Structure Analysis of Oxidation Film of Ignition-Inhibition AZ91D Magnesium Alloy Added with Cerium

The effect of cerium on ignition temperature of AZ91D magnesium alloy was studie d. By the addition of cerium of 1%, the ignition temperature is raised by 180 ℃ , s o the magnesium alloy added with cerium can be melted in air. The burning temper ature increases with the increasing of cerium. The structure and chemical compos itions of the surface oxide film were investigated by XRD and Auger electron spe ctrometry(AES). The results of XRD indicate that the oxide film of the surface o f ignition-inhibition magnesium alloy can change from loose structure of simple magnesia to compact composite structure consisting of magnesia, cerium oxide, M g17 A112 and aluminum oxide, which has excellent ignition-inhibition effect. AE S depth profile analysis shows that the oxide film can be divided into three lay ers. The outside layer is mainly made up of magnesia, the middle layer, which co nsists of cerium oxide, magnesia, and aluminum oxide, is compound and compact. T hermodynamic analysis indicates that the structure of the surface oxide film is accordant to the change of free energy and high vapor pressure of magnesium.

Preparation and Performance of Rare Earths Chemical Conversion Film on Magnesium Alloy

Golden yellow cerium conversion film was obtained on magnesium alloys surface by immersion method and the preparation parameters were established. The influence of different process parameters on the surface morphology and performance of the conversion film were analyzed by means of SEM and electrochemical method. Formation dynamics about cerium conversion film on magnesium alloy in solution containing cerium salt and the anti-corrosion behavior of the conversion film in 3.5% NaCl solution were studied by electrochemical method respectively. The results shows that the conversion film is more compact at room temperature when concentration of cerium sulfate is 10 g·L-1 in the solution; the open circuit potential of the magnesium sample moves up to positive direction about 100 mV, the surface of conversion film becomes even and lustrous, and the adhesion intensity of conversion film increases when adding aluminum nitrate into the solution containing cerium salt. The pH value of the solution and immersion time of the sample in the solution also affect the surface morphology and anti-corrosion property of the conversion film. After covered by rare earths conversion film, the anti-corrosion property of magnesium alloy is obviously improved. Rare earth conversion film has self-repairing capability in corrosion medium.

Characterization of oxide films formed on magnesium alloys using bipolar pulse microarc oxidation in phosphate solutions

The surface morphology and chemical composition of the oxide films formed on pure magnesium and AZ91D alloy in aqueous electrolytes which contained sodium hexafluorinealuminate（Na3AlF6）, potassium hydroxide （KOH）, sodium hexametahposphate（（NaPO3）6）, and triethanolamine were investigated by X-ray diffraction（XRD）, scanning electron microscope（SEM） and energy dispersive spectroscopy（EDX）. The results show that the input of the negative pulse has great influences on the quantity and the appearance of the microdischarges. Three types of pores can be distinguished on the surface of the oxide film and their size ranges are 0.5-1μm, 1-2μm and 4-7μm, respectively. A few microcracks are seen around the large pores. There exists a remarkable fluoride- enriched zone of about 4-6μm for pure magnesium and 3-5μm for AZ91D alloy at the coating/substrate interface.

Hemolysis effect and calcium-phosphate precipitation of heat-organic-film treated magnesium

A heat-organic-films process was employed to induce calcium-phosphate apatites formation on magnesium, consequently the corrosion resistance and hemolysis properties of magnesium were improved for biomedical applications. Firstly, magnesium samples were heat-treated at 773 K for 10 h; secondly, stearic acid films were coated on the surface of the heat-treated magnesium. Then the surface modified magnesium was soaked in simulated body fluid (SBF) to test its corrosion resistance. The results show that the heat treatment process allows magnesium to form a dense oxide layer with a thickness of around 20 μm, thereby the surface modified magnesium has higher corrosion resistance. After 24 h in SBF island apatite was deposited on magnesium. The unevenly precipitates were characterized by XRD and FTIR as the mixture of hydroxyapatite(HA) and octacalcium phosphate(OCP). The preliminary hemolysis experiment indicates that untreated magnesium has hemolytic effect (about 60%); whereas the heat-organic film treated samples has no hemolytic effect. The mechanism of fast nucleation and growth of calcium-phosphate apatites on surface modified magnesium in SBF was also discussed.

Growth characterization of anodic film on AZ91D magnesium alloy in an electrolyte of Na_2SiO_3 and KF

Anodization of AZ91D magnesium alloy in the electrolyte solution of 0.5 mol/L of sodium silicate and 1.0 mol/L of potassium fluoride was investigated. The anodic films were characterized using optical microscopy （OM）, scanning electron microscopy （SEM）, and X-ray diffraction （XRD）. The corrosion resistance of the various anodized alloys was evaluated by a fast corrosion test using the solution of hydrochloric acid and potassium dichromate. The results showed that the addition of KF resulted in the presence of NaF in the anodic film. The thickness of the anodic film formed under a constant current density of 20 mA/cm^2 for 16 rain at 60℃ exceeded 100 gm. The growth of the anodic film could be divided into three stages based on the anodizing time; the growth rate was much faster during stage Ⅱ than in stages I and Ⅲ. The anodic film exhibited the highest corrosion resistance for the AZ91 alloy, which is attributed to the fact that the anodization was maintained until the end of stage Ⅱ.

Influence of Solution Composition on Formation of Golden Yellow Rare Earth Conversion Film on Magnesium Alloy

Cerium sulfate was used as main composite in solution to prepare golden yellow chemical conversion film on magnesium alloy. The influence of solution composition on the surface morphology of golden yellow rare earth conversion film on magnesium alloy was studied by means of SEM; potential-time curves in the formation process of rare earth conversion film and the anti-corrosion property of the conversion film were tested through ECT. The results show that, when there is no other component in the solution besides cerium sulfate, yellow film can be obtained on magnesium alloy, but there are some dusts on the film surface and the solution is not stable. The stability of cerium sulfate solution increases with adding hydrogen peroxide, while the film is thin and its color turn light. After adding combination additive containing Al 3+, smooth and compact golden yellow film was obtained on magnesium alloy. The polarization curves tested in 3.5% NaCl solution show that the anti-corrosion property of magnesium alloy is increased obviously by rare earth conversion film, and the film has self-repairing capability in the corrosion process.

Growth and Corrosion Characteristics of Plasma Electrolytic Oxidation Ceramic Films Formed on AZ31 Magnesium Alloy

The growth characteristics of oxide ceramic films formed on AZ31 magnesium alloy with plasma electrolytic oxidation (PEO) technique in alkaline silicate solution were investigated. The composition, structure and morphology of the coatings were detected by energy dispersive X-ray spectroscope and scanning electron microscope. The amount of dissolved magnesium in the electrolytes during PEO process was measured by atomic absorption spectrometry. The results indicated that the growth process of PEO films had three stages when applied with constant voltage mode. In the first stage, the growth rate of PEO films was low, and concentrations of elements O, Mg and Si varied slightly. After sparking occurred (the second stage), the PEO films showed higher growth rate due to the high transfer rate of ions and electrons, and the existence of plasma reactions. When the growth rate tended to maintain stable with time, the third stage happened. PEO films exhibited different uniform and pitting-corrosion characteristics in different reaction stages. The films formed at 300 V for 30 min performed best corrosion resistance and the phase of ceramic films was mainly composed of MgSiO3 and forsterite Mg2SiO4.

Corrosion action and passivation mechanism of magnesium alloy in fluoride solution

Corrosion action and passive mechanism of magnesium alloy in the fluoride solution were studied by means of scanning electron microscopy(SEM), energy dispersive X-ray spectroscopy(EDS), and electrochemistry methods. The results show that an insoluble MgF2 film is generated on the surface of magnesium alloy activated in the hydrofluoric acid. And the mass of the deposited MgF2 film may reach a constant value, when the mass ratio of Mg/F on the magnesium alloy surface is fixed at 11.3-1. The activated magnesium alloy gains a ‘passivation state’ in a mixture of sulfuric acid and hydrofluoric acid at a volume ratio of less than 1.2. At the same time the mass of magnesium alloy is maintained as a function of the time. When the ratio is above 1.4, the mass of magnesium alloy rapidly decreases. The passive film formed through adsorption of HF2- (or H2F3-, H3F4-) ions by the deposited MgF2 film can protect the magnesium alloy from corrosion in fluoride solution, but not in non-fluoride solutions. The passive state is maintained for activated magnesium alloy in an acidic sulfuric nickel solution with added fluoride. If fluoride and carbonate are added to the acidic sulfuric nickel solution, a replacement reaction between magnesium alloy and solution takes place.

Microstructures and properties of aluminum film and its effect on corrosion resistance of AZ31B substrate

Aluminum films with thickness of 8.78-20.82μm were deposited on the AZ31B magnesium alloys by DC magnetron sputtering.The influences of aluminum film on the micro-mechanical properties and corrosion behavior of the magnesium alloys were investigated.The morphology of aluminum film was examined by scanning electron microscopy and the microstructure of aluminum film was analyzed by X-ray diffiactometry.Nanoindentation and nanoscratch tests were conducted to investigate their micromechanical properties.Moreover,potentiodynamical polarization test performed in 3.5%NaCl solution was carried out to study their anticorrosion performances.The results show that the surface hardness of AZ31B magnesium alloy with aluminum film is 1.38-2.01 GPa,higher than that of the magnesium alloy substrate.The critical load of Al film/AZ31B substrate is in the range of 0.68-2.77 N. The corrosion current density of AZ31B with aluminum film is 2-3 orders of magnitude less than that of bare AZ31B.And the corrosion potential with aluminum film positively shifts.Thus aluminum film can increase the corrosion resistance of Mg alloys obviously.

A novel electroless silver depositing method for magnesium alloys

Depositing silver on magnesium alloy by both electroless plating and organic coatings was studied. The organic coating was made by immersing samples in organosilicon heat-resisting varnish. In this method the organic coating acts as interlayer between the substrate and silver film. When the reaction starts, silver deposits directly on the interlayer. X-ray diffraction and SEM analysis were used to determine the composition and morphology of the interlayer and silver film. The potentiodynamic polarization curves for corrosion studies of coated magnesium alloys were performed in a corrosive environment of 3.5% NaCl(mass fraction) at neutral pH (6.9). The results indicate that compared with the substrate, the corrosion resistance of coated magnesium alloys increases greatly. Moreover, the method proposed in this work is environmentally friendly, non-toxic chemicals were used. In addition, it provides a new concept for the corrosion inhibition of magnesium alloys.

Study on Ignition-Proof AZ91D Magnesium Alloy Added with Rare Earth

Magnesium alloy is prone to burning during its melting and casting processes in air, which is a major factor of obstructing its application. Fluxes and cover gases are currently used for the melting and production processes, and semi-solid casting is also used to shape composites made of magnesium alloy, but there still remain many problems. Alloying is a promising method of preventing magnesium from burning. The effect of RE additions on the ignition temperature of AZ91D magnesium alloy was investigated. The changes of the quality of oxidation film and the as-cast microstructure were analyzed, and the mechanical property was compared with that without rare earth. For AZ91D with RE in the range of 0.08% to 0.12%. It is shown that the ignition temperature point can be greatly heightened, the quality of oxidation film is obviously improved, the as-cast microstructure is refined greatly, and the mechanical property is bettered a little, therefore, such an alloy is promising.

时效态WE43合金表面腐蚀产物膜的显微组织

时效态WE43合金在3.5 wt.%NaCl溶液中形成了致密且具有3层结构的腐蚀产物膜。采用透射电子显微镜分析膜层的显微组织。保护性膜层为3层结构,从内到外依次为RE_(2)O_(3)层、MgO与RE_(2)O_(3)的混合层和Mg(OH)2与RE_(2)O_(3)的混合层。析出相和稀土元素通过外氧化的方式形成大量稀土氧化物颗粒,这是保护性膜层形成的主要原因。RE_(2)O_(3)与MgO存在以下择优位向关系:(211)晶面和[231]晶向分别与MgO的(002)晶面和[110]晶向平行。因此,稀土氧化物颗粒可以填补疏松MgO膜层的空隙,从而提高了膜层的致密性。内层的RE_(2)O_(3)和MgO与RE_(2)O_(3)的混合层对于保护性膜层的形成起到了重要作用。致密的内层腐蚀产物膜能阻止腐蚀介质与镁基体发生反应。

Corrosion resistance of Mg-Mn-Ce magnesium alloy modified by polymer plating

Polymeric nano-film on the surface of Mg-Mn-Ce magnesium alloy was fabricated by polymer plating of 6-dihexylamino-1,3,5-triazine-2,4-dithiol monosodium(DHN) to improve its corrosion resistance.The electrochemical reaction process was analyzed by cyclic voltammetry and two obvious peaks of oxidation reaction were observed.The static contact angle of distilled water on polymer-plated surface can be up to 106.3°while on the blank surface it is 45.8°.Potentiodynamic polarization results show that the polymeric film can increase the corrosion potential from -1.594 V vs SCE for blank to -0.382 V vs SCE.The results of electrochemical impedance spectroscopy indicate that the charge transfer resistances of blank and polymer-plated Mg-Mn-Ce alloy are 485Ω·cm^2 and 2 717Ω·cm^2,respectively.The method of polymer plating can provide a novel approach for fabricating hydrophobic film on Mg-Mn-Ce alloy surface and improving its anti-corrosion property.

Improving wear resistance of magnesium alloy AZ91D by TiN-CrN multilayer coating

Applying a novel method of arc-glow plasma depositing, a 2μm-thick coating with 12 sub-layers of TiN and CrN was deposited alternately on the surface of magnesium alloy AZ91D to improve its wear resistance. The wear behavior was investigated by test of ball on disc sliding. The composition and microstructure of the coating were also analyzed by means of X-ray diffraction (XRD) and glow discharge spectrum (GDS), and the morphology of TiN-CrN film was surveyed through scanning electronic microscopy (SEM) and atom force microscopy (AFM).The adhesion strength between film and matrix was evaluated by ways of stick-peeling test. The surface micro-hardness of the coating is above HK0.011 433, and the specific wear ratio of specimens coated with TiN-CrN films tested decreases greatly compared to that of the bare metal.

镁合金建筑模板的表面化学镀与耐蚀性能

采用化学镀的方法在镁合金建筑模板表面分别制备了单一Sn膜、单一Zn膜和复合Sn-Zn膜,对比分析了pH、温度和膜层数对镁合金表面膜层显微形貌和电化学性能的影响。结果表明:对于单一膜,在pH值为6.0、温度为75℃时制备的单一Sn膜和在pH值为9.5、温度为75℃时制备的单一Zn膜都具有较好成膜质量;当膜层数为9时,复合Sn-Zn膜完全覆盖镁合金基体且膜层成膜质量较好。相较于镁合金基体,单一Sn膜、单一Zn膜、复合Sn-Zn膜的腐蚀电位都发生正向移动,腐蚀电流密度发生不同程度减小,复合Sn-Zn膜的腐蚀电位最正、腐蚀电流密度最小。在镁合金基体表面化学镀单一Sn膜、单一Zn膜、复合Sn-Zn膜都有助于提升镁合金的耐蚀性能,且复合Sn-Zn膜对基体的保护作用要优于单一Sn膜、单一Zn膜。

螯合剂辅助法制备镁合金表面Mg-Al LDHs膜及其耐蚀性

为了降低反应能耗,利用螯合剂辅助法,通过在硝酸铝(Al(NO_(3))_(3))溶液内分别添加乙二胺四乙酸四钠(EDTA-4Na)、柠檬酸钠(SC)和酒石酸钾钠(PST)三种螯合剂制备转化液,然后将镁合金样品直接浸泡在三种转化液中,于60℃,pH值为12.0下反应9 h,即可在镁合金表面制得不同螯合剂掺杂的Mg-Al层状双氢氧化物(layered double hydroxides,LDHs)膜。通过SEM,XRD,FT-IR等分析各LDHs膜的微观形貌、物相组成和耐蚀性。结果表明:螯合剂辅助法可以在常压、60℃环境下于镁合金表面成功制得具有典型层状结构的LDHs膜;并且所得的三种Mg-Al LDHs膜均能有效提高镁合金的耐蚀性。然后通过对比研究三种不同LDHs膜层的结构性能发现:添加PST制备得到的Mg-AlPST LDHs膜致密度最高、厚度最大,可达1.4μm。三种膜层对镁合金耐蚀性的提高效果依次为:Mg-Al-PST LDHs>Mg-Al-SC LDHs>Mg-Al-EDTA LDHs;其中覆盖Mg-Al-PST LDHs膜的镁合金相比空白镁合金,其腐蚀电流密度下降约两个数量级,腐蚀总电阻上升约一个数量级。基于对所得LDHs膜的结构、性能分析可知螯合剂辅助法可在较低能耗条件下,在镁合金表面原位制备耐蚀性较好的Mg-Al LDHs膜的原因可能是:螯合剂中的羧基可加速Al^(3+)在镁基底的沉积,并促进Al^(3+)对Mg(OH)_(2)中部分Mg^(2+)的取代而形成LDHs。

基于阴极沉积Mg(OH)_(2)薄膜的镁合金超疏水表面改性及其耐蚀性研究

为延长镁合金的使役寿命,通过阴极沉积和超疏水改性在ME20M稀土镁合金表面制备超疏水涂层,采用硬脂酸乙醇基溶液对阴极沉积Mg(OH)_(2)薄膜的镁合金进行化学修饰,通过单因素试验分别考察硬脂酸浓度、溶液温度、浸泡时间对表面润湿性的影响规律,确定最优修饰工艺。对典型试样,采用点滴实验、全浸腐蚀实验及现代电化学测试技术评估其耐蚀性,采用划格法评价膜/基结合力,采用SEM、FT-IR及XRD分析试样表面微观形貌及成分。结果表明:阴极沉积Mg(OH)_(2)薄膜经低浓度硬脂酸溶液短暂浸泡即可获得超疏水性,蒸馏水静态接触角SCA高达151.5°,滚动角SA低至1.0°,呈低黏性。阴极沉积/疏水改性复合处理可显著改善镁合金的耐蚀性,与空白试样相比,复合处理试样的点滴液变色时间延长近25倍,在3.5%NaCl溶液中的自腐蚀电流密度Jcorr降低3个数量级,特征阻抗模值|Z|_(0.1 Hz)提高4个数量级。经疏水处理的阴极沉积Mg(OH)_(2)薄膜呈刀片状微纳结构,试样的红外光谱中出现明显的-CH_(3)和-CH_(2)-吸收峰。

化学气相沉积Cr/DLC薄膜对Mg-Gd-Y合金耐蚀性能的改善

Mg-Gd-Y合金作为一种优秀工程材料在石油天然气勘探开发中具有广泛应用。为了改善其在井下工作服役时的耐蚀性能,研究了以Cr为过渡层的类金刚石薄膜(DLC)对Mg-Gd-Y合金耐蚀性能的影响。采用等离子体增强化学气相沉积(PECVD)法制备了以Cr元素为过渡层的类金刚石薄膜,采用拉曼光谱分析DLC膜层的碳结构类型,采用3.5%(质量分数)NaCl盐雾腐蚀试验、电化学极化测试及接触角测试评价了试样的耐蚀性能,采用SEM分析了试样腐蚀前后的表面形貌及断面形貌。结果表明:由拉曼光谱检测数据计算得出,Cr/DLC薄膜的I_D/I_G值为0.64,说明膜层中sp~3杂化键所占比例较多,且组织致密,因此Cr/DLC薄膜在3.5%NaCl溶液中的腐蚀倾向和腐蚀速率降低。Cr/DLC薄膜有效提高了镁合金基体的耐蚀能力。

镁合金原位生长水滑石研究进展

镁合金是常见轻质金属结构材料,但易腐蚀的特性限制了其在工业中的广泛应用。水滑石具有超强的吸附能力和阴离子可交换性等特点,可为镁合金提供有效防护。文章综述了镁合金原位生长水滑石的研究进展,主要包括成膜工艺、成膜机理、防腐蚀机理及在镁合金防腐涂层中的应用。目前常用的制备方法包括原位直接生长法、两步法、阴离子置换法和电沉积法。原位生长法制备较为简单,但会出现较多的副产物;而两步法和阴离子置换法可以通过控制反应条件和调节溶液成分来实现水滑石的原位生长,能够得到较好的涂层质量和性能;电沉积法更为高效快速,但涂层结合力有待提高。现有的水滑石成膜机理大体可以分为4种成膜机理,而水滑石往往会在第二相附近和缺陷处优先形核。水滑石涂层防腐机理可以概括为涂层屏蔽、离子吸附和涂层自愈合。最后对水滑石未来的发展进行了展望。

溶液电导率对ZM5镁合金微弧氧化膜层结构与性能的影响

研究溶液电导率对ZM5镁合金微弧氧化膜层结构和性能的影响。使用涂层测厚仪、粗糙度检测仪、维氏硬度仪、游标卡尺、天平、维氏硬度仪、SEM、EDS、XRD、电化学工作站分别对膜层厚度、粗糙度、外延生长率、致密度、显微硬度、微观形貌、元素组成和分布、晶相结构和电化学性能进行测试分析。结果表明,随着溶液电导率的增加,膜层厚度、粗糙度、外延生长率、显微硬度逐渐增加,外观和致密度无明显变化,微观形貌中放电微孔数量逐渐增加,晶相结构中MgO、MgF_(2)和K_(2)MgF_(4)的含量没有明显差别,Mg和O含量基本保持稳定,F元素的含量随导电率增加下降明显。膜层的耐蚀性随溶液电导率增加而增大,电导率为30ms/cm时,耐蚀性最强。