碳钢表面电镀Ni-TiO2镀层硬脂酸修饰制备超疏水表面

目的 在碳钢基体上制备超疏水表面,提高碳钢的耐海水腐蚀性能。方法 采用恒电流沉积结合硬脂酸修饰的方法,在碳钢表面制备超疏水Ni-TiO2复合镀层。通过扫描电子显微镜（SEM）、EDS能谱分析、傅里叶红外光谱仪（FTIR）、X射线衍射仪（XRD）,对样品的形貌、化学组成及晶型结构进行分析。通过接触角测量仪、自清洁测试,对试样的表面润湿性及自清洁性进行分析。利用电化学工作站测量样品的电化学阻抗谱和极化曲线,从而对样品的耐蚀性进行评价。结果 制备的Ni-TiO2复合镀层呈球形微纳米粗糙结构。经硬脂酸修饰后,接触角高达160.99°,具有良好的超疏水性和自清洁性能。制备的超疏水Ni-TiO2复合镀层在3.5%NaCl溶液中的自腐蚀电流密度为2.42×10-8 A/cm2,腐蚀速率为2.84×10-4 mm/a,对裸碳钢的缓蚀效率为99.41%,具有优异的腐蚀保护作用。此外,在3.5%NaCl溶液中浸泡60天后,超疏水Ni-TiO2复合镀层的电荷转移电阻Rct变化很小,镀层没有破损,具有长期防腐蚀性能。结论 在碳钢表面通过恒电流电沉积结合硬脂酸修饰制备的超疏水表面,能长期有效地提高碳钢对海水的耐腐蚀性能。     

Fabrication and properties of the superhydrophobic ceria-based composite coating on magnesium alloy

A superhydrophobic ceria-based composite coating is developed to improve anticorrosion properties of AZ61 magnesium alloy, fabricating via chemical conversion method followed by hydrothermal treatment. The cerium conversion coating has a block structure with microcracks. After the hydrothermal treatment, a dense CeO₂ layer, porous CeO₂ nanorods, and stearic absorbing layers are grown stepwise on the conversion coating. And the composite coating is hydrophobic or even superhydrophobic and has almost no microcracks. As the hydrothermal reaction time increases, the water contact angle of the composite coating first increases and then decreases, and it reaches the maximum value of 152° after hydrothermal treatment for 4 h. Both the dense CeO₂ layer and the superhydrophobic stearic absorbing layer can effectively prevent the electrolyte from contacting the substrate; the corrosion current density of the superhydrophobic composite coating is lower than that of the hydrophilic composite coating and the cerium conversion coating, and has the best corrosion resistance.     

超疏水Co-MoS2复合镀层的制备及其性能

采用一步电沉积法制备了具有优异耐磨耐蚀的超疏水Co-MoS₂复合镀层。利用扫描电镜、X射线衍射仪、激光共聚焦显微镜、接触角测试仪及电化学工作站等系统研究了电流密度和电沉积时间对复合镀层的微观形貌结构、润湿性、自清洁效果、耐磨和耐蚀性能的影响规律及机理。结果表明,当电流密度为20 A/dm²,电沉积时间为30 min时,Co-MoS₂复合镀层实现超疏水效果,接触角达到最大值约151.4°,具有良好的自清洁防污性能。在2.5 kPa压力下与800 目砂纸摩擦1200 mm后,镀层表面仍具有高于146°接触角的良好疏水性,表现出优异的耐磨性能。该超疏水复合镀层还具有较好的耐腐蚀性能。一步电沉积法简单、经济高效且环保制备了高性能超疏水复合镀层,可望实现超疏水材料的实际应用。     

超疏水超亲油Cu-Ni复合镀层的制备及油水分离应用

针对目前超疏水超亲油表面制备工艺复杂、成本高等问题,采用工艺简单、可控性强的电化学沉积法制备出不锈钢网基底超疏水超亲油表面。通过在不锈钢网表面进行铜镍共沉积,得到一种叶片状的微纳米级粗糙结构,再利用正十二硫醇乙醇溶液对镀层进行表面修饰,最终获得超疏水超亲油Cu-Ni复合镀层。利用扫描电子显微镜(SEM)、接触角测试仪、X射线能谱仪(EDS)、傅里叶变换红外光谱仪(FT-IR)等对镀层表面微观形貌、浸润性以及化学元素组成进行表征分析。结果显示,制备的Cu-Ni复合镀层水接触角为155°±2°,油接触角为0°。对润滑油油水分离效率高达98%,且连续分离2 h后,分离效率仍高于95%,表现出稳定高效的油水分离性能。该制备方法耗时短、成本低,有潜力应用于规模化工业生产。     

修饰不同微结构对疏水性表面浸润性的影响

目的研究修饰微结构对疏水性材料表面浸润性的影响并指导制备超疏水表面。方法基于有限元软件建立了水滴在修饰不同微结构的疏水性表面的润湿模型,通过水滴表观接触角衡量分析了疏水材料表面修饰单一粗糙结构和复合粗糙结构对疏水性提升的效果,利用硅树脂掺杂微粒制备了不同粗糙度的疏水性涂层,涂层固化后测试其实际接触角大小,并与仿真结果对比。结果仿真结果显示,对水滴接触角为100°的表面修饰单一粗糙结构后,由于微结构形成的凹槽滞留空气,阻碍了水滴在表面铺展,使得水滴在表面的接触角增大至133°。在原微结构基础上修饰更小一级的微结构后,水滴在表面的接触角达168°,材料表面达到超疏水效果。实验中,随涂层表面粗糙度的提升,水滴在表面的接触角逐渐增大,掺混两种微粒的疏水涂层固化后,表面形成复合微观结构,水滴接触角达162°,与仿真结果拟合较好。结论在疏水性表面修饰微结构可显著提升其表面疏水性,修饰复合结构后可达到超疏水效果,此方法可用于实际工程制备超疏水表面。     

Corrosion behavior of carbon steel protected with single and bi-layer of silane films filled with silica nanoparticles

The electrochemical behaviour of carbon steel coated with bis-[trimethoxysilylpropyl]amine (BTSPA) filled with silica nanoparticles in naturally aerated 0.1 mol L^− 1 NaCl solutions was evaluated. The coating was prepared by adding different concentrations of silica nanoparticles (100, 200, 300, 400 and 500 ppm) to the hydrolysis solution and then a second layer without silica nanoparticles was applied. The electrochemical behavior of the coated steel was evaluated by means of open-circuit potential (E_OC), electrochemical impedance spectroscopy (EIS) and polarization curves. Surface characterization was made by atomic force microscopy (AFM), and its hydrophobicity assessed by contact angle measurements. EIS diagrams have shown an improvement of the barrier properties of the silane layer with the silica addition, which was further improved on the bi-layer system. However, a dependence on the filler concentration was verified, and the best electrochemical response was obtained for samples modified with 300 ppm of silica nanoparticles. AFM images have shown a homogeneous distribution of the silica nanoparticles on the sample surface; however particles agglomeration was detected, which degraded the corrosion protection performance. The results were explained on the basis of the improvement of the barrier properties of the coating due to the filler addition and on the onset of defective regions on the more heavily filled coatings allowing easier electrolyte penetration.     

基于超疏水和卤代过氧化物酶活性协同防污的氧化铈纳米涂层研究

目的 将特定防污功能的纳米粒子引入到环氧复合涂料中,制备具有超疏水和卤代过氧化物酶活性协同防污的氧化铈纳米涂层。方法 以环氧树脂和羟基封端的聚二甲基硅氧烷为基质,球形氧化铈（CeO₂）纳米颗粒为填料,采用溶液共混的制备方式,通过空气喷涂法构建氧化铈超疏水纳米涂层。借助X射线衍射仪、扫描电子显微镜、接触角测试仪等设备对涂层进行表征,并以典型海洋污损生物芽孢杆菌和三角褐指藻为研究对象分析涂层的防污性能。结果 当涂层中纳米氧化铈的质量分数为55%时,氧化铈纳米涂层具有超疏水特性,接触角达到153°,接触角滞后低至3°。在防污性能方面,相比于环氧复合涂层,超疏水氧化铈纳米涂层对三角褐指藻和芽孢杆菌的防污率分别为97.5%和97.3%。在存在过氧化氢和溴化铵的条件下,失去疏水性能的氧化铈涂层通过卤代过氧化物酶的活性减少了96.2%的三角褐指藻和96.8%的芽孢杆菌贴附。结论 该体系所构建的纳米涂层在初期可以利用其超疏水性能防污,后期利用其卤代过氧化物酶的活性防污,实现防污的长效性。     

超亲水/超疏水镍-纳米三氧化钨复合镀层的制备及特性分析

硬度高、寿命长、适用范围广的金属基自清洁表面的制备是国内外研究的热点和难点。以镍为金属基体,纳米三氧化钨（WO₃）作为功能性材料,采用复合电沉积法在金属基底上制备出超亲水或超疏水可选择的镍-纳米三氧化钨自清洁镀层。使用SEM、S-neox 三维光学轮廓仪、EDS、接触角测量仪等测量其表面形貌特征、力学性能、表面润湿性及光催化性能。结果表明：WO₃质量分数为17%时的镍-纳米三氧化钨复合镀层表面呈现典型的微纳米分级结构特征和超亲水润湿特性,并具有光催化降解甲基橙溶液能力;经氟化处理,复合镀层由超亲水转变为超疏水,接触角高达156.5°;经电化学刻蚀-氟化处理,复合镀层的疏水能力更强,光催化性更好;制备的复合镀层具备超亲水或超疏水特性,具有硬度高、与金属基体结合力大、光催化降解有机物等更加优异的自清洁性能。     

碳钢表面防腐超疏水TiO_2/PDMS涂层的制备及性能

针对碳钢腐蚀电位相对更负、更容易发生腐蚀的特点,在Q235钢表面制备超疏水TiO_2/PDMS涂层以提高其耐蚀性能。采用表面活性剂分散纳米TiO_2并进行改性,然后与PDMS混合,用溶胶凝胶法在Q235钢表面制备有聚二甲基硅氧烷(PDMS)过渡层的TiO_2/PDMS超疏水涂层。借助扫描电镜(SEM)、接触角测量仪、红外光谱(FT-IR)及X射线衍射仪(XRD)表征其表面涂层的表面形貌、化学成分及疏水性能,用电化学试验和浸泡试验测试其防腐性。结果表明:TiO_2/PDMS涂层表面具有独特的微纳结构,与水的接触角达到154.3°;其腐蚀电位由碳钢的-0.77 mV正移至超疏水涂层的-0.24 mV,腐蚀电流密度则下降两个数量级,即从5.02×10~(-6)A·cm~(-2)下降至3.95×10~(-8)A·cm~(-2);超疏水涂层的交流阻抗值高于碳钢基底3个数量级。经过7 d的3.5wt.%NaCl溶液浸泡,超疏水涂层并未发生失重。制备的TiO_2/PDMS超疏水涂层具有超疏水效果和良好的长期耐腐蚀性。     

自相似双层结构自修复超疏水涂层的制备及性能

目的 研究自修复超疏水复合涂层的制备工艺及自修复性能.方法 将环氧树脂、中性硅酮胶和疏水纳米SiO2混合制得涂料底层,纳米SiO2与无水乙醇混合得到涂料面层,采用两步浸涂法在载玻片表面制备出具有自修复功能的自相似双层超疏水涂层.利用扫描电子显微镜、傅里叶变换红外光谱仪和接触角测量仪,对复合涂层的微观形貌、分子结构和润湿...     

Fabrication of patterned TiO2 thin film by a wet process

Hydrophobic/hydrophilic patterned TiO₂ thin film was successfully fabricated on a glass substrate by a wet process. A micro-nano complex structure with a high roughness was fabricated by a layer-by-layer selfassembly and liquid phase deposition (LPD) method. To fabricate superhydrophobic TiO₂ thin films, TiO₂ nanoparticles were deposited on the surface of (PAH/PAA) thin film by a LPD method and the surface of TiO₂ was modified by a hydrophobic treatment using fluoroalkyltrimethoxysilane. The RMS roughness and water contact angle of the prepared TiO₂ thin film were ca. 65.6 nm and ca. 155°. The superhydrophobic surface exposed to UV light changed to a hydrophilic surface by the photocatalytic property of TiO₂ to decompose a hydrophobic group. Finally, hydrophobic/hydrophilic patterned TiO₂ thin film with a 300 ??m dot size was fabricated. The surface morphology, transmittance, surface roughness and water contact angle of the prepared thin films were measured by a field emission scanning electron microscope, an atomic force microscope, a UV-Vis spectrophotometer and a contact angle meter.     

超憎水SiO2/FEVE复合涂层的制备

目的制备超憎水SiO_2/FEVE复合涂层。方法使用物理混合方式将SiO_2填料加入到成膜物FEVE树脂中,制得超憎水涂料,并通过雾化喷涂在玻璃片上形成超憎水涂层。通过指触法测量了涂层的表干时间,利用接触角测量仪、扫描电镜以及原子力显微镜检测了超憎水SiO_2/FEVE复合涂层的憎水性能与微观形貌,并利用划格法评价了涂层的附着力。结果根据溶解度参数相近以及环保性原则选用了乙酸乙酯与乙酸丁酯的混合溶剂,最终得出超憎水SiO_2/FEVE复合涂料的配方为:100 g FEVE树脂、135 g乙酸乙酯、90 g乙酸丁酯、25 g D-SiO_2、10.5 g HDI。涂料配制完成后,采用大雾化量与大流量结合的喷涂工艺便可完成SiO_2/FEVE超憎水涂层的制备。涂层形成了含有内嵌孔洞的珊瑚状结构,表面呈现为规律交替分布的突起和凹陷区构成的粗糙结构,接触角可达152.8°,滚动角为8°。结论调整溶剂种类与固化剂加入量并未对涂层的结合力或成膜性有所改善,填料比例是影响涂层成膜性与憎水性能的关键工艺参数。涂层表面有序分布的微纳米级凹凸结构形成了超憎水表面所需有效的表面微观粗糙结构,这是涂层具有优良憎水性能的主要原因。     

Preparation and corrosion resistance of superhydrophobic coatings on AZ31 magnesium alloy

In order to improve the corrosion resistance of the Mg alloys, the superhydrophobic coatings on AZ31 Mg alloy were prepared by a two-step process of micro-arc oxidation treatment and superhydrophobic treatment in stearic acid ethanol solution. The effects of voltages, frequencies and treatment time on the contact angle of the superhydrophobic treated sample were investigated. The results showed that with increasing the voltage, frequency and treatment time, all of the contact angles of the superhydrophobic treated sample increased first, and then decreased, reaching the maximum values at 350 V, 1000 Hz and 5 min, respectively. The optimal superhydrophobic coating was mainly composed of MgO and Mg₂SiO₄ phases, with the pore diameter of ～900 nm, the thickness of ～6.86 μm and the contact angle of 156.96°. The corrosion current density of the superhydrophobic AZ31 sample decreased by three orders of magnitude, and the amount of hydrogen evolution decreased by 94.77% compared with that of the AZ31 substrate sample.     

硅橡胶超疏水涂层的撒粉法制备

当前在橡胶基体上构建超疏水表面的方法大多较为复杂,不易制备,研究一种简单方法是十分必要的。以高温硫化硅橡胶(HTV)为基体,把基体打磨后在其表面覆盖一层聚二甲基硅氧烷(PDMS),采用表面撒粉法将二氧化硅(SiO₂)粉末均匀撒在未固化PDMS上,固化后制得HTV/PDMS-SiO₂超疏水表面。采用扫描电子显微镜、三维形貌及接触角测量仪对硅橡胶超疏水涂层的微观形貌和疏水特性进行分析。结果表明：HTV/PDMS-SiO₂超疏水表面构建出许多微纳突起粗糙结构,表面粗糙度Sa达到35.695μm;HTV/PDMS-SiO₂超疏水表面的静态接触角平均值达154.5°,相较于原始硅橡胶平均静态接触角112.4°提升了37.5%;液滴体积一定时,液滴接触到超疏水表面后的铺展直径和第一次弹起高度随着滴落高度的增大而增大;液滴滴落高度一定时,液滴铺展直径和初次弹起高度与液滴体积成正比。利用PDMS固化过程结合撒粉工艺构建超疏水微纳结构,可为硅橡胶超疏水表面研究提供一种简单、低成本方案。     

溶胶-凝胶法制备超疏水性纳米复合防腐涂层

通过溶胶-凝胶旋涂法在不锈钢基底上制备了具有超疏水性能的介孔碳复合SiO2涂层。通过TEM,SEM及静态接触角、电化学测试技术(Tafel和EIS)等对其结构、疏水性能和耐蚀性等进行表征。结果表明:在不锈钢基底上形成了乳突状形貌,水在涂层表面静态接触角达到163°。该超疏水性SiO2/介孔碳复合涂层具有优良的防腐性能。     

超疏水Ni-P-Al2O3纳米复合镀层的制备及耐腐蚀性能研究

为提高45钢基体材料的耐腐蚀性能,采用电化学法与氟硅烷修饰相结合的方式在45钢基体表面制备超疏水Ni-P-Al2O3纳米复合镀层,并对镀层的表面形貌、晶相结构、表面粗糙度、润湿性及耐蚀性能进行了研究。结果表明:采用电沉积法制备的Ni-P-Al2O3镀层表面均匀、致密,且无明显气孔缺陷,接触角测试表明其表面达到了超疏水状态,而经电化学加工后,镀层表面形成不规则的微凹坑结构,表面粗糙度值明显增大。经电化学测试,与普通Ni-P-Al2O3镀层相比,超疏水Ni-P-Al2O3镀层的腐蚀电流密度、腐蚀速率均更小,表现出优异的耐腐蚀性能。     

Spray-Deposition of an Organic/Inorganic Blend for Fabrication of a Superhydrophobic Surface: Effect of Admixing with Silica Aerogel and Modified Silica Nanoparticles

Superhydrophobic and self-cleaning glass slides were fabricated using a facile and low-cost method through spray-coating of four types of blends consisting of stearic acid, the mixture of stearic acid and SiO₂ nanoparticles, the mixture of stearic acid and SiO₂ nanoparticles modified with oleic acid, and the mixture of stearic acid and SiO₂ aerogel onto the surface. The nanocoated surfaces were characterized by attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), thermogravimetric analysis (TGA), and water contact angle (WCA) measurements. The results have shown that the mixture of stearic acid and SiO₂ nanoparticles modified with oleic acid coating possessed the highest contact angle of about 158.6° and a low sliding angle while the mixture of stearic acid and SiO₂ aerogel had an almost similar WCA but with a more satisfactory durability. In contrast, the stearic acid coating alone had a hydrophobic property and the mixture of stearic acid and unmodified SiO₂ nanoparticles showed superhydrophobic properties without any self-cleaning and durability features.

     

Corrosion inhibition using superhydrophobic films

Neutron reflectivity (NR) was used to study the effectiveness of superhydrophobic (SH) films as corrosion inhibitors. A low-temperature, low-pressure technique was used to prepare a rough, highly porous organosilica aerogel-like film. UV/ozone treatments were used to control the surface coverage of hydrophobic organic ligands on the silica framework, allowing the contact angle with water to be continuously varied over the range of 160° (SH) to <10° (hydrophilic). Thin (∼5000 Å) nano-porous films were layered onto aluminium surfaces and submerged in 5 wt% NaCl in D₂O. NR measurements were taken over time to observe interfacial changes in thickness, density, and roughness, and therefore monitor the corrosion of the metal. NR shows that the SH nature of the surface prevents infiltration of water into the porous SH film and thus limits the exposure of corrosive elements to the metal surface.     

镁合金表面自清洁、耐高温复合膜层的制备与表征

目的 在镁合金表面制备自清洁、耐高温复合膜层,拓展镁合金在严酷环境中的应用。方法 采用化学转化-沸水封闭-硬脂酸修饰三步处理,在AZ31镁合金表面制备含有耐高温锆化合物组分的低黏附、超疏水复合膜层。利用场发射扫描电子显微镜(FESEM)表征膜层形貌。利用X射线光电子能谱仪(XPS)表征膜层成分。利用接触角测量仪(CA)和高速摄像机(HSC)表征膜层润湿性和黏附性。以粉笔灰为模拟污染物测试膜层在空气和油相中的自清洁性能。通过高温暴露试验和循环沸水浸泡试验测试膜层的耐高温性能。结果 复合膜层主要由锆/镁的(氢)氧化物及硬质酸盐组成,呈被部分填充的纳米纤维组成的微米网络结构。水在膜层表面的静态接触角为160.4°、滚动角为1°,符合“Cassie-Baxter”模型,膜层具有超疏水、低黏附特性;复合膜层具有优异的自清洁性能和耐高温性能。结论 成功制备了含有耐高温锆化合物组分的低黏附、超疏水复合膜层,该膜层具有自清洁、耐高温性能。     

KCC-1/PVDF超疏水与超滑表面的制备及其性能研究

目的将海胆状纳米二氧化硅(KCC-1)微球掺入聚偏氟乙烯(PVDF)中,制备出KCC-1/PVDF超疏水涂层,并在此基础上利用不同涂层修饰剂修饰,进一步制备出超滑涂层。方法以溴化十六烷基吡啶作为模板,结合煅烧法合成了海胆状KCC-1微球,分散到PVDF溶液中,在镁合金表面制备KCC-1/PVDF涂层,并进一步用不同修饰剂(全氟辛基三乙氧基硅烷(PFOTES)、十六烷基三甲氧基硅烷(HDTES)和二甲基硅油)对涂层表面进行改性。结果经过十六烷基三甲氧基硅烷改性,得到水接触角为155°的超疏水涂层,而灌注二甲基硅油后得到滑动角为4.5°的超滑表面。摩擦磨损实验中,超滑表面的耐磨性优于超疏水表面,优于空白镁合金;防覆冰实验结果表明超疏水和超滑表面能有效延缓液滴在表面结冰。结论KCC-1/PVDF超疏水与超滑涂层能有效地保护镁合金基底,且超滑涂层的防腐蚀性优于超疏水涂层,其腐蚀抑制效率IE分别为100%和98.28%。