Effects of phosphate pretreatment and hot-humid environmental exposure on static strength of adhesive-bonded magnesium AZ31 sheets

An innovative phosphate–permanganate surface treatment (PPT) was developed to improve the static strength of adhesive-bonded 4 mm thick magnesium AZ31 sheets. The phosphate coating having the chemical composition of 1.43% P, 1.63% F and 0.15% Mn (in mass %) was formed after the treatment with PPT solution which has the formulation of KMnO₄, K₂HPO₄, Na₂SiO₃ and NaF. The combination of additives NaF and Na₂SiO₃ and the pH values in the range of 5–6 for a phosphate–permanganate solution was found to be the key elements for the formation of the phosphate coating. The appearance of the phosphate coating and corrosion resistance to 3.5%NaCl solution was assessed. To study the durability of the coating, the effect of an exposure in a hot-humid environment (96% R.H. at 40 °C) on the static strength of adhesive-bonded magnesium AZ31 was investigated. Test results showed that the phosphate coating improved not only the static strength of bonded magnesium AZ31 joints in an ambient condition but also the durability in a hot-humid environment. These results suggest that PPT surface pretreatment is capable of improving the static strength and thermal durability of adhesive-bonded magnesium AZ31 sheets.     

以硫酸镍为主盐的AZ91D镁合金化学镀镍研究

研究了以硫酸镍为主盐的AZ91D镁合金化学镀镍.采用无铬前处理在AZ91D镁合金表面形成高锰酸盐和磷酸盐化学转化膜,用SEM、EDX、XRD和极化曲线等方法研究化学转化膜和化学镀镍层的形貌、组成及在3.5%的NaCl溶液中的耐腐蚀性能.结果表明,在高锰酸盐转化膜表面形成的化学镀镍层呈胞状,较致密,有微裂纹;在磷酸盐转化膜上形成的化学镀镍层也呈胞状,晶胞大小不均匀,没有微裂纹.镀层厚度均匀,致密,无孔隙.在3.5%的NaCl溶液中的极化曲线表明化学转化膜对镁合金基体的耐腐蚀性能提高不大,经高锰酸盐和磷酸盐前处理的化学镀镍层腐蚀电位分别为-0.48V_(SCE)和-1.12 V_(SCE).以硫酸镍为主盐的经磷酸盐前处理的化学镀镍层较好地提高了镁合金的耐腐蚀性能.     

AZ91D镁合金表面转化膜腐蚀及防护涂层性能研究

采用高锰酸盐、钼酸盐、锡酸盐转化液分别对AZ91D镁合金进行表面化学转化,得到三种不同的化学转化膜。分别通过SEM、EDS和全浸试验研究不同转化膜的表面微观形貌、成分和腐蚀率,通过划格法和中性盐雾试验法研究转化膜外部有机涂层的附着性能和耐蚀性能。结果表明,高锰酸盐和钼酸盐转化膜表面具有大量微细裂纹,锡酸盐转化膜表面呈鱼鳞状,均为后续涂装提供了具有一定粗糙度的表面。锡酸盐转化膜的耐蚀性最好,高锰酸盐转化后并涂层的附着力和耐蚀性能最好。     

Enhanced corrosion performance of magnesium phosphate conversion coating on AZ31 magnesium alloy

Magnesium phosphate conversion coating (MPCC) was fabricated on AZ31 magnesium alloy for corrosion protection by immersion treatment in a simple MPCC solution containing Mg²⁺ and PO^3?₄ ions. The MPCC on AZ31 Mg alloy showed micro-cracks structure and a uniform thickness with the thickness of about 2.5 µm after 20 min of phosphating treatment. The composition analyzed by energy dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy revealed that the coating consisted of magnesium phosphate and magnesium hydroxide/oxide compounds. The MPCC showed a significant protective effect on AZ31 Mg alloy. The corrosion current of MPCC was reduced to about 3% of that of the uncoated surface and the time for the deterioration process during immersion in 0.5 mol/L NaCl solution improved from about 10 min to about 24 h.     

镁合金表面等离子喷涂Al2O3-TiO2陶瓷涂层的耐腐蚀性研究

采用等离子喷涂技术在AZ31镁合金表面制备Al2O3-13％TiO2陶瓷复合涂层,对涂层的微观组织进行了观察分析,测试了涂层的表面硬度.通过极化曲线和浸泡腐蚀试验,对比研究了镁合金基材及喷涂陶瓷涂层的试样在5％ NaCl溶液中的耐腐蚀性能.结果表明:涂层镁合金试样的硬度和耐腐蚀性优于基体镁合金,但当腐蚀液透过涂层孔隙时...     

Influence of substrate composition on the formation of phytic acid conversion coatings

In this paper, the formation and corrosion resistance of the phytic acid conversion coatings on Mg, Al, and AZ91D magnesium alloy were contrastively investigated using scanning electronic microscopy (SEM), Auger electron spectroscopy (AES), Fourier transform infrared spectroscopy (FTIR), electronic probe microscopic analyzer (EPMA), electronic balance, and electrochemical methods. The influence of phytic acid conversion coating as a middle layer on the properties of the paint on magnesium alloys was also investigated. The results show that the formation process of the conversion coatings is evidently influenced by the compositions of the substrate. The coating on pure aluminum is thinner and compacter than that on pure magnesium and the coating formed on α phase in AZ91D magnesium alloy is thinner but denser than that on β phase. The phytic acid conversion coatings formed on Mg, Al, and AZ91D magnesium alloy can all increase their corrosion resistance. The active functional groups of hydroxyl and phosphate radical are rich in the conversion coatings, which can improve the bonding between the organic paint and magnesium alloy and then improve their corrosion resistance.     

AZ31B镁合金氧化石墨烯掺杂钇盐转化膜耐蚀性研究

目的研究一种绿色环保的表面处理方法,以提高镁合金的耐蚀性。方法采用化学浸泡法,以硝酸钇为成膜物质,在AZ31B镁合金表面成功制备一种新型稀土盐转化膜,并以氧化石墨烯为阻隔剂对该转化膜进行复合掺杂。采用扫描电镜(SEM)对膜层的表面形貌进行观察,采用析氢实验和电化学测试对不同试样在3.5%Na Cl溶液中的耐蚀性进行了研究。结果镁合金钇盐转化膜表面平整均一,覆盖良好。氧化石墨烯掺杂后的钇盐膜层表面出现了大小不均一的瘤状物质,膜层完整,未出现裂痕。析氢实验结果显示,经过处理的转化膜试样可以极大地抑制腐蚀反应的发生。由极化曲线可知,钇盐转化膜的存在使镁合金的腐蚀电位发生了明显正移,正移了150 m V;而氧化石墨烯掺杂的钇盐膜层的腐蚀电位相对于掺杂前变化不大,但其腐蚀电流密度是掺杂前的1/28。电化学交流阻抗谱的测试结果显示,氧化石墨烯掺杂钇盐转化膜的电荷转移电阻最大,Rct为2485?·cm2;钇盐转化膜的电荷转移电阻次之,Rct为1224?·cm2。两者的电荷转移电阻相对于未经处理的镁合金都有明显提升。结论钇盐转化膜可以明显提高AZ31B镁合金的耐蚀性,氧化石墨烯的加入可以进一步提高转化膜层的耐蚀性。     

Influence of interlayers on corrosion resistance of diamond-like carbon coating on magnesium alloy

Diamond-like carbon coating (DLC) was deposited on AZ31 magnesium alloy by ion beam deposition technique in this study. A columnar Cr layer with a (110) preferred texture and a columnar CrN layer with a (111) preferred texture were applied as interlayers in the DLC coating/AZ31 substrate systems. The addition of these interlayers improved the adhesion between coating and substrate effectively, but did not enhance the corrosion resistance of the DLC/AZ31 systems due to the formation of galvanic cell between substrate and interlayer in the region of through-thickness defects in 3.5 wt.% NaCl solution. In addition, the effect of bias voltage on the corrosion resistance of CrN/Cr coatings on magnesium alloys was investigated. Although the application of bias voltage induced the coating denser, it was still difficult for CrN/Cr coating to reduce the corrosion current density of AZ31 due to the large difference between coating and substrate in galvanic series.     

Improvement of corrosion resistance of AZ31 Mg alloy by anodizing with co-precipitation of cerium oxide

Anodizing of AZ31 Mg alloy in NaOH solution by co-precipitation of cerium oxide was investigated. The chemical composition and phase structure of the coating film were determined via optical microscopy, SEM and XRD. The corrosion properties of the anodic film were characterized by using potentiodynamic polarization curves in 17 mmol/L NaCl and 0.1 mol/L Na₂SO₄ solution at 298 K. The corrosion resistance of AZ31 magnesium alloy is significantly improved by adding cerium oxide to alkaline solution. In addition, the surface properties are enhanced and the film contains no crack.     

一步电沉积Ca-P/CTS复合涂层的制备及其耐蚀性

通过一步电沉积法在AZ31镁合金基体表面上沉积钙磷/壳聚糖(Ca-P/CTS)复合涂层,通过共聚焦显微镜(CLSM)、扫描电镜(SEM)和红外光谱分析仪(FT-IR)对Ca-P/CTS复合涂层的形貌、结构以及成分进行分析,采用电化学测试研究了其耐蚀性。结果表明:Ca-P/CTS复合涂层能够有效提高AZ31镁合金基体的耐蚀性,当壳聚糖的质量浓度为0.2g/L时,复合涂层的耐蚀性最好。     

A new method for electroless Ni-P plating on AZ31 magnesium alloy

Coating Ni-P films on AZ31 magnesium alloys via electroless plating and organic coatings (organsilicon heat-resisting varnish), was studied. An organic coating was proposed as the interlayer between Ni-P coating and AZ31magnesium alloy substrate, to replace the traditional chromium oxide plus HF pretreatment. The Ni-P deposited on the interlayer was also characterized by its structure, morphology and corrosion-resistance. The interlayer on the substrate not only reduces the corrosion of magnesium during Ni-P plating process, but also reduces the potential difference between the matrix and the second phase. The result of the cross-cut test indicates the adhesion between the substrate and the interlayer is good enough. A Ni-P film with fine and dense structure was obtained on the AZ31 magnesium alloy. The electrochemical measurements show that the sample with Ni-P film exhibits lower corrosion current density and more positive corrosion potential than the substrate. Furthermore, the Ni-P coating on the AZ31 magnesium alloy exhibits high corrosion resistance in the rapid corrosion test illustrated in this paper. The method proposed in this work is environmentally friendly: no fluoride or hexacalent chromium compounds are used. In addition, it provides a new concept for plating the metals, which are considered difficult to plate due to high reactivity.     

镁合金AZ31无铬无氟无亚硝酸盐磷化膜的制备及耐蚀性能(英文)

以磷酸二氢锰和无氟、无铬、无亚硝酸盐的添加剂为主要成分,通过化学沉积的方法在镁合金AZ31表面获得致密均匀的耐蚀磷化膜。通过硫酸铜点蚀测试、SEM、XRD及电化学极化曲线等表征手段,详细研究了膜层的形貌、组成、相结构及耐蚀性能,讨论了成膜温度和游离酸对膜层微结构、形貌及耐蚀性能的影响。结果表明,磷化膜通过抑制阳极溶解和阴极析氢,有效地提高了镁合金AZ31的耐蚀性能。     

Chemical conversion coating on AZ31B magnesium alloy and its corrosion tendency

The morphology change of the magnesium matrix after pre-treatment and the mor-phology as well as the phase composition of chemical conversion coating formed by phosphate were studied using scanning electron microscope and X-ray diffraction. The corrosion resistance of the coating was studied by salt spray and damp test, and the corrosion tendency during salt immersion test was analyzed. The results show that the phase composition before and after pre-treatment is almost change- less, and the deep microflaw appears between α and β phases during acidic pickling. The phosphate conversion coating is mainly composed of Mg, MgO, and some amor-phous phase, and it can provide a good protection for the AZ31B alloy. Results from corrosive morphology indicate that the growth and the corrosion resistance of the phosphate conversion coating are related to the forming process of the AZ31B matrix.     

Characterization of plasma electrolytic oxide formed on AZ91 Mg alloy in KMnO4 electrolyte

The aim of this work is to investigate microstructure, corrosion resistance characteristics and nanohardness of the oxide layer on AZ91 Mg alloy by applying different voltage with KMnO₄ contained solution. There are lots of closed pores that are filled with another oxide compound compared with the typical surface morphology with pore coated until 350 V of coating voltage. The thickness of oxide layer increases with increasing coating voltage. The oxide layer formed on AZ91 Mg alloy in electrolyte with potassium permanganate consists of MgO and Mn₂O₃. Corrosion potential of the oxide layer on AZ91 Mg alloy obtained at different plasma electrolytic oxidation(PEO) reaction stages increases with increasing coating voltage. The corrosion resistance of AZ91 Mg alloy depends on the existence of the manganese oxide in the oxide layer. The inner barrier layer composed of the MgO and Mn₂O₃ may serve as diffusion barrier to enhance the corrosion resistance and may partially explain the excellent anti-corrosion performance in corrosion test. Nanohardness values increase with increasing coating voltage. The increase in the nanohardness may be due to the effect of manganese oxide in the oxide layer on AZ91 Mg alloy coated from electrolyte containing KMnO₄.     

外加磁场下AZ31镁合金磷化膜结构及耐蚀性研究

为了获得优良的AZ31镁合金磷化膜,采用外加磁场作用于镁合金的磷化过程.利用SEM,AFM,XRD和电化学工作站等仪器,研究转化膜的表面形貌、结构及耐蚀性.研究结果表明:磁场方向垂直于镁合金样品情况下显著促进AZ31镁合金转化膜的形成,转化膜主要由晶态Zn3(PO4)2·4H2O与A1PO4和非晶态Mn化合物组成,外加...     

Preparation and characterization of Ca-P coating on AZ31 magnesium alloy

A Ca-P coating consisting of biodegradableβ-tricalcium phosphate[β-TCP,β-Ca3(PO4)2]accepted for medical application was coated on a biodegradable AZ31 alloy by chemical deposition to improve the corrosion resistance.The good bonding strength of the coating is obtained.The results show that the corrosion potential of the Ca-P coated AZ31 alloy increases significantly,and MG63 cells show good adherence,proliferation and differentiation on the surface of the coated alloy.The Ca-P coating might be an effective way to improve the surface bioactivity of magnesium alloys.     

Stannate and permanganate conversion coatings on AZ31 magnesium alloy

The formation of stannate and permanganate–phosphate conversion coatings on AZ31 magnesium alloy was investigated in situ by EIS measurements and their protective performances were studied by different electrochemical techniques in diluted (0.05 M) sodium sulphate solution.The influence that short or long treatment times exert on the performances of such conversion coatings is discussed. While permanganate–phosphate baths always built layers characterized by penetrating cracks, long stannate baths produced layers without interconnected porosity, but were defective. This accounted for the initial greater protectiveness achieved with the stannate treatment; nevertheless, the easy penetration of the electrolytic solution through such a layer quickly decreased its corrosion resistance.     

Corrosion resistant coatings based on synergistic effects of alkaline etching and molybdate treatment for AZ31D magnesium alloy

Eco-friendly, non-toxic protective coatings deposited from molybdate–based solutions have been developed as undercoat thin-films (for subsequent organic top coats) for AZ31D magnesium alloy. Direct treatment of Mg AZ31D substrates with molybdate–based solutions has no significant effect on the overall surface resistance (charge transfer resistance). Alkaline etching of Mg AZ31D surfaces using KOH solution prior to molybdate conversion coating showed significant enhancement in the corrosion resistances The optimum conditions of alkaline etching and molybdate treatment steps have been determined. The total surface resistance was improved from 2.1?×?10³ Ω.cm² (for as-polished AZ31D) to be 3.2?×?10³ Ω.cm² for the alkaline etched samples followed by 10?g?L^?1 molybdate treatment. The resistance to localised corrosion (pitting and crevice) improved significantly after applying the alkaline etching step. Molybdate–based coatings formed on Mg AZ31D exhibited a network of flower-like and needle-like protective molybdenum oxide structures which are belived to be responsible for the improvement in the pitting and crevice corrosion resistance. They impede the corrosive media from reaching the bare metal and hence improve the pitting and crevice corrosion resistances. This simple eco-friendly, low-toxicity pretreatment approach seems very promising and effective for improving the corrosion resistance of magnesium alloys in chloride containing solutions.     

NH4F浓度对镁合金表面微弧氧化制备氟化物膜层结构和性能的影响

目的 考察乙二醇-氟化铵电解液中氟化铵浓度对镁合金表面微弧氧化制备氟化物膜层结构和性能的影响,提高镁合金氟化物膜层的耐腐蚀性能。方法 在含不同浓度NH4F的EG-NH4F电解液中,采用微弧氧化的方法制备氟化物膜层,NH4F质量浓度分别为40、60、80、100、120 g/L。通过扫描电子显微镜(SEM)、X射线能量色散谱仪(EDS)和X射线衍射仪(XRD),对膜层表面微观形貌和成分组成进行分析,并通过电化学测试表征了膜层的腐蚀防护性能,通过盐雾试验评估了膜层长效防腐蚀行为,通过SEM和EDS表征了腐蚀形貌和腐蚀产物。结果 在EG-NH4F中制备膜层的物相组成主要是MgF2。随着NH4F浓度的提高,微弧氧化的起弧电压与工作电压均逐渐减小,膜层中氟含量逐渐增加,膜层的孔径减小,孔数量分布更加均匀,膜层表面粗糙度降低。质量浓度为100 g/L NH4F的膜层自腐蚀电流密度(Jcorr)为2.226×10^‒7 A/cm²,较镁合金基材降低了1个数量级,极化电阻Rp增大到90.156 kΩ.cm²,其阻抗模量|Z|f=0.01 Hz=8.55×10⁵ Ω.cm²,与镁合金基材的阻抗模量|Z|f=0.01 Hz=8.86×10² Ω.cm²相比,提高了3个数量级。结论 微弧氧化处理能够显著改善AZ31镁合金的腐蚀防护性能。NH4F浓度的增加有利于提高膜层的耐腐蚀性能,质量浓度为100 g/L NH4F的膜层耐腐蚀性能最优。     

AZ31镁合金表面含纳米羟基磷灰石微弧氧化涂层的制备及性能研究

目的改善AZ31镁合金的耐腐蚀性能及生物活性。方法使用微弧氧化技术,分别在以六偏磷酸钠为主盐的电解液和以六偏磷酸钠为主盐、以纳米羟基磷灰石(HA)为添加剂的电解液中,在AZ31镁合金表面制备了微弧氧化涂层。通过扫描电子显微镜(SEM)、能谱仪(EDS)和X射线衍射仪(XRD)表征了涂层的微观形貌、元素特征和相组成。通过电化学方法和浸泡实验考察了涂层的耐蚀性。通过细胞实验评价了两种涂层的细胞相容性。结果电解液中的HA可以进入到微弧氧化涂层中,含HA的微弧氧化涂层较不含HA的更致密,且有封孔现象。电化学方法及浸泡实验结果表明,含HA的微弧氧化涂层的耐腐蚀性能更好。细胞表面粘附实验和细胞增殖实验也表明,经表面纳米HA微弧氧化处理后的AZ31镁合金生物相容性更好,且对MC3T3-E1细胞的增殖有促进作用。结论六偏磷酸钠电解液中添加纳米HA,可以在AZ31镁合金表面制备出含HA的微弧氧化涂层,且其耐腐蚀性能和生物活性均优于不含HA的微弧氧化膜。