CN115518857A - 一种简单易操作、可大批量制备的仿生超润滑涂层及其制备方法 - Google Patents
一种简单易操作、可大批量制备的仿生超润滑涂层及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种简单易操作、可大批量制备的仿生超润滑涂层及其制备方法,属于超润滑涂层技术领域。解决了现有技术中超润滑材料制备工艺复杂、制备周期较长,制备成本较高,且不适用于大批量生产的技术问题。本发明的仿生超润滑涂层的制备方法,先将纳米颗粒、微米颗粒中的一种或两种的混合物分散到液相介质中,得到喷涂液,然后将喷涂液喷涂沉积在基底上,得到粗糙结构表面,再对粗糙结构表面进行0~100秒的热处理,最后将润滑油喷涂到热处理后的粗糙结构表面,静置5分钟以上,移除多余润滑油,得到仿生超润滑涂层。该仿生超润滑涂层的制备方法,工艺简单、可大规模工业化,制备的超润滑涂层性能稳定、功能多样。
Description
技术领域
本发明属于超润滑涂层技术领域,具体涉及一种简单易操作、可大批量制备的仿生超润滑涂层及其制备方法。
背景技术
仿猪笼草超润滑材料(SLIPS)是一种通过将低表面能液体注入微纳孔而形成的固液复合结构材料(Nature,2011,477,443–447)。因其表面具有优异的疏液、自修复、自清洁等特性,同时克服了仿荷叶超疏水材料稳定性差、对低表面能液体的防润湿性能差的问题,逐渐成为表界面领域的研究热点,在金属防腐、防冰防雾、抗菌防污等领域具有广泛的应用前景。
现有技术中报道的超润滑材料,大多需要先通过复杂的方法来构筑粗糙表面(如自组装法、溶胶-凝胶法、刻蚀法、电化学沉积法、水热处理法等),且具有制备周期较长,制备成本较高等缺点(例如:专利US9353646B2及其衍生学术文章Nature,2011,477,443–447,专利CN108978200A、CN103966641B、CN111593393A等)。此外,现有技术中报道的超润滑材料不适用于大批量制备,如专利CN105670348A公开了一种全面疏液的仿生防污自清洁涂层及其制备方法,其采用浸润法将润滑油添加到基底上,而该方法仅限于实验室研究涂层性质使用。再如专利CN107500561B公开了一种高透明、超润滑、自补充性能的玻璃涂层及其制备方法,该方法需要使用烘箱加热来固化二甲基硅油,有限的制备空间极大地限制了润滑材料的生产规模。
发明内容
有鉴于此,本发明为解决现有技术中超润滑材料制备工艺复杂、制备周期较长,制备成本较高,且不适用于大批量生产的技术问题,提供一种简单易操作、可大批量制备的仿生超润滑涂层及其制备方法,实现工艺简单、性能稳定、功能多样、可大规模工业化的超润滑涂层的制备。
本发明解决上述技术问题采取的技术方案如下。
一种简单易操作、可大批量制备的仿生超润滑涂层的制备方法,步骤如下:
步骤一、将纳米颗粒、微米颗粒中的一种或两种的混合物分散到液相介质中,得到喷涂液,喷涂液的形态为悬浮液或干粉;
步骤二、室温下,将喷涂液喷涂沉积在基底上,得到粗糙结构表面;
步骤三、对粗糙结构表面进行0~100秒的热处理,得到热处理后的粗糙结构表面;
步骤四、将润滑油喷涂到热处理后的粗糙结构表面,静置5分钟以上,移除多余润滑油,得到简单易操作、可大批量制备的仿生超润滑涂层;
所述步骤四中,润滑油的粘度为20~500cst,喷涂工艺为:喷涂气体为压缩空气,喷涂压力1.1~10bar;喷涂液流量:150~1000mL/min;喷涂距离为200~400mm。
优选的是,所述步骤一中,纳米颗粒为可溶性淀粉颗粒、聚苯乙烯颗粒、二氧化硅颗粒中的一种或多种的混合,纳米颗粒的粒径范围大于等于0.1微米,小于1微米。
优选的是,所述步骤一中,微米颗粒为可溶性淀粉颗粒、聚苯乙烯颗粒、二氧化硅颗粒中的一种或多种的混合,微米颗粒的粒径范围在1~50微米。
优选的是,所述步骤一中,液相介质为水。
优选的是,所述步骤一中,喷涂液的形态为悬浮液,悬浮液中固含量为0.05~25%(w/v)。
优选的是,所述步骤二中,喷涂工艺为:采用压缩空气喷涂,喷涂压力1.1~10bar;喷涂液流量:150~1000mL/min;喷涂距离:200~400mm。
优选的是,所述步骤二中,基底的材料为木材、橡胶、金属、陶瓷、塑料或玻璃。
优选的是,所述步骤二中,基底经过预处理后,将喷涂液喷涂沉积在预处理后的基底上,基底的材料为金属、陶瓷或塑料,预处理过程为,在室温下,依次用丙酮、乙醇、去离子水超声清洗基底表面,基底的材料为玻璃,预处理过程为,用硫酸:过氧化氢(v:v)=7:3浸泡基底表面4h后,再用去离子水超声清洗3遍,氮气吹干待用。
优选的是,所述步骤三中,所述热处理为使用喷火枪或热气枪对粗糙结构表面进行加热。
优选的是,所述步骤四中,润滑油为合成润滑油、天然润滑油中的一种或多种的混合;更优选的,所述合成润滑油为聚α-烯烃(PAO)、烷基苯、聚丁烯、环脂肪族聚合物、磷酸酯、双酯酸、多元酯、多元醇、二甲基硅油、石油提炼物中的一种或多种的混合;所述天然润滑油为棉籽油、橄榄油、菜籽油、椰子油、玉米油、米糠油、棉籽油、葡萄籽油中的一种或多种的混合。
优选的是,所述步骤四中,喷涂时,喷枪以0.1~0.2m/s速度均匀移动,喷嘴垂直于被喷涂面。
本发明还提供上述简单易操作、可大批量制备的仿生超润滑涂层的制备方法制备的简单易操作、可大批量制备的仿生超润滑涂层。
本发明的原理:本发明的简单易操作、可大批量制备的仿生超润滑涂层利用喷涂、热处理、灌油三步法,可实现超润滑涂层的大规模制备。本发明所述技术手段将纳米粒子/微米粒子分散到基底表面,利用粒子与基底表面之间的范德华相互作用,在基底表面上形成纳米/微米级粗糙结构形貌。若进行热处理,可通过喷火枪(热风枪)快速加热基底以增强纳米/微米粒子与基底之间范德华相互作用,增加粘合力。然后喷涂润滑油,由于液体在基底的浸润效应,所以静置一段时间后液体可以均匀的分散在材料表面,形成一层具有几百纳米到几微米的油膜。利用毛细管效应,即使是低表面张力液体也能通过毛细作用力被嵌入在颗粒之间,形成一层坚固、稳定、不可流淌的润滑层。水滴在润滑层表面的接触角大于85°,滑动角<10°,因此水滴在涂层表面易于滑动,从而可实现基底表面的防水。
与现有技术相比,本发明的有益效果为:
本发明的仿生超润滑涂层的制备方法仅需三步,过程简单,不涉及复杂的表面结构制备,克服了现有的润滑材料制备过程繁琐、不能大规模制备及推广等缺点。
本发明的仿生超润滑涂层的制备方法具有很好的普适性,可涂敷于各种基底表面,可使用的润滑油种类多,以达到除冰、除霜、自清洁等功能。
本发明的仿生超润滑涂层的制备方法制备周期短、原料成本极低,可满足材料的大规模应用需求。
本发明的仿生超润滑涂层的制备方法制备的仿生超润滑涂层性能稳定,经实验检测,10μL水滴在润滑层表面的接触角大于85°,滑动角<10°,因此水滴在涂层表面易于滑动,从而可实现基底表面的防水。
附图说明
为了更清楚地说明本发明实施例中的技术方案,下面将对实施例中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其它的附图。
图1为本发明的仿生超润滑涂层的制备方法的制备流程示意图。
图2为本发明实施例1中在铝板上喷涂聚苯乙烯微米颗粒、二甲基硅油之后的超润滑涂层的水接触角图与滑动角图。
图3为本发明实施例4中水滴在喷涂微米颗粒、椰油之后的玻璃基底上的滑动实物图。
具体实施方式
为了进一步理解本发明,下面对本发明优选实施方案进行描述,但是应当理解,这些描述只是为进一步说明本发明的特征和优点,而不是对本发明权利要求的限制。
如图1所示,本发明的一种简单易操作、可大批量制备的仿生超润滑涂层的制备方法,步骤如下:
步骤一、将纳米颗粒和微米颗粒中的一种或两种的混合分散到液相介质中,得到喷涂液,喷涂液的形态为悬浮液或干粉;
步骤二、室温下,将喷涂液喷涂沉积在基底上,得到粗糙结构表面;
步骤三、对粗糙结构表面进行0~100秒的热处理,得到热处理后的粗糙结构表面;
步骤四、将润滑油喷涂到热处理后的粗糙结构表面,静置5分钟以上,移除多余润滑油,得到简单易操作、可大批量制备的仿生超润滑涂层;
上述技术方案,步骤一中,纳米颗粒优选为可溶性淀粉颗粒、聚苯乙烯颗粒、二氧化硅颗粒中的一种或多种的混合,纳米颗粒的粒径范围大于等于0.1微米,小于1微米。
上述技术方案,步骤一中,微米颗粒优选为可溶性淀粉颗粒、聚苯乙烯颗粒、二氧化硅颗粒中的一种或多种的混合,微米颗粒的粒径范围在1~50微米。
上述技术方案,步骤一中,液相介质优选为水。
上述技术方案,步骤一中,优选喷涂液的形态为悬浮液,悬浮液中固含量为0.05~25%(w/v)。
上述技术方案,步骤二中,优选喷涂工艺为:采用压缩空气喷涂,喷涂压力1.1~10bar;喷涂液流量:150~1000mL/min;喷涂距离:200~400mm。
上述技术方案,步骤二中,基底优选为木材、橡胶、金属、陶瓷、塑料或玻璃。基底可以经过预处理后,将喷涂液喷涂沉积在预处理后的基底上,基底的材料为金属、陶瓷或塑料,预处理过程为,在室温下,依次用丙酮、乙醇、去离子水超声清洗基底表面,基底的材料为玻璃,预处理过程为,用硫酸:过氧化氢(v:v)=7:3浸泡基底表面4h后,再用去离子水超声清洗3遍,氮气吹干待用。
上述技术方案,步骤三中,热处理优选使用商用喷火枪或热气枪对粗糙结构表面基底进行快速加热,表面处理的时间在0~100秒。快速加热可使高分子材料软化熔融、变形成为具有一定流动性的粘流体,以此来产生更多的颗粒-表面接触面积,从而产生较强的分子间作用力。即若含有高分子材料,热处理时间可以为1~100秒,若不含有高分子材料,热处理时间可以为0。
上述技术方案,步骤四中,润滑油为合成润滑油、天然润滑油中的一种或多种的混合;合成润滑油优选为聚α-烯烃(PAO)、烷基苯、聚丁烯、环脂肪族聚合物、磷酸酯、双酯酸、多元酯、多元醇、二甲基硅油、石油提炼物中的一种或多种的混合;天然润滑油优选为棉籽油、橄榄油、菜籽油、椰子油、玉米油、米糠油、棉籽油、葡萄籽油中的一种或多种的混合。
上述技术方案,步骤四中,喷涂工艺对于制备仿生超润滑涂层至关重要,不同的喷涂工艺将直接影响经过润滑油浸润后能否获得超润滑涂层。润滑油的粘度为20~500cst,喷涂工艺为:喷涂气体为压缩空气,喷涂压力1.1~10bar;喷涂液流量:150~1000mL/min;喷涂距离为200~400mm。
上述技术方案,步骤四中,优选喷涂时,喷枪以0.1~0.2m/s速度均匀移动,喷嘴垂直于被喷涂面。
上述技术方案,步骤四中,由于毛细管效应的存在,部分润滑油会被嵌入在纳米颗粒/微米颗粒之间,不会流淌,多余的润滑油可通过将基底表面倾斜一定角度移除。
本发明还提供上述简单易操作、可大批量制备的仿生超润滑涂层的制备方法制备的仿生超润滑涂层。
在本发明中所使用的术语,一般具有本领域普通技术人员通常理解的含义,除非另有说明。为了使本领域的技术人员更好地理解本发明的技术方案,下面将结合实施例对本发明作进一步的详细介绍。
在以下实施例中,未详细描述的各种过程和方法是本领域中公知的常规方法。下述实施例中所用的材料、试剂、装置、仪器、设备等,如无特殊说明,均可从商业途径获得。
以下结合实施例进一步说明本发明。
实施例1
步骤一、将粒径为1微米的聚苯乙烯颗粒加入水中,搅拌,得到质量浓度为2.5%(w/v)的乳状悬浮液;
步骤二、室温下,将步骤一得到的乳状悬浮液喷涂沉积在经过预处理的铝板表面上,干燥后,得到粗糙结构表面;
预处理过程为:依次用丙酮、乙醇、去离子水超声清洗铝板表面后,氮气吹干待用;
喷涂工艺参数为:采用压缩空气喷涂,喷涂压力3bar;喷涂液流量:150mL/min,喷涂距离:300mm;
步骤三、用喷火枪对粗糙结构表面进行2秒的热处理,得到热处理后的粗糙结构表面;
步骤四、将粘度为150cst的二甲基硅油喷涂到热处理后的粗糙结构表面,静置1小时,移除多余润滑油,得到简单易操作、可大批量制备的仿生超润滑涂层;
喷涂工艺参数为:采用压缩空气喷涂,喷涂压力5bar;喷涂料流量:270mL/min,喷涂距离:300mm,直至热处理后的粗糙结构表面全部被二甲基硅油油膜覆盖。
经测试,在毛细作用下,二甲基硅油可以稳定地存在于淀粉涂层中,形成一层稳定的、连续的光滑液体膜,即仿生超润滑涂层。本实施例所得仿生超润滑涂层的性能检测数据列于表1和图2所示。
实施例2
步骤一、将粒径为5微米的淀粉颗粒加入水中,搅拌得到质量浓度为0.5%(w/v)的乳状悬浮液;
步骤二、室温下,将步骤一得到的乳状悬浮液喷涂沉积在经过预处理的陶瓷板表面上,干燥后,得到粗糙结构表面;
预处理过程为:依次用丙酮、乙醇、去离子水超声清洗陶瓷板后,氮气吹干待用;
喷涂工艺参数为:采用压缩空气,喷涂压力3bar;喷涂液流量:150mL/min,喷涂距离:300mm;
步骤三、用喷火枪对粗糙结构表面进行2秒的热处理,得到热处理后的粗糙结构表面;
步骤四、将粘度为100cst的二甲基硅油喷涂到热处理后的粗糙结构表面,静置1小时,移除多余润滑油,得到简单易操作、可大批量制备的仿生超润滑涂层;
喷涂工艺参数为:采用压缩空气,压力3bar;喷涂液流量:270mL/min,喷涂距离:400mm,直至热处理后的粗糙结构表面全部被二甲基硅油油膜覆盖。
经测试,在毛细作用下,二甲基硅油可以稳定地存在于淀粉涂层中,形成一层稳定的、连续的光滑液体膜,即仿生超润滑涂层。本实施例所得仿生超润滑涂层的性能检测数据列于表1。
实施例3
步骤一、将粒径为0.5微米的淀粉颗粒加入水中,搅拌得到质量浓度为1%(w/v)的乳状悬浮液;
步骤二、室温下,将步骤一得到的乳状悬浮液喷涂沉积在经过预处理的聚甲醛板表面上,干燥后,得到粗糙结构表面;
预处理过程为:依次用丙酮、乙醇、去离子水超声清洗聚甲醛板后,氮气吹干待用;
喷涂工艺参数为:采用压缩空气,喷涂压力3bar;喷涂液流量:150mL/min,喷涂距离:300mm;
步骤三、用喷火枪对粗糙结构表面进行2秒的热处理,得到热处理后的粗糙结构表面;
步骤四、将粘度为40cst的棉籽油喷涂到热处理后的粗糙结构表面,静置1小时,移除多余润滑油,得到简单易操作、可大批量制备的仿生超润滑涂层;
喷涂工艺参数为:采用压缩空气,压力3bar;喷涂液流量:200mL/min,喷涂距离:400mm,直至热处理后的粗糙结构表面全部被二甲基硅油油膜覆盖。
经测试,在毛细作用下,棉籽油可以稳定地存在于淀粉涂层中,形成一层稳定的、连续的光滑液体膜,即仿生超润滑涂层。本实施例所得仿生超润滑涂层的性能检测数据列于表1。
实施例4
步骤一、将粒径为5微米二氧化硅颗粒加入水中,搅拌得到质量浓度为5%(w/v)的乳状悬浮液;
步骤二、室温下,将步骤一得到的乳状悬浮液喷涂沉积在经过预处理的玻璃表面上,干燥后,得到粗糙结构表面;
预处理过程为:用硫酸和过氧化氢按体积比7:3的混合溶液将玻璃浸泡4h后,再用去离子水超声清洗3遍,氮气吹干待用;
喷涂工艺参数为:采用压缩空气喷涂,喷涂压力3bar;喷涂液流量:150mL/min,喷涂距离:300mm;
步骤三、用喷火枪对粗糙结构表面进行2秒的热处理,得到热处理后的粗糙结构表面;
步骤四、将粘度为55cst的椰油喷涂到热处理后的粗糙结构表面,静置1小时,移除多余润滑油,得到简单易操作、可大批量制备的仿生超润滑涂层;
喷涂工艺参数为:采用压缩空气,喷涂压力3bar;喷涂液流量:150mL/min,喷涂距离:300mm。
经测试,在毛细作用下,椰油可以稳定地存在于淀粉涂层中,形成一层稳定、连续的光滑液体膜,即仿生超润滑涂层。本实施例所得仿生超润滑涂层的性能检测数据列于表1和图3所示。
表1实施例1-4制备的仿生超润滑涂层的性能检测数据
实施例 | 1 | 2 | 3 | 4 |
接触角(°) | 105 | 102 | 86 | 95 |
滚动角(°) | 6 | 8.2 | 6.2 | 5.3 |
从表1中数据可以看到,各实施例滚动角均小于10°,表明水滴在最后制得的仿生超润滑涂层极易移动,具有防水、自清结等性能。
图2是本发明实施例1中在铝板上喷涂聚苯乙烯微米颗粒、二甲基硅油之后的超润滑涂层的水接触角图(a)与滑动角图(b)。图3是实施例4中水滴在喷涂微米颗粒、椰油之后的玻璃基底上的滑动实物图,倾斜角为5°,水滴用黄色素染色。可以看出制备的仿生超润滑涂层具有抗水性,水滴易于在涂层表面滑动。
上述测试结果表明,本发明采用喷涂技术在基材表面制备微纳米粗糙结构,再利用低表面能润滑液浸润形成仿生超润滑涂层。该制备方法具有工艺简单、实用性强、性能优异,稳定性好,适宜大面积制备等优点。
显然,上述实施方式仅仅是为清楚地说明所作的举例,而并非对实施例的限定。对于所属领域的普通技术人员来说,在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有实施例予以穷举。而由此所引申出的显而易见的变化或变动仍处于本发明创造的保护范围之中。
Claims (10)
1.仿生超润滑涂层的制备方法,其特征在于,步骤如下:
步骤一、将纳米颗粒、微米颗粒中的一种或两种的混合物分散到液相介质中,得到喷涂液,喷涂液的形态为悬浮液或干粉;
步骤二、室温下,将喷涂液喷涂沉积在基底上,得到粗糙结构表面;
步骤三、对粗糙结构表面进行0~100秒的热处理,得到热处理后的粗糙结构表面;
步骤四、将润滑油喷涂到热处理后的粗糙结构表面,静置5分钟以上,移除多余润滑油,得到仿生超润滑涂层;
所述步骤四中,润滑油的粘度为20~500cst,喷涂工艺为:喷涂气体为压缩空气,喷涂压力1.1~10bar;喷涂液流量:150~1000mL/min;喷涂距离为200~400mm。
2.根据权利要求1所述的仿生超润滑涂层的制备方法,其特征在于,所述步骤一中,
纳米颗粒为可溶性淀粉颗粒、聚苯乙烯颗粒、二氧化硅颗粒中的一种或多种的混合,纳米颗粒的粒径范围大于等于0.1微米,小于1微米;
微米颗粒为可溶性淀粉颗粒、聚苯乙烯颗粒、二氧化硅颗粒中的一种或多种的混合,微米颗粒的粒径范围在1~50微米。
3.根据权利要求1所述的仿生超润滑涂层的制备方法,其特征在于,所述步骤一中,液相介质为水。
4.根据权利要求1所述的仿生超润滑涂层的制备方法,其特征在于,所述步骤一中,喷涂液的形态为悬浮液,悬浮液中固含量为0.05~25%(w/v)。
5.根据权利要求1所述的仿生超润滑涂层的制备方法,其特征在于,所述步骤二中,喷涂工艺为:采用压缩空气喷涂,喷涂压力1.1~10bar;喷涂液流量:150~1000mL/min;喷涂距离:200~400mm。
6.根据权利要求1所述的仿生超润滑涂层的制备方法,其特征在于,所述步骤二中,基底的材料为木材、橡胶、金属、陶瓷、塑料或玻璃;
或者,基底经过预处理后,将喷涂液喷涂沉积在预处理后的基底上,基底的材料为金属、陶瓷或塑料,预处理过程为,在室温下,依次用丙酮、乙醇、去离子水超声清洗基底表面,基底的材料为玻璃,预处理过程为,用硫酸:过氧化氢(v:v)=7:3浸泡基底表面4h后,再用去离子水超声清洗3遍,氮气吹干待用。
7.根据权利要求1所述的仿生超润滑涂层的制备方法,其特征在于,所述步骤三中,热处理为使用喷火枪或热气枪对粗糙结构表面进行加热。
8.根据权利要求1所述的仿生超润滑涂层的制备方法,其特征在于,所述步骤四中,润滑油为合成润滑油、天然润滑油中的一种或多种的混合;
所述合成润滑油为聚α-烯烃、烷基苯、聚丁烯、环脂肪族聚合物、磷酸酯、双酯酸、多元酯、多元醇、二甲基硅油、石油提炼物中的一种或多种的混合;
所述天然润滑油为棉籽油、橄榄油、菜籽油、椰子油、玉米油、米糠油、棉籽油、葡萄籽油中的一种或多种的混合。
9.根据权利要求1所述的仿生超润滑涂层的制备方法,其特征在于,所述步骤四中,喷涂时,喷枪以0.1~0.2m/s速度均匀移动,喷嘴垂直于被喷涂面。
10.权利要求1~9任何一项所述的仿生超润滑涂层的制备方法制备的仿生超润滑涂层。
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