CN112323116A - 一种基于沸石咪唑酯骨架的镁合金超疏水涂层的制备方法 - Google Patents
一种基于沸石咪唑酯骨架的镁合金超疏水涂层的制备方法 Download PDFInfo
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Abstract
本发明公开了一种基于沸石咪唑酯骨架的镁合金超疏水涂层的制备方法,属于金属表面改性领域。本发明首先对镁合金进行微弧氧化处理,使其形成一定的粗糙结构,然后通过原位生长法在镁合金表面上生长沸石咪唑酯骨架结构(ZIF‑L),最后采用正辛基三乙氧基硅烷进行表面低能处理,使镁合金表面获得超疏水功能。将蒸馏水滴到该表面上,接触角大于150°,滚动角小于10°,达到了超疏水效果。该方法的反应过程不受基体形状的限制,获得的涂层结合力强,所用试剂对环境友好,易于推广应用。
Description
技术领域
本发明属于金属材料表面改性技术领域,具体涉及对镁合金表面进行微弧氧化处理、沸石咪唑酯骨架结构的生长及表面低能处理,从而使镁合金表面获得超疏水功能的制备方法。
背景技术
自然界存在一些特殊的生物表面现象,如荷叶出淤泥而不染、水黾在水面上自由行走等,这些现象给予研究者们很大的启发,为研究者们进行材料仿生提供了思路。超疏水表面具有广阔的应用前景,在自清洁、防覆冰、耐腐蚀、油水分离、防垢减阻等方面的研究也越来越多。近年来,国内外的研究人员公开发表了众多有关超疏水涂层的制备技术,通过不同的方法在不同基体表面构造了粗糙结构,比如水热法、溶胶凝胶法、阳极氧化和层层自组装等,但是在表面原位生长沸石咪唑酯骨架结构(ZIF-L)以得到超疏水涂层的研究相对较少。
沸石咪唑酯骨架(Zeolitic imidazolate frameworks,ZIFs)材料是金属有机骨架(Metal-organic frameworks,MOFs)材料的一个亚种,具有沸石状多孔结构,由过渡金属和咪唑盐连接组成,具有良好的化学稳定性,在催化、分离、载药等方面有广泛的应用。通过在各种基体表面制备ZIFs粒子从而构建粗糙结构已经成为近年来的研究热点。在国内外已经公开发表的制备技术中,主要通过喷涂、原位生长、自组装以及水热等方法来制备不同形态和不同功能的ZIF涂层。Yuan等(Yuan S,Zhu J,Li Y,et al.Structure architectureof micro/nanoscale ZIF-L on a 3D printed membrane for a superhydrophobic andunderwater superoleophobic surface.Journal of Materials Chemistry A,2019,7:2723-2729.)先在N2氛围中用CO2激光器将聚酰胺粉末烧结成3D打印膜(PA膜),然后将PA膜浸入2-甲基咪唑水溶液中,在搅拌情况下再加入六水合硝酸锌溶液,反应一段时间后将PA膜取出,用清水清洗后干燥,得到ZIF-PA膜,随后将干燥后的ZIF-PA膜浸入另一2-甲基咪唑与Zn2+比值更高的溶液中反应一段时间,反应结束后取出,用清水清洗后干燥,得到多尺度结构的MZIF-PA膜,最后将得到的MZIF-PA膜浸入硅橡胶(PDMS)的正己烷溶液中10min,固化后得到了超疏水PDMS-MZIF-PA膜,该超疏水膜具有优异油水分离性能。中国专利(公开号为CN107858046B,公开日期为2020年4月3日)公开了一种具有自清洁和抗菌功能的超疏水涂层及其制备方法,该方法利用聚偏氟乙烯的有机溶液和小分子量醇制备PVDF固态悬浮液,再加入ZIF纳米颗粒和低表面能的氟化物得到混合溶液,最后将该溶液涂覆在基底上,获得了具有自清洁和抗菌功能的超疏水涂层。中国专利(公开号为CN109293933A,公开日期为2019年2月1日)公开了基于沸石咪唑酯骨架的超疏水自清洁聚合物及其制备方法,该方法先利用水相合成法快速合成ZIF-8,再将全氟辛基三甲氧基硅烷(POTS)与ZIF-8粒子超声混合后干燥,最后把干燥后的ZIF-8-POTS加入配制好的PDMS,配制成ZIF-8-POTS-PDMS溶液用以制备超疏水涂层。通过上文可以看出,目前有关ZIF超疏水涂层的制备方法存在步骤繁琐、试剂繁多的缺点,部分方法需要用到含氟试剂,对环境有害,不利于ZIF超疏水涂层的推广应用。
本专利通过镁合金表面的微弧氧化处理、沸石咪唑酯骨架结构的生长以及表面低能处理等工艺流程在镁合金表面上成功构建出微纳米结构,使镁合金表面获得超疏水功能,其涂层制备不受基体形状的限制,对环境友好,适合推广使用。
发明内容
本发明的目的是开发一种基于沸石咪唑酯骨架的镁合金超疏水涂层的制备方法。
为实现上述目的,本发明的具体工艺流程如下:
(1)用240#、400#、600#、1000#、1500#的金相水磨砂纸逐次打磨AZ31B镁合金试样以去除表面氧化物,然后分别用丙酮和无水乙醇超声清洗试样10min,接着用去离子水冲洗30s,冷风吹干;
(2)将步骤(1)处理好的镁合金试样放入由10-15g/L的硅酸钠和2-4g/L的氢氧化钠组成的电解液中,在13-17A/dm2的电流密度、100Hz的脉冲频率和40%(+)和40%(-)的占空比下微弧氧化处理0-40min,取出用去离子水清洗3min,冷风吹干,得到具有微米结构的微弧氧化陶瓷表面;
(3)将25mL浓度为0.05-0.1mol/L的六水合硝酸锌溶液缓慢倾倒进25mL浓度为0.1-0.8mol/L的2-甲基咪唑溶液中,以500r/min的转速磁力搅拌30min,使六水合硝酸锌和2-甲基咪唑充分反应,形成均匀的沸石咪唑酯骨架结构(ZIF-L)晶种悬浮液,然后将步骤(2)得到的具有微米结构的微弧氧化陶瓷表面的镁合金试样放入其中,室温静置反应10-30min,以便在微弧氧化陶瓷表面上生长出一层均匀的ZIF-L核心,然后将长有ZIF-L核心的镁合金试样取出,放入重新制备的同浓度的六水合硝酸锌和2-甲基咪唑的混合溶液中,室温下再次生长0.5-3h,取出镁合金试样后用去离子水冲洗1min,最后用烘箱在40-80℃下烘干0.5-2h,在镁合金试样表面得到具有微纳米结构的ZIF-L涂层;
(4)将步骤(3)得到的具有ZIF-L涂层的镁合金试样浸入浓度为97%的正辛基三乙氧基硅烷溶液中,在室温下静置1min,取出后用烘箱在40-80℃下烘干12-24h,得到超疏水ZIF-L涂层,蒸馏水在该涂层表面上接触角大于150°,滚动角小于10°。
与现有技术相比,本发明的有益效果是:
(1)本发明获得的超疏水ZIF-L涂层不受基体形状的限制,应用范围广。
(2)本发明获得的超疏水ZIF-L涂层在制备过程中不使用含氟试剂,对环境友好,易于推广使用。
(3)本发明获得的超疏水ZIF-L涂层为复合涂层,其微弧氧化陶瓷膜层与基体以冶金方式进行结合,与基体无明显界限,结合力强,不易脱落,能对基体形成有效保护。
附图说明
图1是本发明实施例一中AZ31B镁合金表面微弧氧化后的微观形貌SEM照片;
图2是本发明实施例一中AZ31B镁合金表面超疏水ZIF-L涂层的微观形貌SEM照片;
图3是本发明实施例一中AZ31B镁合金表面超疏水ZIF-L涂层的静态接触角照片,接触角为159.12°。
具体实施例
下面结合具体实施例和附图对本发明做进一步说明。
本发明的目的是开发一种基于沸石咪唑酯骨架的镁合金超疏水涂层的制备方法。为达到上述目的,本发明以AZ31B镁合金为研究对象,在镁合金表面制备了超疏水ZIF-L涂层。
实施例一:
(1)用240#、400#、600#、1000#、1500#的金相水磨砂纸逐次打磨AZ31B镁合金试样以去除表面氧化物,然后分别用丙酮和无水乙醇超声清洗试样10min,接着用去离子水冲洗30s,冷风吹干;
(2)将步骤(1)处理好的镁合金试样放入由10g/L的硅酸钠和2g/L的氢氧化钠组成的电解液中,在17A/dm2的电流密度、100Hz的脉冲频率和40%(+)和40%(-)的占空比下微弧氧化处理40min,取出用去离子水清洗3min,冷风吹干,得到具有微米结构的微弧氧化陶瓷表面,如图1所示;
(3)将25mL浓度为0.1mol/L的六水合硝酸锌溶液缓慢倾倒进25mL浓度为0.4mol/L的2-甲基咪唑溶液中,以500r/min的转速磁力搅拌30min,使六水合硝酸锌和2-甲基咪唑充分反应,形成均匀的沸石咪唑酯骨架结构(ZIF-L)晶种悬浮液,然后将步骤(2)得到的具有微米结构的微弧氧化陶瓷表面的镁合金试样放入该溶液中,室温静置反应15min,以便在微弧氧化陶瓷表面上生长出一层均匀的ZIF-L核心,然后将长有ZIF-L核心的镁合金试样取出,立即放入重新制备的同浓度的六水合硝酸锌和2-甲基咪唑的混合溶液中,室温下再次生长2h,取出镁合金试样后用去离子水冲洗1min,最后用烘箱在80℃下烘干2h,在镁合金试样表面得到具有微纳米结构的ZIF-L涂层,如图2所示;
(4)将步骤(3)得到的具有ZIF-L涂层的镁合金试样浸入浓度为97%的正辛基三乙氧基硅烷溶液中,在室温下静置1min,取出后用烘箱在80℃下烘干24h,得到超疏水ZIF-L涂层,取3μL去离子水对涂层表面进行测试,发现水滴与该表面的接触角为159.12°(如图3所示),滚动角为3.28°。
实施例二:
(1)用240#、400#、600#、1000#、1500#的金相水磨砂纸逐次打磨AZ31B镁合金试样以去除表面氧化物,然后分别用丙酮和无水乙醇超声清洗试样10min,接着用去离子水冲洗30s,冷风吹干;
(2)将步骤(1)处理好的镁合金试样置于浓度为0.2mol/L的乙酸溶液中在室温下刻蚀10min,用去离子水冲洗1min,冷风吹干,得到具有微米结构的表面;
(3)将25mL浓度为0.1mol/L的六水合硝酸锌溶液缓慢倾倒进25mL浓度为0.4mol/L的2-甲基咪唑溶液中,以500r/min的转速磁力搅拌30min,获得六水合硝酸锌和2-甲基咪唑的混合溶液,然后将步骤(2)得到的具有微米结构表面的镁合金放入此溶液中,室温静置反应15min,反应结束后立即放入重新制备的相同成分、相同浓度的混合溶液中再次生长2h,取出镁合金试样后用去离子水冲洗1min,最后用烘箱在80℃下烘干2h,在镁合金试样表面得到具有微纳米结构的ZIF-L涂层;
(4)将步骤(3)得到的具有ZIF-L涂层的镁合金试样浸入浓度为97%的正辛基三乙氧基硅烷溶液中,在室温下静置1min,取出后用烘箱在80℃下烘干24h,得到超疏水ZIF-L涂层,取3μL去离子水对涂层表面进行测试,发现水滴与该表面的接触角为158.21°,滚动角为3.04°。
实施例三:
(1)用240#、400#、600#、1000#、1500#的金相水磨砂纸逐次打磨AZ31B镁合金试样以去除表面氧化物,然后分别用丙酮和无水乙醇超声清洗试样10min,接着用去离子水冲洗30s,冷风吹干;
(2)将步骤(1)处理好的镁合金试样置于浓度为0.4mol/L的乙酸溶液中在室温下刻蚀5min,用去离子水冲洗1min,冷风吹干,得到具有微米结构的表面;
(3)将25mL浓度为0.05mol/L的六水合硝酸锌溶液缓慢倾倒进25mL浓度为0.1mol/L的2-甲基咪唑溶液中,以500r/min的转速磁力搅拌30min,获得六水合硝酸锌和2-甲基咪唑的混合溶液,然后将步骤(2)得到的具有微米结构表面的镁合金放入此溶液中,室温静置反应30min,反应结束后立即放入重新制备的相同成分、相同浓度的混合溶液中再次生长3h,取出镁合金试样后用去离子水清洗1min,最后用烘箱在80℃下烘干0.5h,在镁合金试样表面得到具有微纳米结构的ZIF-L涂层;
(4)将步骤(3)得到的具有ZIF-L涂层的镁合金试样浸入浓度为97%的正辛基三乙氧基硅烷溶液中,在室温下静置1min,取出后用烘箱在80℃下烘干12h,得到超疏水ZIF-L涂层,取3μL去离子水对涂层表面进行测试,发现水滴与该表面的接触角为154.92°,滚动角为4.72°。
实施例四:
(1)用240#、400#、600#、1000#、1500#的金相水磨砂纸逐次打磨AZ31B镁合金试样以去除表面氧化物,然后分别用丙酮和无水乙醇超声清洗试样10min,接着用去离子水冲洗30s,冷风吹干;
(2)将步骤(1)处理好的镁合金试样置于浓度为0.2mol/L的乙酸溶液中在室温下刻蚀10min,用去离子水冲洗1min,冷风吹干,得到具有微米结构的表面;
(3)将25mL浓度为0.1mol/L的六水合硝酸锌溶液缓慢倾倒进25mL浓度为0.8mol/L的2-甲基咪唑溶液中,以500r/min的转速磁力搅拌30min,获得六水合硝酸锌和2-甲基咪唑的混合溶液,然后将步骤(2)得到的具有微米结构表面的镁合金放入此溶液中,室温静置反应30min,反应结束后立即放入重新制备的相同成分、相同浓度的混合溶液中再次生长3h,取出镁合金试样后用去离子水冲洗1min,最后用烘箱在40℃下烘干2h,在镁合金试样表面得到具有微纳米结构的ZIF-L涂层,;
(4)将步骤(3)得到的具有ZIF-L涂层的镁合金试样浸入浓度为97%的正辛基三乙氧基硅烷溶液中,在室温下静置1min,取出后用烘箱在40℃下烘干24h,得到超疏水ZIF-L涂层,取3μL去离子水对涂层表面进行测试,发现水滴与该表面的接触角为151.78°,滚动角为5.61°。
Claims (1)
1.一种基于沸石咪唑酯骨架的镁合金超疏水涂层的制备方法,其特征在于该方法依次包括以下步骤:
(1)用240#、400#、600#、1000#、1500#的金相水磨砂纸逐次打磨AZ31B镁合金试样以去除表面氧化物,然后分别用丙酮和无水乙醇超声清洗试样10min,接着用去离子水冲洗30s,冷风吹干;
(2)将步骤(1)处理好的镁合金试样放入由10-15g/L的硅酸钠和2-4g/L的氢氧化钠组成的电解液中,在13-17A/dm2的电流密度、100Hz的脉冲频率和40%(+)和40%(-)的占空比下微弧氧化处理0-40min,取出用去离子水清洗3min,冷风吹干,得到具有微米结构的微弧氧化陶瓷表面;
(3)将25mL浓度为0.05-0.1mol/L的六水合硝酸锌溶液缓慢倾倒进25mL浓度为0.1-0.8mol/L的2-甲基咪唑溶液中,以500r/min的转速磁力搅拌30min,获得六水合硝酸锌和2-甲基咪唑的混合溶液,然后将步骤(2)得到的具有微米结构微弧氧化陶瓷表面的镁合金放入该溶液中,室温静置反应10-30min,以便在微米结构微弧氧化陶瓷表面上生长出一层沸石咪唑酯骨架结构(ZIF-L)核心,然后将长有ZIF-L核心的镁合金试样取出,放入重新制备的同浓度的六水合硝酸锌和2-甲基咪唑的混合溶液中,室温下再次生长0.5-3h,取出镁合金试样后用去离子水冲洗1min,最后用烘箱在40-80℃下烘干0.5-2h,在镁合金试样表面得到具有微纳米结构的ZIF-L涂层;
(4)将步骤(3)得到的具有ZIF-L涂层的镁合金试样浸入浓度为97%的正辛基三乙氧基硅烷溶液中,在室温下静置1min,取出后用烘箱在40-80℃下烘干12-24h,得到超疏水ZIF-L涂层,蒸馏水在该涂层表面上接触角大于150°,滚动角小于10°。
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