CN112409884A - 一种环氧树脂/go超疏水防腐涂层的制备方法 - Google Patents
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Abstract
本发明公开了一种环氧树脂/GO超疏水防腐涂层的制备方法,方法步骤如下:S1、利用水热法制备GO‑Fe3O4纳米粒子;S2、GO‑Fe3O4纳米粒子的氨基化;S3、二乙烯三胺固化剂的氟化改性;S4、制备磁诱导环氧树脂/GO复合涂层;S5、疏水化改性。本发明通过在GO表面负载GO‑Fe3O4纳米粒子,成膜过程中通过外加磁场使纳米粒子向涂层表面定向移动,形成粗糙表面结构,再通过改性剂对其表面进行疏水改性,使复合涂层具备超疏水性,静态水接触角达到154.96°。本发明制备的超疏水防腐涂层具备层内渐变结构,在获得表面超疏水特性的同时,涂层基材本身疏水,且层内氧化石墨烯粒子呈渐变密度排列,使涂层兼具氧化石墨烯屏蔽效应和表面超疏水带来的双重防腐效果。
Description
技术领域
本发明涉及复合涂层材料制备领域,尤其涉及一种环氧树脂/GO超疏水防腐涂层的制备方法。
背景技术
近50年来据统计,腐蚀造成的经济损失平均占每个国家GDP的3%-4%,全球腐蚀成本估计为2.5万亿美元,占全球GDP的3.4%。为了避免金属腐蚀造成的经济损失,有机涂层作为最有效的腐蚀方法之一被广泛应用于金属基材。涂层的作用主要是物理阻隔作用:将金属基体与外界环境分离,从而避免金属与周围环境中存在的腐蚀介质作用。但采用涂层防腐仍然面临,涂层本身存在微裂纹、孔隙等缺陷,从而导致金属暴露于腐蚀环境,使涂层破坏处腐蚀加速。为了解决以上难点,近年来出现了选用石墨烯、超疏水材料等制备防腐涂层的新型防腐策略。然而,仅仅采用单一策略难以满足实际生产生活中遇到的各类问题。因此,有必要采用多种防腐策略相互结合的方式,发展一种多功能的多维度相互协同的复合型材料。
发明内容
本发明的目的是为了解决上述技术问题而提出的一种环氧树脂/GO超疏水防腐涂层的制备方法,该方法通过磁诱导手段构筑涂层粗糙表面以及涂层内部GO-Fe3O4纳米粒子的渐变式分布。涂层在超疏水和和屏蔽效应的协同作用下,防腐性能得到显著提高。
为了实现上述目的,本发明采用了如下技术方案:
一种环氧树脂/GO超疏水防腐涂层的制备方法,方法步骤如下:
S1、利用水热法制备GO-Fe3O4纳米粒子;
S2、GO-Fe3O4纳米粒子的氨基化:将步骤S1中制得的GO-Fe3O4纳米粒子超声分散至乙醇水混合溶液中,并加入γ―氨丙基三乙氧基硅烷搅拌,淋洗冷冻干燥制得氨基化GO-Fe3O4纳米粒子;
S3、二乙烯三胺固化剂的氟化改性:将甲基丙烯酸十三氟辛酯,二乙烯三胺,乙醇钠均匀溶解于乙醇中,先低速搅拌,然后在氮气保护下保持中速搅拌,减压蒸馏除去乙醇和未反应的甲基丙烯酸十三氟辛酯,反复用蒸馏水除去DEA和乙醇钠,得到氟化二乙烯三胺固化剂;
S4、制备磁诱导环氧树脂/GO复合涂层:将环氧树脂、步骤S2制得的氨基化GO-Fe3O4纳米粒子、步骤S3制得的氟化二乙烯三胺固化剂与乙醇混合均匀喷涂在金属表面,在成膜过程中将240mT磁铁悬浮在涂层表面一定距离处,定向诱导GO-Fe3O4纳米粒子迁移至纳米复合涂层表面,得到磁诱导环氧树脂/GO涂层;
S5、疏水化改性:将十七氟癸基三甲氧基硅烷在溶解于乙醇水混合溶液中经过低速搅拌均匀分散后,喷洒在制得的磁诱导环氧树脂/GO涂层表面,自然风干制得到导环氧树脂/GO超疏水涂层。
优选的,所述S1中利用水热法制备GO-Fe3O4纳米粒子的步骤为:将聚乙烯吡咯烷酮、四水合氯化亚铁、氨水均匀溶解在蒸馏水中,低速搅拌后,加入GO水分散液,100℃下水热反应5.0h,反复用蒸馏水和乙醇淋洗三次后冷冻干燥,制得GO-Fe3O4纳米粒子。
优选的,所述GO、四水合氯化亚铁的质量比为1:2。
优选的,所述S2中GO-Fe3O4纳米粒子在乙醇水混合溶液中超声分散30min,加入γ―氨丙基三乙氧基硅烷后保持50℃中速搅拌5.0h;乙醇、蒸馏水、γ―氨丙基三乙氧基硅烷、GO-Fe3O4纳米粒子的质量比为18:2:0.5:1。
优选的,所述S3中在氮气保护下,保持70℃中速搅拌12h;甲基丙烯酸十三氟辛酯、二乙烯三胺的质量比为2:1。
优选的,所述S4中环氧树脂、氟化二乙烯三胺固化剂、氨基化GO-Fe3O4纳米粒子、乙醇的质量比为20:5:1:5。
优选的,所述S4中240mT磁铁距离涂层表面的距离为2-5cm。
优选的,所述S5中乙醇、蒸馏水、十七氟癸基三甲氧基硅烷的质量比为18:2:1。
优选的,所述S1、S3、S5中低速搅拌时长均为30min。
另外,本发明还提出一种利用上述制备方法制得的磁诱导构筑粗糙表面的环氧树脂/GO超疏水防腐涂层。
本发明建立在超疏水材料与防腐性能之间的关系对防腐材料进行开发研究,其中的超疏水材料做为一种新型材料,发展的最初灵感来源于荷叶。当材料表面的水接触角(WCA)大于150°,滚动角(RA)小于10°时,该材料被认为是超疏水的。而且,由于其独特的自清洁、防水和防冰性能,超疏水材料在各个领域受到了极大的关注。近年来,有学者研究发现:超疏水涂层能够通过在涂层表面和水之间形成气垫,隔离水中腐蚀性介质对涂层的渗透,从而起到保护材料的作用。
而石墨烯作为一种单层原子的二维纳米材料,因所有的分子和离子几乎都对其不能渗透的特性,对腐蚀性介质具有优异的阻隔效果。仅仅向涂层引入少量的石墨烯,就能使涂层的防腐性能得到明显改善。
因此,本发明结合氧化石墨烯的屏蔽效应和超疏水策略,通过磁诱导技术制备出一种防腐性能优异的环氧树脂基复合材料,解决了现有环氧树脂材料防腐能力不足的问题,在海洋运输,风力发电,建筑维护等领域具有较为广泛的应用价值。
本发明的有益效果为:
(1)本发明结合涂层的疏水性和GO优异的屏蔽效应,采用磁诱导技术构筑环氧树脂/GO超疏水防腐涂层,磁诱导技术通过对外加磁场大小、方向、密度的调节,可实现磁性复合材料的定向移动与排列。在环氧涂层成膜过程中,通过外加磁场的定向诱导,装载GO-Fe3O4纳米粒子的氧化石墨烯纳米片可向涂层表面定向迁移,在涂层中形成渐变式的层内结构,并在表面构造微纳粗糙结构,为后续超疏水改性提供形貌基础的同时极大提升涂层的防腐性能。
(2)本发明通过在GO表面负载GO-Fe3O4纳米粒子,并采用偶联剂对其进行改性,使其在环氧树脂中具备较好的分散能力的同时能够在磁场作用下定向运动,并对作为固化剂的二乙烯三胺做氟化处理。成膜过程中通过外加磁场使纳米粒子向涂层表面定向移动,形成粗糙表面结构,再通过改性剂对其表面进行疏水改性,使复合涂层具备超疏水性,静态水接触角达到154.96°。
(3)本发明制备的超疏水防腐涂层具备层内渐变结构,在获得表面超疏水特性的同时,涂层基材本身疏水,且层内氧化石墨烯粒子呈渐变密度排列,使涂层兼具氧化石墨烯屏蔽效应和表面超疏水带来的双重防腐效果。
附图说明
图1为本发明实施例1中环氧树脂/GO超疏水防腐涂层的制备工艺流程图。
图2为本发明实施例1中环氧树脂/GO超疏水防腐涂层的静态水接触角。
图3为本发明实施例1中氟化固化剂的傅里叶红外光谱图。
图4为本发明实施例1中氟化固化剂的核磁共振氢谱图
具体实施方式
下面将结合本发明实施例中的附图,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。
实施例一
本发明提出一种环氧树脂/GO超疏水防腐涂层的制备方法,方法步骤如下:
S1、制备GO-Fe3O4纳米粒子:将一定质量的聚乙烯吡咯烷酮(PVP)、5.213g四水合氯化亚铁(FeCl2·4H2O)、氨水均匀溶解在100mL蒸馏水中,低速搅拌30min后,加入6.611g氧化石墨烯(GO)水分散液,100℃下,水热反应5.0h。反复用蒸馏水和乙醇淋洗三次后冷冻干燥,制得GO-Fe3O4纳米粒子。
S2、GO-Fe3O4纳米粒子的氨基化:将2.513g GO-Fe3O4纳米粒子分散到100mL乙醇水混合溶液中,超声分散30min后,加入5.012gγ-氨丙基三乙氧基硅烷(KH550),50℃下中速搅拌5.0h。反复用水和乙醇淋洗三次后冷冻干燥,制得氨基化GO-Fe3O4纳米粒子。
S3、二乙烯三胺固化剂的氟化改性:将5.917g甲基丙烯酸十三氟辛酯,3.009g二乙烯三胺(DEA),适量乙醇钠均匀溶解在100mL乙醇中,低速搅拌30min后,在氮气保护下,70℃中速搅拌12h。减压蒸馏除去乙醇和未反应的甲基丙烯酸十三氟辛酯。反复用蒸馏水除去DEA和乙醇钠,得到氟化固化剂(f-DEA)。
S4、磁诱导环氧树脂/GO超疏水防腐涂层:将环氧树脂、f-DEA、GO-Fe3O4纳米粒子、乙醇按照20:5:1:5比例混合均匀喷涂在金属表面后,在成膜过程中将240mT磁铁悬浮在涂层表面2cm处,定向诱导GO-Fe3O4纳米片迁移至纳米复合涂层表面,制得磁诱导环氧树脂/GO涂层。
S5、表面粗糙结构疏水化:将1g十七氟癸基三甲氧基硅烷硅烷均匀分散在20mL乙醇水混合溶液中,低速搅拌30min后,喷洒在制得的磁诱导环氧树脂/GO涂层表面,待其自然风干后,制得磁诱导环氧树脂/GO超疏水涂层。
实施例二
本实施例中的实施方法步骤与实施例一相同。但技术参数有所不同,两者区别之处在于:S4中在成膜过程中将240mT磁铁悬浮在涂层表面3cm处。
实施例三
本实施例中的实施方法步骤与实施例一相同。但技术参数有所不同,两者区别之处在于:S4中在成膜过程中将240mT磁铁悬浮在涂层表面4cm处。
实施例四
本实施例中的实施方法步骤与实施例一相同。但技术参数有所不同,两者区别之处在于:S4中在成膜过程中将240mT磁铁悬浮在涂层表面5cm处。
实施例五
本实施例中的实施方法步骤与实施例一中的方法步骤区别之处在于:S2中不添加γ―氨丙基三乙氧基硅烷(KH550)。
以上,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,根据本发明的技术方案及其发明构思加以等同替换或改变,都应涵盖在本发明的保护范围之内。
Claims (10)
1.一种环氧树脂/GO超疏水防腐涂层的制备方法,其特征在于,方法步骤如下:
S1、利用水热法制备GO-Fe3O4纳米粒子;
S2、GO-Fe3O4纳米粒子的氨基化:将步骤S1中制得的GO-Fe3O4纳米粒子超声分散至乙醇水混合溶液中,并加入γ―氨丙基三乙氧基硅烷搅拌,淋洗冷冻干燥制得氨基化GO-Fe3O4纳米粒子;
S3、二乙烯三胺固化剂的氟化改性:将甲基丙烯酸十三氟辛酯,二乙烯三胺,乙醇钠均匀溶解于乙醇中,先低速搅拌,然后在氮气保护下保持中速搅拌,减压蒸馏除去乙醇和未反应的甲基丙烯酸十三氟辛酯,反复用蒸馏水除去DEA和乙醇钠,得到氟化二乙烯三胺固化剂;
S4、制备磁诱导环氧树脂/GO复合涂层:将环氧树脂、步骤S2制得的氨基化GO-Fe3O4纳米粒子、步骤S3制得的氟化二乙烯三胺固化剂与乙醇混合均匀喷涂在金属表面,在成膜过程中将240mT磁铁悬浮在涂层表面一定距离处,定向诱导GO-Fe3O4纳米粒子迁移至纳米复合涂层表面,得到磁诱导环氧树脂/GO涂层;
S5、疏水化改性:将十七氟癸基三甲氧基硅烷在溶解于乙醇水混合溶液中经过低速搅拌均匀分散后,喷洒在制得的磁诱导环氧树脂/GO涂层表面,自然风干制得到导环氧树脂/GO超疏水涂层。
2.根据权利要求1所述的一种环氧树脂/GO超疏水防腐涂层的制备方法,其特征在于,所述S1中利用水热法制备GO-Fe3O4纳米粒子的步骤为:将聚乙烯吡咯烷酮、四水合氯化亚铁、氨水均匀溶解在蒸馏水中,低速搅拌后,加入GO水分散液,100℃下水热反应5.0h,反复用蒸馏水和乙醇淋洗三次后冷冻干燥,制得GO-Fe3O4纳米粒子。
3.根据权利要求2所述的一种环氧树脂/GO超疏水防腐涂层的制备方法,其特征在于,所述GO、四水合氯化亚铁的质量比为1:2。
4.根据权利要求1所述的一种环氧树脂/GO超疏水防腐涂层的制备方法,其特征在于,所述S2中GO-Fe3O4纳米粒子在乙醇水混合溶液中超声分散30min,加入γ―氨丙基三乙氧基硅烷后保持50℃中速搅拌5.0h;乙醇、蒸馏水、γ―氨丙基三乙氧基硅烷、GO-Fe3O4纳米粒子的质量比为18:2:0.5:1。
5.根据权利要求1所述的一种环氧树脂/GO超疏水防腐涂层的制备方法,其特征在于,所述S3中在氮气保护下,保持70℃中速搅拌12h;甲基丙烯酸十三氟辛酯、二乙烯三胺的质量比为2:1。
6.根据权利要求1所述的一种环氧树脂/GO超疏水防腐涂层的制备方法,其特征在于,所述S4中环氧树脂、氟化二乙烯三胺固化剂、氨基化GO-Fe3O4纳米粒子、乙醇的质量比为20:5:1:5。
7.根据权利要求1或6所述的一种环氧树脂/GO超疏水防腐涂层的制备方法,其特征在于,所述S4中240mT磁铁距离涂层表面的距离为2-5cm。
8.根据权利要求1所述的一种环氧树脂/GO超疏水防腐涂层的制备方法,其特征在于,所述S5中乙醇、蒸馏水、十七氟癸基三甲氧基硅烷的质量比为18:2:1。
9.根据权利要求1所述的一种环氧树脂/GO超疏水防腐涂层的制备方法,其特征在于,所述S1、S3、S5中低速搅拌时长均为30min。
10.一种如权1-9任一所述制备方法制备的环氧树脂/GO超疏水防腐涂层。
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114292426A (zh) * | 2021-12-01 | 2022-04-08 | 湖南科技大学 | 超疏水多孔铝合金-环氧树脂防腐复合材料的制备方法 |
CN114773959A (zh) * | 2022-05-31 | 2022-07-22 | 复旦大学 | 一种高性能透明防腐涂层材料及其制备方法 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103820004A (zh) * | 2014-02-17 | 2014-05-28 | 湖南至诚涂料有限公司 | 一种防腐粉末涂料的制备方法及产品 |
US20160032111A1 (en) * | 2014-07-31 | 2016-02-04 | Chung Yuan Christian University | Anticorrosive Layer Having a Biomimetic Leaf Surface Nano-microstructure And Application Thereof |
CN106977986A (zh) * | 2017-04-28 | 2017-07-25 | 山东欧铂新材料有限公司 | 一种树脂吸波涂料及其制备方法 |
US20170260401A1 (en) * | 2014-12-19 | 2017-09-14 | Tesla Nanocoatings, Inc. | Tunable materials |
CN107189669A (zh) * | 2017-07-01 | 2017-09-22 | 湖南科技大学 | 一种低表面能水性聚氨酯/纳米SiO2海洋防污涂层材料及制备方法 |
CN107916561A (zh) * | 2017-11-15 | 2018-04-17 | 华南理工大学 | 一种磁性超疏水织物及其制备方法 |
CN109294407A (zh) * | 2018-09-14 | 2019-02-01 | 广东华科新材料研究院有限公司 | 一种水性防腐涂料及其制备方法 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0735587B2 (ja) * | 1988-06-30 | 1995-04-19 | 日本鋼管株式会社 | 高耐食性表面処理鋼板の製造方法 |
-
2020
- 2020-11-20 CN CN202011309520.2A patent/CN112409884B/zh active Active
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103820004A (zh) * | 2014-02-17 | 2014-05-28 | 湖南至诚涂料有限公司 | 一种防腐粉末涂料的制备方法及产品 |
US20160032111A1 (en) * | 2014-07-31 | 2016-02-04 | Chung Yuan Christian University | Anticorrosive Layer Having a Biomimetic Leaf Surface Nano-microstructure And Application Thereof |
US20170260401A1 (en) * | 2014-12-19 | 2017-09-14 | Tesla Nanocoatings, Inc. | Tunable materials |
CN106977986A (zh) * | 2017-04-28 | 2017-07-25 | 山东欧铂新材料有限公司 | 一种树脂吸波涂料及其制备方法 |
CN107189669A (zh) * | 2017-07-01 | 2017-09-22 | 湖南科技大学 | 一种低表面能水性聚氨酯/纳米SiO2海洋防污涂层材料及制备方法 |
CN107916561A (zh) * | 2017-11-15 | 2018-04-17 | 华南理工大学 | 一种磁性超疏水织物及其制备方法 |
CN109294407A (zh) * | 2018-09-14 | 2019-02-01 | 广东华科新材料研究院有限公司 | 一种水性防腐涂料及其制备方法 |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114292426A (zh) * | 2021-12-01 | 2022-04-08 | 湖南科技大学 | 超疏水多孔铝合金-环氧树脂防腐复合材料的制备方法 |
CN114292426B (zh) * | 2021-12-01 | 2023-02-28 | 湖南科技大学 | 超疏水多孔铝合金-环氧树脂防腐复合材料的制备方法 |
CN114773959A (zh) * | 2022-05-31 | 2022-07-22 | 复旦大学 | 一种高性能透明防腐涂层材料及其制备方法 |
CN114773959B (zh) * | 2022-05-31 | 2023-03-03 | 复旦大学 | 一种高性能透明防腐涂层材料及其制备方法 |
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