CN116179043A - 超疏水减阻涂层、其制备方法和应用 - Google Patents
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Abstract
本发明公开了一种超疏水减阻涂层、其制备方法和应用,其制备方法包括如下步骤:S1、将微米二氧化硅和纳米ZIF‑8加入SEBS溶液,混合均匀;S2、将步骤S1制得的混合液喷涂于基底上,即得所述超疏水减阻涂层;其中,所述微米二氧化硅、所述纳米ZIF‑8和所述SEBS的用量的质量比为(1.2~2.4):(0.3~0.6):(2.4~3)。本发明制备的涂层接触角可达168.34°,最大减阻率为38%,具有优异的超疏水性能和减阻性能。且本发明制备的涂层具有优良的稳定性,使得在长期服役过程中涂层不易破裂脱落。
Description
技术领域
本发明涉及疏水材料,具体地,涉及一种超疏水减阻涂层、其制备方法和应用。
背景技术
海上行驶的船舶及水下运动设备等正常工作时容易受到来自流体的摩擦阻力,摩擦阻力不仅影响船舶运动速率,而且航行过程中航海设备需要耗费大量的燃油来克服外加粘性阻力。有效降低船体运动带来的阻力不仅有利于船舶速度的提高,而且能够提高船舶能源利用率。超疏水减阻材料操作环境温和,并且得益于自身材料的优良特性,材料表面能够捕获一层空气膜,该空气膜减小了固液接触面积,从而实现减阻的目的,是实现船舶减阻的理想方式。
在金属基体上构建超疏水表面可有效缓解其在使用过程中不耐腐蚀、容易覆冰等问题,同时可赋予其自清洁、油水分离、润滑减阻等特殊功能,其主要方法主要有微弧氧化、气相沉积、阳极氧化、电镀、喷涂等方法,但目前方法还存在很多不足。如微弧氧化的生长是一个包括了成膜、击穿、融化、烧结、再成膜的循环过程,其表层较为粗糙,减阻性能较差;再如气相沉积技术制备的涂层易存在着空隙和夹杂等缺陷,耐腐蚀性不佳;而阳极氧化、电镀等方式也都存在工艺复杂、环境风险大等缺陷。相较而言,喷涂较为适合船舶和大型设备,目前制备高疏水表面喷涂有两步喷涂法和多步喷涂法,主要通过树脂和颜料交替喷涂实现超疏水减阻的性能,但这些方法制备过程复杂、制备周期长,在实际应用中还存在一定困难。
另外,目前超疏水涂层的接触角通常为150~163°(Wang M,et al.Constructionof super-hydrophobic PDMS@MOF@Cu mesh for reduced drag,anti-fouling and self-cleaning towards marine vehicle applications2021,417:129265;Cheng L C,etal.Imparting Superhydrophobicity with a Hierarchical Block CopolymerCoating2020,16(1):1905509.),无法满足越来越严格的使用需求。
因此,十分有必要研发出一种超疏水表面减阻性能好、制备工艺简单、适用性广的超疏水减阻涂层。
发明内容
为提升涂层的超疏水减阻性能,本发明提供了一种超疏水减阻涂层、其制备方法和应用。该方法通过向SEBS混合液中添加不同粒径的微米SiO2和纳米ZIF-8作为填料,以固化接枝在基底上,制备的超疏水减阻涂层接触角可达168.34°,最大减阻率可达38%,极大提升了超疏水涂层的减阻性能。
为了实现上述目的,本发明第一方面提供一种超疏水减阻涂层的制备方法,所述制备方法包括如下步骤:
S1、将微米二氧化硅和纳米ZIF-8加入SEBS溶液,混合均匀;
S2、将步骤S1制得的混合液喷涂于基底上,即得所述超疏水减阻涂层;
其中,所述微米二氧化硅、所述纳米ZIF-8和所述SEBS的用量的质量比为(1.2~2.4):(0.3~0.6):(2.4~3)。
本发明中微米和纳米粒子的结合具有协同作用,超疏水表面的粗糙表面由微米结构的乳突构成,在微米乳突上存在纳米结构使得粗糙结构的构建更具稳定性。与仅用纳米材料相比这种微米结构与纳米结构相结合的层状结构使得超疏水表面具有更高的稳定性且疏水性能较好。
优选地,步骤S1中,所述微米二氧化硅粒径为8~10μm,所述纳米ZIF-8的粒径为250~260nm。
具体地,步骤S1中,按质量份计,所述ZIF-8的制备方法包括如下步骤:
A1、将3~5份硝酸锌溶于80~90份甲醇中;
A2、将9~15份二甲基咪唑溶于80~90份甲醇中;
A3、将步骤A1和步骤A2得到的溶液混合,在30~50℃下搅拌1~3h;
A4、将步骤A3得到的混合液经3~4次洗涤,干燥后研磨,制得ZIF-8粉末。
具体地,步骤S1中,按质量份计,所述SEBS溶液的制备方法包括如下步骤:将2.5~3份SEBS溶于96~97份溶剂中,搅拌0.5~1.5h。
进一步地,所述溶剂为乙酸乙酯或正己烷中的一种或两种。
具体地,步骤S2中,所述基底为铜网。
进一步地,所述铜网在喷涂之前经过清洗、烘干处理。
具体地,步骤S2中,所述喷涂是在距离基底15~20cm处进行水平喷涂,喷涂2~3次,之后将喷涂过的基底置于40~60℃的烘箱中干燥2~3h。
本发明第二方面提供一种由上述制备方法制得的超疏水减阻涂层。
本发明第三方面提供一种上述超疏水减阻涂层在船舶减阻中的应用。
通过上述技术方案,本发明实现了以下有益效果:
1、由于纳米结构和微米结构表面可以降低液滴与材料表面的接触面积,微纳多级结构具有更大的接触角及更小的接触滞后性,因此采用微米SiO2和纳米ZIF-8作为填料可以有效促进超疏水性能的提高。本发明制备的涂层接触角可达168.34°,最大减阻率为38%,具有优异的超疏水性能和减阻性能。
2、因微纳多级结构兼具纳米材料的小尺寸效应以及微米材料的结构稳定性等优点,本发明制备的涂层与基底有着较强的结合力,使得在长期服役过程中涂层不易破裂脱落,具有优良的稳定性。
3、本发明使用喷涂法,克服传统的浸渍法稳定性较低、易发生沉淀、均匀性较差等缺陷,可以通过气压保证良好的稳定性与均匀性,可进行大批量生产。
附图说明
图1为本发明中实施例1、实施例2和实施例3制备的涂层的接触角图;
图2为本发明中实施例1制备的样品和其具有相同规格的未喷涂混合液的铜网在承载力为10g下的时间-速度图;
图3为本发明中实施例1制备的样品和其具有相同规格的未喷涂混合液的铜网在承载力为20g下的时间-速度图;
图4为本发明中实施例1制备的样品和其具有相同规格的未喷涂混合液的铜网在承载力为50g下的时间-速度图。
具体实施方式
以下结合实施例对本发明的具体实施方式进行详细说明。应当理解的是,此处所描述的具体实施方式仅用于说明和解释本发明,并不用于限制本发明。
实施例1
超疏水减阻涂层的制备方法包括如下步骤:
(1)铜网预处理:将铜网使用乙醇进行超声清洗,然后在去离子水中冲洗干净,烘干;
(2)ZIF-8的制备:
A1、将3g硝酸锌溶于80g甲醇中;
A2、将9g二甲基咪唑溶于90g甲醇中;
A3、将步骤A1和步骤A2得到的溶液混合,在30℃下搅拌1h;
A4、将步骤A3得到的混合液经3次离心醇洗,干燥、研磨后过纳米筛,制得纳米级ZIF-8粉末;
(3)SEBS溶液的制备:将2.5g SEBS溶于97g乙酸乙酯中,搅拌0.5h;
(4)将1.2g微米二氧化硅和0.3g步骤(2)制备的纳米ZIF-8加入96g步骤(3)制备的SEBS溶液中,混合均匀;
(5)将步骤(4)制得的混合液倒入喷枪,在距离铜网15cm处进行水平喷涂,喷涂2次,之后将喷涂过的铜网置于60℃的烘箱中干燥2h,即得超疏水减阻涂层。
实施例2
超疏水减阻涂层的制备方法包括如下步骤:
(1)铜网预处理:将铜网使用乙醇进行超声清洗,然后在去离子水中冲洗干净,烘干;
(2)ZIF-8的制备:
A1、将5g硝酸锌溶于90g甲醇中;
A2、将15g二甲基咪唑溶于80g甲醇中;
A3、将步骤A1和步骤A2得到的溶液混合,在50℃下搅拌3h;
A4、将步骤A3得到的混合液经4次离心醇洗,干燥、研磨后过纳米筛,制得纳米级ZIF-8粉末;
(3)SEBS溶液的制备:将3g SEBS溶于50g乙酸乙酯和46g正己烷中,搅拌1.5h;
(4)将2.4g微米二氧化硅和0.5g步骤(2)制备的纳米ZIF-8加入98g步骤(3)制备的SEBS溶液中,混合均匀;
(5)将步骤(4)制得的混合液倒入喷枪,在距离铜网20cm处进行水平喷涂,喷涂3次,之后将喷涂过的铜网置于40℃的烘箱中干燥3h,即得超疏水减阻涂层。
实施例3
超疏水减阻涂层的制备方法包括如下步骤:
(1)铜网预处理:将铜网使用乙醇进行超声清洗,然后在去离子水中冲洗干净,烘干;
(2)ZIF-8的制备:
A1、将4g硝酸锌溶于85g甲醇中;
A2、将10g二甲基咪唑溶于85g甲醇中;
A3、将步骤A1和步骤A2得到的溶液混合,在40℃下搅拌2h;
A4、将步骤A3得到的混合液经3次离心醇洗,干燥、研磨后过纳米筛,制得纳米级ZIF-8粉末;
(3)SEBS溶液的制备:将2.8g SEBS溶于96.5g正己烷中,搅拌1h;
(4)将2g微米二氧化硅和0.6g步骤(2)制备的纳米ZIF-8加入97g步骤(3)制备的SEBS溶液中,混合均匀;
(5)将步骤(4)制得的混合液倒入喷枪,在距离铜网18cm处进行水平喷涂,喷涂2次,之后将喷涂过的铜网置于50℃的烘箱中干燥2.5h,即得超疏水减阻涂层。
性能测试
从图1可以看出,实施例1、实施例2和实施例3制备涂层的接触角分别为167.96°、168.34°和168.04°,平均接触角达到了168.11°,远高于超疏水材料水接触角大于150°的要求,疏水性能优异,其原因是微纳多级结构可以更好地降低液滴与材料表面的接触面积,采用微米SiO2和纳米ZIF-8作为填料有效提升涂层超疏水性能。
分别将实施例1制备的样品和相同规格的未喷涂混合液的铜网折成10cm×10cm的盒状,之后置于长形水槽内,分别承载10g、20g、50g的重物,使用5g砝码给其拉力,计算铜网末端运行速度,其结果分别如图2、图3和图4所示。从图2、图3和图4可以看出,其最大减阻率为38%,实现了较好的减阻效果。
以上各实施例仅用以说明本发明的技术方案,而非对其限制;尽管参照前述各实施例对本发明进行了详细的说明,本领域的普通技术人员应当理解:其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分或者全部技术特征进行等同替换;而这些修改或者替换,并不使相应技术方案的本质脱离本发明各实施例技术方案的范围,其均应涵盖在本发明的权利要求和说明书的范围当中。
Claims (10)
1.一种超疏水减阻涂层的制备方法,其特征在于,所述制备方法包括如下步骤:
S1、将微米二氧化硅和纳米ZIF-8加入SEBS溶液,混合均匀;
S2、将步骤S1制得的混合液喷涂于基底上,即得所述超疏水减阻涂层;
其中,所述微米二氧化硅、所述纳米ZIF-8和所述SEBS的用量的质量比为(1.2~2.4):(0.3~0.6):(2.4~3)。
2.根据权利要求1所述的制备方法,其特征在于,步骤S1中,所述微米二氧化硅粒径为8~10μm,所述纳米ZIF-8的粒径为250~260nm。
3.根据权利要求1所述的制备方法,其特征在于,步骤S1中,按质量份计,所述ZIF-8的制备方法包括如下步骤:
A1、将3~5份硝酸锌溶于80~90份甲醇中;
A2、将9~15份二甲基咪唑溶于80~90份甲醇中;
A3、将步骤A1和步骤A2得到的溶液混合,在30~50℃下搅拌1~3h;
A4、将步骤A3得到的混合液经3~4次洗涤,干燥后研磨,制得ZIF-8粉末。
4.根据权利要求1所述的制备方法,其特征在于,步骤S1中,按质量份计,所述SEBS溶液的制备方法包括如下步骤:将2.5~3份SEBS溶于96~97份溶剂中,搅拌0.5~1.5h。
5.根据权利要求4所述的制备方法,其特征在于,所述溶剂为乙酸乙酯或正己烷中的一种或两种。
6.根据权利要求1所述的制备方法,其特征在于,步骤S2中,所述基底为铜网。
7.根据权利要求6所述的制备方法,其特征在于,所述铜网在喷涂之前经过清洗、烘干处理。
8.根据权利要求1所述的制备方法,其特征在于,步骤S2中,所述喷涂是在距离基底15~20cm处进行水平喷涂,喷涂2~3次,之后将喷涂过的基底置于40~60℃的烘箱中干燥2~3h。
9.一种超疏水减阻涂层,由权利要求1至8任一项所述的制备方法制得。
10.权利要求9所述的超疏水减阻涂层在船舶减阻中的应用。
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