20% Al2O3-SiO2(sf)/AZ91D镁基复合材料微弧氧化陶瓷层电化学腐蚀性能

在磷酸盐体系电解液中,对20%(体积分数)硅酸铝短纤维(Al2O3-SiO2)增强AZ91D镁基复合材料进行微弧氧化表面处理获得陶瓷层。利用扫描电子显微镜(SEM)和X射线衍射(XRD)仪分析陶瓷层的表面形貌、截面组织和相组成,采用动电位极化和电化学阻抗谱(EIS)测试评价微弧氧化陶瓷层的电化学腐蚀性能。结果表明,该陶瓷层主要由MgO和MgAl2O4相组成。陶瓷层的腐蚀电流密度比镁基复合材料基体低3个数量级,电化学阻抗大幅升高,耐腐蚀性能明显高于复合材料基体     

Anti-corrosion microarc oxidation coatings on SiCP/AZ31 magnesium matrix composite

The corrosion-resistant ceramic coatings up to 80 μm thick were fabricated on SiC_P/AZ31 magnesium matrix composite by microarc oxidation (MAO) technique in Na₃PO₄ + KOH + NaF solution. The microstructure, composition and phase constituent of ceramic coatings were analyzed by SEM and XRD, and the electrochemical corrosion behaviour of coatings was evaluated by the electrochemical polarization method. The thicker coating is compact and displays a good adhesion to the composite substrate. The ceramic coatings consist of MgO, Mg₂SiO₄, MgF₂, Mg₃(PO₄)₂, furthermore, a few residual SiC phases were also found in the coatings by means of SEM observation and EDX analysis. Most of SiC reinforced particles in the oxidized composite substrate have transformed into the oxides under microarc discharge sintering, but a few residual SiC reinforcements in the MAO coatings have not disrupted the continuity of coatings. So the corrosion resistance of the SiC_P/AZ31 composite is greatly improved by MAO surface treatment, however, the corrosion resistance of coated composite also depends on the coating thickness.     

C3H8O3含量对AZ91D镁合金微弧氧化过程及膜层特性的影响

在含有不同C₃H₈O₃含量的硅铝复合电解液中,利用交流脉冲电源在AZ91D镁合金基体上制备了一系列微弧氧化膜。利用SEM和膜层测厚仪分别研究了陶瓷膜层的微观形貌特征及厚度,采用全浸泡实验和电化学阻抗谱测试了膜层在3.5%NaCl中性溶液中的耐蚀性能。结果表明,微弧氧化过程中的起弧电压和终止电压均随C₃H₈O₃含量的增加而呈上升的变化趋势。随着C₃H₈O₃含量的增加,膜层耐蚀性先提高后降低,而膜厚变化幅度不大。膜层的耐蚀性主要取决于内部致密层,当C₃H₈O₃含量为5 mL/L时,膜层相对较致密,因而表现出良好的耐蚀性能。     

微弧氧化处理对AZ91D镁合金腐蚀行为的影响

采用碱性硅酸盐溶液,在AZ91D镁合金试样表面制得微弧氧化膜,并利用电化学阻抗方法对镁合金及微弧氧化处理试样在3.5%NaCl溶液中的腐蚀行为进行比较研究.结果表明,镁合金经微弧氧化处理后,腐蚀电位和膜层阻抗均有一定程度的提高.但在浸泡过程中,微弧氧化处理试样的电化学参数呈现出不同的变化规律,初期波动较大,后期则逐渐降低,趋向稳定.     

AZ91D镁合金微弧氧化膜的腐蚀行为研究

利用双向全波脉冲电源对AZ91D镁合金在硅酸盐体系中进行了微弧氧化处理,通过电化学阻抗谱(EIS)测试、极化曲线分析并结合XRD和SEM等分析方法对微弧氧化处理的镁合金腐蚀行为进行了研究.结果表明,微弧氧化膜表面分布着几微米的微孔,微弧氧化膜中主要含有MgF2,Mg2SiO4和Al2O3.AZ91D镁合金经过微弧氧化处理之后,耐蚀性能明显提高,自腐蚀电流密度降低3个数量级,自腐蚀电位高出约300 mV,阻抗值高出3个数量级,研制的微弧氧化膜对镁合金具有很好的防腐保护性能.     

(Al_2O_3-SiO_2)_(sf)／AZ91D镁基复合材料微弧氧化膜的制备及电化学阻抗谱分析

在硅酸盐电解液体系中,采用交流微弧氧化方法在增强体体积分数为33%的(Al_2O_3-SiO_2)_(sf)/AZ91D镁基复合材料表面制备出完整的保护性氧化膜.利用SEM,EDS和XRD分析了氧化膜的形貌、成分和相组成,测量了膜层的显微硬度分布.采用电化学阻抗谱(EIS)评价了微弧氧化表面处理前后复合材料的电化学腐蚀性能,确立了不同浸泡时间对应的等效电路.结果表明,微弧氧化膜主要由MgO和Mg_2SiO_4相组成,最大硬度达到1017 HV.氧化膜电化学阻抗模值|Z|与镁合金基体相比大幅度提高,耐腐蚀性能明显高于基体.在3.5%NaCl溶液里浸泡96 h后,EIS出现感抗弧,显示膜内部开始出现点蚀破坏.氧化膜耐蚀性由膜内致密层特性所决定.     

AZ31B镁合金表面微弧电泳复合膜层微观结构及耐蚀性表征

采用微弧氧化技术在AZ31B镁合金表面制备陶瓷层,利用其表面多孔结构借助电泳技术沉积有机膜层,对比研究陶瓷层和复合膜层表面粗糙度、表面及截面形貌、电化学性能及划伤腐蚀特性。结果表明:陶瓷层表面放电微孔被电泳层完全填充并形成均匀膜层,复合膜层表面粗糙度明显降低;微弧电泳复合膜层腐蚀电流密度与陶瓷层和基体相比分别降低2个和4个数量级,极化电阻分别增大2个和4个数量级,腐蚀倾向降低;微弧电泳复合膜层电化学阻值与陶瓷层相比增加4个数量级,同时电容值降低4个数量级,耐蚀性显著提高;由于陶瓷层与电泳层的机械嵌合作用,复合膜层划伤腐蚀过程表现为基体腐蚀及陶瓷层与基体界面的破坏,复合膜层界面处结合完好。     

Corrosion resistance and molecular dynamics behavior of the MAO/SAM composite coatings on magnesium alloy

To improve corrosion resistance of magnesium alloy AZ91D, y-Mercaptopropyltrimethoxysilane (MPTS) was assembled on the surface of micro-arc oxidation (MAO) treated magnesium alloy by self-assembly membrane (SAM) technique. The surface morphology and chemical components of the MAO/SAM composite coatings were analyzed by scanning electron microscopy (SEM) and energy dispersive spectrometer (EDS). The corrosion resistance of samples was investigated by potentiodynamic polarization, electrochemical impedance spectroscopy and total immersion tests in a 3.5 wt % NaCl solution. The measured EIS data were simulated by an equivalent circuit. Also the molecular dynamic simulation was used to study the adsorption behavior at the molecular level. The results showed that the surface of magnesium alloy was well covered by the MAO/SAM composite coatings with a better corrosion resistance. Chemical adsorption was formed between the organic molecules and the surface of the MAO coating. The approach presented here afforded an effective alternative for surface modification of magnesium-based materials to meet the many aspects of the application requirements.     

Comparative study on corrosion protection properties of electroless Ni‐P‐ZrO2 and Ni‐P coatings on AZ91D magnesium alloy

Electroless Ni‐P‐ZrO₂ and Ni‐P coatings on AZ91D magnesium alloy were prepared, and their corrosion protection properties were compared in this paper. The potentiodynamic curves and electrochemical impedance spectroscopy (EIS) of the coated magnesium alloy in 3.5% NaCl solution showed that the corrosion performance of Ni‐P‐ZrO₂ composite coating was superior to that of Ni‐P coating. The same conclusion was obtained with salt spray and immersion tests. The corrosion morphologies of two kinds of coatings with various immersion time intervals in 3.5% NaCl solution indicated that most corrosion products concentrated on the nodules boundaries of Ni‐P coating and blocked corrosion pit was the main corrosion form. For the Ni‐P‐ZrO₂ coating, tortuous nodules boundaries were not the weak sites of the coating and corrosion initiated from the nickel phosphor alloy around the nanometer powders. Open corrosion pits occurred on the composite coating surface, and the coating was corroded gradually. Thus, the Ni‐P‐ZrO₂ coating exhibited better corrosion protection property to magnesium alloy substrate than Ni‐P coating.     

Porous TiO2 film prepared by micro-arc oxidation and its electrochemical behaviors in Hank's solution

Porous titanium oxide film was prepared by micro-arc oxidation (MAO) method on the surface of titanium alloy in electrolyte containing Ca and P. Surface characterizations of the film were carried out using X-ray diffractometer (XRD), scanning electron microscopy (SEM) and energy dispersive spectrometer (EDS) before and after immersion in Hank's solution. Electrochemical behaviors and corrosion resistance were studied by electrochemical techniques. The film was mainly composed of titania, α-tricalcium phosphate (α-TCP) and amorphous Ca-P compounds. α-TCP and amorphous compounds could transformed into hydroxyapatite (HA) when immersed in Hank's solution. MAO film showed higher corrosion potential and lower corrosion current than the titanium alloy and its chemical stability was slightly changed after formation of HA. Fitted electrochemical impedance spectroscopy (EIS) data indicated that after immersion for 2 weeks the MAO film kept good corrosion resistance. Porous TiO₂ film on titanium alloy by MAO method showed good chemical stability in Hank's solution and the transformation of Ca-P compounds into HA indicated that MAO was an effective method for preparing titanium alloys as bioactive artificial bone substitute even when Ca and P in the tissue environment were not abundant.     

不同镁合金支架材料MAO/PLLA复合膜研究

两种系列的镁合金WE42与AM20微弧氧化(MAO)后用浸渍法对微弧氧化膜进行聚乳酸(PLLA)封孔处理制备复合涂层,通过扫描电镜(SEM)分析微弧氧化膜及聚乳酸封孔膜的表面形貌及结构,X射线衍射(XRD)分析微弧氧化膜的主要成分为MgSiO3和SiO2,通过腐蚀失重测定试样的失重率.在37℃的hank's模拟体液中测...     

Microstructure, spallation and corrosion of plasma sprayed Al2O3–13%TiO2 coatings

The electrochemical corrosion behaviours of the steel substrates coated with three different plasma sprayed Al₂O₃–13%TiO₂ coatings were studied in this paper. The three kinds of Al₂O₃–13%TiO₂ coatings were conventional ME coating, nanostructured NP coating and NS coating. There were micro cracks, laminar splats and straight columnar grains in ME coating. For the two nanostructured coatings, the laminar microstructure and columnar grains were not obvious. The NP coating had the highest hardness and spallation resistance. Electrochemical corrosion behaviour of the three coatings was mainly investigated by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) in aqueous Na₂SO₄ solution.     

Ni/Cu定向结构涂层在不同浓度H2SO4中的耐蚀性能

为了研究Cu元素对Ni基合金定向结构涂层耐腐蚀性能的影响,向Ni60合金粉末中添加了5%Cu(质量分数,下同),制备了定向结构Ni60/Cu复合涂层。采用电化学试验和浸泡试验,评估了涂层在不同浓度H₂SO₄溶液中的电化学腐蚀特性和浸泡腐蚀性能,探讨了涂层在不同浓度H₂SO₄溶液中的腐蚀行为。结果表明,涂层在不同浓度H₂SO₄溶液中的腐蚀均表现为活化-钝化-过钝化的过程,电化学阻抗谱在整个时间常数内具有典型的容抗特征,H₂SO₄溶液浓度从5%增至80%时,电荷转移电阻先减小后增大,涂层的耐腐蚀性呈现先降低后升高的趋势。随着H₂SO₄溶液浓度的增加,涂层表面的腐蚀程度先加剧后逐渐减缓,且在H₂SO₄溶液浓度为40%时,腐蚀电位移至最负,腐蚀电流密度增至最大。但在H₂SO₄溶液浓度达到80...     

Structure and corrosion resistance of ZrO2 ceramic coatings on AZ91D Mg alloys by plasma electrolytic oxidation

The aim of this work is to study the structure and the corrosion resistance of the plasma electrolytic oxidation ZrO₂ ceramic coatings on Mg alloys. The ceramic coatings were prepared on AZ91D Mg alloy in Na₅P₃O₁₀ and K₂ZrF₆ solution by pulsed single-polar plasma electrolytic oxidation (PEO). The phase composition, morphology and element distribution in the coating were investigated by X-ray diffractometry, scanning electron microscopy and energy distribution spectroscopy, respectively. The results show that the coating thickness and surface roughness were increased with the increase of the reaction time. The ceramic coatings were of double-layer structure with the loose and porous outer layer and the compact inner layer. And the coating was composed of P, Zr, Mg and K, of which P and Zr were the main elements in the coating. P in the coating existed in the form of amorphous state, while Zr crystallized in the form of t-ZrO₂ and a little c-ZrO₂ in the coating. Electrochemical impedance spectra (EIS) and the polarizing curve tests of the coatings were measured through CHI604 electrochemical analyzer in 3.5% NaCl solution to evaluate the corrosion resistance. The polarization resistance obtained from the equivalent circuit of the EIS was consistent with the results of the polarizing curves tests.     

Electrodeposition and characterization of Ni-TiB2 composite coatings

Nickel-titanium diboride (Ni-TiB₂) composite coatings were successfully fabricated by pulse electrodeposition techniques from nickel sulfamate bath containing dispersed submicron TiB₂ particles. The effect of TiB₂ codeposition on the morphological, microstructural, microhardness and anti-corrosive properties of the composite coatings have been investigated by using scanning electron microscopy coupled with energy dispersive spectroscopy system, X-ray diffraction (XRD), vickers microhardness, and electrochemical impedance spectroscopy (EIS) techniques. Incorporation of TiB₂ particles into the nickel matrix has modified the regular crystal growth of nickel. The XRD patterns revealed that the preferred (100) crystallite orientation of pure nickel has been modified into mixed orientations by the enhancement of (111) and attenuation of (200) diffraction intensities by the incorporation of TiB₂ particles into the nickel matrix. Vickers microhardness of the Ni-TiB₂ composite coating is found to be increased which is nearly 3 times higher than pure nickel coating. The results obtained by polarization curves and EIS analysis in 3.5 wt% NaCl solution have shown the improved corrosion resistance properties of Ni-TiB₂ composite coating over pure nickel electrodeposit.     

Electrodeposition and corrosion resistance of Ni–P–TiN composite coating on AZ91D magnesium alloy

In order to improve the corrosion resistance and microhardness of AZ91D magnesium alloy, TiN nanoparticles were added to fabricate Ni–P–TiN composite coating by electrodeposition. The surface, cross-section morphology and composition were examined using SEM, EDS and XRD, and the corrosion resistance was checked by electrochemical technology. The results indicate that TiN nanoparticles were doped successfully in the Ni–P matrix after a series of complex pretreatments including activation, zinc immersion and pre-electroplating, which enhances the stability of magnesium alloy in electrolyte and the adhesion between magnesium alloy and composite coating. The microhardness of the Ni–P coating increases dramatically by adding TiN nanoparticles and subsequent heat treatment. The corrosion experimental results indicate that the corrosion resistance of Ni–P–TiN composite coating is much higher than that of uncoated AZ91D magnesium alloy and similar with Ni–P coating in short immersion time. However, TiN nanoparticles play a significant role in long-term corrosion resistance of composite coatings.     

Statistical Process Control

Abstract

In order to improve the corrosion resistance provided by a micro-arc oxidation (MAO) coating on AZ31 magnesium alloy, a polypropylene film was prepared on its surface. Scanning electron microscopy, energy dispersive X-ray analysis and Fourier transform infrared spectroscopy were used to characterise the surfaces of the coatings. The corrosion protective performance of the coatings was evaluated by potentiodynamic polarisation curves, electrochemical impedance spectroscopy and immersion testing. The results show that the microdefects of the MAO coating can be filled by PP and the corrosion resistance of the AZ31 magnesium alloy is improved greatly.     

Microstructure and electrochemical behavior of Ti-coatedZr55Al10Ni5Cu30 bulk metallic glass

In this study, pure Ti was coated on Zr₅₅Al₁₀Ni₅Cu₃₀ bulk metallic glass (BMG) using a physical vapour deposition (PVD) technique with magnetron sputtering. Microstructures of Ti coating, BMG substrate and interface were investigated by conventional and high-resolution transmission electron microscopy (TEM and HREM). The electrochemical behavior of Ti-coated Zr₅₅Al₁₀Ni₅Cu₃₀ BMG was studied by potentiodynamic polarization curves and electrochemical impedance spectroscopy (EIS) in Hanks' solution. Scanning electron microscopy (SEM) was used to characterize the surface morphology of the coating after electrochemical testing. HRTEM observation reveals that the sputtering Ti coating consists of α-Ti nano-scale particles with the size about 10 nm. The polarization curves revealed that the open-circuit potential shifted to a more positive potential and the passive current density was lower after Ti coating was applied in comparison with that of the monolithic Zr₅₅Al₁₀Ni₅Cu₃₀ BMG. Electrochemical impedance spectroscopy (EIS) measurements showed that the Bode plots of Ti-coated Zr₅₅Al₁₀Ni₅Cu₃₀ BMG presented one time constant for 1 h and 12 h immersion and two time constants after 24 h immersion. The good bonding condition between Ti coating and Zr₅₅Al₁₀Ni₅Cu₃₀ BMG substrate may be responsible for the high corrosion resistance of Ti-coated Zr₅₅Al₁₀Ni₅Cu₃₀ BMG.     

The effect of interlayer on corrosion resistance of ceramic coating/Mg alloy substrate in simulated physiological environment

Ceramic coatings are deposited on biodegradable magnesium alloys by physical vapor deposition to reduce the electrochemical activity in the simulated physiological environment. Although an interlayer is generally used to reduce the mismatch between the hard coating and soft substrate, the effects of the interlayer on the electrochemical corrosion behavior have seldom been explored. In this work, AlO_xN_y ceramic coatings were deposited on AZ31 magnesium alloys with Al or Ti interlayers. Polarization tests and electrochemical impedance spectroscopy (EIS) were conducted to evaluate the corrosion resistance in the cell culture medium. The AlO_xN_y ceramic coating significantly improved the bio-corrosion resistance of the magnesium alloy, but the Ti interlayer accelerated the corrosion rate. In comparison, although the addition of an Al interlayer led to smaller enhancement in the surface mechanical properties of the AlO_xN_y coating, corrosion could be impeded effectively. Our results indicate that an Al interlayer is preferred over Ti and the corrosion failure mechanism is discussed from the perspective of defects.     

Comparison of electrochemical corrosion behaviour of MgO and ZrO2 coatings on AM50 magnesium alloy formed by plasma electrolytic oxidation

Two types of PEO coatings were produced on AM50 magnesium alloy using pulsed DC plasma electrolytic oxidation process in an alkaline phosphate and acidic fluozirconate electrolytes, respectively. The phase composition and microstructure of these PEO coatings were analyzed by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The corrosion behaviour of the coated samples was evaluated by open circuit potential (OCP) measurements, potentiodynamic polarization tests, and electrochemical impedance spectroscopy (EIS) in neutral 0.1 M NaCl solution. The results showed that PEO coating prepared from alkaline phosphate electrolyte consisted of only MgO and on the other hand the one formed in acidic fluozirconate solution was mainly composed of ZrO₂, MgF₂. Electrochemical corrosion tests indicated that the phase composition of PEO coating has a significant effect on the deterioration process of coated magnesium alloy in this corrosive environment. The PEO coating that was composed of only MgO suffered from localized corrosion in the 50 h exposure studies, whereas the PEO coating with ZrO₂ compounds showed a much superior stability during the corrosion tests and provided an efficient corrosion protection. The results showed that the preparation of PEO coating with higher chemical stability compounds offers an opportunity to produce layers that could provide better corrosion protection to magnesium alloys.