有机杀菌剂复合锌基镀层的制备及其耐微生物腐蚀与污损性能研究

	有机杀菌剂复合锌基镀层的制备及其耐微生物腐蚀与污损性能研究
	翟晓凡1,2
学位类型	博士
导师	侯保荣
	2015-05-20
学位授予单位	中国科学院大学
学位授予地点	北京
学位专业	海洋腐蚀与防护
关键词	壳聚糖 4 复合锌基镀层 5-二氯-n-辛基-4-异噻唑啉-3-酮硫酸盐还原菌耐蚀防污
摘要	本文利用电沉积方法，通过在硫酸盐镀液体系中添加有机杀菌剂，制备得到了锌基有机杀菌剂复合镀层，通过电化学阻抗谱、极化曲线方法与X射线晶体衍射、扫描电子显微镜、红外吸收光谱分析和电子能谱元素分析等手段研究了镀层的沉积过程与有机杀菌剂的复合机理，采用硫酸盐还原菌和大肠杆菌分别检测了复合镀层的耐微生物腐蚀与耐生物污损性能。具体研究结果如下：（1）成功制备了4,5-二氯-N-辛基-4-异噻唑啉-3-酮复合锌镀层。将4,5-二氯-N-辛基-4-异噻唑啉-3-酮添加入镀液体系中，通过在沉积表面的吸附作用与络合作用，影响了锌的沉积过程，显著改变了镀层的结构与形貌。4,5-二氯-N-辛基-4-异噻唑啉-3-酮复合锌镀层有效抑制了硫酸盐还原菌的腐蚀，并使大肠杆菌的附着显著降低。4,5-二氯-N-辛基-4-异噻唑啉-3-酮的最佳镀液添加浓度为1 mmol L^-1，复合质量分数可达5%。（2）成功制备了壳聚糖复合锌镀层。通过将梯度浓度壳聚糖添加到硫酸盐锌镀液体系中，壳聚糖与锌离子的络合作用和在沉积表面的吸附作用显著改变了锌的沉积过程，改变了镀层的晶体结构与形貌。壳聚糖复合锌镀层有效抑制硫酸盐还原菌的生长代谢，并具有较好的耐蚀性，在大肠杆菌菌液暴露下，其表面细菌附着浓度降低80%以上。壳聚糖的最佳镀液添加浓度为0.6 g L^-1。（3）制备了两类有机杀菌剂复合的锌镍合金镀层，发现4,5-二氯-N-辛基-4-异噻唑啉-3-酮会增大锌镍合金中镍含量，而壳聚糖的添加则会使其减小，两类杀菌剂均显著改变合金镀层的晶体结构与形貌。耐蚀防污性能初步检测显示4,5-二氯-N-辛基-4-异噻唑啉-3-酮复合锌镍合金镀层耐硫酸盐还原菌腐蚀与耐大肠杆菌污损性能最为优异，且最佳镀液添加浓度为2 mmol L^-1。
其他摘要	In this research, a novel organic biocide composite zinc/zinc alloy coating was electrodeposited by adding organic biocide into the electrolytes. By electrochemical impedance spectroscopy, polarization curves, X -ray crystalline diffraction, scanning electron microscope, infrared absorption spectroscopy and energy dispersive spectroscopy, the mechanism of the electrodeposition process was researched. Sulfate reducing bacteria and Escherichia coli were employed in this research to detect the coatings anticorrosion and antifouling property. The specific results of the research are as follows: (1) The 4,5-dichloro-2-N-octyl-4-isothiazolin-3-one-zinc composite coating was electrodeposited from 4,5-dichloro-2-N-octyl-4-isothiazolin-3-one added sulfate electrolytes. By the adsorption effect on surfaces and chelation with zinc, 4,5-dichloro-2-N-octyl-4-isothiazolin-3-one significantly influenced the electrodepositing process, altering coatings structure and morphology. The organic biocide inhibited the sulfate reducing bacteria corrosion and restrained the Escherichia coli attachment. The optimum adding concentration in the electrolyte was determined to be 1 mmol L^-1, which could lead to a 5% mass fraction in the composite coating. (2) The chitosan-zinc composite coating was electrodeposited in gradient concentrations of chitosan added sulfate zinc electrolyte. Chitosan could chelate with zinc and adsorbed on the electrodepositing surfaces, which lead to a significant change in the electrodepositing process. The crystalline structure and morphology were altered by a serious of chitosan addition concentration. Chitosan-zinc composite coating obviously inhibited the sulfate reducing bacteria growth and metabolism, resulting in high corrosion resistance. Under Escherichia coli exposure, the attached concentration of chitosan composite coating could reach an 80% decrease. The optimum adding concentration of chitosan in the sulfate electrolyte was determined to be 0.6 g L^-1. (3) Two kinds of organic biocide Zn-Ni composite alloy coating was electrodeposited from 4,5-dichloro-2-N-octyl-4-isothiazolin-3-one and chitosan added Zn-Ni electrolytes, respectively. 4,5-Dichloro-2-N-octyl-4-isothiazolin-3-one increased the Ni content in the alloy coating, while chitosan decreased it. The two biocides both altered the coating structure and morphology significantly. 4,5-Dichloro-2-N-octyl-4-isothiazolin-3-one-Zn-Ni composite coating showed better corrosion resistance in sulfate reducing bacteria and better antifouling property in Escherichia coli medium, and the optimum adding concentration in the electrolyte was determined to be 2 mmol L^-1.
学科领域	海洋腐蚀与防护
语种	中文
文献类型	学位论文
条目标识符	http://ir.qdio.ac.cn/handle/337002/22783
专题	海洋环境腐蚀与生物污损重点实验室
作者单位	1.中国科学院海洋研究所 2.中国科学院大学
第一作者单位	中国科学院海洋研究所
推荐引用方式 GB/T 7714	翟晓凡. 有机杀菌剂复合锌基镀层的制备及其耐微生物腐蚀与污损性能研究[D]. 北京. 中国科学院大学,2015.

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