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.     

AZ81镁合金压入蠕变性能

采用自制装置对AZ81镁合金进行压入蠕变实验,通过建立稳态压入蠕变本构模型分析合金的蠕变机制,利用扫描电镜(SEM)和X射线衍射(XRD)等方法研究合金蠕变前后的组织和成分。结果表明:压铸AZ81合金在稳态蠕变阶段的应力指数n为2.08,蠕变激活能QC为87.26 kJ/mol;蠕变诱导β相首先由非连续方式析出,到达一定程度后连续析出;沿晶界析出的β相导致合金抗蠕变性能降低;蠕变温度越高,基体和析出相的晶粒尺寸越大;压铸AZ81合金的压入蠕变机制为晶界扩散主导的位错交滑移运动。     

Corrosion protection of AZ31 magnesium alloy by silane film of partly hydrolysed BTESPT

Abstract

The corrosion protective behaviour of bis-[triethoxysilylpropyl]tetrasulphide (BTESPT) silane film formed by partly hydrolysed BTESPT on AZ31 Mg alloy was investigated. Fourier transform infrared spectroscopy (FTIR) was used for structural characterisation of the silane film. Scanning electron microscope (SEM) and energy dispersive X-ray (EDS) analysis were used for observation of surface morphology and elements analysis of the film. The corrosion behaviours of bare and the silane treated AZ31 Mg alloy in 3·5 wt-%NaCl solution were studied using electrochemical polarisation test, electrochemical impedance spectroscopy (EIS) and immersion test. The results demonstrate that bare AZ31 Mg alloy endures severe corrosion even in NaCl water solution at pH 12, although the corrosion is lighter than that in neutral and acidic NaCl water solution, and that the BTESPT silane film can improve the corrosion protection performances of AZ31 Mg alloy and a lower corrosion rate correlated with higher pH.     

Microstructure and mechanical properties of AZ81 magnesium alloy with Y and Nd elements

The effects of rare earth（RE） elements Y and Nd （w（Y）/w（Nd）=3：2） with total content of 1%-4% on microstructures and elevated temperature mechanical properties of AZ81 magnesium alloy were investigated. The results show that, proper content of rare earth elements makes the microstructures of AZ81 magnesium alloy refine obviously and the quantity offl-MglTAll2 phases reduce, and Al2Y and Al2Nd form. After solid solution treatment, with increasing content of rare earth elements, the tensile strength and elongation of the alloys （at room temperature, 150 ℃ and 250 ℃） increase first, then decrease. When the content of rare earth elements is up to 2%, the values of tensile strength at room temperature and 150 ℃ are up to their maxima simultaneously, 282 MPa and 212 MPa, respectively. Meanwhile, the values of elongation at room temperature and at elevated temperature are also up to their maxima, 13% and 15%, respectively.     

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.     

Formation and properties of stannate conversion coatings on AZ61 magnesium alloys

The effects of solution composition and temperature on the microstructure and corrosion resistance of stannate conversion coatings on AZ61 magnesium alloys were investigated. The conversion coating consisted of a porous layer as under layer intimately contacted with the magnesium plate and a hemispherical particle layer as major overlay formed right on top of the porous layer. During the coalescence of the hemispherical particles to form a complete coating on the magnesium alloy, some sites of discontinuity inevitably left and determined the corrosion resistance of the coating evaluated using a salt spray test. Increasing bath stannate ion concentration and lowering bath pH increased the population density of the hemispherical particles whose size was accordingly reduced. The corrosion resistance of the conversion coating was improved with finer particles, which were preferably formed at less alkaline solution with higher stannate ion contents. Furthermore, the conditions favoring the formation of finer particles also reduced the immersion time necessary for producing the conversion coating with optimal corrosion resistance.     

Effect of surface pretreatment by acid pickling on the density of stannate conversion coatings formed on AZ91 D magnesium alloy

Hydrofluoric and hydrochloric acid solutions and a mixture of them were tested as pickling solutions for AZ91 D Mg alloy before application of stannate coatings. Optical microscopy and energy dispersive X-ray spectroscopy (EDX) of the alloy surface after the pickling process showed that the Mg-rich α phase dissolved preferentially rather than the Al-rich β phase in hydrochloric acid solution. On the other hand, in hydrofluoric acid solution, Mg dissolved in a form of pitting corrosion. Pickling pretreatment with a mixture of these acids at an optimal concentration and an optimal pickling time resulted in relatively uniform dissolution of the alloy surface. The potentiodynamic polarization technique was used to investigate the anodic behavior of the uncoated and coated magnesium alloy in borate buffer solution. The morphology of the coatings was observed using a scanning electron microscope (SEM) before and after corrosion tests. The experimental results showed that coating film density and corrosion resistance of stannate-coated samples prepared with pickling pretreatment were improved compared with those of the coated sample without pickling pretreatment.     

Effect of side transmission of power ultrasonic on structure of AZ81 magnesium alloy

In order to promote the application of power ultrasonic in metallurgic industry, ultrasonic vibration is introduced from the side of AZ81 ingot by adopting the automatic-attracting amplitude transformer horn which has independently been designed and produced, and the effect of the side transmission of ultrasonic on the solidification structure of metal is investigated. The results show that under this experimental condition, power ultrasonic can greatly improve the solidification structure of AZ81 magnesium alloy. Compared with the traditional modification methods in which inoculants are added into melt, power ultrasonic has a better performance. The present research gives us a new way for the application of ultrasonic refinement technique.     

稀土元素Y、Nd对AZ81镁合金组织和高温性能的影响

研究了稀土元素Y、Nd对AZ81镁合金组织和高温力学性能的影响。结果表明，稀土元素Y、Nd的加入明显细化了AZ81镁合金的显微组织，减少了β（Mg17Al12）相的析出。分析认为，稀土元素Y和Nd主要是通过固溶强化、析出强化和细晶强化提高了合金的室温和高温强度，改善了合金的塑性。复合加入2％的Y和Nd，合金的室温强度最高，达282．5MPa，与未加稀土的AZ81相比，约提高了39％。含1％Y的AZ81合金在150℃下的高温强度高达220MPa，与不含稀土的AZ81相比高温强度约提高40％。     

Electrodeposition of zinc on AZ91D magnesium alloy pre‐treated by stannate conversion coatings

A stannate chemical conversion process followed by an activation procedure was employed as the pre‐treatment process for AZ91D magnesium alloy substrate. Zn was electroplated onto the pre‐treated AZ91D magnesium alloy surface from pyrophosphate bath to improve the corrosion resistance and the solderability. The surface morphologies of conversion coating and zinc coating were examined with scanning electron microscope (SEM). The phase composition of conversion coating was investigated by X‐ray diffraction (XRD). The electrochemical corrosion behavior of the coatings in the corrosive solution was investigated by potentiodynamic polarization curves and electrochemical impedance spectroscopy (EIS). The experimental results showed that the activated stannate chemical conversion coating provided a suitable interface between zinc coating and the AZ91D magnesium alloy substrate. The corrosion resistance of the AZ91D substrate was improved by the zinc coating.     

Organic-magnesium complex conversion coating on AZ91D magnesium alloy

An organic-magnesium complex conversion (OMCC) coating on AZ91D magnesium alloy was obtained by treating in a solution containing organic compounds. SEM, FESEM and XPS were used to examine the surface morphology, thickness and structure of the conversion coatings. The results show that the continuous and uniform conversion coating is deposited on AZ91D alloy and the main component of the coatings is organic compound containing benzene ring, which forms a chemical bond with magnesium. The polarization measurement and salt spray test show that the corrosion resistance of the conversion coating is much higher than that of traditional chromate conversion coating.     

Corrosion properties ofAZ31 magnesium alloy and protective effects of chemical conversion layers and anodized-coatings

The corrosion properties of AZ31 magnesium alloys were studied by potentiodynamic polarization curves and electrochemical impedance spectroscopy（E1S） techniques, meanwhile, the protective properties of two environmentally protective types of chemical conversion layers and anodized coatings of AZ31 magnesium alloys were also discussed. The component of chemical conversion bath is NaH2PO4·12H2O 20 g/L, H3PO4 7.4 mL/L, NaNO2 3 g/L, Zn（NO3）2·6H2O 5 g/L and NaF 1 g/L, and components of the anodization bath is Na2SiO3 60 g/L, C6H5Na3O7·2H2O 50 g/L, KOH 100 g/L and Na2B4O7·2H2O 20 g/L. The results show that the corrosion resistance of AZ31 magnesium increases with the increase of pH value of the corrosive medium. For the chemical conversion layer acquired at 80 ℃, 10 min is the best processing time and the charge transfer resistance of the chemical conversion layer is enhanced nearly by 10 times. The optimum processing time for the anodization of AZ31 is 60 min, the charge transfer resistance value of the anodized sample at the early immersion stage is nearly 26 times of that of the blank sample and the corrosion type of the anodized samples is pitting.     

Effect of treatment time on a PEO-coated AZ31 magnesium alloy

Plasma electrolytic oxidation (PEO) coatings were formed in a phosphate–silicate-based electrolyte containing K₂ZrF₆ on an AZ31 Mg alloy. The physical and chemical properties of the coatings were investigated using scanning electron microscopy, atomic force microscopy, X-ray diffraction (XRD), potentiodynamic polarization, and electrochemical impedance spectroscopy (EIS). The results showed that the thickness of the PEO coatings increased linearly with increased treatment times. Additionally, the micropores on the coating surfaces increased in size, but decreased in porosity with increased PEO treatment time. The XRD results showed that the coatings were mainly composed of MgO, MgF₂, MgSiO₃, and ZrO₂, and the electrochemical tests revealed that the corrosion resistance of the coatings increased with increased treatment time. Besides, the EIS results correlated well with the potentiodynamic polarization test results.     

Preparation and corrosion resistance of superhydrophobic coatings on AZ31 magnesium alloy

In order to improve the corrosion resistance of the Mg alloys, the superhydrophobic coatings on AZ31 Mg alloy were prepared by a two-step process of micro-arc oxidation treatment and superhydrophobic treatment in stearic acid ethanol solution. The effects of voltages, frequencies and treatment time on the contact angle of the superhydrophobic treated sample were investigated. The results showed that with increasing the voltage, frequency and treatment time, all of the contact angles of the superhydrophobic treated sample increased first, and then decreased, reaching the maximum values at 350 V, 1000 Hz and 5 min, respectively. The optimal superhydrophobic coating was mainly composed of MgO and Mg₂SiO₄ phases, with the pore diameter of ～900 nm, the thickness of ～6.86 μm and the contact angle of 156.96°. The corrosion current density of the superhydrophobic AZ31 sample decreased by three orders of magnitude, and the amount of hydrogen evolution decreased by 94.77% compared with that of the AZ31 substrate sample.     

Effects of C6H18O24P6 on properties of micro arc coatings formed on AZ91HP magnesium alloy in Na2SiO3 electrolyte

In a basic solution containing 18 g/L Na2SiO3, the anodizing of AZ91HP magnesium alloy was investigated with and without addition of phytic acid （C6H18O24P6）. The thickness, composition and morphologies of anodic coatings formed at different concentrations of C6H18O24P6 were determined. The corrosion resistance of anodized samples was evaluated by salt spray test in 5% （mass fraction） NaCl solution. The results show that C6H18O24P6, which is harmless and environmentally friendly, greatly affects the properties of anodic coatings. Under the same electric parameters, the final voltage increases with the concentrations of C6H18O24P6. The coating thickness slightly increases from 8 μm formed in the base electrolyte without C6H18O24P6 to 9 10μm in C6H18O24P6 solution. The P content and color of anodic coatings separately increases and darkens with the addition of C6HIsO24P6. After the anodizing solutions were changed from 0 to 16 g/L addition of C6H18O24P6, the largest size of micropores decreases from 4 μm to 3 μm, while the number of micropores per area on coating surface decreases from 0.076 to 0.047μm 2. The salt spray test shows that C6H18O24P6 can improve the corrosion resistance of the anodic coatings and the coating formed in the electrolyte containing 12 g/L C6H18O24P6 exhibits the highest corrosion resistance.     

Barium phosphate conversion coating on die-cast AZ91D magnesium alloy

Poor corrosion resistance limits the application of magnesium alloys.Conversion coating is widely used to protect magnesium alloys because of easy operation and low cost.A novel conversion coating on die-cast AZ91D magnesium alloy containing barium salts was studied.The optimum concentrations of Ba(NO_3)_2,Mn(NO_3)_2 and NH_4H_2PO_4 are 25 g/L,15 mL/L and 20 g/L,respectively,based on orthogonal test results.The treating time,solution temperature and pH value are settled to be 5-30 min, 50-70℃and 2.35-3.0...     

Preparation and property evaluation of electroless Ni-P coatings on AZ91D magnesium alloy

Taking a bath with basic nickel carbonate as the source of nickel, sodium hypophosphite as the reducing agent and citric acid as the complexing agent, the N i-P coatings on AZ91D magnesium alloy were prepared. The influence of pH value of the bath on the content of phosphorus, microhardness and corrosion resistance of the deposits was examined. The XRD analysis results show that the Ni-P coatings plated under all conditions have a mixed microstructure of amorphous and nanocrystalline and undergo a phase transformation to crystalline nickel and nickel phosphide upon heat-treatment. The microhardness of the Ni-P coatings increases with the increase ofpH value of the bath and has a maximum at pH=6. The potentiodynamic polarization test in 3.5%（mass fraction） NaCl solution reveals that the Ni-P coatings exhibit a very good corrosion resistance to protecting AZ91D magnesium alloy.     

挤压铸造AZ81镁合金均匀化热处理工艺研究

为改善挤压铸造AZ81镁合金组织的不均匀性,对铸态试样进行均匀化热处理。采用金相显微镜、X射线衍射仪和扫描电镜对AZ81镁合金的组织与性能进行分析。结果表明:经400℃、8h均匀化处理后,AZ81合金有效地消除了枝晶偏析,改善了材料的组织状态;合金硬度由HRE73.72下降到HRE57.68,屈服强度由130MPa增加到138MPa,抗拉强度由226MPa增加到258MPa,伸长率则由7.6%增加到13.6%;试样的室温拉伸断口均为准解理断裂,经均匀化处理后断裂方式由沿晶界的脆性断裂转变为韧性穿晶断裂。     

挤压态AZ81镁合金的热压缩变形行为

在温度为320～440℃、应变率为0.001～1s-1的变形条件下,采用Gleeble-1500热模拟机对挤压态AZ81镁合金的热压缩变形行为进行研究.结果表明挤压态AZ81镁合金的流变应力随变形温度的升高而降低,随应变率的升高而升高,且随应变的增加,流动应力很快达到峰值,然后逐渐降低并趋于稳定.为评价挤压态AZ81镁合金在热模压成形过程中流动应力,结合Arrhenius方程并引入Zener-Hollomon参数,对流动应力做出相应的修正,根据修正后的流动应力构建挤压态AZ81镁合金流变应力高温变形本构模型.模拟结果表明该模型的应力预测值与试验值吻合较好,计算精度较高,为后续的模压近／净终成形工艺参数的制定提供一定的理论参考.     

Effects of electrolytes on properties of anodic coatings formed on AZ91HP magnesium alloy

In a basic solution containing 10 g/L NaOH, the thickness, morphology and corrosion resistance of anodic coatings formed in solutions without and with additions of Na2SiO3, Na2CO3, Na2B4O7 and Na2SnO3 were separately determined and evaluated. The results show that the electrolytes used above take part in the coating formation and the obtained anodic coatings contain elements from the electrolytes. These electrolytes, especially Na2SiO3 and Na2B4OT, contribute to the film thickness. The coating uniformity obtained by addition of Na2SiO3 is the best, while Na2CO3, Na2B4O7 and Na2SnO3 decrease the number of pores per area on the coatings surface though they worsen the uniformity of the anodic coatings. In addition, the anodic coatings formed in solutions with addition of Na2CO3 or Na2SnO3 exhibit loose and net-like structure. Na2SiO3 and Na2B4O7 can significantly improve the corrosion resistance of the anodic coatings while Na2CO3 and Na2SnO3 have minor effects on improving the coating corrosion resistance.