水热法制备铝合金超疏水表面及电化学性能研究

在金属表面构建超疏水膜层是一种有效的防腐技术,本文采用水热处理和自组装技术在铝合金表面构建了超疏水膜层来提升铝合金的耐蚀性能. 通过对不同水热时间下制备的铝合金超疏水表面的电化学性能以及表面形貌进行测试分析,发现当水热反应时间为6 h时,制备的超疏水铝合金超疏水性和电化学性能达到最佳,接触角能达到155.5^o,在模拟海水溶液中保护效率能达到99.6%.     

铝合金表面用化学刻蚀和阳极氧化法制备的超疏水膜层的耐蚀性能

通过化学刻蚀和阳极氧化在AA2024铝合金表面制备超疏水表面。当化学刻蚀时间超过3 min时,表面在很宽pH值范围内显示出水静态接触角大于150°。SEM和AFM照片表明化学刻蚀时间决定了试样表面形貌和粗糙度。FTIR用来研究氟硅烷(G502)与AA2024表面的结合。结果说明FAS(氟硅烷)分子与铝合金表面的三氧化二铝发生反应,并在阳极氧化膜层表面展示出优异的结合性能。超疏水表面的耐腐蚀性能通过在质量分数为3.5%的NaCl溶液中进行动电位极化和交流阻抗(EIS)测试。电化学测试结果和等效电路模型显示出超疏水表面显著改善抗腐蚀性能。     

镁合金表面原位生长有机膦酸盐薄膜及耐蚀行为

利用超声辅助的浸渍涂布方法,在AZ91D镁合金表面原位生长了氨基二乙酸亚甲基膦酸镁铝薄膜,其中包含具有纳米尺度的变形六边形板状颗粒。塔菲尔极化曲线、电化学阻抗谱测量表明,修饰后的AZ91D镁合金的耐腐蚀行为依赖于浸渍所用的膦酸浓度、pH值、温度及时间等。在3.5%NaCl溶液中,未修饰的AZ91D其腐蚀活化能是18.1 kJ.mol-1,而在1.5 mmol.L-1膦酸溶液中pH值分别是1.7、11.5时浸渍涂布有机膦酸盐薄膜后,AZ91D的腐蚀活化能分别是27.9、37.8 kJ.mol-1。     

十二烷基苯磺酸钠在AZ31镁合金表面的吸附及其缓蚀作用

采用电化学阻抗谱(EIS)和极化曲线研究十二烷基苯磺酸钠(SDBS)对AZ31镁合金在3.5%(w, 质量分数)NaCl腐蚀介质中的吸附行为及缓蚀作用. 结果表明: SDBS可有效抑制AZ31镁合金在NaCl介质中的腐蚀, 其浓度为0.008 mol·L-1时缓蚀效率可达90%以上; 升高温度并不利于提高SDBS的缓蚀效率. SDBS在AZ31镁合金表面主要发生物理吸附, 吸附过程为放热、熵增的自发过程, 近似符合Langmuir单分子层吸附模型; SDBS为混合抑制型缓蚀剂, 但主要抑制阳极反应.     

阳极氧化AZ91D镁合金在氯化钠稀溶液中的腐蚀行为

利用盐雾实验、极化曲线扫描、电化学阻抗谱和电化学噪声技术等电化学研究方法结合扫描电镜表面观测技术对AZ91D镁合金氧化膜在1%(w)氯化钠溶液中的耐蚀性能进行了评价. 结果表明, 氧化前后的镁合金腐蚀行为发生明显改变, 如未封孔的阳极氧化膜耐中性5%氯化钠盐雾试验时间超过200 h; 氧化后的镁合金自腐蚀电位明显正移, 点蚀诱导期延长; 阳极氧化膜的高频阻抗约为裸露镁合金的数千倍, 这些变化证明阳极氧化处理使镁合金获取了十分优异的耐蚀性能. 首次利用分形维数Df的变化规律初步描述氧化后AZ91D镁合金的腐蚀过程. 可以发现随着浸泡时间的延长, Df呈现出初期快速增长, 随后出现波动, 最后稍有降低的变化过程. 这种现象对应于氧化后AZ91D 镁合金在1%氯化钠溶液中腐蚀的三个阶段.     

Slippery liquid-infused porous surface via thermally induced phase separation for enhanced corrosion protection

Slippery liquid-infused porous surface (SLIPS) is a rising star in corrosion protection owing to its outstanding corrosive medium resistance and self-healing property. The large-area and facile fabrication of SLIPS remains a challenge lying on the way of its practical application. Herein, we develop a novel SLIPS based on a porous polyvinylidene fluoride (PVDF) substrate fabricated by thermally induced phase separation. A sphere-packing structure can be easily obtained by blade-coating followed by cooling. The SLIPS exhibits an extremely low sliding angle of 5.8° so that it can resist the fouling of even the Chinese ink, ascribing to its slippery dynamic surface with low surface energy. We also evaluated the anti-corrosion performance of the SLIPS and superhydrophobic PVDF coating by electrochemical impedance spectroscopy (EIS) and scanning Kelvin probe technique (SKP), both of which exhibited enhanced corrosion resistance in 3.5 wt% NaCl solution due to the physical oil and air barriers against the corrosive medium penetration. Nevertheless, the SLIPS coatings performed outstanding self-healing properties because of the high fluidity of infused oil to recover the surface damages, and the self-healing process was recorded by the SKP.     

铝合金表面改性对有机涂层附着力的影响及腐蚀防护性能研究

利用电化学阻抗（EIS）、扫描微参比技术（SRET）、接触角、粗糙度、附着力、盐雾等测试方法,研究了铝合金阳极氧化与贻贝黏附蛋白（MAP）/CeO₂/硅烷γ-APS（MCA）表面复合修饰的腐蚀防护性能以及对改性聚氨酯涂层附着力和耐蚀性的影响。结果表明,MCA复合膜可抑制铝合金的腐蚀,并具有一定的自修复功能;阳极氧化和MCA表面复合修饰可为铝合金提供有效的早期腐蚀防护作用,且能提高铝合金表面粗糙度和润湿性,显著提升改性聚氨酯涂层在铝合金表面的附着力和耐蚀性,因而结合改性聚氨酯涂层和表面复合修饰可实现对铝合金长期有效的腐蚀防护。     

(NaPO3)6对AZ91D镁合金微弧氧化陶瓷层电化学腐蚀特性的影响

在Na2SiO3-KOH电解液体系中添加一定量的(NaPO3)6, 利用微弧氧化(MAO)技术在AZ91D 镁合金表面制备了原位生长的陶瓷层. 采用动电位极化和电化学阻抗谱(EIS)技术研究了添加(NaPO3)6前后, 制备的陶瓷层在3.5%(w) NaCl溶液中的室温电化学行为. 结果表明, 添加(NaPO3)6后, 陶瓷层的自腐蚀电位显著上升, 自腐蚀电流密度明显减小. 这主要是由于(NaPO3)6增加了反应过程中基体镁合金表面的“氧空位”和溶液中PO3-4的含量, 促使元素Mg在金属/膜层(M/F)界面上快速形成相应氧化物, 从而增加了陶瓷层的厚度和致密性. 根据电化学反应体系和陶瓷层的特殊结构, 建立了合理的等效电路, 并结合EIS 数据, 分析了添加(NaPO3)6提高陶瓷层耐电化学腐蚀性能的机理.     

Effect of Aluminum Alloy Surface Modification on Adhesion of the Modified Polyurethane Coating and Its Corrosion Protective Performance北大核心CSCD

The ordinary organic coatings on aluminum alloy usually encounter a problem of low adhesion to the substrate, which results in destruction and failure of the long-term protective performance of the anticorrosion systems. The surface modification of aluminum alloy is able to enhance the adhesion of organic coating on aluminum alloys, and to improve their protective performance. In this work, a combined surface modification of anodic oxidation and mussel adhesion protein/CeO2/3-aminopropyltriethoxysilane composite film (MCA) was developed on the aluminum alloy. The adhesion of modified polyurethane coated on the treated aluminum alloy and its corrosion protective performance were evaluated comprehensively by using contact angle, adhesion strength, electrochemical impedance spectroscopy (EIS), and scanning reference electrode technique (SRET). The measurements of EIS and SRET demonstrated that the MCA composite film on anodic oxidized Al possessed self-healing function and provided effective protection against early corrosion of aluminum alloy. The pull-off test showed that both anodic oxidation treatment and MCA composite film modification were able to increase the adhesion of modified polyurethane coating on aluminum alloy, and their combined action were supposed to remarkably enhance the adhesion strength up to 17.1 MPa. The reason for the improvement of adhesion was that the anodic oxidation treatment and MCA composite film modification could improve the surface roughness of aluminum alloy, and enhance the surface wettability and surface polarity, which is beneficent to enhance the bonding of the modified polyurethane coating to aluminum alloy surface. The EIS results showed that no any corrosion occurred for the modified polyurethane coating on the treated aluminum alloy during 65 d immersion in 3.5wt.% NaCl solution. The impedance value in low frequency range of the modified polyurethane coating always maintained at a high order of magnitude on the aluminum alloy treated by anodic oxidation and MCA composite film modification, showing an excellent protective performance of the coating system. The evaluation of Neutral Salt Spray (NSS) indicated that the modified polyurethane coating on the treated aluminum alloy owned superior corrosion protection performance, and the adhesion strength remained 13.1 MPa and no any corrosion was found at the scratch locations even after 1200 h of salt spray testing. It was concluded that combination of anodic oxidation and MCA composite film were capable of significantly improving the adhesion of modified polyurethane coating on aluminum alloy and providing long-term effective corrosion protection for aluminum alloy. © 2021 Authors. All rights reserved.     

Superhydrophobic ceria on aluminum and its corrosion resistance

Superhydrophobic ceria on the aluminum substrate was fabricated, and its corrosion resistance was investigated by different techniques. For example, the so‐obtained superhydrophobic sample was immersed into the NaCl aqueous solution, and the variations in the surface wettability as well as the surface morphology were monitored; potentiodynamic polarization in the NaCl aqueous solution was adopted to evaluate its electrochemical corrosion resistance; a droplet of the aqueous solution HCl was dripped onto the superhydrophobic surface, and the corrosion process as well as the surface morphology after corrosion was monitored. The experimental results showed that the superhydrophobic ceria possessed a good corrosion resistance because of the entrapped air in the solid/liquid interface. Copyright © 2016 John Wiley & Sons, Ltd.     

AZ31镁合金表面聚吡咯的化学氧化合成及其耐蚀性能

以对甲苯磺酸钠为掺杂剂, 三氯化铁为氧化剂, 用化学氧化聚合法在AZ31 镁合金表面制备聚吡咯(PPy)膜. 采用傅里叶变换红外(FTIR)光谱分析了镁合金表面聚吡咯膜结构, 通过电化学极化曲线、电化学阻抗谱(EIS)研究了其耐蚀性能, 通过扫描电子显微镜(SEM)、X射线能量散射谱(EDS)分析了表面形貌和成分. 和镁合金裸样相比, 聚吡咯膜对镁合金腐蚀有一定的抑制作用. 硅烷预处理改善了镁合金/聚吡咯体系的耐腐蚀性能, 使腐蚀电位较镁合金裸样正移了110 mV, 电流密度减小了约2个数量级.     

Electrochemical and microgravimetric characterization of magnetron-sputtered Fe–Cr–Ni–Ta and Fe–Cr–Ni alloy films in neutral and strongly acidic media

The Fe–Cr–Ni and Fe–Cr–Ni–Ta alloy films were deposited on quartz substrates by magnetron-sputtering using targets of AISI 316 stainless steel and in combination with pure tantalum. The conventional melting of the Fe–Cr–Ni–Ta alloy formed is virtually impossible because the melting point of tantalum is higher than the boiling points of the other components. Elemental content of the films was determined by XPS analysis. Corrosion behaviour of both alloy films was studied in 5% NaCl and 10 M HCl by electrochemical quartz crystal microgravimetry (EQCM), electrochemical impedance spectroscopy (EIS) and dc-voltammetry. The corrosion resistance of Fe–Cr–Ni–Ta appeared to be significantly higher than that of Fe–Cr–Ni in both neutral (5% NaCl) and strongly acidic (10 M HCl) media. The Fe–Cr–Ni–Ta specimen exhibited an extremely high corrosion resistance in 10 M HCl, where the corrosion rates were about one order of magnitude lower than those of Fe–Cr–Ni in neutral solution. EQCM measurements in NaCl solution indicated accumulation of corrosion products on the Fe–Cr–Ni–Ta surface, which was evident from a distinctive increase in electrode mass. By contrast, the mass of the tantalum-free alloy film decreased with a constant rate, which indicated alloy dissolution to prevail. The corrosion current calculated from the mass decrease was in good agreement with that derived from voltammetric measurements. The EQCM data showed that the corrosion resistance of the Fe–Cr–Ni–Ta alloy film in 10 M HCl was about two orders of magnitude higher than that of the Fe–Cr–Ni.     

An Electrochemical Study on the Corrosion Inhibition of Stainless Steel by Polyaniline Film

Polyaniline(PANI)film was electrosynthesized on 304 stainless steel by cyclic voltammetry using aqueous oxalic acid as supporting electrolyte.The potential sweep rates were changed to achieve the PANI film with different thickness and structures.Protective properties of the PANI film for corrosion of stainless steel in 3% NaC1 aqueous solution were investigated by monitoring potentiodynamic polarization curves and electrochemical impedance spectroscopy(EIS).The results showed that the PANI film which was formed with lower sweep rate led to more positive shift of corrosion potential and greater charge transfer resistance,reflecting higher inhibition for corrosion of the stainless steel.     

超疏水性聚苯胺微/纳米结构的合成及防腐蚀性能

以苯胺为单体, 过硫酸铵为氧化剂, 通过改变不同的掺杂剂, 采用"无模板"法合成了具有不同浸润性的聚苯胺微/纳米结构, 并得到超疏水聚苯胺微/纳米结构. 采用红外吸收光谱、 紫外-可见吸收光谱、 X射线衍射及扫描电镜对聚苯胺微/纳米结构及形貌进行了表征, 测定了聚苯胺微/纳米结构的接触角, 并通过Tafel极化曲线和电化学交流阻抗研究了不同疏水性的聚苯胺微/纳米结构在0.1 mol/L H₂SO₄溶液中对碳钢的腐蚀防护作用, 探讨了聚苯胺微/纳米结构的表面浸润性对腐蚀防护性能的影响. 研究结果表明, 随着聚苯胺微/纳米结构疏水性的增强, 对碳钢的腐蚀防护作用增强, 当掺杂剂为全氟辛酸时所制备的超水聚苯胺微/纳米结构表现出最佳的防腐蚀性能(η= 94.70%).     

Formation of superhydrophobic cerium oxide surfaces on aluminum substrate and its corrosion resistance properties

Superhydrophobic cerium oxide film was introduced to aluminum substrate by an in‐situ growth process and surface modification. Different molar ratios between Ce(NO₃)₃ · 6H₂O and C₆H₁₂N₄ were involved in this research. The morphologies, chemical compositions and wetting properties of the films were analyzed by scanning electron microscopy (SEM), energy dispersive X‐ray detector, Fourier transfer infrared spectrometer and water contact angle (WCA) measurement, respectively. A great WCA of 158.8^o with a low angle hysteresis of about 3^o was obtained. Combination of uniform hierarchical micro‐nanostructure as revealed by SEM together with the hydrophobic alkyl groups from stearic acid was found to be responsible for the superior superhydrophobic property. The corrosion resistance performance of the superhydrophobic surface was evaluated by immersing in sodium chloride aqueous solution, the WCA kept as high as 152.1^o after immersion for 21 days, indicating our superhydrophobic surfaces had high chemical stability and durability in corrosive medium. Copyright © 2013 John Wiley & Sons, Ltd.     

AZ31和AZ61镁合金在模拟海水中的腐蚀电化学行为

应用极化曲线、电化学阻抗谱方法研究了两种Mg-Al-Zn系合金——AZ31和AZ61在模拟海水中的腐蚀电化学行为.根据两种镁合金在浸泡过程中腐蚀介质pH值的变化以及扫描电子显微镜对合金微观金相组织和腐蚀形貌的观察,讨论了镁合金的腐蚀机理及合金元素Al的含量对镁合金耐蚀性能的影响.结果表明,AZ61镁合金具有比AZ31镁合金更好的耐蚀性能,其原因主要是AZ61镁合金中Al含量较高使合金的微观组织结构更有利于耐蚀性能的提高.     

AM60镁合金在汽车发动机冷却液中的腐蚀电化学行为

研究AM60镁合金在3种(A、B、C)市售汽车发动机冷却液中的腐蚀电化学行为.极化曲线、电化学阻抗谱测试表明,冷却液A对AM60镁合金的腐蚀性最强,B腐蚀性略低于A,C腐蚀性最弱,最适于镁合金汽车发动机使用.冷却液对发动机镁合金材料的腐蚀性与其电阻有关系,电阻越大,腐蚀性越小;冷却液中的乙二醇和添加剂组分在镁合金表面的竞争吸附对镁合金的腐蚀行为也有重要影响.     

Corrosion behavior of AZ91D magnesium alloy in distilled water

The corrosion of AZ91D magnesium alloy has received extensive attention due to the continuous expansion of its application field in recent years. However, the corrosion of AZ91D magnesium alloy in distilled water is relatively few. In this paper, the corrosion behavior of AZ91D magnesium alloy was studied in distilled water by electrochemical tests in combination with weight loss and surface analysis methods. The results indicated that the corrosion rate of AZ91D magnesium alloy increased with the increase of temperature and immersion time. The increase of the corrosion rate of AZ91D magnesium alloy with the increase of immersion time might be attributed to the damage of the structure of corrosion product film by hydrogen evolution, significantly accelerating the anodic process of AZ91D magnesium alloy. It was interesting that, in distilled water, the EIS of AZ91D magnesium alloy excluded an inductive arc in the low frequency region, which indicated that there was no the adsorption and desorption of aggressive ions or the damage and repair of film. The corrosion product film of AZ91D magnesium alloy in distilled water was composed of a compact inner corrosion product film and a loose outer corrosion product film.     

覆铜板在NaCl溶液中的腐蚀电化学行为

应用线性极化、循环伏安(CV)及电化学阻抗谱(EIS)等电化学方法对覆铜板(CCL)和纯铜的腐蚀电化学行为进行了研究和比较. 结果表明, 覆铜板的耐蚀性弱于纯铜, 其阳极溶解过程与纯铜有所不同; 在较低电位下, CCL 以铜的氯化络合物的形式溶解, CuCl-2的扩散为该过程的控制步骤; 随着电位的升高, 腐蚀产物CuCl在电极表面形成疏松多孔的膜, Cl-在膜中的传输成为溶解过程的控制步骤. 电极表面CuCl 膜的消长过程是产生感抗弧的主要原因.     

One‐step immersion method for fabricating superhydrophobic aluminum alloy with excellent corrosion resistance

This work develops a facile one‐step immersion method for preparing the superhydrophobic aluminum alloy, i.e. the aluminum alloy is treated with stearic acid (STA)–ethanol–H₂O solution at 60 °C for 35 h. Results show that the aluminum alloy achieves flower‐like structure with both a great deal of pillars and pores, while the long hydrophobic alkyl chains are chemically grafted onto the hierarchical surface. Meanwhile, the water contact angle at the aluminum alloy surface gradually enhances with the decrease of the ethanol–H₂O volume ratio, and the water contact angle and rolling angle of 156.2° and 5°, respectively, are obtained when the ethanol–H₂O volume ratio is 1:3. Moreover, results show that the higher water contact angle at the aluminum alloy, the better corrosion resistance of the aluminum alloy. Consequently, the aluminum alloy with the superhydrophobic property has the best corrosion resistance, durability, and stability in corrosive environments. Copyright © 2016 John Wiley & Sons, Ltd.