Plasma electrolytic oxidation of AZ91D magnesium alloy in biosafety electrolyte for the surgical implant purpose

Plasma electrolytic oxidation (PEO) of AZ91D magnesium alloy in biosafety electrolyte was studied. The prepared PEO coating and its stability in the simulated body fluid (SBF) were investigated by scanning electron microscopy (SEM), X-ray diffraction (XRD), energy dispersive spectrometry (EDS), potentio-dynamic polarization, electrochemical impedance spectroscopy (EIS) and immersion test. The SEM results show that a kind of smooth, compact and well adhesive PEO coating is prepared in the proposed biosafety electrolyte. The electric analytical results show that the corrosion resistance of the PEO coating is excellent even in harsh environment. Immersion test shows that the PEO coating is stable enough in the SBF solution. The weight loss, the average corrosion rate and the pH variation of the PEO treated magnesium alloy are far lower than the untreated ones. From these highly positive results, the proposed PEO process is promising in the treatment of the surgical magnesium alloy materials.     

Bioactivity Performance of Pure Mg after Plasma Electrolytic Oxidation in Silicate-Based Solutions

The biodegradable metals, including magnesium (Mg), are a convenient alternative to permanent metals but fast uncontrolled corrosion limited wide clinical application. Formation of a barrier coating on Mg alloys could be a successful strategy for the production of a stable external layer that prevents fast corrosion. Our research was aimed to develop an Mg stable oxide coating using plasma electrolytic oxidation (PEO) in silicate-based solutions. 99.9% pure Mg alloy was anodized in electrolytes contained mixtures of sodium silicate and sodium fluoride, calcium hydroxide and sodium hydroxide. Scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), contact angle (CA), Photoluminescence analysis and immersion tests were performed to assess structural and long-term corrosion properties of the new coating. Biocompatibility and antibacterial potential of the new coating were evaluated using U2OS cell culture and the gram-positive Staphylococcus aureus (S. aureus, strain B 918). PEO provided the formation of a porous oxide layer with relatively high roughness. It was shown that Ca(OH)₂ was a crucial compound for oxidation and surface modification of Mg implants, treated with the PEO method. The addition of Ca²⁺ ions resulted in more intense oxidation of the Mg surface and growth of the oxide layer with a higher active surface area. Cell culture experiments demonstrated appropriate cell adhesion to all investigated coatings with a significantly better proliferation rate for the samples treated in Ca(OH)₂-containing electrolyte. In contrast, NaOH-based electrolyte provided more relevant antibacterial effects but did not support cell proliferation. In conclusion, it should be noted that PEO of Mg alloy in silicate baths containing Ca(OH)₂ provided the formation of stable biocompatible oxide coatings that could be used in the development of commercial degradable implants.     

Active protective Al–Ce alloy coating electrodeposited from ionic liquid

The electrochemical co-deposition of Al–Ce metallic protective coating with active inhibiting effect was performed for the first time using an ionic liquid as an electrolyte. Cerium was successfully co-deposited with aluminium on surface of Pt and AA2024 aluminium alloy forming uniform films with globular micro-structure and thickness up to 75 μm.Cerium was introduced into the aluminium coating as a potential corrosion inhibitor which can be liberated during sacrificial dissolution of the galvanic layer deposited on the alloy surface. The released inhibitor provides an additional active corrosion protection slowing down the corrosion processes in the defects.     

A facile method for fabrication of superhydrophobic coating on aluminum alloy

A superhydrophobic coating applied in corrosion protection was successfully fabricated on the surface of aluminum alloy by chemical etching and surface modification. The water contact angle on the surface was measured to be 161.2° ± 1.7° with sliding angle smaller than 8°, and the superhydrophobic coating showed a long service life. The surface structure and composition were then characterized by means of SEM and XPS. The electrochemical measurements showed that the superhydrophobic coating significantly improved the corrosion resistance of aluminum alloy. The superhydrophobic phenomenon of the prepared surface was analyzed with Cassie theory, and it was found that only about 6% of the water surface is in contact with the metal substrate and 94% is in contact with the air cushion. Copyright © 2011 John Wiley & Sons, Ltd.     

Facile Spray-Coating for Fabrication of Superhydrophobic SiO2/PVDF Nanocomposite Coating on Paper Surface

A facile and low-cost superhydrophobic nanocomposite coating on paper surface was fabricated through one-step simply spraying dispersion, using hydrophobic silica nanoparticles as a filter (SiNPs) and polyvinylidene fluoride (PVDF) as a film-forming material. Hydrophobic SiNPs were fabricated via co-hydropholysis and condensation of TEOS and long-chain alkyl silane based on a simple sol-gel process, and the surface chemical structure of SiNPs was characterized by Fourier transform infrared (FTIR) spectra. The wettability and morphology of the coating surface were measured by contact angle (CA) measurement and scanning electron microscope, respectively. The influence of the mass ratio of hydrophobic SiNPs to PVDF (M(SiNPs:PVDF)) on the superhydrophobicity of paper surface was studied. The results showed that when M(SiNPs:PVDF) was 3:1, the water CA was 156.0 ± 1.0° for the nanocomposite coating with micro/nano-hierarchical structure on paper surface. Further, such superhydrophobic nanocomposite coatings on paper surface showed little adhesive property with water. In addition, the prepared superhydrophobic nanocomposite coating could be applied in other substrates, such as wood, aluminum sheet, stainless steel, polytetrafluoroethylene (PTFE), etc.     

Electrochemical corrosion behavior of nanocrystalline zinc coatings in 3.5% NaCl solutions

The corrosion behavior of electrodeposited nanocrystalline (NC) zinc coatings with an average grain size of 43 nm was investigated in 3.5% NaCl solutions in comparison with conventional polycrystalline (PC) zinc coatings by using electrochemical measurement and surface analysis techniques. Both polarization curve and electrochemical impedance spectroscopy (EIS) results indicate that NC and PC coatings are in active state at the corrosion potentials, and NC coatings have much higher corrosion resistance than PC ones. The corrosion products on both coating surfaces are mainly composed of ZnO and Zn₅(OH)₈Cl₂·H₂O, but the corrosion products can form a relatively more protective layer on NC coating surfaces than on PC coatings. The EIS characteristics and corrosion processes of PC and NC zinc coatings during 330 h of immersion were discussed in detail.     

(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 the feeding mode of cross-linker and microcapsule on the corrosion resistance and hydrophobicity of composite coatings

The interface combination of anti-corrosive materials and polymer matrix has a significant effect on the overall performance of the composite coating. However, past research has focused on blending anti-corrosive materials to improve the performance of the polymer matrix. Herein, we proposed a layer-by-layer spray-coating process to further enhance the reinforcing effect of anti-corrosive materials on the polymer matrix by changing their feeding modes. In this paper, taking waterborne polyacrylate (WPA) as an example, two kinds of reinforcement materials commonly used to improve the corrosion resistance of polymer matrix were introduced into the coating system and then applied to the tinplate: cross-linker and microcapsule. Firstly, five types of WPA composite coating systems were designed according to the feeding mode of aziridine cross-linker and the position of benzotriazole@zinc oxide microcapsules (BTA@ZnO MCs). Electrochemical impedance spectroscopy (EIS) and electrical equivalent circuits were used to evaluate the corrosion resistance of these composite coating systems and analyze their electrochemical processes. By spraying the mixture of WPA and aziridine crosslinker as the bottom layer and BTA@ZnO MCs as the top layer, the resulting composite coating exhibited higher corrosion resistance and hydrophobic properties. Scanning electron microscope (SEM) and contact angle tests indicated that the feeding mode of aziridine cross-linker and the position of BTA@ZnO MCs played important roles in the compactness and hydrophobicity of the composite coating. Subsequently, the effects of the amount of aziridine cross-linker and BTA@ZnO MCs on the corrosion resistance and physical properties of the composite coating were further analyzed by EIS, water absorption test, contact angle test and atomic force microscopy (AFM). The significant improvement in the corrosion resistance of this composite coating was mainly attributed to the synergistic effect of highly cross-linked network structure and superhydrophobic surface.     

Optimisation of the plasma electrolytic oxidation process efficiency on aluminium

Plasma electrolytic oxidation (PEO) is a surface treatment technology enabling fabrication of adherent thick (50–150 µm) coatings on light metal alloys with significantly enhanced hardness, wear and corrosion resistance compared with other conventional treatments. The technology has the potential to play a significant role in the transport sector for replacement of steel with light‐weight materials of improved durability. A main limitation of PEO lies in its relatively high cost, associated with high energy consumption and low coating efficiency. The present work explores possible routes to improve the process efficiency. It is shown that a combination of conventional pre‐anodising with sequential PEO treatment reduces specific energy consumption up to five times because of an increase of the coating growth rate, up to 10 µm/min, compared with existing PEO processes. A further approach to improved coating efficiency involves PEO in electrolytes with suspended fine or nanoparticles, which results in the formation of thicker coatings in reduced time as a result of the incorporation of the particles from the electrolyte into the coating. Additionally, melting of the coating material during the micro‐arc discharge process leads to formation of stabilised high‐temperature phases, such as tetragonal and cubic zirconia, which provide significantly improved microhardness of the coating material and give a potential for thermal barrier applications. Copyright © 2009 John Wiley & Sons, Ltd.     

Anticorrosion composite coatings on biodegradable Mg alloys: Electrochemical studies

Calcium phosphate coatings consisting of magnesium oxide and hydroxyapatite, which accelerates osteogenesis (bone formation), were formed on magnesium alloys of the Mg–Mn–Ce and Mg–Zn–Zr systems by plasma electrolytic oxidation (PEO). The phase and elemental composition, morphology, and anticorrosion properties of the coatings were studied. Approaches to the formation of composite protective coatings on the basis of the PEO layer using superdispersed polytetrafluoroethylene were developed. Treatment of the PEO-coating with a polymer material reduces the adverse effect of different-level defects. After a single polymer deposition, corrosion protection effect of the composite layer substantially (by more than three orders of magnitude) increases with respect to the base PEO coating.     

One‐step electrochemical deposition to achieve superhydrophobic cobalt incorporated amorphous carbon‐based film with self‐cleaning and anti‐corrosion

Exploiting a superhydrophobic surface is very significant due to its excellent water repellency which has many practical applications in various fields. In this work, the cobalt incorporated amorphous carbon‐based (Co/a‐C:H) film was prepared successfully on Si substrate via a simple 1‐step electrochemical deposition where electrochemical deposition technology was using cobalt (II) acetylacetonate methanol solution as electrolyte under high voltage, atmospheric pressure, and low temperature. Surprisingly, the as‐prepared film showed a superior superhydrophobic surface with a water contact angle of 153 ± 1° and a sliding angle of 7.6° without any further modification of low surface energy materials. Especially, the tape adhesive, corrosion resistance, and self‐cleaning tests demonstrated that the as‐prepared carbon‐based film could possess fairly well adhesion, superior anti‐corrosion resistance, and self‐cleaning ability, respectively. It indicated that the superhydrophobic Co/a‐C:H film might have potential promising applications in the field of anti‐fouling, anti‐corrosion, and drag resistance, such as the above‐deck structures on icebreaker vessels, ship hulls, and offshore wind turbine blades.     

Corrosion resistance and durability of superhydrophobic surface formed on magnesium alloy coated with nanostructured cerium oxide film and fluoroalkylsilane molecules in corrosive NaCl aqueous solution

The corrosion resistant performance and durability of the superhydrophobic surface on magnesium alloy coated with nanostructured cerium oxide film and fluoroalkylsilane molecules in corrosive NaCl aqueous solution were investigated using electrochemical and contact angle measurements. The durability of the superhydrophobic surface in corrosive 5 wt% NaCl aqueous solution was elucidated. The corrosion resistant performance of the superhydrophobic surface formed on magnesium alloy was estimated by electrochemical impedance spectroscopy (EIS) measurements. The EIS measurements and appropriate equivalent circuit models revealed that the superhydrophobic surface considerably improved the corrosion resistant performance of magnesium alloy AZ31. American Society for Testing and Materials (ASTM) standard D 3359-02 cross cut tape test was performed to investigate the adhesion of the superhydrophobic film to the magnesium alloy surface. The corrosion formation mechanism of the superhydrophobic surface formed on the magnesium alloy was also proposed.     

The electrodeposition of composite coatings: Diversity,applications and challenges

A wide range of coatings can be produced by incorporating particles into an electrodeposit. The matrix may be a metal, conductive polymer or conductive ceramic, whereas the particle can be metallic, polymeric, ceramic or combinations of spheroidal, irregular or layered inclusions. Nanostructured, gradient, multilayer and sandwich layer deposit further widen possibilities. Electrochemical approaches to the deposition of composite coatings offer the benefits of good control over deposition rate (hence thickness), coating composition and deposit properties. Both faradaic electrodeposition and electrophoresis are usually involved. This review focuses on nanosized inclusions in a metal matrix over the last two decades. Interactions between bath composition, particle dispersion, operational variables and resultant deposit properties are poorly documented in the literature. Our understanding of the mechanism of composite deposition remains patchy, despite progress and computer models are scarce. Electrode geometry, electrolyte hydrodynamics and current distribution remain poorly treated. Markets in electronics, surface engineering, aerospace, corrosion protection and electrochemical energy conversion have been stimulated by newer uses for self-cleaning, superhydrophobic and biocompatible surfaces. Challenges to be met by further research and development are prioritised.     

特殊浸润性表面的液滴凝结

以铝片为基底, 经电化学腐蚀和沸水处理制备了多级微纳米结构; 通过气相沉积和涂油分别制备了超疏水表面、 疏水超润滑(slippery)表面和亲水slippery表面; 探究了表面不同的特殊浸润性(超亲水、 超疏水、 疏水slippery和亲水slippery)对液滴凝结的影响. 结果表明, 超亲水表面的液滴凝结属于膜状冷凝, 超疏水表面和slippery表面的液滴凝结均属于滴状冷凝. 超疏水表面液滴合并时, 合并的液滴会不定向弹离表面. 疏水slippery表面和亲水slippery表面由于表面浸润性的不同导致液滴成核密度和液滴合并的差异, 亲水slippery表面凝结液滴的最大体积远大于疏水slippery表面凝结液滴的最大体积. 4种表面的雾气收集效率由大到小依次为亲水slippery表面>疏水slippery表面>超亲水表面>超疏水表面.     

Protection of carbon steel with superhydrophobic coating against corrosion in NaCl solution

Corrosion and kinetics of partial electrode reactions on carbon steel St3 with superhydrophobic coatings of three types were studied in 0.5 M NaCl and 50 g/L NaCl +400 mg/L H₂S solutions. The investigations were carried out on electrodes made of carbon steel St3 with a chemical composition, wt. %: C – 0.20; Mn – 0.50; Si – 0.15; P – 0.04; S – 0.05; Cr – 0.30; Ni – 0.20; Cu – 0.20, and Fe – 98.36. To obtain the type I coating, the metal surface was textured by an IR laser radiation of nanosecond duration followed by chemisorption of fluorobutylsilane out of a solution in n-decane. To obtain a coating of type II, a nanoscale composite layer consisting of aggregates of aerosil nanoparticles was applied additionally to the outcome of type I method. To obtain a coating of type III, the metal surface after being textured by the infrared (IR) laser radiation of nanosecond duration was followed by chemisorption of fluoroxy silane. The influence of duration τ of the medium corrosive impact on protective effect of the superhydrophobic coating is considered. It was shown that upon reaching a steady state (after 72 h), the corrosion rate of steel with a superhydrophobic coating of I and II types in a 0.5 M NaCl solution is reduced by 23 ± 3 times compared with unprotected samples. Approximately the same picture is characteristic of electrodes with a coating of type III in a solution of 50 g/L NaCl +400 mg/L H₂S.     

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%).     

铝合金表面超疏水涂层的制备及其耐蚀性能

基于含氟聚氨酯和纳米SiO₂的协同作用, 在铝合金表面成功制备了一层超疏水涂层. 用红外光谱、扫描电镜和电化学测试等技术对超疏水涂层进行了表征和分析. 红外光谱结果表明, 硅烷偶联剂(A1100)成功键合到纳米SiO₂表面. 扫描电镜和接触角测定仪对涂层的表面形貌表征结果表明, 涂层表面存在微米鄄亚微米尺度的粗糙结构, 接触角可达到156°, 滚动角小于5°. 电化学测试(交流阻抗和极化曲线)结果表明, 所得到的涂层极大地提高了铝合金的耐蚀性能.     

电沉积非晶态Ni-W-B/ZrO2复合镀层及其结构与性能

在含有二氧化锆的Ni-W-B电解液中，电沉积获得Ni-W-B/ZrO2复合镀层.用差示扫描量热分析(DSC)、X射线衍射(XRD)、扫描电子显微镜(SEM)和电化学技术较系统地研究了Ni-W-B/ZrO2复合镀层的电沉积、热处理过程，以及镀层的结构、表面形貌、显微硬度和耐腐蚀性能.结果表明, 复合镀层的质量组成为Ni 47.5％、W 40.9％、B 0.9％和ZrO2 10.7％. DSC和XRD结果清楚说明, 二氧化锆对基质Ni-W-B镀层的结构有明显影响, 使得复合镀层的非晶态结构特征更加明显 .复合镀层比Ni-W-B合金有更高的显微硬度, 呈现团粒状结构, 晶块之间不存在裂纹但晶界清晰可辨; 二氧化锆粒子分散于Ni-W-B基质镀层中. 400 ℃、1 h热处理后, Ni-W-B基质镀层中W向镀层表面偏析, 镀层呈现固溶体晶态结构特征, 表面形貌特征基本不变, 复合镀层的显微硬度进一步提高, 抗腐蚀性能增强, 但镀层表层中的二氧化锆粒子大量脱落.     

Facile Electrochemical Method for the Fabrication of Stable Corrosion-Resistant Superhydrophobic Surfaces on Zr-Based Bulk Metallic Glasses

Both surface microstructure and low surface energy modification play a vital role in the preparation of superhydrophobic surfaces. In this study, a safe and simple electrochemical method was developed to fabricate superhydrophobic surfaces of Zr-based metallic glasses with high corrosion resistance. First, micro–nano composite structures were generated on the surface of Zr-based metallic glasses by electrochemical etching in NaCl solution. Next, stearic acid was used to decrease surface energy. The effects of electrochemical etching time on surface morphology and wettability were also investigated through scanning electron microscopy and contact angle measurements. Furthermore, the influence of micro–nano composite structures and roughness on the wettability of Zr-based metallic glasses was analysed on the basis of the Cassie–Baxter model. The water contact angle of the surface was 154.3° ± 2.2°, and the sliding angle was <5°, indicating good superhydrophobicity. Moreover, the potentiodynamic polarisation test and electrochemical impedance spectroscopy suggested excellent corrosion resistance performance, and the inhibition efficiency of the superhydrophobic surface reached 99.6%. Finally, the prepared superhydrophobic surface revealed excellent temperature-resistant and self-cleaning properties.     

Characterization and corrosion resistance of pure Mg modified by micro‐arc oxidation using phosphate electrolyte with/without NaOH

Magnesium and its alloys have been suggested as potential absorbable implant materials due to their excellent biodegradability and biocompatibility. Current researchers focus on reducing the rapid corrosion rate of Mg and its alloys by alloying and surface modification. To improve the corrosion resistance, pure Mg is modified by micro‐arc oxidation (MAO) in phosphate electrolyte containing sodium hydroxide and its properties are compared with those formed using only phosphate or sodium hydroxide as electrolytes. A uniform and stable coating layer is formed on Mg after MAO treatment in phosphate electrolyte containing sodium hydroxide. The corrosion resistance of MAO‐coated Mg is evaluated by potentiodynamic polarization study and immersion test. The results reveal that MAO coating enables a good improvement in corrosion resistance, and among them, coatings treated using phosphate electrolyte containing sodium hydroxide offer the best performance. Copyright © 2013 John Wiley & Sons, Ltd.