【作者】 王莉贤；

【导师】 郭强；

【作者基本信息】 上海大学 ， 材料学， 2013， 博士

【摘要】 铝合金作为一种性能优异的轻质金属材料在建筑、机械、电子、航空及军事领域被广泛使用，应用领域的增加亦对铝合金表面的防护性能和装饰效果提出了更高的要求。铝合金表面可经阳极氧化形成具有较高耐磨性和耐蚀性的阳极氧化膜（AAO膜），还可通过多种方式对其增强改性和表面着色，以提高防护性能和装饰效果。近年来，对AAO膜的结构、形成机理及着色工艺的探索一直是该领域的研究热点之一。本文采用电化学方法，在含有无机酸和有机酸的混和电解液中加入带负电荷的含硅超微粒子和辅助添加剂，从而在铝合金表面形成具有高防护性能的掺硅复合AAO膜。与普通AAO膜相比，这种新型复合膜结构紧密、孔隙率低、硬度更高、防护效果优良、孔径分布均匀且易于着色。微观分析表明：掺硅复合AAO膜中硅元素主要是以NaAlSi₃O₈长石型结构存在。采用N,N′-二苯基丙二酰胺衍生物与取代苯重氮盐反应的方法得到了9种苯偶氮N,N′-二苯基丙二酰胺衍生物（AZO），核磁共振谱和质谱分析表明其中7种为新化合物。通过原位偶合反应的方法，将以上产物嵌入到掺硅复合AAO膜的微孔中从而形成耐光、色艳、色调丰富的着色膜。该着色膜克服电解着色和整体着色法获得的着色膜颜色发暗、色调单一、装饰效果不佳等缺点，同时具备化学染色法所不具备的优异耐候性能。配方的优化试验结果表明硫酸体系交流氧化制得的复合AAO膜着色效果最佳，呈均匀的黄色，其中电流密度和反应时间对着色效果影响较小，而温度影响较大，最佳着色反应温度在25℃～35℃。红外和电镜等微观分析表明：原位着色法的反应机理是先将有机颜料一组分（Ⅰ）通过化学键合和物理吸附作用，沉积在复合AAO膜孔中，作为有机颜料另一组分（Ⅱ）的锚基；然后在复合AAO膜上Ⅱ与锚基Ⅰ进行反应，生成有机颜料（Ⅲ），从而使Ⅲ象铆钉一样紧紧嵌入复合AAO膜的微孔中。对复合AAO着色膜的防护性能测试结果表明：336h耐盐雾实验腐蚀评级为10级，10周期（240h）的耐交变湿热实验试片膜层无变化，28d（672h）耐霉菌实验长霉为0级，连续1Y（365天）自然气候暴露实验腐蚀评级为10级。复合着色膜光谱性能测试结果表明：着色剂AZO在复合膜中光反射情况和从膜中剥离得到的着色剂在溶液中的光吸收情况相吻合，表现在380～480nm（λmax）有吸收，其互补色对应黄及黄绿色。总之，该膜防护性能优异，可满足多种严酷条件下（如潮湿、含工业气体、盐分和尘埃的大气中）的应用要求；装饰效果良好，可同时具备电解着色技术形成的着色膜的耐光性和化学染色（有机着色）技术形成的着色膜的丰富色调和艳丽色泽。本文中着色复合膜的制备工艺及方法为铝合金表面阳极氧化膜的增强改性和着色研究提供了一条具有特色的新思路，进一步推动了AAO着色膜技术的发展。更多还原

【Abstract】 Aluminium anodizing oxide （AAO） film is a kind of porous ceramic film withexcellent wear resistance and corrosion resistance, which could be fabricated byanodizing the surface of aluminium alloy and be coloured with several coloringmethods to obtain colour film with good protective and decorative fuction. With theextensive uses of aluminum and alloy thereof in architecture, aviation and military,the requirements for the protective performance and decorative effect of AAO fiombecame much more stringent. Therefore, investigation of the AAO film and coloringtechnic was the hotpoint in this field.The main routes at present to improve the protective performance of AAO filmare hard anodic oxidation or composite anodic oxidation. Hard anodic oxidationcould form a compact hard oxide film with high hardness, high corrosion resistanceand high wear resistance on the surface of aluminum or alloy thereof by applyingdifferent oxidation electrolyte or changing the wave shape of power source. However,hard anodic oxidation films also give a poor mechanical strength and not easy topigment. Composite anodic oxidation is a kind of new route developed recently.When some insoluble powders such as Al2O3and TiO3were added into the oxidationsolution, the insoluble powder can be deposited on the film after electric reactionwith the oxidation film, which could improve the hardness, wear resistance andcorrosion resistance of oxidation film. Unfortunately, the composite anodic oxidationis not easy to be electrolytic colored twice. Generally, there are three colouringmethods for AAO film i.e. electrolytic colouring, chemical colouring and wholebody colouring. Films by electrolytic colouring have high corrosion resistance andlightfastness, but also show less varieties, dark tones and poor brilliance. Chemicalcolouring has the advantages of simple process, easy operation and brilliant colour,but the obtained film has poor lightfastness and weather resistance thus is notsuitable for use out-of-doors. The whole body colouring could obtain films withexcellent corrosion resistance, moisture resistance and lightfastness, but also has less varieties and poor brilliance, as well the high energy consumption. To improve theprotective performance and decorative effect, more research has emphasized on theprocess, reaction mechanism, structure and colouring routes of AAO film.When electrolytic mechanical route has been applied, several kinds ofnegatively charged silicon-containing superfine particle have been added toelectrolyte containing inorganic acid and organic acid to form a poroussilicon-containing composite AAO film on surface of aluminum or alloy. Accordingto the structure of AAO film obtained from different electrolyte such as inorganicacid, organic acid and alkali, the electrolyte composition and process technic tofabricate porous silicon-containing AAO film have been established. Furthermore,the structure and composition of AAO film have also been investigated. The resultsshow that the silicon contained in AAO film exists primarily of NaAlSi3O8withfeldspar structure. and the obtained composite AAO film gives apparent density of3.53g·cm^-3, porosity of10.6%and thickness of over20μm.In the systhsis process for dying agents, malonic acid diethyl ester was used andreact with aniline derivant to prepare several kinds of N,N’-diphenylmalondiamidederivant. N,N’-diphenylmalondiamide derivant could further react with substitutedbenzene diazonium salt resulting in nine kinds of azobenzeneN,N’-diphenylmalondiamide derivant of which seven kinds are new compound. Thefactors influencing the synthesis of N,N’-diphenylmalondiamide derivant andazobenzene N,N’-diphenylmalondiamide derivant have been investigated detailly.Furthermore, UV-Vis spectra, IR spectra, HNMR and MS have been used to analyzethe structure of products.When azobenzene N,N’-diphenylmalondiamide derivant was embedded into themicropores of silicon-containing composite AAO film by in situ coupling reaction, akind of composite colouring film with high lightfastness, excellent brilliance andabundant varieties can be obtained. According to the research on the relationbetween structure and preparation condition, the optimal technic condition has been established. To investigate the structure of synthesized dying material, the colouringfilm was stripped from the surface of aluminum by chemical method and dyingmaterial was then obtained by extraction method. According to the analysis byUV-Vis spectra, IR spectra, HNMR and MS, it is determined that the dying materialis azobenzene N,N’-diphenylmalondiamide derivantThe protective and decorative performance of silicon-containing compositecoloured AAO film has been investigated by a series of tests. After336h salt fog test,the grade of composite AAO film is level10. After ten period （240h） alternating hotand humid experiment, the composite AAO film gives no change. After28day（672h） mould test, the grade of composite AAO film is classified of level0. After1year （365day） physioclimate exposion test, the grade of composite AAO film isclassified of level10. Spectrum analysis results show that the reflect spectrum ofsilicon-containing composite AAO film is in line with the absorption spectrum ofcolorant in solution. Absoption is at λmax of380-480nm and the complementarycolours are yellow or yellow green, which is in accordance with visual inspection.Tests and analysises results show that, the coloured silicon-containingcomposite AAO film by in situ chemical reaction colouring method can meet thehigh requirement of protection at different stringent condition, such as humid,industrial gas contained, high salinity and dusted atmosphere. Furthermore,composite AAO film not only gives the high corosion resistance and lightfastnessequal to that of coloured film from electrolytic coloring method, but also shows theabundant varieties and bright colour equal to that of coloured film form chemicalcolouring method. Therefore, the in situ chemical reaction colouring method is aimportant progress of process and principle for high protective and decorativecomposite film on aluminum surface and will push forward the industrialdevelopment in this field significantly.更多还原