超临界CO_2快速膨胀法制备SiO_2/聚氨酯超疏水涂层的研究
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摘要
随着现代仪器检测技术的飞速发展，人们对超疏水材料的认识逐渐深入，其广泛的应用前景引起各国科学家们的极大兴趣。虽然目前制备超疏水涂层的方法有几十种，但没有一种超疏水产品得到普遍应用，其主要原因是工艺条件限制，不能大面积制备，并且很多方法制备的超疏水涂层耐久性、耐划伤性很差，不能长时间应用。因此探索成本低廉、工艺简单、耐久性好、力学性能优异、能大面积制备的超疏水涂层工艺是当前研究的重点和难点。
首先，采用纳米粒子表面修饰技术，制备出了表面接枝氟和双键官能团的改性纳米SiO_2粒子。研究了在超声作用下，不同溶剂的空化作用对纳米SiO_2粒子的分散效果。采用红外光谱、TEM、TG-DSC以及激光粒度分布仪对改性后纳米SiO_2粒子的结构和性能进行了测试分析，研究表明：F8261和KH-570两种偶联剂均已被接枝到纳米SiO_2表面，粒子粒径和粒径分布随之变小和变窄；当偶联剂添加量为10%时，纳米SiO_2粒子改性达到饱和，且当偶联剂KH-570/F8261摩尔比为1：1时，改性后的纳米SiO_2粒子呈现超双疏性质。采用溶胶分散体系的“光散射”理论研究了纳米SiO_2粒子在超临界CO_2中的分散情况，探索了SiO_2粒子粒径和浓度与超临界CO_2微乳液颜色的变化机理，并且分析了纳米SiO_2粒子在超临界CO_2中的粒径和浓度变化情况。研究结果表明：当温度为70~90℃、压力为12~16MPa时，乳液呈蓝色，纳米粒子粒径最小，说明此时分散性最好。
以磺酸型低聚醚二元醇(DPSA)和1,4-丁烯二醇-2-磺酸钠(BDSA)作为混合亲水扩链剂，甲基丙烯酸-β-羟乙酯(HEMA)作为双键封端剂，采用逐步聚合-自乳化的方法制备了高固含量低粘度双键封端的水性聚氨酯(WPUA)乳液。研究了乳液的粒径形态和结构对固含量及稳定性的影响，结果表明：WPUA乳液呈多元粒度分布的特征，胶粒呈核-壳的结构。随着DPSA/BDSA质量配比从2/10增大到8/10，乳液的固含量先升高后降低；当DPSA/BDSA质量比为5/10，固含量最高达54%以上，但仍具有较好的流动性，能够满足超疏水涂层基底材料的要求。由于WPUA稳定性机理以“静电稳定”作用和“空间”稳定作用为主，而且粒子表面呈“毛发-双电层”结构，因此，WPUA乳液具有较好耐电解质性能、抗冻结性、耐高温及贮存稳定性。
为了提高涂层的疏水性，以含硅的二元醇（PES）和聚醚二醇(PPG)为混合软链段，TDI和复合亲水扩连剂1,2-二羟基-3-丙磺酸钠(DHPS)和二羟甲基丙酸(DMPA)为硬链段，以γ-氨丙基三乙氧基硅烷(KH-550)作为封端剂，采用自乳化法制备了一系列高固含量有机硅/聚氨酯(Si/PU)复合乳液。研究了乳液的形成机理，分析了PES和PPG质量配比对乳液及涂膜性能的影响。形成机理研究表明：Si/PU乳液的形成，本质上是由于PU高分子表面活性剂的存在，使得疏水的PES/PU大分子在水中得以均匀分散，而且在Si/PU结构体系中，PU高分子表面活性剂的分子模型属于“支链型”结构模型。性能测试和结构分析表明：乳液为非牛顿流体，并且具有高固含量的特征，当KH550含量为2.0%，PES/PPG比值为5/10时，固含量高达58%。；乳液粒径呈宽粒径分布，粒子呈核壳结构；乳液的稳定性随着PES/PU的增大略有下降，但仍能够满足要求；胶膜接触角大于90°，具有较好的疏水性能，有利于聚氨酯超疏水涂层的制备。
采用乳液聚合方法，设计并合成了超疏水基底涂层增稠乳液。研究了单体的选择及用量对乳液增稠性能的影响，发现马来酸酐的加入能增加乳液的透明性和粘稠拉丝性，加甲基丙烯酸的乳液比加丙烯酸的乳液有更优良的稳定性。用BEM+平平加-20+SE-10作为乳化剂，乳液稳定性相当好；研究还发现：pH对粘度影响较大，当pH>4.5时，乳液粘度急剧增大，而pH=7.5时粘度达到最大值；羧酸单体的加入方式对乳液增稠性能也有重要影响，电导率测定法证明：乳液的增稠性能取决于乳胶粒表面的羧基链段的分布和数量，同时也证明了羧酸单体的加入方式对乳液增稠的机理。
将上述的三种乳液（双键封端的聚氨酯乳液、有机硅/聚氨酯(Si/PU)复合乳液、基底涂层增稠乳液）按比例混合，调剂pH值增稠至一定粘度后，制备了超疏水基底涂膜，再采用超临界CO_2快速膨胀法，将纳米粒子喷射到基底涂层上，UV固化干燥后制备出超疏水涂层。研究了基底涂膜粘度与增稠剂含量关系，涂膜的厚度和UV辐照时间对固化率和固化效率的影响。结果分析表明：当增稠剂含量为40%时，涂膜表面喷涂纳米SiO_2粒子后形貌最粗糙；随着Si/PU乳液含量的提高，涂层的拉伸强度逐渐降低，而断裂伸长率逐渐增大，涂层的剥离强度先增大后减小，直至趋于平缓。
最后，重点对超临界CO_2快速膨胀法制备超疏水涂层的工艺进行了研究，结果表明：当在喷嘴和釜内温度均为90℃，釜内压力为16MPa，F8261和KH-570配比为1:1，Si/PU乳液添加9%时，涂层的静态水接触角超过165°，所制得涂层具有很好的超疏水性。沙漏冲击实验证明：采用超临界CO_2快速膨胀法制备的超疏水涂层，不仅具有优异的耐磨、耐刮伤性，而且该法高效环保，涂层性能优良，适于大面积制备。具有广阔的应用前景。
With the rapid development of technology on modern instrument detection, super-hydrophobic materials are recognized gradually in depth, its broad application prospects havecaused great interest of national scientists. Although there are dozens of preparation of super-hydrophobic coating, without a super-hydrophobic products are universally applied. The mainreason is that the process conditions led to the not a large area of preparation, durability andscratch resistance of super-hydrophobic coating using existing preparing methods are poor,which resulting super-hydrophobic coating not be a long time applications. Therefore, explorea large area preparation of super-hydrophobic coating with low-cost, simple technology, gooddurability, and excellent mechanical properties is the focus and difficulty of the currentresearch.
Firstly, nano-SiO_2particles were prepared with the surface grafted fluorine couplingagents and double bond by using surface modification technology. Dispersion effect ofnano-SiO_2particles were studied in different solvents ultrasound cavitations. Test resultsshowed in infrared spectroscopy, TEM and laser particle size distribution analyzer that bothF8261and KH-570have been grafted onto the surface of nano-SiO_2, particle size anddistribution of nano-SiO_2after modified by the two coupling agent became smaller and morenarrow; Tg-DSC analysis showed that when the amount of the coupling agent is up to10%,fluorine coupling agent and double bond grafted onto surface of nano-SiO_2particles reach thesaturation. Dispersion characteristics of nano-SiO_2particles in supercritical CO_2were studiedby light scattering theory of sol dispersion, concentration and particle size of SiO_2insupercritical CO_2, the change mechanism of supercritical CO_2micro-emulsion color, and wereexplored. The results showed that emulsion is blue in a temperature from70°C to90°C and apressure range from12MPa to16MPa region, particle size of the nano-particles is the smallest,in which the dispersibility of nano-SiO_2particles in supercritical CO_2is preferably.
The aqueous polyurethane(WPUA) emulsion with high solid content-low viscosity anddouble bond capped were prepared by stepwise polymerization and the self-emulsifying usingpolyethyleneglycol lows ulfonicacidtype polyesterdiol(DPSA) and1,4-butenediol-2-sulfonate(BDSA) as mixed hydrophilic chain extender, a methacrylic acid-of β-hydroxyalkylmethacrylate (HEMA) as a double bond in the terminal blocking agent. Influences of the massratio of DPSA and BDSA on properties of polyurethane emulsions were analyzed. The resultsshowed that obtained emulsions were multivariate distribution in particle size and werespherical particles approximatively. Emulsions exhibit a pseudo-plastic behavior. It wasnoticed that with increasing proportion average, particle diameter became bigger,poly-dispersion became wider, and when the mass ratio of DPSA and BDSA ranges from2/10to8/10, solid concent of emulsions first increase and then decrease. When the mass ratio ofDPSA and BDSA is5/10, solid concent reaches above54%, but still have good fluidity, andcould meet the requirements of the base material of the super-hydrophobic coating. Becausethe stability mechanism of WPUA emulsion depends on the role of electrostatic stabilizationand steric stabilization role, and the surface of the particles is “hair-double layer structure”,WPUA emulsion has a better electrolyte resistance, anti-freeze resistance, high temperatureand storage stability.
In order to improve the hydrophobicity of the coating, a polyol consists of siliconechains and epoxy acrylate structures, referred to as PES, and was used to prepare cross-linkedSi/PU emulsion. Both PES and propylene oxide glycol (PPG) were mixed as soft segments.Formation mechanism of the emulsion and the effects weight ratio of PES to PPG onproperties of the resultant polyurethane dispersions were studied. It is shown that theformation of the Si/PU emulsion, essentially due to the exist of PU polymer surfactant, so thatthe hydrophobic PES/PU macromolecules are dispersed the water to in uniformly. In theSi/PU emulsion structure system, and molecular structure of the PU polymer surfactant doesnot belong to a “multi-block” model, but belongs to the “branched-structure” model. It isfound that the Si/PU dispersions possessed wider particle size distribution and higher averageparticles diameter due to the use of PES which contains cross-linked silicone side chains. The Si/PU dispersions have higher solid content. When the ratio of PES and PPG is5:10, solidcontent of the Si/PU dispersions is up to58%. It is also noticed that apparent viscosity of theSi/PU dispersions decreased with increasing PES to PPG ratio. In addition, stability of theemulsions decreases slightly at high temperature and low temperature, however, which canmeet the basically requirements. Overall contact angle of the film prepared is more than90°,which shows polyurethane film are basically able to exhibit good hydrophobic properties, andis conducive to preparation of polyurethane super-hydrophobic coating.
Super-hydrophobic substrate coating thickening lotion was designed and synthesizedusing emulsion polymerization. The effects selection and amount of monomer on thethickening properties of the emulsion were studied. It is shown that emulsion stability isquite good using BEM+and PinPin20+SE-10as emulsifier, even in the case of the minimumamount of0.3%, in emulsion the only small amount of precipitation produce. Before the pHvalue of is less than4, the viscosity decreases with the pH value change slowly, the viscosityincreases sharply when the pH>4.5, the viscosity reached maximum at pH=7.5, then theviscosity decreases as the pH value increasing.
A Super-hydrophobic substrate coating was prepared by mixing the doublebond-terminated polyurethane (WPUA) emulsions, silicone/polyurethane (Si/PU) emulsion,and acrylic thickening emulsion in proportion, and swapping the pH value thickening to acertain viscosity. Subsequently, the nano-silica particles were injected onto surface of thepolyurethane coating making use of rapid expansion of supercritical CO_2, and then were UVdried towards forming a stable rough structure because for the nano-silica particles beinggrafted on the polyurethane coating. This way, a SiO_2/PU film with super-hydrophobic surfacewas obtained. The relationship between the content of thickener and viscosity of the substratecoating was studied SEM analysis showed that when content of the thickener is40%, thesurface morphology of coating with nano-SiO_2particles is the most rough. The influence ofthe thickness of the coating and UV irradiation time on the curing rate and curing efficiencywere studied. With the content of Si/PU emulsion increasing, the tensile strength of thecoating is gradually reduced, and elongation at break gradually increasing, the peel strength of the coating first increases and then decreases until it leveled off.
The process of preparing super-hydrophobic coating by the rapid expansion ofsupercritical CO_2was studied, the results showed that: the static water contact angle of thecoating can be up to (169.1±0.6)°, when temperature of the nozzle and the reaction kettle areall90℃, the reaction kettle pressure is16MPa, and ratio of F8261and KH-570is1:1. Theobtained films have a good super-hydrophobic, and have excellent scratch resistance.Increasing F8261coupling agent, the water contact angle of coating gradually increases, afterflatten. The addition of9%Si/PU emulsion, water contact angle of the super-hydrophobiccoating prepared exceeds165°. In addition, hourglass shock experiments showed thatsuper-hydrophobic coatings have very excellent wear resistance, scratch resistance, andsuper-hydrophobic coating is environmental, but also could be produced cost-effectively inlarge scale.
首先，采用纳米粒子表面修饰技术，制备出了表面接枝氟和双键官能团的改性纳米SiO_2粒子。研究了在超声作用下，不同溶剂的空化作用对纳米SiO_2粒子的分散效果。采用红外光谱、TEM、TG-DSC以及激光粒度分布仪对改性后纳米SiO_2粒子的结构和性能进行了测试分析，研究表明：F8261和KH-570两种偶联剂均已被接枝到纳米SiO_2表面，粒子粒径和粒径分布随之变小和变窄；当偶联剂添加量为10%时，纳米SiO_2粒子改性达到饱和，且当偶联剂KH-570/F8261摩尔比为1：1时，改性后的纳米SiO_2粒子呈现超双疏性质。采用溶胶分散体系的“光散射”理论研究了纳米SiO_2粒子在超临界CO_2中的分散情况，探索了SiO_2粒子粒径和浓度与超临界CO_2微乳液颜色的变化机理，并且分析了纳米SiO_2粒子在超临界CO_2中的粒径和浓度变化情况。研究结果表明：当温度为70~90℃、压力为12~16MPa时，乳液呈蓝色，纳米粒子粒径最小，说明此时分散性最好。
以磺酸型低聚醚二元醇(DPSA)和1,4-丁烯二醇-2-磺酸钠(BDSA)作为混合亲水扩链剂，甲基丙烯酸-β-羟乙酯(HEMA)作为双键封端剂，采用逐步聚合-自乳化的方法制备了高固含量低粘度双键封端的水性聚氨酯(WPUA)乳液。研究了乳液的粒径形态和结构对固含量及稳定性的影响，结果表明：WPUA乳液呈多元粒度分布的特征，胶粒呈核-壳的结构。随着DPSA/BDSA质量配比从2/10增大到8/10，乳液的固含量先升高后降低；当DPSA/BDSA质量比为5/10，固含量最高达54%以上，但仍具有较好的流动性，能够满足超疏水涂层基底材料的要求。由于WPUA稳定性机理以“静电稳定”作用和“空间”稳定作用为主，而且粒子表面呈“毛发-双电层”结构，因此，WPUA乳液具有较好耐电解质性能、抗冻结性、耐高温及贮存稳定性。
为了提高涂层的疏水性，以含硅的二元醇（PES）和聚醚二醇(PPG)为混合软链段，TDI和复合亲水扩连剂1,2-二羟基-3-丙磺酸钠(DHPS)和二羟甲基丙酸(DMPA)为硬链段，以γ-氨丙基三乙氧基硅烷(KH-550)作为封端剂，采用自乳化法制备了一系列高固含量有机硅/聚氨酯(Si/PU)复合乳液。研究了乳液的形成机理，分析了PES和PPG质量配比对乳液及涂膜性能的影响。形成机理研究表明：Si/PU乳液的形成，本质上是由于PU高分子表面活性剂的存在，使得疏水的PES/PU大分子在水中得以均匀分散，而且在Si/PU结构体系中，PU高分子表面活性剂的分子模型属于“支链型”结构模型。性能测试和结构分析表明：乳液为非牛顿流体，并且具有高固含量的特征，当KH550含量为2.0%，PES/PPG比值为5/10时，固含量高达58%。；乳液粒径呈宽粒径分布，粒子呈核壳结构；乳液的稳定性随着PES/PU的增大略有下降，但仍能够满足要求；胶膜接触角大于90°，具有较好的疏水性能，有利于聚氨酯超疏水涂层的制备。
采用乳液聚合方法，设计并合成了超疏水基底涂层增稠乳液。研究了单体的选择及用量对乳液增稠性能的影响，发现马来酸酐的加入能增加乳液的透明性和粘稠拉丝性，加甲基丙烯酸的乳液比加丙烯酸的乳液有更优良的稳定性。用BEM+平平加-20+SE-10作为乳化剂，乳液稳定性相当好；研究还发现：pH对粘度影响较大，当pH>4.5时，乳液粘度急剧增大，而pH=7.5时粘度达到最大值；羧酸单体的加入方式对乳液增稠性能也有重要影响，电导率测定法证明：乳液的增稠性能取决于乳胶粒表面的羧基链段的分布和数量，同时也证明了羧酸单体的加入方式对乳液增稠的机理。
将上述的三种乳液（双键封端的聚氨酯乳液、有机硅/聚氨酯(Si/PU)复合乳液、基底涂层增稠乳液）按比例混合，调剂pH值增稠至一定粘度后，制备了超疏水基底涂膜，再采用超临界CO_2快速膨胀法，将纳米粒子喷射到基底涂层上，UV固化干燥后制备出超疏水涂层。研究了基底涂膜粘度与增稠剂含量关系，涂膜的厚度和UV辐照时间对固化率和固化效率的影响。结果分析表明：当增稠剂含量为40%时，涂膜表面喷涂纳米SiO_2粒子后形貌最粗糙；随着Si/PU乳液含量的提高，涂层的拉伸强度逐渐降低，而断裂伸长率逐渐增大，涂层的剥离强度先增大后减小，直至趋于平缓。
最后，重点对超临界CO_2快速膨胀法制备超疏水涂层的工艺进行了研究，结果表明：当在喷嘴和釜内温度均为90℃，釜内压力为16MPa，F8261和KH-570配比为1:1，Si/PU乳液添加9%时，涂层的静态水接触角超过165°，所制得涂层具有很好的超疏水性。沙漏冲击实验证明：采用超临界CO_2快速膨胀法制备的超疏水涂层，不仅具有优异的耐磨、耐刮伤性，而且该法高效环保，涂层性能优良，适于大面积制备。具有广阔的应用前景。
With the rapid development of technology on modern instrument detection, super-hydrophobic materials are recognized gradually in depth, its broad application prospects havecaused great interest of national scientists. Although there are dozens of preparation of super-hydrophobic coating, without a super-hydrophobic products are universally applied. The mainreason is that the process conditions led to the not a large area of preparation, durability andscratch resistance of super-hydrophobic coating using existing preparing methods are poor,which resulting super-hydrophobic coating not be a long time applications. Therefore, explorea large area preparation of super-hydrophobic coating with low-cost, simple technology, gooddurability, and excellent mechanical properties is the focus and difficulty of the currentresearch.
Firstly, nano-SiO_2particles were prepared with the surface grafted fluorine couplingagents and double bond by using surface modification technology. Dispersion effect ofnano-SiO_2particles were studied in different solvents ultrasound cavitations. Test resultsshowed in infrared spectroscopy, TEM and laser particle size distribution analyzer that bothF8261and KH-570have been grafted onto the surface of nano-SiO_2, particle size anddistribution of nano-SiO_2after modified by the two coupling agent became smaller and morenarrow; Tg-DSC analysis showed that when the amount of the coupling agent is up to10%,fluorine coupling agent and double bond grafted onto surface of nano-SiO_2particles reach thesaturation. Dispersion characteristics of nano-SiO_2particles in supercritical CO_2were studiedby light scattering theory of sol dispersion, concentration and particle size of SiO_2insupercritical CO_2, the change mechanism of supercritical CO_2micro-emulsion color, and wereexplored. The results showed that emulsion is blue in a temperature from70°C to90°C and apressure range from12MPa to16MPa region, particle size of the nano-particles is the smallest,in which the dispersibility of nano-SiO_2particles in supercritical CO_2is preferably.
The aqueous polyurethane(WPUA) emulsion with high solid content-low viscosity anddouble bond capped were prepared by stepwise polymerization and the self-emulsifying usingpolyethyleneglycol lows ulfonicacidtype polyesterdiol(DPSA) and1,4-butenediol-2-sulfonate(BDSA) as mixed hydrophilic chain extender, a methacrylic acid-of β-hydroxyalkylmethacrylate (HEMA) as a double bond in the terminal blocking agent. Influences of the massratio of DPSA and BDSA on properties of polyurethane emulsions were analyzed. The resultsshowed that obtained emulsions were multivariate distribution in particle size and werespherical particles approximatively. Emulsions exhibit a pseudo-plastic behavior. It wasnoticed that with increasing proportion average, particle diameter became bigger,poly-dispersion became wider, and when the mass ratio of DPSA and BDSA ranges from2/10to8/10, solid concent of emulsions first increase and then decrease. When the mass ratio ofDPSA and BDSA is5/10, solid concent reaches above54%, but still have good fluidity, andcould meet the requirements of the base material of the super-hydrophobic coating. Becausethe stability mechanism of WPUA emulsion depends on the role of electrostatic stabilizationand steric stabilization role, and the surface of the particles is “hair-double layer structure”,WPUA emulsion has a better electrolyte resistance, anti-freeze resistance, high temperatureand storage stability.
In order to improve the hydrophobicity of the coating, a polyol consists of siliconechains and epoxy acrylate structures, referred to as PES, and was used to prepare cross-linkedSi/PU emulsion. Both PES and propylene oxide glycol (PPG) were mixed as soft segments.Formation mechanism of the emulsion and the effects weight ratio of PES to PPG onproperties of the resultant polyurethane dispersions were studied. It is shown that theformation of the Si/PU emulsion, essentially due to the exist of PU polymer surfactant, so thatthe hydrophobic PES/PU macromolecules are dispersed the water to in uniformly. In theSi/PU emulsion structure system, and molecular structure of the PU polymer surfactant doesnot belong to a “multi-block” model, but belongs to the “branched-structure” model. It isfound that the Si/PU dispersions possessed wider particle size distribution and higher averageparticles diameter due to the use of PES which contains cross-linked silicone side chains. The Si/PU dispersions have higher solid content. When the ratio of PES and PPG is5:10, solidcontent of the Si/PU dispersions is up to58%. It is also noticed that apparent viscosity of theSi/PU dispersions decreased with increasing PES to PPG ratio. In addition, stability of theemulsions decreases slightly at high temperature and low temperature, however, which canmeet the basically requirements. Overall contact angle of the film prepared is more than90°,which shows polyurethane film are basically able to exhibit good hydrophobic properties, andis conducive to preparation of polyurethane super-hydrophobic coating.
Super-hydrophobic substrate coating thickening lotion was designed and synthesizedusing emulsion polymerization. The effects selection and amount of monomer on thethickening properties of the emulsion were studied. It is shown that emulsion stability isquite good using BEM+and PinPin20+SE-10as emulsifier, even in the case of the minimumamount of0.3%, in emulsion the only small amount of precipitation produce. Before the pHvalue of is less than4, the viscosity decreases with the pH value change slowly, the viscosityincreases sharply when the pH>4.5, the viscosity reached maximum at pH=7.5, then theviscosity decreases as the pH value increasing.
A Super-hydrophobic substrate coating was prepared by mixing the doublebond-terminated polyurethane (WPUA) emulsions, silicone/polyurethane (Si/PU) emulsion,and acrylic thickening emulsion in proportion, and swapping the pH value thickening to acertain viscosity. Subsequently, the nano-silica particles were injected onto surface of thepolyurethane coating making use of rapid expansion of supercritical CO_2, and then were UVdried towards forming a stable rough structure because for the nano-silica particles beinggrafted on the polyurethane coating. This way, a SiO_2/PU film with super-hydrophobic surfacewas obtained. The relationship between the content of thickener and viscosity of the substratecoating was studied SEM analysis showed that when content of the thickener is40%, thesurface morphology of coating with nano-SiO_2particles is the most rough. The influence ofthe thickness of the coating and UV irradiation time on the curing rate and curing efficiencywere studied. With the content of Si/PU emulsion increasing, the tensile strength of thecoating is gradually reduced, and elongation at break gradually increasing, the peel strength of the coating first increases and then decreases until it leveled off.
The process of preparing super-hydrophobic coating by the rapid expansion ofsupercritical CO_2was studied, the results showed that: the static water contact angle of thecoating can be up to (169.1±0.6)°, when temperature of the nozzle and the reaction kettle areall90℃, the reaction kettle pressure is16MPa, and ratio of F8261and KH-570is1:1. Theobtained films have a good super-hydrophobic, and have excellent scratch resistance.Increasing F8261coupling agent, the water contact angle of coating gradually increases, afterflatten. The addition of9%Si/PU emulsion, water contact angle of the super-hydrophobiccoating prepared exceeds165°. In addition, hourglass shock experiments showed thatsuper-hydrophobic coatings have very excellent wear resistance, scratch resistance, andsuper-hydrophobic coating is environmental, but also could be produced cost-effectively inlarge scale.
引文
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