夹杂物和贝氏体对高强钢的超高周疲劳性能的影响

IMR OpenIR

	夹杂物和贝氏体对高强钢的超高周疲劳性能的影响
	柳洋波
学位类型	博士
导师	李守新
	2011
学位授予单位	中国科学院金属研究所
学位授予地点	北京
学位专业	腐蚀科学与防护
关键词	电镀锌钢无铬耐指纹家电用化学转化钛/锆基硅烷/有机膦酸 Electrogalvanized Steel Non-chromium Anti-fingerprint Chemical Conversion Ti/zr Based Silane/phosphonic Acid Organic/inorganic Composite Coating
摘要	" 为实现目前电镀锌钢无铬耐指纹涂层存在的导电性与耐蚀性这一主要矛盾的统一性，本研究提出了以高导电性无机系无铬化学转化膜层作为导电性能提高组份，高耐蚀性和涂装附着力有机系偶联膜层作为耐蚀性能提高组份，以阳离子型复合水性树脂为主成膜物，制备具有“金字塔”结构的家电用电镀锌钢有机/无机复合无铬耐指纹涂层的研究思路。基于此思路，本研究首次提出了在电镀锌钢基体上制备高导电性钛/锆基无铬化学转化膜和高耐蚀性硅烷/有机膦酸复合无铬化学转化膜的新技术，并在此基础上进一步制备出了良导电性有机/无机复合无铬耐指纹涂层。对于所制备的三种膜层，分别通过SEI和AFM考察了其表面形貌，利用EDS、XPS和FTIR研究了膜层组成，并采用动电位极化曲线、循环极化曲线、电化学阻抗谱和Mott-Schottky曲线研究了膜层的腐蚀电化学行为。另外，还分别考察了工艺参数和膜层组成对所制备膜层耐腐蚀性、耐指纹性、导电性、涂装附着力、加工性、耐磨性、耐擦伤性、耐热性、耐黑变性、耐溶剂性、耐碱性能等综合性能的影响机制，并根据试验结果分别探讨了上述三种膜层作为家电用电镀锌钢无铬耐指纹涂层的可行性。最后，对本研究领域今后的发展趋势进行了预测。利用氟钛酸、氟锆酸和氢氟酸等，在电镀锌钢基体上获得了一种新型高导电性钛/锆基无铬化学转化膜。该膜层由ZnF2 和Zn、Ti、Zr的含水氧化物等组成，晶粒尺度为50～80 nm，厚度为600～700 nm，且呈现出良好的均匀致密性。所制备膜层具有优良的导电性（四探针表面电阻值在0.03～0.5 mΩ·cm之间），其电化学性能参数与铬酸盐钝化膜处于同一量级，但耐蚀性（NSS 72 h）仍不能超过后者。综合性能测试表明，该膜层不适合作为家电用电镀锌钢无机系无铬耐指纹涂层。利用N-(β-氨乙基)-γ-氨丙基三甲氧基硅烷、γ-(2,3-环氧丙氧基)丙基三甲氧基硅烷和1-羟基亚乙基-1,1-二膦酸等，在电镀锌钢基体上制备了一种新型高耐蚀性硅烷/有机膦酸复合无铬化学转化膜。所制备转化膜是主要由Zn-O-C、Zn-O-P、Si-O-Si、Si-O-P等组成的主链内包含-P-O-P-等次级链的三维网状致密复合化学转化膜。该膜层具有良好的致密度，膜厚在800 nm～1 µm之间，与成分变化不具有相关性，电化学参数普遍高于铬酸盐钝化膜。所制备复合转化膜具有突出的耐腐蚀性能（NSS 144h）和涂装附着力，同时具有较高的绝缘性能（四探针表面电阻值在MΩ量级）。综合性能测试表明，该膜层不适合作为家电用电镀锌钢良导电性有机系无铬耐指纹涂层。以再次优化后的钛/锆基无铬化学转化液作为导电性增强组份，硅烷/有机膦酸复合无铬化学转化液为耐蚀性和涂装附着力增强组份，以阳离子型水性丙烯酸树脂和聚氨酯为主成膜物，制备出了具有良好加工后耐蚀性的电镀锌钢有机/无机复合无铬耐指纹涂层。所制备涂层具有良好的致密度和均匀性，厚度在1～2 µm之间。该涂层具有良好的耐蚀性（NSS 试验加工前出锈时间为192 h，加工后为96～144 h）和涂装附着力。所制备复合涂层中，作为耐蚀性和涂装附着力提高组份的硅烷/有机膦酸复合无铬化学转化组份的作用得到明显体现。然而由于高导电性优势被有机树脂层所掩盖，作为导电性能提高组分的钛/锆基无铬化学转化膜作用难以得到体现，使本研究以所制备钛/锆基无铬化学转化膜用于提高“金字塔”结构有机/无机复合耐指纹涂层导电性的宗旨未能得到很好的实现。综合性能测试表明，该膜层适合作为家电用电镀锌钢良导电性无铬耐指纹涂层，但其耐碱性与国外先进水平相比仍有一定差距。"
其他摘要	"Preparation and properties of non-chromium anti-fingerprint coating of electrogalvanized steel for household electric appliances Yong Guan (Corrosion Science and Protection) Supervised by Prof. Chuanwei Yan In this study, a new design philosophy of pyramidal non-chromium anti-fingerprint (AFP) coating of electrogalvanized steel for household electric appliances was proposed to achieve the unitarity of contradiction between electrical conductivity and corrosion resistance. Based on the philosophy, two new types of preparation techniques, a high- electrical-conductivity Ti/Zr based non-chromium chemical conversion coating and a high- corrosion-resistance silane/phosphonic acid composite non-chromium chemical conversion coating were firstly put forward in this thesis, and a good electrical conductivity organic/inorganic composite non-chromium AFP coating was furtherly prepared on this foundation using cationic composite waterborne resins as the main film-former. These three coatings were inverstigated by SEI, coupled with EDS, AFM, XPS and FTIR. The potentiodynamic polarization, circular polarization, EIS and Mott-Schottky plot techniques were used to study the electrochemical corrosion behaviors of the coatings. In addition, effect mechanisms of technological parameters and coating constitutions on the integrated performances of AFP coating were investigated, such as corrosion resistance, fingerprint resistance, electrical conductivity, paint adhesion, machining property, abrasive resistance, scratch resistance, heat resistance, black tarnish resistance, solvent resistance, alkali resistance, etc. According to the test results, the feasibilities of these three coatings used as non-chromium AFP coatings of electrogalvanized steel for household electric appliances were discussed respectively. And finally the development tendency of this field was forecasted. A novel high-electrical-conductivity Ti/Zr based non-chromium chemical conversion coating was developed for electrogalvanized steel using fluotitanate acid, fluozirconate acid and hydrofluoric acid, etc. The conversion coating with the thickness of 600~700 nm was compact and uniform, and consisted of ZnF2 and hydrated oxides of Zn, Ti and Zr elements with a grain scale of about 50~80 nm. This coating had good electrical conductivity of which the four point probe surface resistance was about 0.03~0.5 mΩ•cm. The electrochemical property parameters were at the same level with chromate passivation coating. However, its corrosion resistance was much lower than the latter, and the rusts appearance time was 72 hours after NSS test. The integrated performances test results showed that this coating was inappropriate for the AFP coating of electrogalvanized steel for household electric appliances. A new high corrosion resistance silane/phosphonic acid composite conversion coating has been developed for the electrogalvanized steel, which was prepared by N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, γ-(2,3-epoxypropoxy) propyltri- methoxy-silane and 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid. This coating had a three-dimensional network constituted by Zn-O-C, Zn-O-P, Si-O-Si, Si-O-P backbones and -P-O-P- subprime chains. The thickness of the compact conversion coating was about 800 nm~1 µm and had nothing to do with the components variation. The prepared coating had outstanding corrosion resistance with the the rusts appearance time of 144 hours after NSS test, and excellent insulation property with the four point probe surface resistance order of MΩ level. The integrated performances test results showed that the composite conversion coating was inappropriate for the high-electrical-conductivity AFP coating of electrogalvanized steel for household electric appliances. A good electrically conductive organic/inorganic composite non-chromium AFP coating was prepared for electrogalvanized steel using re-optimized Ti/Zr based non-chromium chemical conversion solution as electrical conductivity enhance component, silane/phosphonic acid composite conversion solution as corrosion resistance and paint adhesion enhance component, and cationic acrylic/polyurethane composite waterborne resin as the main film-former, respectively. This coating had good corrosion resistance and paint adhesion with the the rusts appearance time of NSS 192 hours before machining and NSS 96~144 h after machining. The corrosion resistance and paint adhesion enhance functions resulting from silane/phosphonic acid component were obviously reflected in the organic/inorganic composite coating. However, high electrical conductivity superiority of Ti/Zr component was masked by the low conductivity organic resin coating. For this reason, the aim of using Ti/Zr based non-chromium chemical conversion coating as electrical conductivity enhance component of the pyramidal non-chromium AFP coating was difficult to achieve in this study. The integrated performances test results showed that the organic/inorganic composite coating was appropriate for using as the good electrical conductivity AFP coating of electrogalvanized steel for household electric appliances, but there was still some way to go with the alkali resistance of this coating compared with the advanced world standard of this field."
文献类型	学位论文
条目标识符	http://ir.imr.ac.cn/handle/321006/64291
专题	中国科学院金属研究所
推荐引用方式 GB/T 7714	柳洋波. 夹杂物和贝氏体对高强钢的超高周疲劳性能的影响[D]. 北京. 中国科学院金属研究所,2011.