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1、七届会征文-功能复合材料海上风力发电定子用常温固化氟碳涂料研究*收到初稿日期：2010-08-20 通讯作者：邓强作者简介：邓强(1982)，男， 湖南长沙人，主要从事工业防腐涂料研究邓 强，刘含茂，曾德淼，李强军，姜其斌 (株洲时代新材料科技股份有限公司，湖南 株洲 412007)摘 要： 以常温固化四氟型氟碳树脂为基料和超细云母粉、硅微粉等绝缘填料，制备了适合海上风力发电定子用表面防护涂料。对影响涂料性能的主要因素进行了研究，结果表明：该防护涂料具有良好的电绝缘性能、耐盐雾性能及耐化学品性能。关键词： 风力发电；氟碳涂料；防护涂料；制备 中图分类号： 文献标识码：A1 引 言当前，国家正大
2、力提倡建设“资源节约型，环境友好型”的两型社会，风力发电已成为世界上公认的竞争力最强的可再生能源技术之一。风力发电电机中定子组件是核心设备，其状态直接关系到整个风力发电机组的安全运行。对于沿海或近海区域的风力发电机组，其定子腐蚀环境按ISO12944标准判断为C5-M，为严重腐蚀环境。鉴于此，对风力发电定子表面防护涂料提出了极高的要求。由于氟碳树脂主要结构为C-F键，键能高（486.5KJ/mol）,键程短（0.142nm），氟含量高（35%-40%）。因此其具有极为优异的耐候性、耐盐雾性、耐化学品性及耐沾污性。本文拟采用常温固化四氟型氟碳树脂为基料，制备能够满足海洋环境对风力发电定子表面防护
3、用涂料。2 试 验21表面防护涂料的制备 按配方量称取氟碳树脂、分散剂和混合溶剂，分散均匀，加入颜填料和助剂，高速分散30分钟，研磨至细度15m；在制得的漆料中加入其他剩余助剂和混合溶剂，调节粘度100-120秒（涂-4#杯），过滤出料，所制得的漆料组分与固化剂组分按4:1（重量比）配置成表面防护涂料。22 性能测试 涂料按GB/T1727-1992要求制得试板，按GB/T1981-89测试电气性能，按GB/T1771-2007测试耐盐雾性能，按GB/T1768-79测试耐磨性能，按其他相应国标测试性能。3 结果与讨论3.1润湿分散剂的选择 由于氟碳树脂极性低，对颜料润湿性能差，易产生返粗、浮
4、色发花等弊病。因此需要加入适量润湿分散剂以提高对颜料的润湿性能。树脂与各润湿分散剂相容性及对涂料贮存稳定性影响如下表。表1 润湿分散剂对涂料性能影响Table 1 Coating performance affected by dispersing angent 项目1#分散剂2#分散剂3#分散剂与树脂相容性良好，清澈透明良好，清澈透明轻微浑浊研磨时间1.5h2h2h初始状态细度20m，均匀流体，无沉淀细度20m，均匀流体，无沉淀细度20m，均匀流体，无沉淀6030d状态细度40m，略沉淀，可搅匀细度20m，均匀流体，无沉淀细度40m，均匀流体，无沉淀-1030d状态细度30m，略沉淀，可搅匀
5、细度20m，均匀流体，无沉淀细度40m，均匀流体，无沉淀常温贮存90d状态细度40m，略沉淀，可搅匀细度20m，均匀流体，无沉淀细度40m，均匀流体，无沉淀 由表1可以看出， 1#分散剂与树脂相容性良好，研磨时间较短，但贮存试验明显不合格。这是因为，1#分散剂为聚羧酸类低分子分散剂，润湿性能较好，但由于分子量较小，空间位阻效果差，因此在贮存试验中，细度增长较快。2#分散剂与3#分散剂同样为聚氨酯类高分子分散剂，但3#分散剂分子量较高（MW=9509）,且分子量分布分散性较大（Polydispersity=2.35），因此其与树脂相容性较差，造成贮存试验不合格。选择中等分子量且分子量分布分散性较
6、小的2#分散剂（MW=6325, Polydispersity=1.25）是合适的。3.2催干剂加入量对漆膜性能影响催干剂能有效促进-OH基与-NCO基反应，促进漆膜实干，其加量对漆膜附着力、冲击强度、柔韧性及电气绝缘性能等均有显著影响。不同催干剂加入量对漆膜性能影响如表2所示。表2 催干剂加量对漆膜性能影响Table2 Coating performance affected by drier angent项目催干剂用量（以对漆料总量计）0.01%0.02%0.03%0.04%实干时间(h)2412108附着力(MPa)914108冲击强度(cm)50504020柔韧性(mm)1123体积电
7、阻率(.m)3.21096.510136.710137.21013电气强度(MV/mm)32687072活化期（h）7421 由表2可以看出，随着催干剂加入量的增大，固化速度加快，固化时间缩短，电气绝缘性能明显提高。但是催干剂用量过大，漆膜脆性增加，会导致漆膜附着力降低、抗冲击强度降低、活化期缩短。综合各方面性能，配方中催干剂加入量为0.02%时较为合适。3.3不同防锈填料及颜基比对漆膜耐盐雾性能影响 防锈填料可分为物理防锈填料和化学防锈填料两类，物理防锈填料主要通过屏蔽作用，延长水汽、盐分等腐蚀性介质透过漆膜对底材产生腐蚀的时间。化学防锈填料主要通过与腐蚀介质产生化学反应，或使底材表面产生钝
8、化或极化，从而保护底材避免腐蚀。不同防锈填料及颜基比对漆膜耐盐雾性能影响如表3所示。表3 不同防锈填料及颜基比对漆膜耐盐雾性能影响Table 3 Salt spray resisistence affected by antisepsis filler and P/B方案耐盐雾试验耐盐雾试验后附着力（MPa）配方一P/B=0.5200h漆膜起泡,划痕处腐蚀2mm2P/B=1.0500h漆膜起泡,划痕处腐蚀2mm3P/B=1.5600h漆膜起泡,划痕处腐蚀2mm2配方二P/B=0.5300h漆膜起泡,划痕处腐蚀2mm5P/B=1.0500h漆膜起泡,划痕处腐蚀2mm6P/B=1.5800h漆膜起
9、泡,划痕处腐蚀2mm5配方三P/B=0.5600h漆膜起泡,划痕处腐蚀2mm8P/B=1.01000h漆膜不起泡,划痕处腐蚀2mm12P/B=1.51000h漆膜不起泡,划痕处腐蚀2mm7由表3可以看出，配方三的耐介质腐蚀性能优于配方一和配方二，主要是因为配方三采用物理和化学双重防腐机理。配方中添加了一定量的物理防锈颜料超细云母粉，具有片状结构的超细云母粉的加入增加了漆膜的致密性，降低了腐蚀介质的渗透率，对腐蚀介质起着屏蔽作用。同时配方三中还含有一定量的三聚磷酸铝，三聚磷酸铝离解产生的磷酸根可使金属表面钝化，引起阳极极化，而铝离子在阴极产生难溶物而引起阴极极化，大大提高了漆膜的耐盐雾腐蚀能力。
10、虽然配方三中P/B=1.0及P/B=1.5时，耐盐雾腐蚀性能相同，但由于P/B=1.5时，漆膜颜填料含量过多，引起漆膜耐盐雾试验后附着力下降。因此，配方中颜基比P/B=1.0时较为合适。3.4流变助剂加入量对漆膜性能影响 在重防腐涂料中，普遍认为漆膜与厚度与其防腐能力成正比。本文所论述的风力发电定子的使用环境为海洋性重腐蚀环境，因此，对定子表面防护涂料的厚度提出了较高要求，通常设计干膜厚度为150m200m。为保证一次施工达到该厚度而不产生流挂缺陷，配方中需加入适量流变助剂。流变助剂加入量对漆膜性能影响如表4所示。表4 流变助剂加入量对漆膜性能影响Table 4 Coating perform
11、ance affected by rheological agent项目流变助剂加入量（对配方总量）%0.30.51.0极限流挂膜厚（m）125225250漆膜吸水率（%）0.50.81.5由表4可以看出，随着流变助剂加入量增大，漆膜极限流挂膜厚随之增加。本文使用的为改性脲类型的流变助剂，其主要通过在涂料体系中建立可逆三维结构，产生假塑性和触变性，而达到防流挂的效果。但该类型流变助剂对潮气较为敏感，因此，随着加入量增大，漆膜吸水率也增大。综合极限流挂膜厚和漆膜吸水率，配方中流变助剂加入量为0.5%时较为合适。3.5不同漆膜耐化学品性能影响 由于风力发电机使用环境为近海和海上区域，因此，受到酸、
12、碱等腐蚀也较严重。采用国产氟碳树脂与进口氟碳树脂进行对比。测试漆膜耐碱性（10%NaOH溶液）及耐酸性(10%H2SO4溶液)，结果如图1及图2所示。图1 漆膜光泽与耐碱性关系图Fig.1 Coating gloss affected by alkali resistance图2 漆膜色差与耐酸性关系图Fig.2 Aberration affected by acid resistance 由图1及图2可以看出，四氟氟碳树脂的耐酸性及耐碱性均优于三氟氟碳树脂，原因是制备四氟型氟树脂的氟单体具有良好的耐化学物质攻击性能，而且氟单体与共聚单体的交替共聚倾向，一定程度保护了共聚单体，降低了四氟型氟碳
13、树脂对酸碱等化学物质攻击的敏感性。但是三氟氟碳树脂中的醋酸乙烯酯单体在碱性环境下会产生酯化反应，造成涂膜变色、失光。3.6不同固化剂对漆膜耐磨性影响 风力发电机安装于近海区域，存在一定风沙吹蚀等破坏现象，对定子表面防护涂料的耐磨性提出了一定要求。不同固化剂交联固化的漆膜耐磨蚀性能如图3所示。图3 砂轮转速与磨耗量关系图Fig.3 Friction depletion affected by grinding wheel roating speed 从图3可知，HDI缩二脲与HDI弹性固化剂交联固化的涂膜具有很好的耐磨性能。主要原因是HDI弹性固化剂是由柔性聚酯多元醇和二异氰酸酯反应生成的一种预
14、聚物，其分子链中含有柔性的多元醇分子链骨架，两端带有反应性的异氰酸酯基团，异氰酸酯基团和氟碳树脂中的羟基反应聚合以后最终形成聚氨酯弹性体的基本结构，这种结构存在着大量如氨基甲酸酯、脲基等高极性基团，同时聚氨酯大分子链间又可形成大量的氢键，使漆膜具有较好的拉伸强度和良好的弹性，其耐磨性特别优良。当漆膜受到外界风沙的冲刷时，具有弹性的漆膜能通过产生形变而减弱风沙的冲击力，从而提高了漆膜的耐磨性。 另外， HDI弹性体固化剂为低分子预聚物，NCO含量较低，反应活性较低，单独使用，会造成漆膜干燥速度慢，固化不完全，影响漆膜附着力和耐腐蚀性能。因此，需采用HDI缩二脲固化剂与其拼用，提高漆膜干燥速度和交
15、联密度。3.7定子表面防护涂料性能表征 3.7.1定子表面防护涂料热失重（TG）曲线如下图所示。图4 表面防护涂料的热失重曲线图Fig.4 Thermal failure curve by protective coating从图4可看出，299.5前失重部分主要为配方中低分子量的有机物，重量约为15左右，有机高分子聚合物分解50时的温度为376。据热失重曲线，由割线法求得表面防护涂料中的氟碳树脂和固化剂交联固化后的耐热温度指数为160，说明研制的涂料热稳定性能好，可满足风力发电定子的耐热需要。3.7.2 定子表面防护涂料红外谱图（IR）如下所示。图5 表面防护涂料的红外谱图Fig.5 Inf
16、rared spectrogram by protective coating从图5可以看出，1732cm处为酯基（OCO）的特征吸收峰；1243cm处的尖锐吸收峰为CF键的特征吸收峰。从该谱图中可以看出：OCO键和CF键的吸收峰是谱图中最强的主特征峰，故可确定此涂层为氟碳涂层。3.8研制的定子表面防护涂料主要性能指标 研制的定子表面防护涂料主要性能指标如表5所示。由表中可以看出，定子表面防护涂料的检测结果均符合设计目标，能够满足海上风力发电定子组件对防护涂料的要求。表5 定子表面防护涂料主要性能指标Table 5 Main performance by potective coating序号
17、检测项目单位技术指标检测结果试验方法1细度m2015GB/T1724-792附着力MPa614GB/T5210-063柔韧性mm21GB/T1731-934铅笔硬度/H2HGB/T6739-965冲击性能cm50通过GB/T1733-936耐磨性能（1kg,500转）mg4016GB/T1768-797体积电阻率.m1.010126.51013GB/T1981-798电气强度MV/m25689耐酸性（10% H2SO4）240h/无起泡，脱落和变色合格GB9274-8810耐碱性（10%NaOH）240h/无起泡，脱落和变色合格11耐盐雾性能（1000h）/漆膜无起泡、脱落，划痕处锈蚀宽度2m
18、m合格GB/T1771-084 结 论 本文对海上风力发电定子组件用表面防护涂料用树脂、颜填料及相关助剂进行了筛选和研究。当选用四氟型氟碳树脂为基料，配合物理和化学防锈颜料及弹性固化剂，制得的海上风力发电定子用表面防护涂料具有良好的防护性能、电绝缘性能、耐化学品性能及耐磨性能。耐盐雾试验1000h后，漆膜附着力可达到12MPa，体积电阻率为6.51013.m，电气强度为68 MV/m，耐酸及耐碱均可240h无起泡、脱落和变色，1kg负载，500转后磨耗量仅为16mg。可满足海上风力发电定子组件表面防护的需求。参考文献：1 倪玉德， FEVE氟碳树脂与氟碳涂料. M.北京：化学工业出版社，200
19、6.2 李国莱，张慰盛，管从胜.重防腐涂料M.北京：化学工业出版社，1999. 3 李运德. 两种FEVE氟碳涂料的性能比较 J. 中国涂料, 2008.104 赵德仁,张慰盛.高聚物合成工艺学M.北京：科学工业出版社，1997.5 虞兆年.防腐蚀涂料和涂装（第二版）M.北京：化学工业出版社,2002.Room Temperature Curing Fluoride Coating Of Offshore Wind Power Generator Stator Deng Qiang, Liu Han-mao,Zeng De-miao, Li Qiang-Jun,Jiang Qi-bin(Zhu
20、 Zhou Times New Material Technology CO.LTD, Zhuzhou 412007，China)Abstract: The protective coating which used on offshore wind power generator stator made by the base material which is room curing fluorocarbon resin and insulation filler which is mica powder and silica powder. The article analyzed ma
21、in properties of the protective coating. The results showed that the protective coating has good electrical insulation properties, resistance to salt spray and chemical resistance. Key words: Wind Power Generator; Fluoride Coating; Protective coating; PreparationEditors note: Judson Jones is a meteo
22、rologist, journalist and photographer. He has freelanced with CNN for four years, covering severe weather from tornadoes to typhoons. Follow him on Twitter: jnjonesjr (CNN) - I will always wonder what it was like to huddle around a shortwave radio and through the crackling static from space hear the
23、 faint beeps of the worlds first satellite - Sputnik. I also missed watching Neil Armstrong step foot on the moon and the first space shuttle take off for the stars. Those events were way before my time.As a kid, I was fascinated with what goes on in the sky, and when NASA pulled the plug on the shu
24、ttle program I was heartbroken. Yet the privatized space race has renewed my childhood dreams to reach for the stars.As a meteorologist, Ive still seen many important weather and space events, but right now, if you were sitting next to me, youd hear my foot tapping rapidly under my desk. Im anxious
25、for the next one: a space capsule hanging from a crane in the New Mexico desert.Its like the set for a George Lucas movie floating to the edge of space.You and I will have the chance to watch a man take a leap into an unimaginable free fall from the edge of space - live.The (lack of) air up there Wa
26、tch man jump from 96,000 feet Tuesday, I sat at work glued to the live stream of the Red Bull Stratos Mission. I watched the balloons positioned at different altitudes in the sky to test the winds, knowing that if they would just line up in a vertical straight line we would be go for launch.I feel t
27、his mission was created for me because I am also a journalist and a photographer, but above all I live for taking a leap of faith - the feeling of pushing the envelope into uncharted territory.The guy who is going to do this, Felix Baumgartner, must have that same feeling, at a level I will never re
28、ach. However, it did not stop me from feeling his pain when a gust of swirling wind kicked up and twisted the partially filled balloon that would take him to the upper end of our atmosphere. As soon as the 40-acre balloon, with skin no thicker than a dry cleaning bag, scraped the ground I knew it wa
29、s over.How claustrophobia almost grounded supersonic skydiverWith each twist, you could see the wrinkles of disappointment on the face of the current record holder and capcom (capsule communications), Col. Joe Kittinger. He hung his head low in mission control as he told Baumgartner the disappointin
30、g news: Mission aborted.The supersonic descent could happen as early as Sunday.The weather plays an important role in this mission. Starting at the ground, conditions have to be very calm - winds less than 2 mph, with no precipitation or humidity and limited cloud cover. The balloon, with capsule at
31、tached, will move through the lower level of the atmosphere (the troposphere) where our day-to-day weather lives. It will climb higher than the tip of Mount Everest (5.5 miles/8.85 kilometers), drifting even higher than the cruising altitude of commercial airliners (5.6 miles/9.17 kilometers) and in
32、to the stratosphere. As he crosses the boundary layer (called the tropopause), he can expect a lot of turbulence.The balloon will slowly drift to the edge of space at 120,000 feet (22.7 miles/36.53 kilometers). Here, Fearless Felix will unclip. He will roll back the door.Then, I would assume, he wil
33、l slowly step out onto something resembling an Olympic diving platform.Below, the Earth becomes the concrete bottom of a swimming pool that he wants to land on, but not too hard. Still, hell be traveling fast, so despite the distance, it will not be like diving into the deep end of a pool. It will b
34、e like he is diving into the shallow end.Skydiver preps for the big jumpWhen he jumps, he is expected to reach the speed of sound - 690 mph (1,110 kph) - in less than 40 seconds. Like hitting the top of the water, he will begin to slow as he approaches the more dense air closer to Earth. But this wi
35、ll not be enough to stop him completely.If he goes too fast or spins out of control, he has a stabilization parachute that can be deployed to slow him down. His team hopes its not needed. Instead, he plans to deploy his 270-square-foot (25-square-meter) main chute at an altitude of around 5,000 feet
36、 (1,524 meters).In order to deploy this chute successfully, he will have to slow to 172 mph (277 kph). He will have a reserve parachute that will open automatically if he loses consciousness at mach speeds.Even if everything goes as planned, it wont. Baumgartner still will free fall at a speed that
37、would cause you and me to pass out, and no parachute is guaranteed to work higher than 25,000 feet (7,620 meters).It might not be the moon, but Kittinger free fell from 102,800 feet in 1960 - at the dawn of an infamous space race that captured the hearts of many. Baumgartner will attempt to break that record, a feat that boggles the mind. This is one of those monumental moments I will always remember, because there is no way Id miss this.
