【作者】 李运德；

【导师】 左禹；

【作者基本信息】 北京化工大学 ， 材料科学与工程， 2009， 博士

【摘要】 本文研究了不同类型FEVE氟碳涂料的性能,积累了FEVE氟碳涂料基础数据;制备了高性能的FEVE氟碳涂料,对FEVE氟碳涂料进行耐粘污性研究和碳纳米管改性研究;并且系统地研究了氟碳防腐涂层配套体系设计、缺陷与施工质量控制。主要研究工作如下:1、通过多种试验方法和表征手段研究了FEVE氟碳涂料的耐候性、热稳定性、力学性能和防腐性能。1)通过天然曝晒试验、人工加速老化试验和环境扫描电镜（ESEM）分析,研究了FEVE氟碳涂料优异的耐候性,不同类型FEVE氟碳涂料耐候性差异以及FEVE氟碳涂料耐候性的地区差异,结果表明:醚类单体或位阻型大单体合成的FEVE氟碳树脂具有更优异的耐候性;FEVE氟碳涂料对湿热、盐雾环境较敏感,而对单纯强紫外线照射环境不敏感;2)通过热空气老化试验、热失重试验以及老化后的力学性能试验,分析了FEVE氟碳涂料热稳定性,结果表明:FEVE氟碳树脂中含有四氟乙烯单体比三氟氯乙烯单体、醚类单体比酯类单体具有更好的耐热性;3)研究了不同类型FEVE氟碳涂料的拉伸应力—应变行为以及氟碳涂料与环氧底漆的相容性,结果表明:FEVE氟碳涂料具有良好的力学性能,并且与环氧底涂层匹配性良好;4)比较了不同类型FEVE氟碳涂料的耐酸碱性能和耐溶剂性能,结果表明:所有类型FEVE氟碳涂料均具有优异的耐酸性,醚类或酯类大单体共聚型FEVE氟碳涂料耐碱性优异,而醋酸乙烯酯类型FEVE氟碳涂料耐碱性较差;各种类型FEVE氟碳涂料在非极性溶剂中溶胀度很低（三氟氯乙烯—乙烯基酯共聚型FEVE氟碳涂料几乎不溶于非极性溶剂）,在弱极性溶剂中溶胀度很高,而在强极性溶剂中溶胀度稍低;5)采用交流阻抗法（EIS）测试各类FEVE氟碳涂料的防腐蚀性能,结果表明:在3.5%NaCl水溶液中,氟碳涂层（厚度23μm）在较长时间内（40d）保持为一个电阻值大、电容值小的隔绝层,说明涂层具有很好的抗渗透防腐性能。2、选用四氟乙烯—乙烯基醚型FEVE氟碳树脂为成膜物,通过固化剂、溶剂、及助剂的选择制备了漆膜外观优异,耐候性能和防腐性能突出的环保型氟碳面漆。氟碳防腐涂层体系按GB/T1865人工加速老化5000h后漆膜很轻微变色、很轻微失光;耐盐雾5000h漆膜无异常;北京地区自然曝晒4年,不变色、不失光;海南地区曝晒2年,不变色、轻微失光。3、研究了采用氟化硅氧烷亲水化剂、改性有机硅防涂鸦助剂、TiO₂光催化剂三种方法提高FEVE氟碳涂层耐粘污性的效果,结果表明:通过添加氟化硅氧烷亲水化剂使FEVE氟碳涂料膜表面产生亲水性,从而提高涂膜的自洁性和耐粘污性,是一种切实可行的方法。采用光电子能谱（XPS）、接触角测定仪对亲水化漆膜表面元素和与水接触角进行表征,结果表明,亲水化剂在漆膜表面明显富集,并且在较短时间内水解形成亲水化基团,获得了稳定的亲水性,漆膜表面与水接触角维持在35°以下。4、制备了碳纳米管/FEVE氟碳复合涂膜,研究了碳纳米管在常温固化氟碳树脂溶液中的分散性以及复合涂膜的力学性能、热稳定性和导电性能。结果显示:采用DISPERBYK-2050润湿分散助剂可使碳纳米管很好地分散在FEVE基体中;碳纳米管的加入显著提高了氟碳树脂涂膜的拉伸强度,稍稍提高氟碳涂膜的耐热性,并赋予氟碳涂层良好的导静电性能。更多还原

【Abstract】 In this dissertation, the properties of various FEVE paints were studied, and so the basic data of FEVE paints were accumulated; High-performance FEVE paints, and FEVE / CNTs paints were prepared, and the dirt resistance of FEVE paints were investigated; the design of FEVE coating systems and the strict control of construction quality were also studied.1. The weathering resistance, thermal stability, mechanical property and anti-corrosive performance were investigated by various test methods and means. 1) The excellent weathering resistance of FEVE paints, the type and district differences of weathering resistance, of different types of FEVE paints, were investigated by weather exposure test, weatherometer test, and ESEM analysis. The results show that The FEVE resins polymerizated by these ether or big vinyl monomers have more excellent weathering resistance; The FEVE paints are sensitive to humid tropical condition and salt fog, but are not sensitive to only ultraviolet light. 2) The thermal stability of FEVE fluorocarbon coatings was investigated, by air oven ageing, thermo-gravimetric analysis（TG）, and tensile property after hot air ageing, the results show that The FEVE resins with TFE have better heat resistance than CTFE, and with vinyl ether than with vinyl esters. 3) The tensile stress-strain curve of various FEVE paints, and the compatibility of FEVE paint and epoxy primer were investigated, the results show that FEVE paints have good mechanical properties, and good matching with epoxy primer. 4) The different types of FEVE paints resistance to acid and alkali and resistance to organic solvent were compared and analyzed, the results show that all types of FEVE paints have good resistance to acid, the vinyl ether and big vinyl esther FEVE paints has good resistance to alkali, but the vinyl acetate FEVE paints has poorer resistance to alkali; All FEVE paints have very low degree of swelling in nonpolar solvent（trifluorochloroethylene vinyl acetate copolymer hardly resolves in nonpolar solvent）, have high degree of swelling in weak polar solvent, and have lower degree of swelling in strong polar solvent. 5 ) Electrochemical Impedance Spectroscopy （EIS） was applied as a principal tool to appraise the corrosion resistance of FEVE paints, the results show that FEVE coating films （23μm） keep as an isolated layer with large resistance value and small capacitance value in 3.5% NaCl water solution in longer time （40d）, indicating that FEVE coating films have good permeation resistance and anti-corrosion. 2. FEVE paints with excellent weathering resistance, good anti-corrosion, and good appearance of film, were prepared, with tetrafluoroethylene vinyl ether copolymer as film forming resin, by the choice of curing agents, solutions, and additives. The films of FEVE anti-corrosive coating systems have very slight discoloration and very slight blinding after 5000h weatherometer test （GB/T1865）; The films have no abnormal after 5000h salt fog resistance test; The films have no discoloration and no blinding after four years weather exposure test in Beijing distract; The films have no discoloration and only slight blinding after two years weather exposure test in Hainan distract.3. The effects to improve the Dirt Resistance of Air Curing FEVE Paints with siloxane fluoride hydrophilic additive, modified organic silicon antigraffiti additive, or TiO₂ photocatalyst were analyzed, the results show that it is the most effective means with the proper hydrophilic additive to improve the self-cleanliness and dirt resistance of paint film. Surface elements and water contact angle of coating films were characterized by using XPS and measuring apparatus for contact angle. The results show that the hydrophilic additive evidently accumulates on the surface of paint films, and hydrolyzes rapidly to produce hydrophilic groups, so steady hydrophlicity of the surface is accomplished, and water contact angle keeps below 35°.4. Carbon nanotubes/FEVE fluorocarbon composite coatings were prepared. The dispersibility of carbon nanotubes in FEVE matrix, mechanical property, thermal stability and conductivity of composite coatings were investigated. The results show that carbon nanotubes were well dispersed in the fluorocarbon resin solution by adding the wetting and dispersing additive Disperbyk?-2050. Adding carbon nanotubes improves the tensile strength of the fluorocarbon resin coating films obviously, slightly improve heat resistance and endows conductive property of the fluorocarbon resin coating films.更多还原