Corrosion resistance of AZ91D magnesium alloy with electroless plating pretreatment and Ni–TiO2 composite coating

In this paper, a protective multilayer coating, with electroless Ni coating as bottom layer and electrodeposited Ni–TiO₂ composite coating as top layer, was successfully prepared on AZ91D magnesium alloy by a combination of electroless and electrodeposition techniques. Scanning electron microscopy and X-ray diffraction were employed to investigate the surface, cross-section morphologies and phase structure of coatings, respectively. The electrochemical corrosion behaviors of coatings in 3.5 wt.% NaCl solutions were evaluated by electrochemical impedance spectroscopy, open circuit potential and potentiodynamic polarization techniques. The results showed that the corrosion process of Ni–TiO₂ composite coating was mainly composed of three stages in the long-term immersion test in the aggressive media, and could afford better corrosion and mechanical protection for the AZ91D magnesium alloy compared with single electroless Ni coating. The micro-hardness of the Ni–TiO₂ composite coating improved more than 5 times than that of the AZ91D magnesium alloy.     

Electroless deposition of Ni–P–B4C composite coating on AZ91D magnesium alloy and investigation on its wear and corrosion resistance

In the present work, the effect of applying ternary Ni–P–B₄C composite coating from an electroless plating bath containing sulfate nickel, sodium hypophosphate and suspended B₄C particles, on the corrosion and wear resistance of an AZ91D, high aluminum cast magnesium alloy, was investigated. Regarding low corrosion resistance of magnesium alloys, chromium oxide plus HF (Hydro Fluoric Acid) pretreatment was applied to prepare the substrate for coating treatment in electroless bath. The pH value and temperature of the electroless bath were 9 and 82 °C, respectively. The coating was characterized for its micro structure, morphology, microhardness, wear and corrosion resistance. SEM (Scanning Electron Microscope) observation showed dense and coarse nodules in the ternary composite coating and the cross section of Ni–P–B₄C coating offered presence of well dispersed B₄C particles in the coating. The hardness of the Ni–P–B₄C composite coatings was around 1200 MPa, more than what can be obtained for Ni–P coatings (about 700 MPa). The wear test which was carried out by using pin on disc method, showed that ternary Ni–P–B₄C composite coating had a good wear resistance and more superior than Ni-P coating. The polarization test results for ternary Ni–P–B₄C composite coating exhibited good corrosion resistance properties in protecting the AZ91D magnesium alloy, but not better than Ni–P coating.     

镁合金微弧氧化陶瓷膜的微观结构、相成分和耐腐蚀性能

为获得耐腐蚀性优良的镁合金表面膜层,在含5 g/L硅酸钠、2 g/L磷酸钠和1 g/L氢氧化钠的复合溶液中,用自制设备对AZ91D镁合金进行了微弧氧化.利用扫描电镜和X射线衍射分析了AZ91D 镁合金表面微弧氧化陶瓷膜的表面形貌、截面结构和相组成.结果表明:AZ91D 微弧氧化陶瓷膜由疏松层和致密层组成,疏松层陶瓷膜疏松,厚度较大,且存在一些孔洞;致密层陶瓷膜与基体金属结合紧密,陶瓷膜主要由MgO,Mg2SiO4,Mg3(PO4)2和MgAl2O4组成.在3.5%的NaCl溶液中,微弧氧化陶瓷膜的自腐蚀电位为-1 390 mV,而镁合金基体的为-1 540 mV,表明经微弧氧化处理后AZ91D 镁合金的耐蚀性有较大提高.     

Fabrication and characterization of bioactive composite coatings on Mg–Zn–Ca alloy by MAO/sol–gel

High corrosion rate and accumulation of hydrogen gas upon degradation impede magnesium alloys’ clinical application as implants. In this work, micro-arc oxidation (MAO) was used to fabricate a porous coating on magnesium alloys as an intermediate layer to enhance the bonding strength of propolis layer. Then the composite coatings were fabricated using sol–gel method by dipping sample into the solution containing propolis and polylactic acid at 40°C. The corrosion resistance of the samples was determined based on potentiodynamic polarization experiments and immersion tests. Biocompatibility was designed by observing the attachment and growth of wharton’s jelly-derived mesenchymal stem cells (WJCs) on substrates with MAO coating and substrates with composite coatings. The results showed that, compared with that of Mg–Zn–Ca alloy, the corrosion current density of the samples with composite coatings decreased from 5.37 × 10⁻⁵ to 1.10 × 10⁻⁶ A/cm² and the corrosion potential increased by 240 mV. Composite coatings exhibit homogeneous corrosion behavior and can promote WJCs cell adhesion and proliferation. In the meantime, pH value was relatively stable during the immersion tests, which may be significant for cellular survival. In conclusion, our results indicate that composite coatings on Mg–Zn–Ca alloy fabricated by MAO/sol–gel method provide a new type bioactive material.     

电解液组成对AZ91D镁合金微弧氧化的影响

在含有NaAlO2、KF的电解质溶液中,采用恒电流方式对AZ91D镁合金进行微弧氧化获得陶瓷膜.研究了电解液组分及浓度对陶瓷氧化膜厚度及表面形貌的影响,同时,采用动电位极化曲线及电化学交流阻抗评价了陶瓷氧化膜的耐蚀性.研究发现:NaAlO2单独存在时即可产生火花放电现象,但得到的氧化膜较薄;氟化钾的加入可以显著增加氧化膜厚度,膜厚的增长速度与氟化钾的加入量呈线性关系.SEM表面形貌分析表明:电解质浓度较低时产生的氧化膜宏观上较粗糙、微观上颗粒结合紧密;高浓度时得到的氧化膜宏观上细致光滑,微观上存在明显的孔洞和放电隧道,呈熔融状态结合在一起.动电位极化曲线及电化学交流阻抗的测试一致表明,经微弧氧化处理后的镁合金耐蚀性显著提高.     

AZ91D镁合金表面钙系磷酸盐膜层的制备及其耐蚀性

为了降低AZ91D镁合金活泼的化学性质,使其成为耐蚀性更好的医用金属材料,在不同pH值及反应温度等条件下对AZ91D镁合金进行钝化,观察了不同条件下制备的膜层的表面形貌、元素构成,并测试了其电化学性质,研究了磷化的pH值和温度对磷化膜性能的影响。结果表明:磷化液的温度及pH值对磷化膜性能有重要影响,当pH值为2.8,温度为40℃时,制备的磷化膜为针状鳞片、尺寸均一,膜层覆盖最为致密细腻,表面膜层中主要生成了CaHPO_4·2H_2O化合物,即DCPD,还有少量Ca_3(PO_4)_2,膜层在AZ91D表面形成了稳定的钝化层,有效降低了其化学活泼性,大幅提高了其耐蚀性。     

Preparation and Corrosion Resistance of Magnesium Coatings by Magnetron Sputtering Deposition

Magnesium coatings were fabricated on stainless steel substrates (1Cr11Ni2W2MoV) by a plane magnetron sputtering technique. The argon pressure and the substrate condition (including temperature and the substrate was rotated or fixed) were varied in order to evaluate the influence of the parameters on the crystal orientation and morphology of the coating. The corrosion behavior of the coatings in 1 wt pct NaCl solution was studied by electrochemical methods.The results showed that all coatings exhibited preferred orientation (002) as the argon pressure increased from 0.2 to 0.4 Pa. The morphologies of the coatings varied with the argon pressure and with whether the substrate was rotated or fixed. The open circuit potential of the coatings was more positive than that of cast AZ91D magnesium alloy.However, the immersion test in 1 wt pct NaCI solution showed that the corrosion rates of the coatings were higher than that of cast AZ91D magnesium alloy.     

The surface chemistry of 3-mercaptopropyltrimethoxysilane films deposited on magnesium alloy AZ91

Magnesium and its alloys have desirable physical and mechanical properties for a number of applications. Unfortunately, these materials are highly susceptible to corrosion, particularly in the presence of aqueous solutions. The purpose of this study is to develop a uniform, non-toxic surface treatment to enhance the corrosion resistance of magnesium alloys. This paper reports the influence of the coating bath parameters and alloy microstructure on the deposition of 3-mercaptopropyltrimethoxysilane (MPTS) coatings on magnesium alloy AZ91. The surface chemistry at the magnesium/MPTS interface has also been explored. The results indicate that the deposition of MPTS onto AZ91 was influenced by both the pH and MPTS concentration in the coating bath. Furthermore, scanning electron microscopy results showed that the MPTS film deposited uniformly on all phases of the magnesium alloy surface. X-ray photoelectron spectroscopy studies revealed that at the magnesium/MPTS interface, the molecules bond to the surface through the thiol group in an acid-base interaction with the Mg(OH)₂ layer, whereas in the bulk of the film, the molecules are randomly oriented.     

镁合金铈化学转化工艺及性能研究

镁合金稀土转化膜技术是一种环保型镁合金表面处理新技术.通过正交实验对压铸镁合金AZ91D铈化学转化处理工艺进行了研究,并对膜层性能进行了测试.结果表明,铈转化处理工艺能够在压铸镁合金AZ91D表面形成均匀、完整的转化膜;膜层主要由Ce2O3、CeO2和MgO以及少量的Al2O3组成;铈转化处理提高了镁合金的耐腐蚀性能.     

Hydrophobic epoxy resin coating with ionic liquid conversion pretreatment on magnesium alloy for promoting corrosion resistance

A hydrophobic epoxy resin coating with an environmental-friendly deep eutectic solvent(DES)-based conversion pretreatment was proposed to enhance the corrosion resistance of magnesium alloys. The hydrophobic epoxy resin coatings on the AZ31B magnesium alloy with and without the DES-based conversion pretreatment were thoroughly compared. It is found that the DES-based conversion film on the AZ31B magnesium alloy is mainly composed of MgH_2, MgO and MgCO_3. Furthermore, the conversion film possesses porous structure, which provides more anchor points for the following epoxy resin coating.However, without the DES-conversion pretreatment, the epoxy resin is difficult to be attached on the substrate during the dip-coating process. The double layered hybrid coating system promotes the corrosion resistance of the magnesium alloys significantly, which can be ascribed to the unique architecture and component including the hydrophobicity of the surface layer, the dense and interlocked epoxy resin,and the corrosion resistant DES-based conversion pretreatment.     

AZ31B镁合金铈基-植酸复合转化膜研究

为了进一步提高镁合金转化膜防腐性能的影响,将铈基转化复合于在AZ31B镁合金植酸转化膜表面,制备了一种铈基一植酸复合转化膜,应用析氢实验、Tafel分析方法及SEM、EDS对AZ31B镁合金不同转化膜的防腐性能及表面微观结构及成份进行了研究。结果表明复合转化膜表面主要由C、O、P、Ce、Mg及Al元素所组成,复合转化膜相比于植酸转化膜及铈基转化膜具有更好的致密性,从而复合转化膜相比于植酸转化膜及铈基转化膜具有更好的防腐性能。     

The effect of PVD coatings on the corrosion behaviour of AZ91 magnesium alloy

In this study, multilayered AlN (AlN + AlN + AlN) and AlN + TiN were coated on AZ91 magnesium alloy using physical vapour deposition (PVD) technique of DC magnetron sputtering, and the influence of the coatings on the corrosion behaviour of the AZ91 alloy was examined. A PVD system for coating processes, a potentiostat for electrochemical corrosion tests, X-ray difractometer for compositional analysis of the coatings, and scanning electron microscopy for surface examinations were used. It was determined that PVD coatings deposited on AZ91 magnesium alloy increased the corrosion resistance of the alloy, and AlN + AlN + AlN coating increased the corrosion resistance much more than AlN + TiN coating. However, it was observed that, in the coating layers, small structural defects e.g., pores, pinholes, cracks that could arise from the coating process or substrate and get the ability of protection from corrosion worsened were present.     

植酸浓度对AZ91D镁合金表面植酸转化膜的影响

选择AZ91D镁合金为实验材料,在通过正交实验优化镁合金表面植酸转化膜成膜工艺的基础上,利用扫描电镜、能谱分析、点蚀实验和电化学测量等分析手段研究了植酸浓度对植酸转化膜表面形貌、表面成分及其耐蚀性的影响.结果表明植酸转化膜主要由Mg、A1、O、P和C元素组成,其中Mg元素含量随着植酸浓度的增大而减小,而P元素含量随着植...     

Influence of phytic acid concentration on performance of phytic acid conversion coatings on the AZ91D magnesium alloy

In this study, the phytic acid conversion coating, a new environmentally friendly chemical protective coating for magnesium alloys, was prepared. The influences of phytic acid concentration on the formation process, microstructure, chemical state and corrosion resistance of the conversion coatings on AZ91D magnesium alloy were investigated by means of weight gain measurement, field-emission scanning electron microscopy (FESEM), Fourier transform infrared (FTIR) spectroscopy, potentiodynamic polarization method and electrochemical impedance spectroscopy (EIS), respectively. And the depth profile of all elements in the optimal conversion coatings was analyzed by auger electron spectroscopy (AES).The results show that the growth, microstructure, chemical state and corrosion resistance of the conversion coatings are all obviously affected by the phytic acid concentration. The concentration of 5 g l⁻¹ corresponds to the maximum weight gain. The main elements of the coating are Mg, Al, O, P, and C, which are distributed gradually in depth. The functional groups of conversion coatings formed in higher concentration phytic acid solution are closer to the constituent of phytic acid than those formed in lower concentration phytic acid solution. The coatings formed in 1–5 g l⁻¹ are integrated and uniform. However, those formed in 20–50 g l⁻¹ have some micro-cracks on the α phase. The coating formed in 5 g l⁻¹ has the best corrosion resistance, whose open circuit current density decreases about six orders than that of the untreated sample, although the coatings deposited in 1–20 g l⁻¹ can all improve the corrosion resistance of AZ91D.     

Biodegradable poly(lactide-co-glycolide) coatings on magnesium alloys for orthopedic applications

Polymeric film coatings were applied by dip coating on two magnesium alloy systems, AZ31 and Mg4Y, in an attempt to slow the degradation of these alloys under in vitro conditions. Poly(lactic-co-glycolic acid) polymer in solution was explored at various concentrations, yielding coatings of varying thicknesses on the alloy substrates. Electrochemical corrosion studies indicate that the coatings initially provide some corrosion protection. Degradation studies showed reduced degradation over 3 days, but beyond this time point however, do not maintain a reduction in corrosion rate. Scanning electron microscopy indicates inhomogeneous coating durability, with gas pocket formation in the polymer coating, resulting in eventual detachment from the alloy surface. In vitro studies of cell viability utilizing mouse osteoblast cells showed improved biocompatibility of polymer coated substrates over the bare AZ31 and Mg4Y substrates. Results demonstrate that while challenges remain for long term degradation control, the developed polymeric coatings nevertheless provide short term corrosion protection and improved biocompatibility of magnesium alloys for possible use in orthopedic applications.     

AZ91D镁合金表面植酸转化时间对膜组织结构及耐蚀性的影响

为了进一步探讨工艺条件对镁合金表面植酸转化膜的影响,采用扫描电镜、能谱分析、点蚀试验和电化学测量等研究AZ91D镁合金表面不同成膜时间对植酸转化膜表面形貌、成分及其耐蚀性的影响规律.结果表明:植酸转化膜主要由Mg,Al,O,P,C元素组成,其中Mg的质量分数随成膜时间的延长而减小,而P的质量分数随成膜时间的延长逐渐增大...     

Investigation on a Non-cyanide Plating Process of Ni-P Coating on Magnesium Alloy AZ91D

In this research we presented a non-cyanide plating process of Ni-P alloy coating on Mg alloy AZ91D. By applying a new process flow of electroless nickel plating in which zinc coating is used as transition of Ni-P coating on Mg alloy AZ91D, the process of copper transition coating plated in the cyanides bath can be replaced. A new bath composed of NiSO4 was established by orthogonal test. The results show that zinc transition coating can increase the adhesion and pH 4.0 and 95℃, respectively. The present process flow is composed of ultrasonic cleaning→alkaline cleaning→acid pickling→activation→double immersing zinc→electroplating zinc→electroless nickel plating→passivation treatment.The present non-cyanide process of electroless nickel plating is harmless to our surroundings and Ni-P coating on Mg alloy AZ91D produced by present process possesses good adhesion and corrosion resistance.     

A study of corrosion performance of electroless Ni–P and Ni–W–P coatings on AZ91D magnesium alloy

The autocatalytic nature of the electroless nickel‐based alloy coating process will inevitably produce H₂ bubbles which may be left in electroless nickel‐based alloy coating. If the H₂ cannot be removed and left in the coating, it can lead to its poor corrosion resistance due to hydrogen cracks. So, the post treatment is an essential step for electroless deposition process. In this paper, electroless Ni–P and Ni–W–P coatings with chromium‐free pretreatment and dehydrogenation post treatment have been successfully prepared on AZ91D magnesium alloy, and the corrosion behaviors of the two kind coating samples in NaCl solution, HCl solution, and H₂SO₄ solution have been investigated. Both the polarization test and immersion tests show that the electroless Ni–W–P coating has better corrosion resistance than that of electroless Ni–P coating.     

Microstructure and corrosion properties of as sub-rapid solidification Mg–Zn–Y–Nd alloy in dynamic simulated body fluid for vascular stent application

Magnesium alloy stent has been employed in animal and clinical experiment in recent years. It has been verified to be biocompatible and degradable due to corrosion after being implanted into blood vessel. Mg–Y–Gd–Nd alloy is usually used to construct an absorbable magnesium alloy stent. However, the corrosion resistant of as cast Mg–Y–Gd–Nd alloy is poor relatively and the control of corrosion rate is difficult. Aiming at the requirement of endovascular stent in clinic, a new biomedical Mg–Zn–Y–Nd alloy with low Zn and Y content (Zn/Y atom ratio 6) was designed, which exists quasicrystals to improve its corrosion resistance. Additionally, sub-rapid solidification processing was applied for preparation of corrosion-resisting Mg–Zn–Y–Nd and Mg–Y–Gd–Nd alloys. Compared with the as cast sample, the corrosion behavior of alloys in dynamic simulated body fluid (SBF) (the speed of body fluid: 16 ml/800 ml min⁻¹) was investigated. The results show that as sub-rapid solidification Mg–Zn–Y–Nd alloy has the better corrosion resistance in dynamic SBF due to grain refinement and fine dispersion distribution of the quasicrystals and intermetallic compounds in α-Mg matrix. In the as cast sample, both Mg–Zn–Y–Nd and Mg–Y–Gd–Nd alloys exhibit poor corrosion resistance. Mg–Zn–Y–Nd alloy by sub-rapid solidification processing provides excellent corrosion resistance in dynamic SBF, which open a new window for biomedical materials design, especially for vascular stent application.     

AZ91D镁合金化学镀Ni-P/Ni-W-P双层镀层研究

为了提高镁合金的耐磨耐蚀性,研究了一种镁合金直接化学镀Ni-P/Ni-W-P双层镀层的方法.采用扫描电镜(SEM)和X-射线衍分析射仪(XRD)分析了镀层的微观结构.对镀层进行了极化曲线分析,并进行了盐酸腐蚀试验和结合力试验.结果表明,该复合镀层组织致密无孔,具有较高的显微硬度和高耐蚀性.镀层硬度可达622HKV,试样在10%的HCl溶液中可保持近3h不腐蚀基体,对镁合金起到很好的保护作用.