection efficiency is about 87.5%. SEM images of BTESPT coated sample show 260 nm of organic layer with dense and uniform surface. Overall, current densities of silane treated carbon steel decreased almost 90% and the thin silane layers exhibit phosphatic film alternative corrosion resistance.
引文
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