發(fā)布時(shí)間：2018-03-19 03:19

  本文選題：二氧化鈦　切入點(diǎn)：多孔微球　出處：《浙江大學(xué)》2014年博士論文　論文類(lèi)型：學(xué)位論文

【摘要】：建筑物圍護(hù)結(jié)構(gòu)的隔熱是降低建筑能耗、提高建筑物居住和使用功能的重要途徑之一,其關(guān)鍵是隔熱材料及體系。在各種建筑隔熱材料及體系中,隔熱涂料以其隔熱性能好、經(jīng)濟(jì)性高、施工方便以及對(duì)熱應(yīng)力不敏感等特點(diǎn)而受到廣泛關(guān)注,特別是反射型隔熱涂料既可有效降低圍護(hù)結(jié)構(gòu)表面的溫度,從源頭上減少熱流的傳入,又在一定程度上改善城市熱島效應(yīng),降低光化學(xué)煙霧的生成幾率。反射型隔熱涂料的功能主要來(lái)自功能性隔熱填料,但目前反射型隔熱涂料用功能性隔熱填料種類(lèi)較少,功能較為單一。因此,亟需開(kāi)發(fā)新的應(yīng)用于反射型隔熱涂料的功能性隔熱填料。 本文在綜合論述了隔熱涂料研究現(xiàn)狀的基礎(chǔ)上,針對(duì)隔熱涂料用填料存在的問(wèn)題,開(kāi)展了新型反射型隔熱填料及輻射型隔熱填料的制備機(jī)理及應(yīng)用技術(shù)研究,重點(diǎn)研究了核殼結(jié)構(gòu)中空二氧化鈦微球、多孔二氧化鈦微球、二氧化鈦/乙基纖維素復(fù)合多孔微球等基于多孔結(jié)構(gòu)的反射型隔熱填料以及納米片狀氧化鋅、氧化鋅納米片球狀團(tuán)簇、氧化鋅納米棒/云母復(fù)合粉體等氧化鋅(ZnO)基輻射型隔熱填料的制備機(jī)理,并通過(guò)制備反射型隔熱涂料,分析了反射型填料與輻射型填料對(duì)涂層隔熱效果的影響,從而為新型功能性隔熱填料的開(kāi)發(fā)及應(yīng)用奠定理論基礎(chǔ)。主要研究結(jié)果如下： (一)開(kāi)展了核殼結(jié)構(gòu)中空二氧化鈦微球及多孔二氧化鈦微球的制備研究,系統(tǒng)研究原料組分以及制備工藝對(duì)多孔微球形貌及內(nèi)部結(jié)構(gòu)的影響,實(shí)現(xiàn)了核殼結(jié)構(gòu)中空二氧化鈦微球以及具有大孔結(jié)構(gòu)的多孔二氧化鈦徼球的可控制備.采用乳液法結(jié)合溶膠凝膠法,在螯合劑乙酰乙酸乙酯與前驅(qū)體鈦酸四正丁酯摩爾比為1：1,鈦酸四正丁酯與油相溶劑正辛醇體積比為1：2條件下,制備出具有良好球狀形貌的二氧化鈦凝膠微球；以制備的二氧化鈦凝膠微球?yàn)樵?采用快速升溫法制備出具有核殼結(jié)構(gòu)的中空二氧化鈦微球；在二氧化鈦凝膠微球的制備體系中,引入相分離劑聚乙烯吡咯烷酮(PVP),借助相分離機(jī)理制備具有多孔結(jié)構(gòu)的二氧化鈦微球；隨著PVP用量的增加,所得微球的內(nèi)部孔徑逐漸變大,當(dāng)PVP用量增至1.903g時(shí),微球平均大孔孔徑為～1.3μm。 (二)開(kāi)展了二氧化鈦/乙基纖維素復(fù)合多孔微球的制備研究,實(shí)現(xiàn)了二氧化鈦/乙基纖維素復(fù)合多孔微球的可控制備。采用乳液法制備了乙基纖維素多孔微球,當(dāng)油相溶液中乙基纖維素/乙酸乙酯質(zhì)量比分別為0.4/10、0.8/10和1.2/10時(shí),制得的微球具有較好的球狀結(jié)構(gòu),其平均粒徑分別為2.6、15.7和23.1μm,通孔孔隙率為72%、74%和68%；在乙基纖維素多孔微球制備體系中,添加納米二氧化鈦粒子后,所得二氧化鈦/乙基纖維素復(fù)合粒子形貌均為球狀結(jié)構(gòu),納米二氧化鈦粒子并未對(duì)其形貌產(chǎn)生顯著影響；添加納米二氧化鈦對(duì)所得微球內(nèi)部孔結(jié)構(gòu)有一定的影響,納米二氧化鈦與乙基纖維素質(zhì)量比分別為0.1/0.8、0.2/0.8和0.4/0/8時(shí),所得復(fù)合多孔微球的通孔孔隙率分別為56%、54%和51%。 (三)開(kāi)展了高紅外輻射率納米氧化鋅的制備研究,實(shí)現(xiàn)了納米片狀氧化鋅以及氧化鋅納米片球狀團(tuán)簇的可控制備,對(duì)比分析了納米片狀氧化鋅及氧化鋅納米片球狀團(tuán)簇紅外輻射性能的差異。以二水合乙酸鋅為原料,NaOH為礦化劑,采用水熱法制備出分散性較好的納米片狀氧化鋅粉體,其大小約在400nm,厚度在20～50nm之間；在納米片狀氧化鋅的制備體系中,添加乳酸、檸檬酸以及聚丙烯酸鈉等多官能度改性劑,促使納米片狀氧化鋅粒子通過(guò)自組裝形成氧化鋅納米片球狀團(tuán)簇；所得納米片狀氧化鋅粒子與氧化鋅納米片球狀團(tuán)簇在8-14岫光譜區(qū)域內(nèi)的紅外輻射率分別為0.90以及0.88。 (四)開(kāi)展了氧化鋅納米棒/云母復(fù)合粉體的制備研究,實(shí)現(xiàn)了云母表面負(fù)載氧化鋅納米棒沉積密度的調(diào)節(jié),闡明了納米粒子團(tuán)簇結(jié)構(gòu)的形成對(duì)粉體紅外輻射性的影響。采用液相沉積法制備了氧化鋅/云母復(fù)合粉體,研究了云母表面晶種化以及氧化鋅納米棒在云母表面的沉積過(guò)程,ZnO在經(jīng)過(guò)表面晶種化的云母顆粒表面以(002)面取向生長(zhǎng)成棒狀,其直徑約為150nm,長(zhǎng)度約為550nm；通過(guò)改變ZnO膠體粒子濃度可調(diào)節(jié)云母表面晶種化密度,從而控制云母表面氧化鋅納米棒的沉積密度；隨著云母表面氧化鋅沉積密度的增加,所得復(fù)合粉體的紅外輻射率逐漸增加,最高達(dá)到0.863,而氧化鋅納米棒構(gòu)成的球狀粒子,其紅外輻射率為0.851。 (五)應(yīng)用二氧化鈦/乙基纖維素復(fù)合多孔微球?yàn)榉瓷湫吞盍?氧化鋅納米片球狀團(tuán)簇為輻射型填料制備反射型隔熱涂料,研究了反射型填料與輻射型填料的隔熱協(xié)同作用。以二氧化鈦/乙基纖維素復(fù)合多孔微球?yàn)榉瓷湫吞盍现苽浞瓷湫透魺嵬苛?并考察了二氧化鈦/乙基纖維素復(fù)合多孔微球添加量對(duì)涂層隔熱性能的影響,當(dāng)二氧化鈦/乙基纖維素復(fù)合多孔微球添加量為5.0wt.%時(shí),所得涂層具有較好的隔熱性能,覆有涂層的樣板經(jīng)半小時(shí)紅外燈照射之后,其溫度僅為67.7℃,而涂覆未添加多孔微球涂層的樣板溫度達(dá)到85.6℃；在此基礎(chǔ)上,進(jìn)一步考察了氧化鋅納米片球狀團(tuán)簇添加量對(duì)涂層隔熱性能的影響,發(fā)現(xiàn)添加氧化鋅納米片球狀團(tuán)簇進(jìn)一步改善了涂層的隔熱性能,當(dāng)氧化鋅納米片球狀團(tuán)簇添加量為1.0wt.%時(shí),所得涂層的隔熱性能最好,覆有涂層的樣板經(jīng)半小時(shí)紅外燈照射之后,其溫度進(jìn)一步下降至63.9℃,表明反射型填料與輻射型填料具有一定的協(xié)同隔熱作用。
[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.

【學(xué)位授予單位】：浙江大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2014
【分類(lèi)號(hào)】：TU551

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