CN107245705B - 一种铝合金表面疏冰涂层及其制备方法 - Google Patents
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Abstract
本发明公开了一种铝合金表面疏冰涂层及其制备方法，该涂层由以下成分组成：氢氧化镍，氧化石墨烯，棕榈酸；其中氢氧化镍呈纳米球结构，氧化石墨烯呈片状均匀镶嵌在氢氧化镍纳米球之间，形成微纳复合结构，棕榈酸覆盖在微纳复合结构表面。本发明涂层疏冰效果好，能显著降低冰在表面的剪切强度、延长结冰时间，制备方法简便，成本较低，具有很好的应用价值。
Description
一、技术领域
本发明涉及表面工程领域，具体的说是一种铝合金表面疏冰涂层及其制备方法。
二、背景技术
由于严寒天气导致的结冰对于城市电缆、通讯塔基、飞行器机翼等的安全运行产生了严重威胁，通常的解决方法是结冰后通过外部加热或者物理敲打等方式让结冰破裂后脱落，这种方法对于结冰时间长、冰层较厚、结冰面较广时处理效率较低，因此，需要发展能疏冰的涂层，主动防覆冰，降低结冰所带来的风险。
目前报道的疏冰涂层较多，如Richard Menini等在铝合金表面发展了一种Al2O3/PTFE的疏冰涂层，结果发现该涂层对水的接触角为130～140°，对冰的剪切强度可降低至原来的2/5，具有很好的疏冰效果[Menini R,Farzaneh M.Elaboration of Al2O3/PTFEicephobic coatings for protecting aluminum surfaces[J].Surface&CoatingsTechnology,2009,203(14):1941-1946]。朱林采用低表面能的硅橡胶涂层为主体，用二甲基硅油改性，当添加45％含量的甲基硅油时，表面覆冰的对拉强度从280kPa降低至25kPa[朱林，纳米阵列超疏水特性及有机桂涂层疏冰性研究[D]，南京大学，2014]。从疏冰涂层的制备方法看，主要包括了化学刻蚀、阳极氧化、电纺法等，但是由于具体工艺的差别导致涂层的性能相差极大。此外，由于成本较高，制备难度较大等原因导致疏冰涂层目前在铝合金表面工业化应用还比较少，亟需发展一种成本低、制备难度小的铝合金表面疏冰涂层及其制备方法。
三、发明内容
本发明针对现有技术的不足，目的就是要提供一种铝合金表面疏冰涂层及其制备方法。
本发明通过以下技术方案来实现：
本发明一种铝合金表面疏冰涂层，其特点在于：由以下质量份成分组成：氢氧化镍186-372份，氧化石墨烯0.012-0.5份，棕榈酸25.6-76.8份；其中氢氧化镍呈纳米球结构，氧化石墨烯呈片状均匀镶嵌在氢氧化镍纳米球之间，形成微纳复合结构，棕榈酸覆盖在微纳复合结构表面；所述的氧化石墨烯为片层直径0.5-3μm，比表面积大于1000m2/g，氧含量30～40％的单层或双层氧化石墨烯。
上述铝合金表面疏冰涂层的制备方法，包括以下步骤：
(1)将铝合金材料放在0.5-2mol/L稀盐酸溶液中进行浸泡5-10min，取出后用去离子水冲洗至表面呈中性，然后置于无水乙醇中超声10-15min，取出后于40-60℃干燥；
(2)在0.02-0.04mol/L NiSO4溶液中，加入0.1-0.6mol/L稀HF溶液，使F和Ni的原子比为1-2:1，然后加入氧化石墨烯至溶液中含量为0.01-0.5mg/L，搅拌均匀后，将步骤(1)处理后得到的铝合金材料悬置于溶液中，向溶液中缓慢滴加浓氨水，调节溶液pH值至8-8.2，然后将体系在50-60℃保温搅拌反应1-2h，升温至70-80℃保温搅拌反应2-3h，将铝合金材料取出后，用去离子水冲洗至表面呈中性，置于真空干燥箱中40-60℃真空干燥；
(3)将上述涂层后样品置于浓度为0.01-0.03mol/L棕榈酸的乙醇溶液中进行表面修饰处理，经过3-5h后取出，室温下风干即得。
与现有技术相比，本发明的优势体现在：
1)本发明的涂层疏冰效果好，与水的接触角可达150°以上，可显著降低冰在表面的剪切强度，可达涂层前的1/3以下，且结冰时间可显著延长至涂层前的2倍以上。
2)本发明的涂层与铝合金基体的结合力强、耐磨性强，对多次摩擦后表面仍然能保持良好的疏水疏冰性。
3)本发明的制备方法简便，易于工业化生产，成本较低。本发明的方法由刻蚀、涂层、表面修饰等几个基本的单元操作组成，易于实现。
四、具体实施例
以下实施例中所述的氧化石墨烯为片层直径0.5-3μm，比表面积大于1000m2/g，氧含量30～40％的单层或双层氧化石墨烯，所选用的铝合金材料为7075铝板，以下所述均为质量份。
实施例1：
(1)将铝合金材料放在0.5mol/L稀盐酸溶液中进行浸泡8min，取出后用去离子水冲洗至表面呈中性，然后置于无水乙醇中超声12min，取出后于45℃干燥；
(2)在0.02mol/L NiSO4溶液中，加入0.2mol/L稀HF溶液，使F和Ni的原子比为2:1，然后加入氧化石墨烯至溶液中含量为0.03mg/L，搅拌均匀后，将步骤(1)处理后得到的铝合金材料悬置于溶液中，向溶液中缓慢滴加浓氨水，调节溶液pH值至8，然后将体系在53℃保温搅拌反应1h，升温至75℃保温搅拌反应2.5h，将铝合金材料取出后，用去离子水冲洗至表面呈中性，置于真空干燥箱中50℃真空干燥；
(3)将上述涂层后样品置于浓度为0.01mol/L棕榈酸的乙醇溶液中进行表面修饰处理，经过4.5h后取出，室温下风干即得。
实施例2：
(1)将铝合金材料放在1mol/L稀盐酸溶液中进行浸泡6min，取出后用去离子水冲洗至表面呈中性，然后置于无水乙醇中超声13min，取出后于60℃干燥；
(2)在0.04mol/L NiSO4溶液中，加入0.4mol/L稀HF溶液，使F和Ni的原子比为2:1，然后加入氧化石墨烯至溶液中含量为0.4mg/L，搅拌均匀后，将步骤(1)处理后得到的铝合金材料悬置于溶液中，向溶液中缓慢滴加浓氨水，调节溶液pH值至8.2，然后将体系在60℃保温搅拌反应1h，升温至80℃保温搅拌反应2h，将铝合金材料取出后，用去离子水冲洗至表面呈中性，置于真空干燥箱中50℃真空干燥；
(3)将上述涂层后样品置于浓度为0.03mol/L棕榈酸的乙醇溶液中进行表面修饰处理，经过3.5h后取出，室温下风干即得。
将上述实施例1、2所得铝合金表面疏冰涂层测试后发现，与水的接触角可达152°、158°，冰在表面的剪切强度分别降低至涂层前的1/4、1/5，结冰时间延长至涂层前的3倍、4倍。
Claims (2)
1.一种铝合金表面疏冰涂层，其特征在于，由以下质量份成分组成：氢氧化镍186-372份，氧化石墨烯0.012-0.5份，棕榈酸25.6-76.8份；其中氢氧化镍呈纳米球结构，氧化石墨烯呈片状均匀镶嵌在氢氧化镍纳米球之间，形成微纳复合结构，棕榈酸覆盖在微纳复合结构表面；所述的氧化石墨烯为片层直径0.5-3μm，比表面积大于1000m2/g，氧含量30～40％的单层或双层氧化石墨烯。
2.一种权利要求1所述的铝合金表面疏冰涂层的制备方法，其特征在于，包括以下步骤：
(1)将铝合金材料放在0.5-2mol/L稀盐酸溶液中进行浸泡5-10min，取出后用去离子水冲洗至表面呈中性，然后置于无水乙醇中超声10-15min，取出后于40-60℃干燥；
(2)在0.02-0.04mol/L NiSO4溶液中，加入0.1-0.6mol/L稀HF溶液，使F和Ni的原子比为1-2:1，然后加入氧化石墨烯至溶液中含量为0.01-0.5mg/L，搅拌均匀后，将步骤(1)处理后得到的铝合金材料悬置于溶液中，向溶液中缓慢滴加浓氨水，调节溶液pH值至8-8.2，然后将体系在50-60℃保温搅拌反应1-2h，升温至70-80℃保温搅拌反应2-3h，将铝合金材料取出后，用去离子水冲洗至表面呈中性，置于真空干燥箱中40-60℃真空干燥；
(3)将上述涂层后样品置于浓度为0.01-0.03mol/L棕榈酸的乙醇溶液中进行表面修饰处理，经过3-5h后取出，室温下风干即得。
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