【作者】 刘晓芳；

【导师】 徐庆； 董云会；

【作者基本信息】 武汉理工大学 ， 材料工程， 2002， 硕士

【摘要】 功能材料与建筑材料相结合以制备新型环境友好型建筑材料是目前建筑材料的 发展趋势之一，研制和开发具有抑菌、保健等生态功能的红外辐射内墙涂料是近年来 国际上内墙涂料新的发展动态，高性能的红外辐射材料是发展环境友好型红外辐射内 墙涂料的关键材料。本研究研制了过渡金属离子固溶堇青石体系红外辐射材料，着重 研究了过渡金属离子的种类与含量、合成温度、颗粒粒度对材料红外辐射性能的影响 及其作用机制，其目的在于为堇青石固溶体系红外辐射材料在内墙涂料中的应用打下 基础。 采用固相法制备了2(l-x)Mgo·2xZnO·2Al2O3·5SiO2(x≤0.6)、2(l-x)MgO·2x TiO2·2(l+x)Al2O3·(5-4x)SiO2(x≤0.7)和2(l-x)MgO·2xZrO2·2(l+x)Al2O3·(5-4x) SiO2(x≤0.6)三个体系的红外辐射材料。由红外辐射性能研究发现，在体系中引入适 量的ZnO、TiO2等过渡金属氧化物可以显著提高材科的红外辐射性能。 研究了2(l-X)MgO·2XZnO·2Al2O3·5SiO2(x≤0.6)、2(l-x)MgO·2xTiO2·2(l+x) Al2O3·(5-4x)SiO2(x≤0.7)两个体系样品的结构和红外辐射性能。XRD、IR和红外辐 射性能的研究结果表明，当ZnO、TiO2的含量较低时样品中形成以堇青石为主体的晶 体结构，样品的红外辐射性能明显提高。2(l-x)MgO·2xZnO·2Al2O3·5SiO2体系中 X=0．2时样品的红外辐射性能达到最佳，2(l-x)MgO·2xTiO2·2(l+x)Al2O3·(5-4x)SiO2 体系中0.05≤x≤0.10时样品的红外辐射性能达到最佳，其法向全波段的辐射率分别 达到0．89和0．88，在8~14μm波段的辐射率都达到0．90以上。当2(l-x)MgO·2x ZnO·2Al2O3·5SiO2体系中ZnO的含量较高时(0.4.≤x≤0.60),体系中形成大量的红 外辐射性能较弱的Zn2+固溶镁铝尖晶石，使样品的红外辐射性能明显降低。当2(l-x) MgO·2xTiO2·2(l+x)Al2O3·(5-4x)SiO2体系中TiO2的含量较高时(0．50≤X≤0．70)， 样品中形成大量的莫来石固溶体，样品的红外辐射性能略有降低。 采用MAS NMR和XPS研究了1.6MgO·0．4 ZnO·2Al2O3·5SiO2和1.8MgO· 0．2TiO2·2．2Al2O3·4.6SiO2堇青石固溶体样品的结构。MASNMR研究结果表明，Zn2+、 Ti4-的固溶对样品中的堇青石结构具有重要的影响，使得样品中的堇青石由六方结构 α-堇青石向四方结构β-堇青石转变。同时由MAS NMR研究还发现，在样品1．8 MgO·0．2TiO2·2.2Al2O3·4．6SiO2中用作价态补偿的过量Al3+全部进入六元环T2位 宜上。XPS的研究发现，Zn‘”、T广的同溶使茧青石结构中的川、St等元素出现了多 种化学状态。本研究认为，适量的过渡金属离子占据茧青石结构中Mg》的位置使品格 振动的非简谐效应增强，从而提高了材料的红外辐射性能。 研究了合成温度对 1．6MgO·0．4 ZnO·ZAI。O。·SSIO。和 1．8 MgO·0，ZTIO。·2二 ＊1。0。·4．65iQ茧青石固溶体样品结构与红外辐射性能的影响。＊p、IR和红外辐射 性能分忻的研究结果表明，合成温度较低时样品中存在镁铝尖晶石等红外辐射能力较 弱的中间相，茧青石固溶体结构未能充分形成，使得样品的红外辐射性能不理想；提 高合成温度则有利于固相反应充分进行和样品红外辐射性能的提高。在 1350－1420C 的合成温度范围内可制备出红外辐射性能优良的＊n’”固溶茧青人和n’”固溶笔青石体 系红外辐射材料。 本研究采用SEM、粒度分析和红外辐射性能测试等方法研究了颗粒粒度对样品 1．6MgO·0．4 ZnO·ZAI。O。·SSIO。和 l．8 MgO·0二卫，·2二 AI，O。·4．6SIOZ M青石同 溶体红外辐射性能的影响。研究结果表明，在200～500目的粒度范围内，粒度大小对 材料红外辐射性能影响不明显。这可能是由于这类陶瓷材料的颗粒中含有许多小晶 粒，晶粒构成材料红外辐射的基本辐射元，因而颗粒尺寸效应的作用不明显。更多还原

【Abstract】 Developing advanced environmental-friendly building materials by combing functional materials with building materials has become a recent tendency in the development of the building materials. The infrared radiation inner wall coating exhibiting ecological characteristics such as antibacterial function and health protection function is a novel kind of the inner wall coating,in which the ceramic powders with fine infrared radiation properties are the key materials. The development of cordierite based infrared radiation materials with the substitution of partial Mg2+ ions by transitional metal ions has been presented,and the influences and their mechanisms of the substitution of partial Mg2 ions by transitional metal ions,synthesis temperatures and particle size on the infrared radiation materials have been investigated,which aims at promoting the application of the infrared radiation materials in the inner wall coating.Three systems of infrared radiation materials including 2(l-x)MgO2x ZnO2A12O35SiO2(x<0.6),2(l-x)MgO2xTi022(l+x)Al2O3(5-4x)SiO2 (x<0.7) and 2 (1-x) MgO2xZrO22(1+x) A1203(5-4x)SiO2 (x<0.6) were fabricated by solid state reaction method. The results of the investigation on infrared radiation properties show that the introduction of transitional metal oxides such as ZnO or Ti02 into the systems can significantly improve infrared radiation properties of the materials.Structure features and infrared radiation properties of the 2(l-x)MgO 2x ZnO 2Al2O3 5Si02(x<0.6) and 2(1-x)MgO -2xTiO2 -2(l+x) A12O3 (5-4x)SiO2 (x^0.7) systems have been investigated. The results of XRD,IR and infrared radiation property measurement show that a crystalline structure with the cordierite solid solution as the main phase can be produced when ZnO or TiO2 with relatively low content were introduced,while the infrared radiation properties of the samples were significantly improved compared with that of the sample without introduction of transitional metal oxides. The optimized infrared radiation property can be obtained in the sample of x=0.2 for the 2(1-x)MgO -2x ZnO -ZAl2O3 -5SiO:system,exhibiting the infrared emissivities of 0.89 in the whole band and 0.90-0.94 in the 8-14 u m band respectively,while the optimized infrared radiation properties can beproduced within the composition range of 0.05<x 0.10 for the 2(l-x)MgO2xTiO22(1+x) A12O3 (5-4x)SiO2 system,having the infrared emissivities of 0.88 in the whole band and 0.90-0.94 in the 8-14 u m band respectively. When ZnO with relatively high contents (0.40 x 0.60) was introduced,large amount of Zn2 substituted MgAl2O4 solid solution with low infrared emissivities was generated in the samples of 2(l-x)MgO2x ZnO 2A12O3 SSiO system,and the infrared radiation properties of the samples apparently decreased correspondingly. When TiO2 with relatively high contents (0.50 x 0.70) was introduced,large amount of mullite solid solution was formed in the samples of 2(l-x)MgO2xTiO22(l+x) A12O3(5-4x)SiO2 system,which demonstrate slightly decreased infrared radiation properties.The microstructure of the cordierite solid solution with the composition of 1.6MgO -0.4 ZnO 2Al2O3 5SiO2 and 1.8 MgO -0.2TiO2 -2.2 Al2O3 -4.6SiO2 have been investigated by MAS NMR and XPS. The results of MAS NMR analysis indicate that the crystalline structure of cordierite was considerably changed by the incorporation of the Zn2 ions or Ti "" ions,leading to the partial transition from a -cordierite with a hexagonal crystalline structure to P -cordierite with a orthorhombic crystalline structure. Meanwhile,it was detected that the excess A13+ ions,to compensate the positive charge caused by thesubstitution of partial Mg" ions by Ti ions,occupy the T2 site in the six-membered rings in the sample of 1.8 MgO 0.2TiO2 2.2 A12O34.6SiO2. The results of XPS analysis show that there are two different chemical states of Al and Si element respectively in the structure of the two samples because of the incorporation of Zn2+ or Ti4+. The incorporation of moderate contents of transitional metal ions at the sites of Mg2更多还原