CN106423789A - Durable ice-resistant super-hydrophobic coating and preparation method thereof - Google Patents

Durable ice-resistant super-hydrophobic coating and preparation method thereof Download PDF

Info

Publication number
CN106423789A
CN106423789A CN201610934541.0A CN201610934541A CN106423789A CN 106423789 A CN106423789 A CN 106423789A CN 201610934541 A CN201610934541 A CN 201610934541A CN 106423789 A CN106423789 A CN 106423789A
Authority
CN
China
Prior art keywords
coating
anti
icing
molecular weight
Prior art date
Application number
CN201610934541.0A
Other languages
Chinese (zh)
Inventor
熊党生
王楠
Original Assignee
南京理工大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 南京理工大学 filed Critical 南京理工大学
Priority to CN201610934541.0A priority Critical patent/CN106423789A/en
Publication of CN106423789A publication Critical patent/CN106423789A/en

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING LIQUIDS OR OTHER FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING LIQUIDS OR OTHER FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/002Pretreatement
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING LIQUIDS OR OTHER FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING LIQUIDS OR OTHER FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING LIQUIDS OR OTHER FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING LIQUIDS OR OTHER FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/08Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING LIQUIDS OR OTHER FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING LIQUIDS OR OTHER FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING LIQUIDS OR OTHER FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING LIQUIDS OR OTHER FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50Multilayers
    • B05D7/52Two layers
    • B05D7/54No clear coat specified
    • B05D7/544No clear coat specified the first layer is let to dry at least partially before applying the second layer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING LIQUIDS OR OTHER FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING LIQUIDS OR OTHER FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2202/00Metallic substrate
    • B05D2202/10Metallic substrate based on Fe
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING LIQUIDS OR OTHER FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING LIQUIDS OR OTHER FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2301/00Inorganic additives or organic salts thereof
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING LIQUIDS OR OTHER FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING LIQUIDS OR OTHER FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2350/00Pretreatment of the substrate
    • B05D2350/30Change of the surface
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING LIQUIDS OR OTHER FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING LIQUIDS OR OTHER FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2507/00Polyolefins
    • B05D2507/01Polyethylene

Abstract

The invention discloses a durable ice-resistant super-hydrophobic coating and a preparation method thereof. The durable ice-resistant super-hydrophobic coating consists of a metal trench structure at the bottom, a macromolecule layer in the middle and a nanoparticle-macromolecule composite layer on the upper part, smooth steel is used as a substrate, after a trench structure is etched by laser, a pure macromolecule coating coats the trench structure, and then a macromolecule-nano composite coating is sprayed on the pure macromolecule coating to obtain the durable ice-resistant super-hydrophobic coating. The preparation method comprises the following steps: firstly, etching the regular trench structure in the surface of the smooth steel by laser; secondly, after carrying out O2 plasma treatment on the steel, spraying ultra high molecular weight polyethylene in a molten state at high temperature, and drying to form a film; and finally, spraying an ultra high molecular weight polyethylene and hydrophobic nano Al2O3 mixture, and drying to obtain the required coating. The super-hydrophobic coating has good mechanical stability and environmental persistence, and has excellent ice resistance.

Description

一种耐久性抗冰超疏水涂层及其制备方法 A durable anti-icing superhydrophobic coating and preparation method

技术领域 FIELD

[0001] 本发明属于材料领域,涉及一种耐久性抗冰超疏水涂层及其制备方法。 [0001] The present invention belongs to the field of materials, relates to a durable anti-icing superhydrophobic coating and preparation method thereof. 背景技术 Background technique

[0002] 自然界中荷叶表面具有对水的极度不浸润性,称之为超疏水现象。 [0002] The extreme nature lotus leaf surface having no wettability to water, the phenomenon known as superhydrophobic. 人们通过研究发现,荷叶表面具有微米、纳米的二级层次结构,且表面覆盖了一层低表面能的蜡质,故而具备超疏水性能。 It was found through the study, two hierarchical lotus leaf surface having micron, the nanometer, and a wax layer covering the surface of a low surface energy, and therefore with ultra-hydrophobic properties. 因此,通过各种方式制备这种分级结构和后期的低表面能修饰,可以获得仿生超疏水界面。 Thus, the hierarchical structure and a low surface prepared by post can be modified in various ways, can be obtained biomimetic super-hydrophobic interface. [〇〇〇3] 超疏水界面因其优异的抗水、斥水性能,在水下减阻、自清洁表面、金属防护以及防冰抗冰领域有巨大的应用前景。 [〇〇〇3] superhydrophobic interface because of their excellent resistance to water, water repellency, underwater drag reduction, since the cleaning surface, the metal protective anti-icing and anti-icing art has great prospects. 目前超疏水涂层存在的主要问题是脆弱的表面结构。 The main problems of the superhydrophobic coating is fragile surface structures. 虽然制备超疏水界面的方式多种多样,但在很轻外界刮擦情况下,表面结构即可遭到破坏,从而失去超疏水性,这是制约其大范围实际工业化的瓶颈问题。 Although superhydrophobic interface a variety of ways, but in the case of very light outside scratching the surface structure can be destroyed, thus losing superhydrophobic, which is the bottleneck restricting its wide range of practical industrialization.

[0004] Peng等在纯错表面制备了具有耐磨性能的超疏水涂层(Chemically Stable and Mechanically Durable Superamphiphobic Aluminum Surface with a Micro/Nanoscale Binary Structure,^4CS4ppJ.Mater.1nterfaces, 2014,6 (17),pp 15188-15197)。 [0004] Peng et pure wrong superhydrophobic coating having abrasion resistance (Chemically Stable and Mechanically Durable Superamphiphobic Aluminum Surface with a Micro / Nanoscale Binary Structure, ^ 4CS4ppJ.Mater.1nterfaces, 2014,6 (17) Surface Preparation , pp 15188-15197). 他们将纯铝打磨、超生清洗后,放入2.5 M的HC1溶液中进行刻蚀,然后将涂层干燥后放入120 °C的高压反应釜中进行水热反应,以获得界面微纳米结构;最后,将涂层浸置于全氟硅烷中进行表面改性,获得超疏水涂层。 They polished aluminum, bounce back after washing, into a solution of 2.5 M HC1 in etching, and then drying the coating into the autoclave to 120 ° C in a hydrothermal reaction, to obtain a micro-nano interface structure; Finally, the dip coating disposed perfluoro silane surface modification to obtain superhydrophobic coatings. 这种方式对基底种类限定较为严格,只能在铝合金表面进行。 In this manner the kind of the substrate is defined more strictly, only the aluminum alloy surface. 同时,由于需要水热反应进行表面微纳米化,因此对样品尺寸、大小有严格规定。 Meanwhile, since a hydrothermal reaction of micro and nano surface, so the sample size, the size of the strict regulations. CPWong课题组成功的在娃片上制备了具有一定机械稳定性的超疏水涂层(Mechani ca 11 y robust superhydrophobicity on hierarchically structured Si surfaces, Nanotechnology 21 (2010) 155705)。 CPWong successful research group superhydrophobic coating having a mechanical stability (Mechani ca 11 y robust superhydrophobicity on hierarchically structured Si surfaces, Nanotechnology 21 (2010) 155705) sheet was prepared in the baby. 他们利用H2O2和HF酸协同刻蚀的方式,在Si片上制备出纳米结构,并进行了摩擦测试。 They Using H2O2 and HF acid etching synergistic manner, the Si substrate was prepared in the nanostructure, and friction testing. 虽然具备一定的机械稳定性,但是其在较为光滑的抹布上进行的摩擦,且最大摩擦25 cm以后便失去了超疏水性,因此稳定性仍需提高。 Although a certain degree of mechanical stability, but it is done on a more smooth cloth friction, friction and maximum 25 cm after they lost the super-hydrophobicity, stability still needs to improve. 发明内容 SUMMARY

[0005] 本发明的目的在于提供一种耐久性抗冰超疏水涂层及其制备方法,该界面底部金属沟槽结构、中间高分子层、上部纳米颗粒-高分子复合层组成。 [0005] The object of the present invention is to provide a durable and superhydrophobic coatings prepared anti-icing, the interface trench bottom metal structure, the intermediate polymer layer, an upper portion of the nanoparticle - polymer composite layers. 所述耐久性抗冰超疏水涂层通过利用激光将打磨抛光后的钢材进行处理,得到底部沟槽结构;然后将超高分子聚乙烯溶液喷涂至沟槽结构表面后干燥,得到中间高分子层;最后,将超高分子聚乙烯和改性疏7jCAl203纳米颗粒的混合物喷涂在基底上,得到上部纳米颗粒_高分子复合层。 The durability of the anti-icing superhydrophobic coatings processed using a laser after polishing the polished steel, to give bottom of the trench structure; ultra high molecular weight polyethylene solution was then sprayed onto the dried surface of the trench structure, to obtain an intermediate polymer layer ; Finally, a mixture of ultra high molecular polyethylene, and modified nanoparticles 7jCAl203 repellent coating on a substrate to obtain an upper layer polymer composite nanoparticles _. 该涂层经过外界磨损后仍具有超疏水性和优异的抗冰效果。 After the coating is still outside superhydrophobic wear resistance and excellent anti-icing effect.

[0006] 实现本发明目的的技术解决方案为:一种耐久性抗冰超疏水涂层,由部金属沟槽结构、中间高分子层、上部纳米颗粒-高分子复合层组成。 [0006] The purpose of the present invention is a technical solution: a durable anti-icing superhydrophobic coating, a portion of the metal structure of the trench, an intermediate polymer layer, an upper portion of the nanoparticle - polymer composite layers.

[0007] 进一步,所述金属沟槽结构是利用激光打磨抛光后的钢材沟槽结构;所述的沟槽凹形结构深度为200~300 ym,宽度为50~150 mi;凸形结构宽度为100~200 ym。 [0007] Further, the metal structure is a trench with a laser polished steel after polishing the trench structure; concave configuration of the groove depth is 200 ~ 300 ym, a width of 50 ~ 150 mi; width of the mesa structure 100 ~ 200 ym.

[0008] 所述高分子层是将超高分子聚乙烯溶液喷涂至沟槽结构表面后干燥得到;所述的超高分子聚乙烯分子量为5000000,喷涂所用溶剂均为十氢化萘。 [0008] The polymer layer is an ultra high molecular weight polyethylene solution was sprayed and dried to give the surface of the trench structure; molecular weight of the ultrahigh molecular weight polyethylene 5,000,000, the solvents were sprayed with decalin.

[0009] 所述的纳米Al2〇3颗粒粒径为50~100 nm,其疏水处理为将纳米颗粒浸在0.05〜0.08 mol/L的十七氟癸基三乙氧基硅烷的乙醇溶液中,浸泡温度为50~60 °C,浸泡时间为3〜4 h。 [0009] The particle diameter of nanoparticles Al2〇3 50 ~ 100 nm, which is a hydrophobic treatment nanoparticles immersed in 0.05~0.08 mol / L ethanol solution of heptadecafluorodecyl triethoxysilane, the soaking temperature is 50 ~ 60 ° C, a soak time of 3~4 h.

[0010] 上述耐久性抗冰超疏水涂层的制备方法,包括以下步骤:1) 利用激光将打磨抛光后的钢材进行处理,得到底部沟槽结构;2) 将超高分子聚乙烯溶液喷涂至沟槽结构表面后干燥,得到中间高分子层;3) 将超高分子聚乙烯和改性疏水Al2〇3纳米颗粒的混合物喷涂在基底上,得到上部纳米颗粒-高分子复合层。 [0010] Ice superhydrophobic coating method for preparing the anti-durability, comprising the following steps: 1) using a laser polished steel after polishing, to give the bottom of the trench structure; 2) spraying the solution to ultra high molecular weight polyethylene drying the rear surface of the trench structure, to obtain an intermediate polymer layer; 3) a mixture of ultra high molecular polyethylene, and modified nanoparticles hydrophobic Al2〇3 sprayed on a substrate to obtain an upper nanoparticle - polymer composite layer.

[0011] 所述的超高分子聚乙烯溶液的浓度为2〜5 g/L,喷涂温度为150 °C。 [0011] The concentration of UHMWPE solution is 2~5 g / L, spray temperature of 150 ° C. [〇〇12] 所述的疏水纳米Al2〇3颗粒的浓度为20~40 g/L,超高分子量聚乙烯浓度为6〜10 g/L,喷涂温度为150 °C。 [〇〇12] Al2〇3 concentration of said hydrophobic nano-particles is 20 ~ 40 g / L, the concentration of ultrahigh molecular weight polyethylene 6~10 g / L, spray temperature of 150 ° C.

[0013] 与现有技术相比,本发明其显著优点为:1)以超高分子聚乙烯的优异机械稳定性为纳米颗粒提供机械支撑,涂层具有良好的耐磨性;2)本发对基底材料的尺寸、形状没有要求,可实现大范围的制备;3)本发明具有优异的抗冰性能。 [0013] Compared with the prior art, the present invention is its remarkable advantages: 1) ultrahigh molecular weight polyethylene is excellent in mechanical stability provides mechanical support to the nanoparticles, a coating having good abrasion resistance; 2) present the size of the base material, the shape is not required, the preparation of a wide range can be achieved; 3) of the present invention have excellent anti-icing performance. 附图说明 BRIEF DESCRIPTION

[0014] 图1为实施例1耐久性抗冰超疏水涂层的水滴接触角、滚动角。 [0014] Example 1 FIG. 1 is a superhydrophobic coating durability anti-icing water droplet contact angle of the embodiment, the roll angle.

[0015] 图2为实施例1耐久性抗冰超疏水涂层磨损后的水滴接触角、滚动角。 [0015] Figure 2 is Example 1 drops after abrasion durability anti-icing embodiment superhydrophobic coating contact angle, roll angle.

[0016] 图3为实施例1涂层的结冰状况对比图。 [0016] FIG. 3 is a comparison of icing conditions in Example 1 of the coating. 具体实施方式 Detailed ways

[0017] 下面结合实施例对本发明作进一步详细的说明。 [0017] below with reference to embodiments of the present invention will be further described in detail.

[0018] 实施例1(1) 钢材经过抛光后,用激光处理得到沟槽结构,凹形结构深度为250 M1,宽度为100 ym;凸形结构宽度为120 ym;(2) 将步骤(1)得到的样品清洗后,将浓度为4 g/L超高分子聚乙烯的十氢化萘溶液喷涂至沟槽结构表面后干燥,得到中间高分子层。 [0018] Example 1 (1) of steel is polished to obtain a trench structure by laser processing, a depth of the concave structure 250 M1, a width of 100 ym; width of the mesa structure 120 ym; (2) the step (1 ) sample obtained after washing, a concentration of 4 g / L decalin solution of ultrahigh molecular weight polyethylene to drying after spraying the surface of the trench structure, to obtain an intermediate polymer layer.

[0019] (3)将粒径为70 nm的Al2〇3颗粒,浸在0.06 mol/L的十七氟癸基三乙氧基硅烷的乙醇溶液中,浸泡温度为55 °C,浸泡时间为3.5 h。 [0019] (3) the particle size of 70 nm Al2〇3 particles, immersed in an ethanol solution of 0.06 mol / L of heptadecafluorodecyl triethoxysilane, the soaking temperature of 55 ° C, soak time 3.5 h.

[0020] (4)将步骤(3)得到的疏水纳米Al2〇3颗粒、超高分子聚乙烯加入十氢化萘中,保持Al2〇3浓度为35 g/L,超高分子量聚乙烯浓度为8 g/L。 [0020] (4) The step (3) obtained Al2〇3 hydrophobic nano particles, ultrahigh molecular weight polyethylene in decalin was added to maintain the concentration of Al2〇3 L, ultrahigh molecular weight polyethylene concentration of 35 g / 8 g / L. 将上述混合加热至150 °C后喷涂在步骤(2)所述的涂层上干燥,得到上部纳米颗粒-高分子复合层。 After drying the above mixture was heated to 150 ° C in the coating step (2) coating, to obtain an upper nanoparticle - polymer composite layer. [〇〇21]制备得到涂层上,水滴静态接触角达到160°,滚动角为2°,如图1所示。 [〇〇21] prepared on the coating, the static water droplet contact angle 160 °, the roll angle of 2 °, as shown in FIG. 在5kPa、 200#砂纸上打磨2 m后,接触角为155°、滚动角为5°,如图2所示。 2 m on the polished 5kPa, 200 # sandpaper, a contact angle of 155 °, the rolling angle of 5 °, as shown in FIG. 摩擦测试后,放置于-20 ° C、90%湿度的冷凝结冰测试环境下,涂层表面未出现明显的冰霜,说明涂层具备优异的抗冰性能,如图3所示。 After the rubbing test, placed in a -20 ° C, 90% humidity environment test condensing icing, frost coating surface appear not explicitly described have excellent anti-icing coating properties, as shown in FIG. [〇〇22] 实施例2(1) 钢材经过抛光后,用激光处理得到沟槽结构,凹形结构深度为200 ym,宽度为150 ym;凸形结构宽度为100 wii;(2) 将步骤(1)得到的样品清洗后,将浓度为5 g/L超高分子聚乙烯的十氢化萘溶液喷涂至沟槽结构表面后干燥,得到中间高分子层。 [〇〇22] Example 2 (1) After the steel after polishing, to obtain a trench structure by laser processing, a depth of the concave structure 200 ym, a width of 150 ym; width of the mesa structure 100 wii; (2) the step of after washing the samples (1) obtained at a concentration of 5 g / L decalin solution of ultrahigh molecular weight polyethylene surface of the trench structure after spraying and dried to obtain an intermediate polymer layer. [〇〇23] (3)将粒径为50 nm的Al2〇3颗粒,浸在0.07 mol/L的十七氟癸基三乙氧基硅烷的乙醇溶液中,浸泡温度为50 °C,浸泡时间为4 h。 [〇〇23] (3) the particle size of 50 nm Al2〇3 particles, immersed in an ethanol solution of 0.07 mol / L of heptadecafluorodecyl triethoxysilane, the soaking temperature of 50 ° C, soaking time of 4 h. [〇〇24] (4)将步骤(3)得到的疏水纳米A1203颗粒、超高分子聚乙烯加入十氢化萘中,保持Al2〇3浓度为40 g/L,超高分子量聚乙烯浓度为6 g/L。 [〇〇24] (4) The step (3) to give A1203 hydrophobic nano particles, ultrahigh molecular weight polyethylene in decalin was added to maintain the concentration of Al2〇3 L, ultrahigh molecular weight polyethylene concentration of 40 g / 6 g / L. 将上述混合加热至150 °C后喷涂在步骤(2)所述的涂层上干燥,得到上部纳米颗粒-高分子复合层。 After drying the above mixture was heated to 150 ° C in the coating step (2) coating, to obtain an upper nanoparticle - polymer composite layer. [〇〇25] 制备得到涂层上,水滴静态接触角达到155°,滚动角为4°。 [〇〇25] prepared on the coating, the static water droplet contact angle 155 °, the rolling angle is 4 °. 在5kPa、200#砂纸上打磨2 m后,接触角为153°、滚动角为8°。 2 m on the polished 5kPa, 200 # sandpaper, a contact angle of 153 °, the roll angle of 8 °. 摩擦测试后,放置于-20 °C、90%湿度的冷凝结冰测试环境下,涂层表面未出现明显的冰霜,说明涂层具备优异的抗冰性能。 After the rubbing test, placed in a -20 ° C, 90% humidity environment test condensing icing, frost coating surface appear not explicitly described have excellent anti-icing coating properties. [0〇26] 实施例3(1) 钢材经过抛光后,用激光处理得到沟槽结构,凹形结构深度为300 ym,宽度为50 ym;凸形结构宽度为200 ym;(2) 将步骤(1)得到的样品清洗后,将浓度为3 g/L超高分子聚乙烯的十氢化萘溶液喷涂至沟槽结构表面后干燥,得到中间高分子层。 [0〇26] Example 3 (1) of steel is polished to obtain a trench structure by laser processing, a depth of the concave structure 300 ym, a width of 50 ym; width of the mesa structure 200 ym; (2) the step of after washing the samples (1) obtained at a concentration of 3 g / L decalin solution of ultrahigh molecular weight polyethylene surface of the trench structure after spraying and dried to obtain an intermediate polymer layer. [〇〇27] (3)将粒径为90 nm的Al2〇3颗粒,浸在0.08 mol/L的十七氟癸基三乙氧基硅烷的乙醇溶液中,浸泡温度为60 °C,浸泡时间为3 h。 [〇〇27] (3) the particle size of 90 nm Al2〇3 particles, immersed in an ethanol solution of 0.08 mol / L of heptadecafluorodecyl triethoxysilane, the soaking temperature of 60 ° C, soaking time of 3 h. [〇〇28] (4)将步骤(3)得到的疏水纳米A1203颗粒、超高分子聚乙烯加入十氢化萘中,保持Al2〇3浓度为30 g/L,超高分子量聚乙烯浓度为8 g/L。 [〇〇28] (4) The step (3) to give A1203 hydrophobic nano particles, ultrahigh molecular weight polyethylene in decalin was added to maintain the concentration of Al2〇3 L, ultrahigh molecular weight polyethylene concentration of 30 g / 8 g / L. 将上述混合加热至150 °C后喷涂在步骤(2)所述的涂层上干燥,得到上部纳米颗粒-高分子复合层。 After drying the above mixture was heated to 150 ° C in the coating step (2) coating, to obtain an upper nanoparticle - polymer composite layer. [〇〇29] 制备得到涂层上,水滴静态接触角达到154°,滚动角为3°。 [〇〇29] prepared on the coating, the static water droplet contact angle 154 °, the rolling angle is 3 °. 在5kPa、200#砂纸上打磨2 m后,接触角为151°、滚动角为4°。 2 m on the polished 5kPa, 200 # sandpaper, a contact angle of 151 °, the rolling angle is 4 °. 摩擦测试后,放置于-20 °C、90%湿度的冷凝结冰测试环境下,涂层表面未出现明显的冰霜,说明涂层具备优异的抗冰性能。 After the rubbing test, placed in a -20 ° C, 90% humidity environment test condensing icing, frost coating surface appear not explicitly described have excellent anti-icing coating properties.

[0030]对比例1(1) 钢材经过抛光后,用激光处理得到沟槽结构,凹形结构深度为200 ym,宽度为150 ym;凸形结构宽度为100 wii;(2) 将步骤(1)得到的样品清洗后,将浓度为2 g/L超高分子聚乙烯的十氢化萘溶液喷涂至沟槽结构表面后干燥,得到中间高分子层。 [0030] Comparative Example 1 (1) After the steel after polishing, to obtain a trench structure by laser processing, a depth of the concave structure 200 ym, a width of 150 ym; width of the mesa structure 100 wii; (2) the step (1 ) sample obtained after cleaning with a concentration of 2 g / L decalin solution is sprayed onto the ultrahigh molecular weight polyethylene surface of the trench structure and dried, to obtain an intermediate polymer layer.

[0031] (3)将粒径为50 nm的Al2〇3颗粒,浸在0.05 mol/L的十七氟癸基三乙氧基硅烷的乙醇溶液中,浸泡温度为550 °C,浸泡时间为3.5 h。 [0031] (3) the particle size of 50 nm Al2〇3 particles, immersed in an ethanol solution of 0.05 mol / L of heptadecafluorodecyl triethoxysilane, the soaking temperature of 550 ° C, soak time 3.5 h. [〇〇32] (4)将步骤(3)得到的疏水纳米A1203颗粒、超高分子聚乙烯加入十氢化萘中,保持Al2〇3浓度为20 g/L,超高分子量聚乙烯浓度为7 g/L。 The resulting [〇〇32] (4) The step (3) hydrophobic particles of nano A1203, ultrahigh molecular weight polyethylene in decalin was added, maintaining Al2〇3 concentration of 20 g / L, the concentration of ultrahigh molecular weight polyethylene 7 g / L. 将上述混合加热至150 °C后喷涂在步骤(2)所述的涂层上干燥,得到上部纳米颗粒-高分子复合层。 After drying the above mixture was heated to 150 ° C in the coating step (2) coating, to obtain an upper nanoparticle - polymer composite layer. [〇〇33]制备得到涂层上,水滴静态接触角达到130°,不具备超疏水性能。 [〇〇33] prepared on the coating, the static water droplet contact angle 130 °, does not have super-hydrophobic properties. 放置于-20 °C、 90%湿度的冷凝结冰测试环境下,涂层表面出现明显的冰霜,说明涂层不具备抗冰性能。 Placed at -20 ° C, 90% humidity condensing icing test environment, significant frost coating surface, the coating does not have the described anti-icing properties. [0〇34] 对比例2(1) 钢材经过抛光后,用激光处理得到沟槽结构,凹形结构深度为300 ym,宽度为150 ym;凸形结构宽度为120 ym;(2) 将步骤(1)得到的样品清洗后,将浓度为2 g/L超高分子聚乙烯的十氢化萘溶液喷涂至沟槽结构表面后干燥,得到中间高分子层。 [0〇34] Comparative Example 2 (1) of steel is polished to obtain a trench structure by laser processing, a depth of the concave structure 300 ym, a width of 150 ym; (2) the step of; width of the mesa structure 120 ym after washing the samples (1) obtained, a concentration of 2 g / L decalin solution of ultrahigh molecular weight polyethylene surface of the trench structure after spraying and dried to obtain an intermediate polymer layer. [〇〇35] (3)将粒径为100 nm的Al2〇3颗粒,浸在0.06 mol/L的十七氟癸基三乙氧基硅烷的乙醇溶液中,浸泡温度为55 °C,浸泡时间为3.5 h。 [〇〇35] (3) the particle size of 100 nm Al2〇3 particles, immersed in an ethanol solution of 0.06 mol / L of heptadecafluorodecyl triethoxysilane, the soaking temperature of 55 ° C, soaking time was 3.5 h. [〇〇36] (4)将步骤(3)得到的疏水纳米A1203颗粒、超高分子聚乙烯加入十氢化萘中,保持Al2〇3浓度为25 g/L,超高分子量聚乙烯浓度为10 g/L。 The resulting [〇〇36] (4) The step (3) hydrophobic particles of nano A1203, ultrahigh molecular weight polyethylene in decalin was added to maintain the concentration of Al2〇3 L, ultrahigh molecular weight polyethylene concentration of 25 g / 10 g / L. 将上述混合加热至150 °C后喷涂在步骤(2)所述的涂层上干燥,得到上部纳米颗粒-高分子复合层。 After drying the above mixture was heated to 150 ° C in the coating step (2) coating, to obtain an upper nanoparticle - polymer composite layer.

[0037]制备得到涂层上,水滴静态接触角达到100°,不具备超疏水性能。 [0037] Preparation of the coating obtained, static contact angle of water drop reaches 100 °, does not have super-hydrophobic properties. ,放置于-20 °C、 90%湿度的冷凝结冰测试环境下,涂层表面出现明显的冰霜,说明涂层不具备抗冰性能。 Placed at -20 ° C, 90% humidity condensing icing test environment, significant frost coating surface, the coating does not have the described anti-icing properties.

Claims (8)

1.一种耐久性抗冰超疏水涂层,其特征在于:该涂层由底部金属沟槽结构、中间高分子层、上部纳米颗粒-高分子复合层组成,所述纳米颗粒-高分子复合层为疏水纳米Al2〇3颗粒和超高分子聚乙烯复合涂层。 An anti-icing durability superhydrophobic coating, characterized in that: the coating of metal from the bottom of the trench structure, the intermediate polymer layer, an upper portion of the nanoparticle - polymer composite layer, the nanoparticles - Polymer Composite Al2〇3 hydrophobic nano-particle layer and ultrahigh molecular weight polyethylene composite coating.
2.根据权利要求1所述的耐久性抗冰超疏水涂层,其特征在于:所述金属沟槽结构是利用激光打磨抛光后的钢材沟槽结构。 2. The durability of the anti-icing superhydrophobic coating according to claim 1, wherein: said trench structure with a laser metal steel polished after polishing the trench structure.
3.根据权利要求1所述的耐久性抗冰超疏水涂层,其特征在于:所述金属沟槽结构为: 凹形结构,深度为200~300 ym,宽度为50~150 Mi;凸形结构,宽度为100~200 ym。 3. The durability of the anti-icing superhydrophobic coating according to claim 1, wherein: said metal structure is a trench: concave configuration, a depth of 200 ~ 300 ym, a width of 50 ~ 150 Mi; male structure, a width of 100 ~ 200 ym.
4.根据权利要求1所述的耐久性抗冰超疏水涂层,其特征在于:所述高分子层是将超高分子聚乙烯溶液喷涂至沟槽结构表面后干燥得到;所述的超高分子聚乙烯分子量为5000000,喷涂所用溶剂均为十氢化萘。 4. The durability of the anti-icing superhydrophobic coating according to claim 1, wherein: said layer is a polymer obtained by drying after spraying the super structure surface of the trench to a polyethylene polymer solution; the ultrahigh a molecular weight of 5,000,000 molecular weight polyethylene, the solvents were sprayed with decalin.
5.根据权利要求1所述的耐久性抗冰超疏水涂层,其特征在于:所述的纳米Al2〇3颗粒粒径为50~100 nm,其疏水处理为将纳米颗粒浸在0.05〜0.08 mol/L的十七氟癸基三乙氧基硅烷的乙醇溶液中,浸泡温度为50~60 °C,浸泡时间为3〜4 h。 The durability of the anti-icing superhydrophobic coating according to claim 1, wherein: said nano Al2〇3 particle diameter of 50 ~ 100 nm, which is a hydrophobic treatment nanoparticles immersed in 0.05~0.08 ethanol solution mol / L of heptadecafluorodecyl triethoxysilane, the soaking temperature is 50 ~ 60 ° C, a soak time of 3~4 h.
6.—种权利要求1所述的耐久性抗冰超疏水涂层的制备方法,其特征在于包括以下步骤:1) 利用激光将打磨抛光后的钢材进行处理,得到底部沟槽结构;2) 然后将超高分子聚乙烯溶液喷涂至沟槽结构表面后干燥,得到中间高分子层;3) 将超高分子聚乙烯和改性疏水Al2〇3纳米颗粒的混合物喷涂在基底上,得到上部纳米颗粒-高分子复合层。 Durability anti-icing method for preparing a superhydrophobic coating, seed 6.- claimed in claim 1, characterized by comprising the following steps: 1) using a laser polished steel after polishing, to give the bottom of the trench structure; 2) ultra high molecular weight polyethylene solution was then sprayed onto the surface of the trench structure and dried, to obtain an intermediate polymer layer; 3) a mixture of ultra high molecular polyethylene, and modified nanoparticles hydrophobic Al2〇3 sprayed on a substrate to give an upper nano particle - polymer composite layer.
7.根据权利要求6所述的耐久性抗冰超疏水涂层的制备方法,其特征在于:所述的超高分子聚乙烯溶液的浓度为2〜5 g/L,喷涂温度为150 °C。 7. Ice preparing a superhydrophobic coating, according to the durability of anti claimed in claim 6, wherein: the concentration of the UHMWPE solution is 2~5 g / L, spray temperature of 150 ° C .
8.根据权利要求6所述的耐久性抗冰超疏水涂层的制备方法,其特征在于:所述的疏水纳米Al2〇3颗粒的浓度为20~40 g/L,超高分子量聚乙烯浓度为6〜10 g/L,喷涂温度为150 ° C〇 Durability anti-icing method for preparing a superhydrophobic coating, according to claim 6, wherein: the concentration of the hydrophobic particles is nano Al2〇3 20 ~ 40 g / L, the concentration of ultrahigh molecular weight polyethylene is 6~10 g / L, a temperature of 150 ° spray C〇
CN201610934541.0A 2016-11-01 2016-11-01 Durable ice-resistant super-hydrophobic coating and preparation method thereof CN106423789A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610934541.0A CN106423789A (en) 2016-11-01 2016-11-01 Durable ice-resistant super-hydrophobic coating and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610934541.0A CN106423789A (en) 2016-11-01 2016-11-01 Durable ice-resistant super-hydrophobic coating and preparation method thereof

Publications (1)

Publication Number Publication Date
CN106423789A true CN106423789A (en) 2017-02-22

Family

ID=58177759

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610934541.0A CN106423789A (en) 2016-11-01 2016-11-01 Durable ice-resistant super-hydrophobic coating and preparation method thereof

Country Status (1)

Country Link
CN (1) CN106423789A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107267030A (en) * 2017-07-26 2017-10-20 弘大科技(北京)股份公司 Super hydrophobic paint and preparation and construction methods thereof

Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1791646A (en) * 2003-05-20 2006-06-21 帝斯曼知识产权资产管理有限公司 Nano-structured surface coating process, nano-structured coatings and articles comprising the coating
CN1820058A (en) * 2003-05-20 2006-08-16 帝斯曼知识产权资产管理有限公司 Hydrophobic coatings comprising reactive nano-particles
CN101225755A (en) * 2006-12-19 2008-07-23 通用电气公司 Articles having antifouling surfaces and methods for making
CN101333078A (en) * 2008-08-05 2008-12-31 广州市白云化工实业有限公司 Fluorosilicate self-cleaning glass nanophase material and producing method thereof
CN101456016A (en) * 2008-12-30 2009-06-17 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of polymer hydrophobic surface
CN101466481A (en) * 2006-06-23 2009-06-24 3M创新有限公司 Articles having durable hydrophobic surfaces
CN102138009A (en) * 2008-08-05 2011-07-27 美铝公司 Metal sheets and plates having friction-reducing textured surfaces and methods of manufacturing same
CN102277060A (en) * 2011-08-10 2011-12-14 天津大学 Hydrophobic coatings and anti-ice coating method of preparing fluorosilicone acrylate copolymer
CN102503170A (en) * 2011-10-19 2012-06-20 河南大学 Super-hydrophobic coating for icing flashover prevention of insulator as well as icing flashover resistant insulator and preparation method thereof
CN103180060A (en) * 2010-10-28 2013-06-26 3M创新有限公司 Superhydrophobic film constructions
CN103282133A (en) * 2010-10-28 2013-09-04 3M创新有限公司 Superhydrophobic films
CN103753908A (en) * 2013-12-31 2014-04-30 浙江大学 Super-hydrophobic coating and preparation method thereof
CN104822777A (en) * 2012-09-28 2015-08-05 Ut-巴特勒有限责任公司 Durable superhydrophobic coatings
CN106009791A (en) * 2016-05-16 2016-10-12 东南大学 Super-hydrophilic particle hybridized super-hydrophobic coating and preparation method thereof

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1820058A (en) * 2003-05-20 2006-08-16 帝斯曼知识产权资产管理有限公司 Hydrophobic coatings comprising reactive nano-particles
CN1791646A (en) * 2003-05-20 2006-06-21 帝斯曼知识产权资产管理有限公司 Nano-structured surface coating process, nano-structured coatings and articles comprising the coating
CN101466481A (en) * 2006-06-23 2009-06-24 3M创新有限公司 Articles having durable hydrophobic surfaces
CN101225755A (en) * 2006-12-19 2008-07-23 通用电气公司 Articles having antifouling surfaces and methods for making
CN102138009A (en) * 2008-08-05 2011-07-27 美铝公司 Metal sheets and plates having friction-reducing textured surfaces and methods of manufacturing same
CN101333078A (en) * 2008-08-05 2008-12-31 广州市白云化工实业有限公司 Fluorosilicate self-cleaning glass nanophase material and producing method thereof
CN101456016A (en) * 2008-12-30 2009-06-17 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of polymer hydrophobic surface
CN103180060A (en) * 2010-10-28 2013-06-26 3M创新有限公司 Superhydrophobic film constructions
CN103282133A (en) * 2010-10-28 2013-09-04 3M创新有限公司 Superhydrophobic films
CN102277060A (en) * 2011-08-10 2011-12-14 天津大学 Hydrophobic coatings and anti-ice coating method of preparing fluorosilicone acrylate copolymer
CN102503170A (en) * 2011-10-19 2012-06-20 河南大学 Super-hydrophobic coating for icing flashover prevention of insulator as well as icing flashover resistant insulator and preparation method thereof
CN104822777A (en) * 2012-09-28 2015-08-05 Ut-巴特勒有限责任公司 Durable superhydrophobic coatings
CN103753908A (en) * 2013-12-31 2014-04-30 浙江大学 Super-hydrophobic coating and preparation method thereof
CN106009791A (en) * 2016-05-16 2016-10-12 东南大学 Super-hydrophilic particle hybridized super-hydrophobic coating and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107267030A (en) * 2017-07-26 2017-10-20 弘大科技(北京)股份公司 Super hydrophobic paint and preparation and construction methods thereof

Similar Documents

Publication Publication Date Title
Zhang et al. Superhydrophobic surfaces: from structural control to functional application
Cao et al. Design and fabrication of micro-textures for inducing a superhydrophobic behavior on hydrophilic materials
Ebert et al. Transparent, superhydrophobic, and wear-resistant coatings on glass and polymer substrates using SiO2, ZnO, and ITO nanoparticles
Gao et al. “Artificial lotus leaf” prepared using a 1945 patent and a commercial textile
Xu et al. Transparent, superhydrophobic surfaces from one-step spin coating of hydrophobic nanoparticles
Wang et al. Preparation of a durable superhydrophobic membrane by electrospinning poly (vinylidene fluoride)(PVDF) mixed with epoxy–siloxane modified SiO2 nanoparticles: A possible route to superhydrophobic surfaces with low water sliding angle and high water contact angle
Ebert et al. Durable Lotus-effect surfaces with hierarchical structure using micro-and nanosized hydrophobic silica particles
Huang et al. Robust superhydrophobic TiO 2@ fabrics for UV shielding, self-cleaning and oil–water separation
Hsieh et al. Fabrication and superhydrophobicity of fluorinated carbon fabrics with micro/nanoscaled two-tier roughness
Xu et al. Preparation of superhydrophobic cotton fabrics based on SiO2 nanoparticles and ZnO nanorod arrays with subsequent hydrophobic modification
Zhang et al. Superhydrophobic surfaces for the reduction of bacterial adhesion
Ganesh et al. A review on self-cleaning coatings
Deng et al. Laundering durability of superhydrophobic cotton fabric
Xue et al. Long-lived superhydrophobic surfaces
US9956743B2 (en) Superhydrophobic and superoleophobic nanosurfaces
Li et al. Self-cleaning antireflective coatings assembled from peculiar mesoporous silica nanoparticles
US20060235143A1 (en) Process for producing detachable dirt- and water-repellent surface coatings
Jiang et al. Biomimetic superoleophobic surfaces: focusing on their fabrication and applications
Liao et al. Fabrication of superhydrophobic surface on aluminum by continuous chemical etching and its anti-icing property
Latthe et al. Development of sol–gel processed semi-transparent and self-cleaning superhydrophobic coatings
JP5881602B2 (en) Hydrophilic coating, articles, coating compositions and methods
Zhang et al. Spray-coating of superhydrophobic aluminum alloys with enhanced mechanical robustness
Sheen et al. New approach to fabricate an extremely super‐amphiphobic surface based on fluorinated silica nanoparticles
Ragesh et al. A review on ‘self-cleaning and multifunctional materials’
US6683126B2 (en) Compositions for producing difficult-to-wet surface

Legal Events

Date Code Title Description
C06 Publication
C10 Entry into substantive examination