功能性隔热填料的制备及其在反射型隔热涂层中的应用

发布时间：2018-03-19 03:19

本文选题：二氧化钛　切入点：多孔微球　出处：《浙江大学》2014年博士论文　论文类型：学位论文

【摘要】：建筑物围护结构的隔热是降低建筑能耗、提高建筑物居住和使用功能的重要途径之一,其关键是隔热材料及体系。在各种建筑隔热材料及体系中,隔热涂料以其隔热性能好、经济性高、施工方便以及对热应力不敏感等特点而受到广泛关注,特别是反射型隔热涂料既可有效降低围护结构表面的温度,从源头上减少热流的传入,又在一定程度上改善城市热岛效应,降低光化学烟雾的生成几率。反射型隔热涂料的功能主要来自功能性隔热填料,但目前反射型隔热涂料用功能性隔热填料种类较少,功能较为单一。因此,亟需开发新的应用于反射型隔热涂料的功能性隔热填料。本文在综合论述了隔热涂料研究现状的基础上,针对隔热涂料用填料存在的问题,开展了新型反射型隔热填料及辐射型隔热填料的制备机理及应用技术研究,重点研究了核壳结构中空二氧化钛微球、多孔二氧化钛微球、二氧化钛/乙基纤维素复合多孔微球等基于多孔结构的反射型隔热填料以及纳米片状氧化锌、氧化锌纳米片球状团簇、氧化锌纳米棒/云母复合粉体等氧化锌(ZnO)基辐射型隔热填料的制备机理,并通过制备反射型隔热涂料,分析了反射型填料与辐射型填料对涂层隔热效果的影响,从而为新型功能性隔热填料的开发及应用奠定理论基础。主要研究结果如下： (一)开展了核壳结构中空二氧化钛微球及多孔二氧化钛微球的制备研究,系统研究原料组分以及制备工艺对多孔微球形貌及内部结构的影响,实现了核壳结构中空二氧化钛微球以及具有大孔结构的多孔二氧化钛徼球的可控制备.采用乳液法结合溶胶凝胶法,在螯合剂乙酰乙酸乙酯与前驱体钛酸四正丁酯摩尔比为1：1,钛酸四正丁酯与油相溶剂正辛醇体积比为1：2条件下,制备出具有良好球状形貌的二氧化钛凝胶微球；以制备的二氧化钛凝胶微球为原料,采用快速升温法制备出具有核壳结构的中空二氧化钛微球；在二氧化钛凝胶微球的制备体系中,引入相分离剂聚乙烯吡咯烷酮(PVP),借助相分离机理制备具有多孔结构的二氧化钛微球；随着PVP用量的增加,所得微球的内部孔径逐渐变大,当PVP用量增至1.903g时,微球平均大孔孔径为～1.3μm。 (二)开展了二氧化钛/乙基纤维素复合多孔微球的制备研究,实现了二氧化钛/乙基纤维素复合多孔微球的可控制备。采用乳液法制备了乙基纤维素多孔微球,当油相溶液中乙基纤维素/乙酸乙酯质量比分别为0.4/10、0.8/10和1.2/10时,制得的微球具有较好的球状结构,其平均粒径分别为2.6、15.7和23.1μm,通孔孔隙率为72%、74%和68%；在乙基纤维素多孔微球制备体系中,添加纳米二氧化钛粒子后,所得二氧化钛/乙基纤维素复合粒子形貌均为球状结构,纳米二氧化钛粒子并未对其形貌产生显著影响；添加纳米二氧化钛对所得微球内部孔结构有一定的影响,纳米二氧化钛与乙基纤维素质量比分别为0.1/0.8、0.2/0.8和0.4/0/8时,所得复合多孔微球的通孔孔隙率分别为56%、54%和51%。 (三)开展了高红外辐射率纳米氧化锌的制备研究,实现了纳米片状氧化锌以及氧化锌纳米片球状团簇的可控制备,对比分析了纳米片状氧化锌及氧化锌纳米片球状团簇红外辐射性能的差异。以二水合乙酸锌为原料,NaOH为矿化剂,采用水热法制备出分散性较好的纳米片状氧化锌粉体,其大小约在400nm,厚度在20～50nm之间；在纳米片状氧化锌的制备体系中,添加乳酸、柠檬酸以及聚丙烯酸钠等多官能度改性剂,促使纳米片状氧化锌粒子通过自组装形成氧化锌纳米片球状团簇；所得纳米片状氧化锌粒子与氧化锌纳米片球状团簇在8-14岫光谱区域内的红外辐射率分别为0.90以及0.88。 (四)开展了氧化锌纳米棒/云母复合粉体的制备研究,实现了云母表面负载氧化锌纳米棒沉积密度的调节,阐明了纳米粒子团簇结构的形成对粉体红外辐射性的影响。采用液相沉积法制备了氧化锌/云母复合粉体,研究了云母表面晶种化以及氧化锌纳米棒在云母表面的沉积过程,ZnO在经过表面晶种化的云母颗粒表面以(002)面取向生长成棒状,其直径约为150nm,长度约为550nm；通过改变ZnO胶体粒子浓度可调节云母表面晶种化密度,从而控制云母表面氧化锌纳米棒的沉积密度；随着云母表面氧化锌沉积密度的增加,所得复合粉体的红外辐射率逐渐增加,最高达到0.863,而氧化锌纳米棒构成的球状粒子,其红外辐射率为0.851。 (五)应用二氧化钛/乙基纤维素复合多孔微球为反射型填料,氧化锌纳米片球状团簇为辐射型填料制备反射型隔热涂料,研究了反射型填料与辐射型填料的隔热协同作用。以二氧化钛/乙基纤维素复合多孔微球为反射型填料制备反射型隔热涂料,并考察了二氧化钛/乙基纤维素复合多孔微球添加量对涂层隔热性能的影响,当二氧化钛/乙基纤维素复合多孔微球添加量为5.0wt.%时,所得涂层具有较好的隔热性能,覆有涂层的样板经半小时红外灯照射之后,其温度仅为67.7℃,而涂覆未添加多孔微球涂层的样板温度达到85.6℃；在此基础上,进一步考察了氧化锌纳米片球状团簇添加量对涂层隔热性能的影响,发现添加氧化锌纳米片球状团簇进一步改善了涂层的隔热性能,当氧化锌纳米片球状团簇添加量为1.0wt.%时,所得涂层的隔热性能最好,覆有涂层的样板经半小时红外灯照射之后,其温度进一步下降至63.9℃,表明反射型填料与辐射型填料具有一定的协同隔热作用。
[Abstract]:The structure of the building envelope insulation is one of the important ways to reduce energy consumption, improve the building housing and the use of the function, the key is the heat insulation material and system. In all kinds of building insulation materials and insulation coating system, with its good insulation properties, high economical efficiency, convenient construction and the thermal stress insensitive characteristics are widely attention, especially the reflective insulation coating can effectively reduce the surface temperature of envelope, from the source to reduce heat and improve the introduction of urban heat island effect to a certain extent, reduce the rate of photochemical smog formation. The main function of the reflective insulation coating from functional insulation filler, but the reflective insulation coating with functional insulation filler type less, has single function. Therefore, the urgent need to develop new functional heat-insulating filler used in reflective insulation coating.
In this paper based on the comprehensive research status of thermal insulation coatings, insulation coatings for packing problems, carry out a new reflective insulation filler and filler type heat radiation mechanism and Application Research of preparation technology, focusing on the core-shell structure hollow titanium dioxide micro ball, porous TiO2 microspheres, composite porous TiO2 / ethyl cellulose microsphere reflective heat-insulating filler porous structure and nano sheet based on Zinc Oxide, Zinc Oxide nano globular clusters, Zinc Oxide Nanorods / mica composite powder such as Zinc Oxide (ZnO) and preparation mechanism based radiation type heat insulation fillers, and through the reflective insulation coatings, analyzes the influence of reflection type filler and filler on the radiation type thermal insulation effect, so as to lay the theoretical foundation for the development and application of new functional heat-insulating filler. The main results are as follows:
(a) the core-shell structure hollow titania microspheres and porous titania microspheres preparation research, system composition of raw materials and the influence of the preparation process of porous microspheres morphology and internal structure, the core-shell structure and hollow titania microspheres with large pore structure of porous TiO2 micro ball controlled preparation of combination. Sol gel method by emulsion method, the chelating agent of ethyl acetoacetate and precursors of butyl titanate four molar ratio of 1:1, butyl titanate four solvent n-octanol and oil phase volume ratio is 1:2, the preparation of titanium dioxide microspheres with good spherical morphology; titania gel microspheres were prepared by using fast as raw material. Heating prepared hollow titania microspheres with core-shell structure; the titania Gel Microspheres preparation system, agent polyvinylpyrrolidone into phase separation (PVP) the porous titanium dioxide microspheres were prepared by phase separation mechanism. With the increase of PVP dosage, the inner diameter of the microspheres increased gradually. When the amount of PVP increased to 1.903g, the average pore size of the microspheres ranged from 1.3 to m..
(two) the TiO2 / ethyl cellulose composite porous microsphere preparation research, the TiO2 / ethyl cellulose composite porous microspheres can be prepared. Ethyl cellulose porous microspheres were prepared by emulsion method, when the oil phase solution in ethyl cellulose / ethyl acetate mass ratio were 0.4/10,0.8/10 and 1.2/10, prepared has a globular structure better, the average particle size were 2.6,15.7 and 23.1 m, hole porosity was 72%, 74% and 68%; in the ethyl cellulose porous microsphere preparation system, adding nano TiO2 particles, the TiO2 / ethyl cellulose composite nanoparticles are spherical structure, nano titanium dioxide particles did not have a significant impact the morphology; adding nano-TiO2 has some influence on the pore structure of the microspheres, nano titanium dioxide and fiber quality than ethyl respectively. For 0.1/0.8,0.2/0.8 and 0.4/0/8, the pore porosity of the composite porous microspheres was 56%, 54% and 51%., respectively.
(three) the high infrared radiation ratio of nano preparation of Zinc Oxide, the controllable preparation of nano flake Zinc Oxide and Zinc Oxide nano globular clusters, analyzes the differences between Zinc Oxide and Zinc Oxide Nanoflake nano spherical cluster infrared radiation properties. In two hydrated zinc acetate as raw materials and NaOH as mineralizer prepared by hydrothermal method, dispersion of nano flake zinc oxide good body, its size is about 400nm, thickness between 20 and 50nm; adding lactic acid in the preparation of nano scale Zinc Oxide system, and citric acid and sodium polyacrylate as polyfunctional modifying agent, nano scale particles by self prompting Zinc Oxide assemble to form Zinc Oxide nano globular clusters; the nano scale particles and Zinc Oxide Zinc Oxide nano spherical clusters of infrared radiation in the spectral region 8-14 Xiuyan rate were 0.90 and 0.88.
(four) the Zinc Oxide Nanorods / mica composite powder preparation research, the mica surface load regulation Zinc Oxide nanorods deposition density, the formation of nanoparticle clusters of infrared radiation. The powder was prepared by liquid phase deposition method Zinc Oxide / mica composite powder on mica surface the seed of Zinc Oxide and nanorods in the deposition process of the mica surface, ZnO after surface crystal of mica particles on the surface of (002) plane orientation into a rod, its diameter is about 150nm, the length is about 550nm; the adjustable mica surface seeding density change of ZnO colloidal particle concentration, deposition density and control the surface of mica nanorods increase with Zinc Oxide; Zinc Oxide mica surface deposition density, the infrared radiation composite powder rate is gradually increased, the highest reached 0.863, while Zinc Oxide nanorods formed The spherical particle, its infrared radiation rate is 0.851.
(five) the application of TiO2 / ethyl cellulose composite porous microspheres as reflective filler, Zinc Oxide nano spheric cluster radiation type filler reflective insulation coatings, of reflective filler and filler type radiation insulation synergistic effect. Using TiO2 / ethyl cellulose composite porous microspheres as reflective filler to prepare reflective insulation paint, and the effects of TiO2 / ethyl cellulose composite porous microspheres content on the coating performance, when TiO2 / ethyl cellulose composite porous microsphere dosage is 5.0wt.%, the coating has good heat-insulating property, coated with the coating sample after half an hour after the infrared lamp, the temperature is only 67.7 degrees, and without the addition of coated porous microspheres coated sample temperature reached 85.6 degrees; on this basis, further study of Zinc Oxide nano spheric cluster content on coating Effect of heat insulation performance, found that adding nano globular clusters of Zinc Oxide to further improve the heat insulation performance, when Zinc Oxide nano globular cluster content is 1.0wt.%, the best performance of the heat insulation coating, coated with a coating layer model of infrared lamp after half an hour later, the temperature dropped further to 63.9 DEG C, show that reflection packing and radiation type packing has a synergistic effect of heat insulation.

【学位授予单位】：浙江大学
【学位级别】：博士
【学位授予年份】：2014
【分类号】：TU551

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