CN115922092A - Ant-crypt-shaped super-hydrophobic surface and preparation method thereof - Google Patents
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Abstract
Description
技术领域technical field
本发明涉及激光加工技术领域,具体提供一种蚁穴状超疏水表面及其制备方法。The invention relates to the technical field of laser processing, and specifically provides an ant-hill-like super-hydrophobic surface and a preparation method thereof.
背景技术Background technique
超疏水材料表面具有自清洁、抗腐蚀、减阻等功能,因而受到人们广泛关注。一般情况下,超疏水材料的制备过程是通过在材料表面制备微纳结构并涂覆低表面能有机化学物质来实现超疏水性能。尽管目前在超疏水材料制备方面已经取得了重要研究进展,但是由于其表面普遍存在机械强度低和化学稳定性差等缺点,使得其在实际应用中仍面临诸多重要挑战。The surface of superhydrophobic materials has functions such as self-cleaning, anti-corrosion, and drag reduction, so it has attracted widespread attention. In general, the preparation process of superhydrophobic materials is to achieve superhydrophobic properties by preparing micro-nano structures on the surface of materials and coating low surface energy organic chemicals. Although important research progress has been made in the preparation of superhydrophobic materials, they still face many important challenges in practical applications due to the common disadvantages of low mechanical strength and poor chemical stability on the surface.
事实上,超疏水材料表面对接触液体的非浸润和排斥作用,在很大程度上是由于微纳结构内部空气层的存在,但是这些气囊在实际应用环境中经常是不稳定的,例如当材料处在海水浸泡、蒸汽冷凝、紫外线照射等环境中容易导致气囊体积减小甚至消失,最终使得表面由Cassie–Baxter状态变为Wenzel状态。In fact, the non-wetting and repelling effect of the superhydrophobic material surface on the contact liquid is largely due to the existence of the air layer inside the micro-nano structure, but these air pockets are often unstable in the actual application environment, for example, when the material In environments such as seawater immersion, steam condensation, and ultraviolet radiation, the volume of the air pockets is likely to decrease or even disappear, and eventually the surface changes from the Cassie–Baxter state to the Wenzel state.
针对这一问题研究人员通过改变表面结构形貌进一步增强气垫的防破坏能力。Domingues等人,比较了简单柱形、单凹型腔以及双凹型腔结构在润湿环境下的稳定性。结果表明,水在简单柱形结构上的突破压力为0kPa,而在双凹型腔结构表面的突破压力一般大于100kPa。此外,双凹型腔结构中的空气层表现出更好的稳定性,与简单柱形结构相比延长了7个数量级以上。Sun等人制备的多层双凹型腔微结构为侵入液体提供了多重能量屏障,使得最大的突破压力比单层凹型腔结构提升2~3倍。但是目前通过设计结构增强表面热力学稳定性的方法存在制备工艺较为复杂,不可避免需要进行低表面能涂层修饰且在表面气垫受到损坏后难以修复等问题。此外,超疏水表面在真实环境中总是暴露于摩擦、拉伸、弯曲以及雨水的冲刷冲击等各种外力的直接作用下,会导致表面结构发生磨损、破裂、变平和剥落,使得表面丧失液体排斥性。研究人员通过设计更为复杂的结构以提升表面的机械耐久性。例如,有研究人员设计了铠甲超疏水表面,通过循环磨损实验发现该表面较传统的超疏水表面其机械耐久性可延长10倍,但该表面要实现超疏水性能依然需要低表面能有机物进行修饰。公开日期为2022年3月26日、申请号为202210308182.3的中国专利公开了一种金属基巢穴式微结构超疏水表面及其制备方法,通过将样品浸入特殊溶液并通电反应制备巢穴结构,之后浸入肉豆蔻酸溶液通电反应降低表面能,得到金属基巢穴式微结构超疏水表面。显然,该方法在本质上是基于电化学原理,不仅工艺过程复杂而且所得巢穴式结构尺寸也为微米量级,难以获得纳米量级的制备;另外,这种巢穴结构仅是在表面开口处与蚂蚁巢穴有一定类似性,而并未在巢穴内部制备出更加有助于提升超疏水持久性能的复杂微细结构。To solve this problem, the researchers further enhanced the anti-destructive ability of the air cushion by changing the surface structure morphology. Domingues et al. compared the stability of simple cylindrical, single-cavity, and double-cavity structures in wet environments. The results show that the breakthrough pressure of water on the simple cylindrical structure is 0kPa, while the breakthrough pressure on the surface of the double concave cavity structure is generally greater than 100kPa. In addition, the air layer in the double-concave cavity structure exhibits better stability, extending more than 7 orders of magnitude compared with the simple cylindrical structure. The multilayer double concave cavity microstructure prepared by Sun et al. provides multiple energy barriers for the intruding liquid, making the
因此,亟需一种制备工艺简单、抗腐蚀性强、疏水效果好的超疏水表面及其制备方法。Therefore, there is an urgent need for a superhydrophobic surface with simple preparation process, strong corrosion resistance and good hydrophobic effect and a preparation method thereof.
发明内容Contents of the invention
本发明为解决上述问题,提供了一种蚁穴状超疏水表面及其制备方法,主要通过超快激光在金属表面加工微米沟槽,在超快激光作用下将非晶氧化硅掺杂到微米沟槽中,并利用超快激光产生的瞬时高温高压将微米沟槽熔融分解,形成蚁穴状超疏水表面。In order to solve the above problems, the present invention provides an ant-hill-shaped superhydrophobic surface and its preparation method, mainly processing micron grooves on the metal surface by ultrafast laser, and doping amorphous silicon oxide to micron under the action of ultrafast laser. In the groove, and use the instantaneous high temperature and high pressure generated by the ultrafast laser to melt and decompose the micron groove to form an ant-hill-like super-hydrophobic surface.
本发明提供的蚁穴状超疏水表面,采用金属表面,并在金属表面上开有微米沟槽,在金属表面和微米沟槽上分布有多个蚁穴堆,蚁穴堆构成周期性微米结构,蚁穴堆包括穴口和自上而下弯曲延伸的通道,穴口的临近位置分布有多个纳米颗粒,纳米颗粒之间形成气囊,通道由不同曲率的曲面构成。The ant nest-like super-hydrophobic surface provided by the present invention adopts a metal surface, and micron grooves are opened on the metal surface, and a plurality of ant nest piles are distributed on the metal surface and the micron grooves, and the ant nest piles form a periodic micron structure , the ant nest heap includes a hole opening and a channel extending curvedly from top to bottom. A plurality of nanoparticles are distributed near the hole opening, air pockets are formed between the nanoparticles, and the channel is composed of curved surfaces with different curvatures.
优选的,微米沟槽深度为60~80μm。Preferably, the depth of the micron groove is 60-80 μm.
优选的,穴口的开口尺寸为100~500nm。Preferably, the opening size of the hole is 100-500 nm.
优选的,纳米颗粒的尺寸为10~30nm。Preferably, the size of the nanoparticles is 10-30 nm.
优选的,蚁穴状超疏水表面为本征疏水。Preferably, the anthill-like superhydrophobic surface is intrinsically hydrophobic.
优选的,微米沟槽呈周期分布。Preferably, the micro-grooves are distributed periodically.
一种蚁穴状超疏水表面的制备方法,包括以下步骤:A method for preparing an ant-hill-like super-hydrophobic surface, comprising the following steps:
S1、采用超快激光在金属表面加工形成微米量级的第一微米沟槽,超快激光的脉冲宽度为30fs~300ps、激光功率为400mw~900mw、扫描速度为0.1mm/s~5mm/s、扫描间距为30μm~100μm;S1. Use ultrafast laser to process the first micron groove on the metal surface. The pulse width of the ultrafast laser is 30fs~300ps, the laser power is 400mw~900mw, and the scanning speed is 0.1mm/s~5mm/s , The scanning distance is 30μm~100μm;
S2、将含掺杂物的透光物质放置在第一微米沟槽上,利用超快激光照射含掺杂物的透光物质,掺杂物掺杂到第一微米沟槽中,超快激光产生的瞬时热量和压强将第一微米沟槽进行熔融并分解,形成蚁穴状超疏水表面。S2. Place the light-transmitting substance containing the dopant on the first micron groove, and irradiate the light-transmitting substance containing the dopant with an ultrafast laser. The dopant is doped into the first micron groove, and the ultrafast laser The resulting instantaneous heat and pressure melt and disintegrate the first micron grooves, forming an ant-hill-like superhydrophobic surface.
优选的,第一微米沟槽的深度为30~60μm。Preferably, the depth of the first micro-groove is 30-60 μm.
优选的,在S2中,超快激光作用于含掺杂物的透光物质与金属表面的接触界面上,超快激光将第一微米沟槽加深后形成第二微米沟槽,第二微米沟槽的深度为60~80μm。Preferably, in S2, the ultrafast laser acts on the contact interface between the dopant-containing light-transmitting material and the metal surface, and the ultrafast laser deepens the first micron groove to form a second micron groove, and the second micron groove The depth of the groove is 60-80 μm.
优选的,金属表面采用铝合金、钛合金、不锈钢。Preferably, the metal surface is made of aluminum alloy, titanium alloy, or stainless steel.
优选的,含掺杂物的透光物质采用无机玻璃、有机玻璃或氟化钙晶体。Preferably, inorganic glass, organic glass or calcium fluoride crystal is used as the light-transmitting substance containing dopant.
与现有技术相比,本发明能够取得如下有益效果:Compared with the prior art, the present invention can achieve the following beneficial effects:
本发明的超疏水表面为仿生蚁穴微纳结构,具有在空间复杂性,同时,蚁穴结构的穴口极小,并在其附近堆积有大量纳米颗粒,蚁穴结构可有效锁住其中空气层,防止水滴进入,极大提高了材料表面的超疏水性能。The super-hydrophobic surface of the present invention is a bionic ant-nest micro-nano structure, which has spatial complexity. At the same time, the ant-nest structure has a very small opening, and a large number of nanoparticles are accumulated near it, and the ant-nest structure can effectively lock the air layer in it. , prevent water droplets from entering, and greatly improve the superhydrophobic performance of the material surface.
本发明的超疏水表面采用金属材料,不仅具有高稳定的超疏水效应,同时具有优异的防腐蚀效果。The super-hydrophobic surface of the present invention adopts metal materials, which not only has a highly stable super-hydrophobic effect, but also has an excellent anti-corrosion effect.
本发明的蚁穴设计不仅可应用于抗腐蚀和超疏水领域,还可应用于自清洁、防污染和抗覆冰等领域。The ant nest design of the present invention can not only be applied to the fields of anti-corrosion and superhydrophobic, but also can be applied to the fields of self-cleaning, anti-pollution, anti-icing and the like.
附图说明Description of drawings
图1是根据本发明实施例提供的第一微米沟槽的微观结构图;FIG. 1 is a microstructure diagram of a first micro-groove provided according to an embodiment of the present invention;
图2是根据本发明实施例提供的蚁穴状超疏水表面的局部形貌图;Fig. 2 is the local topography diagram of the anthill-like superhydrophobic surface provided according to the embodiment of the present invention;
图3是根据本发明实施例提供的蚁穴状超疏水表面的制备方法的流程图;Fig. 3 is the flow chart of the preparation method of the anthill-like superhydrophobic surface provided according to the embodiment of the present invention;
图4是根据本发明实施例提供的蚁穴状超疏水表面的超疏水持久性能表征对比图。Fig. 4 is a comparison chart of the superhydrophobic durability performance of the anthill-shaped superhydrophobic surface provided according to an embodiment of the present invention.
其中的附图标记包括:Reference signs therein include:
蚁穴状超疏水表面的接触角和滚动角测量曲线1、常规微米沟槽结构表面的接触角和滚动角测量曲线2。
具体实施方式Detailed ways
在下文中,将参考附图描述本发明的实施例。在下面的描述中,相同的模块使用相同的附图标记表示。在相同的附图标记的情况下,它们的名称和功能也相同。因此,将不重复其详细描述。Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings. In the following description, the same blocks are denoted by the same reference numerals. With the same reference numerals, their names and functions are also the same. Therefore, its detailed description will not be repeated.
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合附图及具体实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅用以解释本发明,而不构成对本发明的限制。In order to make the object, technical solution and advantages of the present invention clearer, the present invention will be further described in detail below in conjunction with the accompanying drawings and specific embodiments. It should be understood that the specific embodiments described here are only used to explain the present invention, but not to limit the present invention.
图1示出了根据本发明实施例提供的第一微米沟槽的微观结构。FIG. 1 shows the microstructure of a first micro-groove provided according to an embodiment of the present invention.
如图1所示,本发明实施例提供的蚁穴状超疏水表面,采用铝合金材料,此外也可采用其他能够产生蚁穴结构的金属材料,铝合金表面开设有图1所示的微米沟槽,微米沟槽呈周期态分布,即微米沟槽。As shown in Figure 1, the ant-nest-shaped super-hydrophobic surface provided by the embodiment of the present invention is made of aluminum alloy material, and other metal materials that can produce ant-nest structure can also be used, and the aluminum alloy surface is provided with micron grooves as shown in Figure 1 Grooves and micro-grooves are distributed in a periodic state, that is, micro-grooves.
图2示出了根据本发明实施例提供的蚁穴状超疏水表面的局部形貌。Fig. 2 shows the partial morphology of an ant-hill-like superhydrophobic surface provided according to an embodiment of the present invention.
如图2中的(a)示出的,在铝合金表面和微米沟槽内均分布有大量蚁穴堆,该铝合金表面是指在相邻微米沟槽形成的突起处的上表面,该微米沟槽是指沟槽侧壁及底部位置,蚁穴堆形貌复杂,为周期性微米结构,通常情况下,蚁穴堆的长度在10~100μm之间。As shown in (a) in Figure 2, a large number of ant nests are distributed on the surface of the aluminum alloy and in the micro-grooves. The aluminum alloy surface refers to the upper surface of the protrusions formed by the adjacent micro-grooves. The micro-groove refers to the position of the side wall and the bottom of the groove. The shape of the ant nest is complex and is a periodic micron structure. Usually, the length of the ant nest is between 10 and 100 μm.
如图2中的(b)示出的,蚁穴堆的表面具有穴口,通常情况下,穴口的开口尺寸在100~500nm之间。此外,在穴口附近位置密集分布着大量纳米颗粒。As shown in (b) of Figure 2, the surface of the ant nest has openings. Usually, the opening size of the openings is between 100 and 500 nm. In addition, a large number of nanoparticles are densely distributed near the hole mouth.
如图2中的(c)示出的,通常情况下,纳米颗粒的尺寸在10~30nm之间,纳米颗粒之间可以形成细小的空气气囊,气囊可有效阻止水滴进入。As shown in (c) of Figure 2, under normal circumstances, the size of the nanoparticles is between 10 and 30 nm, and tiny air pockets can be formed between the nanoparticles, which can effectively prevent the entry of water droplets.
图2中的(d)示出的是蚁穴堆整体的截面形貌,图2中的(e)是蚁穴堆截面的局部放大形貌,可以看出,蚁穴堆内部的通道呈现错综复杂、自上而下弯曲延伸的状态,通道由多种不同的曲率表面组成,从而有助于牢牢锁住其中的空气层,使得蚁穴状超疏水表面即使在海水浸泡环境中也能持久保持。(d) in Figure 2 shows the overall cross-sectional appearance of the ant nest, and (e) in Figure 2 is a partially enlarged appearance of the cross-section of the ant nest. It can be seen that the channels inside the ant nest are intricate , The state of bending and extending from top to bottom, the channel is composed of a variety of surfaces with different curvatures, which helps to firmly lock the air layer in it, making the ant-hill-like super-hydrophobic surface durable even in seawater immersion environments .
如图2中的(f)示出的,第二微米沟槽深度为60~80μm。As shown in (f) of FIG. 2 , the depth of the second micrometer trench is 60˜80 μm.
为验证蚁穴状超疏水表面的制备方法的有效性,给出如下三个实施例:In order to verify the effectiveness of the preparation method of ant-hill-like super-hydrophobic surface, the following three examples are given:
实施例一Embodiment one
图3示出了根据本发明实施例提供的蚁穴状超疏水表面的制备方法的流程。Fig. 3 shows the process flow of the preparation method of the ant-hill-shaped superhydrophobic surface provided according to the embodiment of the present invention.
如图3所示,本发明实施例提供的蚁穴状超疏水表面的制备方法,包括以下步骤:As shown in Figure 3, the preparation method of the ant-hill-like super-hydrophobic surface provided by the embodiment of the present invention includes the following steps:
S1、利用砂纸对6061铝合金表面进行抛光处理,利用去离子水对6061铝合金表面进行超声清洗,并用氮气吹干,保证待加工表面洁净干燥,此外也可采用其他清洗方法。S1. Use sandpaper to polish the surface of 6061 aluminum alloy, use deionized water to ultrasonically clean the surface of 6061 aluminum alloy, and blow dry with nitrogen to ensure that the surface to be processed is clean and dry. In addition, other cleaning methods can also be used.
S2、将清洗完毕后的6061铝合金置于精密三维移动平台上,通过聚集超快激光在材料表面烧蚀形成微米量级的第一微米沟槽,其深度为30μm,超快激光的脉冲宽度为30fs、激光功率为400mw、扫描速度为0.1mm/s、扫描间距为30μm。S2. Place the cleaned 6061 aluminum alloy on a precise three-dimensional mobile platform, and ablate the surface of the material by gathering ultrafast laser to form the first micron groove on the order of microns, with a depth of 30 μm and the pulse width of the ultrafast laser The laser power is 30fs, the laser power is 400mw, the scanning speed is 0.1mm/s, and the scanning distance is 30μm.
S3、在S2加工形成的第一微米沟槽表面上放置一片含有掺杂物的透光物质,本实施例中采用含有非晶氧化硅的熔融石英玻璃片,将与S2中相同参数的超快激光照射在熔融石英玻璃片与6061铝合金的接触界面,在该激光作用下,氧化硅掺杂到第一微米沟槽中,并且超快激光产生的瞬时高温高压将第一微米沟槽进行熔融并分解,形成自上而下延伸的蚁穴结构,超快激光将第一微米沟槽加深后形成了第二微米沟槽,第二微米沟槽的深度加深为60μm。S3. Place a piece of light-transmitting material containing dopants on the surface of the first micron groove formed by processing in S2. In this embodiment, a fused silica glass sheet containing amorphous silicon oxide is used, and the ultrafast glass with the same parameters as in S2 is placed The laser is irradiated on the contact interface between the fused silica glass sheet and the 6061 aluminum alloy. Under the action of the laser, silicon oxide is doped into the first micron groove, and the instantaneous high temperature and high pressure generated by the ultrafast laser melts the first micron groove. And decompose to form an ant nest structure extending from top to bottom. The ultrafast laser deepens the first micron groove to form the second micron groove, and the depth of the second micron groove is deepened to 60 μm.
S4、再次采用去离子水对S3获得的6061铝合金表面超声清洗30分钟,再将其进行低温退火处理,降低材料表面能,即完成蚁穴状超疏水表面的制备。将蚁穴状超疏水表面进行疏水性能测试,蚁穴状超疏水表面对水滴的接触角为154°。S4. Ultrasonic cleaning the surface of the 6061 aluminum alloy obtained in S3 for 30 minutes again with deionized water, and then performing low-temperature annealing treatment to reduce the surface energy of the material, that is, to complete the preparation of an ant-nest-shaped superhydrophobic surface. The ant-nest-like superhydrophobic surface was tested for hydrophobic performance, and the contact angle of the ant-nest-like superhydrophobic surface to water droplets was 154°.
作为一种优选的实施例,制备蚁穴状超疏水表面的金属并不局限于铝合金,还包括其他能够产生蚁穴结构的金属材料。As a preferred embodiment, the metal used to prepare the ant-nest superhydrophobic surface is not limited to aluminum alloys, but also includes other metal materials that can produce ant-nest structures.
作为一种优选的实施例,激光加工过程中的掺杂物不仅局限于氧化硅,还可采用其他含有氧元素的物质,或者其他可以和金属表面中的金属元素生成非晶体合金或金属化合物的物质。当金属表面采用铝合金时,掺杂物的主要作用是将氧元素与铝合金中的铝进行反应生成金属氧化物,在激光作用下形成非晶体状态,增强蚁穴状超疏水表面的硬度和超疏水效果。而透光物质仅作为掺杂物在激光照射过程中的掺杂物的载体,需要保证具有较好的透光效果即可。含掺杂物的透光物质具体可采用无机玻璃、有机玻璃或氟化钙晶体等。As a preferred embodiment, the dopant in the laser processing process is not limited to silicon oxide, but other substances containing oxygen, or other substances that can form amorphous alloys or metal compounds with metal elements on the metal surface substance. When the metal surface is made of aluminum alloy, the main function of the dopant is to react the oxygen element with the aluminum in the aluminum alloy to form a metal oxide, which forms an amorphous state under the action of the laser, and enhances the hardness and superhydrophobic effect. The light-transmitting material is only used as the carrier of the dopant during the laser irradiation process, and it needs to ensure that it has a good light-transmitting effect. Specifically, inorganic glass, organic glass or calcium fluoride crystal can be used as the light-transmitting material containing dopant.
图4示出了根据本发明实施例提供的蚁穴状超疏水表面的超疏水持久性能表征曲线。Fig. 4 shows the superhydrophobic durability characteristic curve of the anthill-shaped superhydrophobic surface provided according to an embodiment of the present invention.
为验证本发明实施例提出的蚁穴状超疏水表面及制备方法的有效性,依据上述制备方法制备获得了蚁穴状超疏水表面,并对其进行验证性对比试验,将蚁穴状超疏水表面和常规微米沟槽结构表面浸泡在浓度为3.5%的氯化钠(NaCl)溶液中,用于模拟在海水中的浸泡情况,测量其表面接触角和滚动角随浸泡时间的变化情况,并绘蚁穴状超疏水表面的接触角和滚动角测量曲线1和常规微米沟槽结构表面的接触角和滚动角测量曲线2,结果如图4所示,蚁穴状超疏水表面在模拟海水溶液中浸泡100天,接触角和滚动角变化量较小,仍具有明显的疏水性,但是常规微米沟槽结构表面在模拟海水中浸泡一周后表面即转变为亲水性,其疏水性能已遭到破坏。In order to verify the effectiveness of the ant-nest-shaped super-hydrophobic surface and the preparation method proposed in the embodiment of the present invention, an ant-nest-like super-hydrophobic surface was prepared according to the above-mentioned preparation method, and a confirmatory comparative test was carried out on it. The surface and the conventional micro-groove structure surface were immersed in a 3.5% sodium chloride (NaCl) solution to simulate the immersion in seawater, and the changes of the surface contact angle and rolling angle with the immersion time were measured, and Draw the contact angle and rolling
据实验可知,制备获得的蚁穴状超疏水表面不仅具有高稳定的超疏水效应,同时具有优异的防腐蚀效果。According to experiments, the prepared ant-hill-like superhydrophobic surface not only has a highly stable superhydrophobic effect, but also has an excellent anti-corrosion effect.
本发明的蚁穴设计不仅可应用于抗腐蚀和超疏水领域,还可应用于自清洁、防污染和抗覆冰等领域。The ant nest design of the present invention can not only be applied to the fields of anti-corrosion and superhydrophobic, but also can be applied to the fields of self-cleaning, anti-pollution, anti-icing and the like.
实施例二Embodiment two
按照实施例一的步骤进行蚁穴状超疏水表面的制备,区别在于:According to the steps of Example 1, the preparation of an ant-hill superhydrophobic surface is carried out, the difference is that:
S2中第一微米沟槽的深度为60μm,超快激光的脉冲宽度300ps、激光功率为900mw、扫描速度为5mm/s、扫描间距为100μm。The depth of the first micron groove in S2 is 60 μm, the pulse width of the ultrafast laser is 300 ps, the laser power is 900 mw, the scanning speed is 5 mm/s, and the scanning distance is 100 μm.
S3中第二微米沟槽的深度加深为80μm。The deepened depth of the second micron trench in S3 was 80 μm.
该实施例获得的蚁穴状超疏水表面对水滴的接触角为151°。利用该蚁穴状超疏水表面进行验证性对比试验的结果曲线与实施例一的结果曲线基本一致。The anthill-like superhydrophobic surface obtained in this embodiment has a contact angle of 151° to water droplets. The result curve of the confirmatory comparative test using the ant-hill-like superhydrophobic surface is basically consistent with the result curve of Example 1.
实施例三Embodiment Three
按照实施例一的步骤进行蚁穴状超疏水表面的制备,区别在于:According to the steps of Example 1, the preparation of an ant-hill superhydrophobic surface is carried out, the difference is that:
S2中第一微米沟槽的深度为50μm,超快激光的脉冲宽度40fs、激光功率为600mw、扫描速度为1mm/s、扫描间距为60μm。The depth of the first micron groove in S2 is 50 μm, the pulse width of the ultrafast laser is 40 fs, the laser power is 600 mw, the scanning speed is 1 mm/s, and the scanning distance is 60 μm.
S3中第二微米沟槽的深度加深为70μm。The deepened depth of the second micron trench in S3 was 70 μm.
该实施例获得的蚁穴状超疏水表面对水滴的接触角为158°。利用该蚁穴状超疏水表面进行验证性对比试验的结果曲线与实施例一的结果曲线基本一致。The anthill-like superhydrophobic surface obtained in this embodiment has a contact angle of 158° to water droplets. The result curve of the confirmatory comparative test using the ant-hill-like superhydrophobic surface is basically consistent with the result curve of Example 1.
尽管上面已经示出和描述了本发明的实施例,可以理解的是,上述实施例是示例性的,不能理解为对本发明的限制。本领域的普通技术人员在本发明的范围内可以对上述实施例进行变化、修改、替换和变型。Although the embodiments of the present invention have been shown and described above, it should be understood that the above embodiments are exemplary and should not be construed as limitations on the present invention. Those skilled in the art can make changes, modifications, substitutions and modifications to the above-mentioned embodiments within the scope of the present invention.
以上本发明的具体实施方式,并不构成对本发明保护范围的限定。任何根据本发明的技术构思所做出的各种其他相应的改变与变形,均应包含在本发明权利要求的保护范围内。The above specific implementation manners of the present invention do not constitute a limitation to the protection scope of the present invention. Any other corresponding changes and modifications made according to the technical concept of the present invention shall be included in the protection scope of the claims of the present invention.
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Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101219506A (en) * | 2008-01-07 | 2008-07-16 | 江苏大学 | Laser preparation method of metal-based superhydrophobic microstructure surface |
US20100219506A1 (en) * | 2005-12-21 | 2010-09-02 | University Of Virginia Patent Foundation | Systems and Methods of Laser Texturing and Crystallization of Material Surfaces |
US20140356578A1 (en) * | 2011-12-20 | 2014-12-04 | Eads Deutschland Gmbh | Method for Structuring a Surface of a Workpiece |
US20150136226A1 (en) * | 2006-09-29 | 2015-05-21 | University Of Rochester | Super-hydrophobic surfaces and methods for producing super-hydrophobic surfaces |
US20180066131A1 (en) * | 2016-09-05 | 2018-03-08 | NanoSD Inc. | Polymer nanoparticle thermal insulators |
CN110167877A (en) * | 2016-11-06 | 2019-08-23 | 威廉马歇莱思大学 | Manufacture the method for graphene and combinations thereof of induced with laser |
KR102308050B1 (en) * | 2020-04-10 | 2021-10-01 | 울산대학교 산학협력단 | Superhydrophobic surface making method and Superhydrophobic substrate repairing method same using |
JP2022069342A (en) * | 2020-10-23 | 2022-05-11 | 博 小林 | Fine crystals of a metal compound that precipitates a metal or metal oxide by thermal decomposition are surrounded by a liquid organic compound, and nanoparticles of the metal or metal oxide are surrounded by a liquid organic compound and precipitated, and the nano of the metal or metal oxide is formed. A method of precipitating particles without agglomerating them |
CN115193666A (en) * | 2022-05-20 | 2022-10-18 | 大连海事大学 | A method for preparing superhydrophobic surface with micro-nano-scale cascade structure for anti-icing |
CN115717231A (en) * | 2023-01-09 | 2023-02-28 | 中国科学院长春光学精密机械与物理研究所 | A kind of subcrystalline metal material, its preparation method and application |
-
2023
- 2023-03-15 CN CN202310244098.4A patent/CN115922092B/en active Active
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20100219506A1 (en) * | 2005-12-21 | 2010-09-02 | University Of Virginia Patent Foundation | Systems and Methods of Laser Texturing and Crystallization of Material Surfaces |
US20150136226A1 (en) * | 2006-09-29 | 2015-05-21 | University Of Rochester | Super-hydrophobic surfaces and methods for producing super-hydrophobic surfaces |
CN101219506A (en) * | 2008-01-07 | 2008-07-16 | 江苏大学 | Laser preparation method of metal-based superhydrophobic microstructure surface |
US20140356578A1 (en) * | 2011-12-20 | 2014-12-04 | Eads Deutschland Gmbh | Method for Structuring a Surface of a Workpiece |
US20180066131A1 (en) * | 2016-09-05 | 2018-03-08 | NanoSD Inc. | Polymer nanoparticle thermal insulators |
CN110167877A (en) * | 2016-11-06 | 2019-08-23 | 威廉马歇莱思大学 | Manufacture the method for graphene and combinations thereof of induced with laser |
KR102308050B1 (en) * | 2020-04-10 | 2021-10-01 | 울산대학교 산학협력단 | Superhydrophobic surface making method and Superhydrophobic substrate repairing method same using |
JP2022069342A (en) * | 2020-10-23 | 2022-05-11 | 博 小林 | Fine crystals of a metal compound that precipitates a metal or metal oxide by thermal decomposition are surrounded by a liquid organic compound, and nanoparticles of the metal or metal oxide are surrounded by a liquid organic compound and precipitated, and the nano of the metal or metal oxide is formed. A method of precipitating particles without agglomerating them |
CN115193666A (en) * | 2022-05-20 | 2022-10-18 | 大连海事大学 | A method for preparing superhydrophobic surface with micro-nano-scale cascade structure for anti-icing |
CN115717231A (en) * | 2023-01-09 | 2023-02-28 | 中国科学院长春光学精密机械与物理研究所 | A kind of subcrystalline metal material, its preparation method and application |
Non-Patent Citations (1)
Title |
---|
王锁成 董世运 闫世兴 刘晓亭: "《飞秒激光制备金属表面微纳结构及其技术应用》", 《《激光与光电子学进展》 * |
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