铸造AZ91镁合金在CO32-/HCO3-体系中的应力腐蚀行为

用电化学实验、浸泡实验与慢应变速率拉伸实验研究铸造AZ91 镁合金在不同浓度比例的CO₃^2-/HCO₃^-溶液体系中的应力腐蚀(SCC)行为。结果表明,随着溶液pH值的升高,AZ91 镁合金的应力腐蚀敏感性降低。点蚀是AZ91镁合金在该实验体系下的裂纹萌生源,随着实验时间的延长,萌生于点蚀底部的微裂纹会逐渐扩展形成主裂纹,主裂纹靠吞并其前端的微裂纹向前扩展,直至发生SCC失效。     

Corrosion Resistance of AZ91 Mg Alloy Modified by High-Current Pulsed Electron Beam

The high-current pulsed electron beam(HCPEB) treatment with current density 6 J/cm~2 was applied on AZ91 Mg alloy to improve its corrosion resistance. Results showed that the net-like Mg_(17)Al_(12) disappeared on the surface of AZ91 Mg alloy after irradiation by HCPEB, which was instead of supersaturated Al element on the surface. Nevertheless, the application of HCPEB also led to the formation of crater-like and groove-like structures as well as micro-cracks on the surface of AZ91 Mg alloy. After HCPEB treatment by 3, 5 and 10 pulses, the AZ91 Mg alloy exhibited better corrosion resistance.However, the increasing amount of micro-cracks reduced the anti-corrosive properties of AZ91 Mg alloy as the pulse increased to 20 and 30.     

NaCl水溶液中AZ91与A3钢的接触腐蚀

研究了NaCl水溶液中AZ9l镁合金与A3钢的接触腐蚀特性。试验结果表明，NaCl水溶液中，镁合金与A3钢接触时发生严重的接触腐蚀，腐蚀主要集中在镁合金与A3钢接触部附近；点蚀的平均孔深和腐蚀质量损失随NaCl浓度的增加和浸泡时间的延长而增加；镁合金接触腐蚀的主要腐蚀产物为Mg(OH)2，MgCO3和MgAl2O4，产物中还检测到因基体腐蚀而脱落的第二相Mgl7Al12。     

压铸镁合金AZ91D在酸性NaCl溶液中的腐蚀行为

采用电化学方法研究了压铸镁合金AZ91D在酸性NaCl溶液中的腐蚀行为,并用扫描电镜观察了腐蚀形貌,对腐蚀产物进行了能谱分析.研究结果表明:在酸性溶液环境下,随着Cl-浓度的升高,镁合金的平衡腐蚀电位降低,线性阻抗减小,腐蚀电流增大;随着pH值的减小,晶界出现腐蚀开裂现象;富Al相的耐蚀性高于基体相,在酸性环境中,腐蚀产物主要为MgO和Mg(OH)2     

States and transport of hydrogen in the corrosion process of an AZ91 magnesium alloy in aqueous solution

Mott–Schottky measurement and secondary ion mass spectroscopy (SIMS) were used to investigate the states and transport of hydrogen during the corrosion behavior of an AZ91 magnesium alloy in 0.1 M sodium sulfate solution. The results showed that when samples were immersed or charged in solution, hydrogen atoms diffused into the film and reacted with vacancy to cause the increases of the carrier concentration (excess electron or hole carrier) and diffusion rate of hydrogen. Some hydrogen atoms diffused to interior of matrix and enriched in β phase while others resorted in the corrosive film. With the increase of immersion or charging time, magnesium hydride would be brittle fractured when the inner stress caused by hydrogen pressure and expansion stress of formation of magnesium hydride was above the fracture strength, which provided the direct experimental evidence of the hydrogen embrittlement (HE) mechanism of magnesium and its alloys. After immersion in solution, the transfer of excess electrons to the interfaces of corrosion film and solution would destroy the charge equilibrium in the film and stimulate the adsorption of , which resulted in the initiation of localized corrosion; after cathodic charging and then immersion, the enrichment of hydrogen atoms at interior of corrosion film would combine into hydrogen gas to form high pressure and result in the rupture of corrosion film, and localized corrosion initiated and developed at surface. Therefore, localized corrosion nucleated earlier on the charged samples than on the uncharged samples. Hydrogen invasion accelerated the corrosion of matrix.     

Stress corrosion cracking of a recent rare-earth containing magnesium alloy,EV31A,and a common Al-containing alloy,AZ91E

Stress corrosion cracking of the magnesium alloy Elektron 21 (ASTM–EV31A) and AZ91E was studied using constant load test in 0.1 M NaCl solution (saturated with Mg(OH)₂), and slow strain rate test using glycerol, distilled water and Mg(OH)₂ saturated, 0.01 M and 0.1 M NaCl solutions. Slow strain rate test indicated that EV31A was less susceptible to stress corrosion cracking than AZ91E. Under less intense loading of constant load, EV31A was found to be resistant to stress corrosion cracking. Fractography of EV31A specimens showed little evidence of hydrogen embrittlement. The superior resistance of EV31A is attributed to a more robust oxide/hydroxide layer.     

AZ91D镁合金电偶腐蚀的研究

在自来水和3.5%NaCl溶液中测试了铸造AZ91D镁合金与铝合金、锌合金、Q235碳钢和Cu偶合后的电偶腐蚀行为,研究了腐蚀环境、偶接材料和阴阳极面积比(CAAR)对铸造AZ91D镁合金电偶腐蚀行为的影响。在电偶腐蚀过程中测量溶液的pH值以及电偶腐蚀电流;用失重法计算了铸造AZ91D镁合金的电偶腐蚀速率,利用SEM观察了AZ91D镁合金的腐蚀形貌,并对腐蚀产物进行XRD分析。结果表明,AZ91D镁合金在电偶腐蚀过程中会使溶液的pH值升高,并伴有以Mg(OH)₂为主的腐蚀产物的生成;溶液中Cl^-的存在会加速AZ91D镁合金的电偶腐蚀速率;低氢过电位金属Q235碳钢和Cu对AZ91D镁合金的电偶腐蚀加速效果明显高于中氢过电位金属铝合金和锌合金,偶接材料的极化性能对AZ91D镁合金的电偶腐蚀速率有较大影响。同时,大的阴阳极面积比会加速AZ91D镁合金的电偶腐蚀速率,且AZ91D镁合金的电偶腐蚀电流随阴阳极面积比的增大而呈线性增长趋势。     

Effects of Mn on Corrosion Resistant Property of AZ91 Alloys

采用电化学、静态失重、盐雾腐蚀法研究了Mn对热处理态AZ91合金耐蚀性能的影响,利用扫描电镜观察试样的微观形貌,用X射线衍射仪分析合金的物相组成和腐蚀产物。结果表明,Mn与AZ91合金中的Al形成了独立相Al6Mn,该相溶解到Mg固溶体中提高了Mg的电极电位,进而提高了合金的耐腐蚀性;Mn加入后使合金的自腐蚀电位升高,自腐蚀电流密度降低,降低了合金的腐蚀速率,进而提高了合金的耐腐蚀性能,且三种实验方法都表明AZ91-0.8Mn合金的耐腐蚀性能最好。     

Corrosion resistance of WE43 and AZ91D magnesium alloys with phosphate PEO coatings

The corrosion performance of WE43-T6 and AZ91D magnesium alloys with and without treatment by plasma electrolytic oxidation (PEO) was investigated by electrochemical measurements in 3.5 wt.% NaCl solution. For untreated WE43-T6 alloy, formation of a uniform corrosion layer (Mg(OH)₂) was accompanied by initial pits around magnesium-rare earth intermetallic compounds. The AZ91D alloy disclosed increased corrosion susceptibility, with localized corrosion around the β-phase, though the β-phase network phase acted as a barrier for corrosion progression. PEO treatment in alkaline phosphate electrolyte improved the corrosion resistance of WE43-T6 alloy only at the initial stages of immersion in the test solution. However, PEO-treated AZ91D alloy revealed a relatively high corrosion resistance for much increased immersion times, contrary to the relative corrosion resistances of the untreated alloys. The improved performance of the PEO-treated AZ91D alloy appears to be related to the formation of a more compact coating.     

混合稀土对AZ91镁合金组织和性能的影响

在ZA91镁合金基础上添加不同含量的混合稀土（MM），对其铸态和固溶时效的组织及性能进行了研究。结果表明，MM显著改变AZ91合金的铸态组织，使Mg17Al12相细化，并出现针状相，从而使硬度，强度提高，但冲击韧度值及伸长率下降，进一步的固溶时效证明该针状相并不固溶于基体中，MM的加入，推迟了AZ91的时效硬化过程。     

Influence of rare earth element Ce and La addition on corrosion behavior of AZ91 magnesium alloy

Two types of AZ91 magnesium alloys containing rare earth element Ce or La were fabricated. Hydrogen evolution and electrochemical tests were carried out to evaluate the corrosion behavior of new AZRE (RE = Ce or La) and AZ91 alloys in 3.5% NaCl solutions (pH 6.50). Various corrosion rate tests indicated that addition of RE obviously enhanced corrosion resistance of AZ91 magnesium alloy. The optimal content of RE was 0.92% for Ce and 0.66% for La. Scanning electron microscopy (SEM), energy dispersive spectrometer (EDS), and low‐angle X‐ray diffraction (XRD) were used to characterize the effect of RE addition on microstructure and corrosion product film of AZ91 magnesium alloy. The refined β phase and formation of γ phase in AZRE alloy were observed by SEM, which resulted in the improvement of corrosion resistance due to the depression of microgalvanic couples. Moreover, the enhanced protective effectiveness of corrosion products was another reason for the improved corrosion resistance.     

Characterization and wear resistance of macro-arc oxidation coating on magnesium alloy AZ91 in simulated bedy fluids

The mechanical characteristics ofthe macro-arc oxidation(MAO) coating on Mg alloy AZ91 were examined by means of nano scratch tester.The corrosion and erosion corrosion behavior of AZ91 with and without MAO coating were investigated by using potentiodynamic electrochemical technique and micro-abrasion tribometer in simulated body fluids,respectively.The influence of HCO3-ions on the erosion corrosion was discussed.The results show that the coating and its substrate are in a pronounced bond.The MAO coating inereases1-2 orders of magnitude of the corrosion resistance of AZ91 alloy.HCO3-ions enhance the corrosion rates of the AZ91 alloys more significantly than the alloys with MAO coating.However,there exists an obvious passivation process of AZ91 without coating in the HCO3-solutions.Moreover,an MgCO3 film formed in HCO3-containing solutions leads to an enhancement in micro-wear resistance.MAO coating deteriorates the erosion corrosion resistance of AZ91 alloy due to the formation of oxidation debris resulted from the broken MAO coating.     

Roles of β phase in the corrosion process of AZ91D magnesium alloy

For better understanding of the roles of β phase in the corrosion processes of AZ91D alloy, corrosion behavior of a cast (α + β phase) and a homogenized (α phase) AZ91D alloy was investigated in NaCl aqueous solution by gas collection and electrochemical measurements. According to the hydrogen evolution properties during corrosion, two different types of corrosion tend might be differentiated. For type I, hydrogen diffused into alloy, which evoked the decreasing of hydrogen evolution rate (HER) and the weakening of negative difference effect (NDE). For type II, in the corrosion process, hydrogen in the alloys diffused into the product film (P-type semiconductor), which suggested that hydrogen entering the film would be ionized. The generated electrons during ionization decreased the concentration of vacancies in the valence band of the product films, indicating an improvement of corrosion resistance of AZ91D alloy.     

AZ91镁合金表面电化学沉积羟基磷灰石涂层的制备及其耐蚀性

采用电化学沉积方法在AZ91镁合金表面制备了羟基磷灰石(HA)涂层,研究了电沉积工艺参数对羟基磷灰石涂层形貌和相组成的影响,并通过腐蚀浸泡试验、极化曲线测试等方法对该涂层的耐蚀性进行了研究。结果表明:当溶液pH为4.5,温度为60℃时,涂层的致密性最好,呈放射状的结构,主要成分为HA相,涂层的厚度约为60~70μm,与基体结合较好;HA涂层对镁合金基体具有较好的保护作用,显著提高了基体合金在生理溶液中的耐蚀性。     

Corrosion behaviour of Mg/Al alloys in high humidity atmospheres

The influence of relative humidity (80–90–98% RH) and temperature (25 and 50 °C) on the corrosion behaviour of AZ31, AZ80 and AZ91D magnesium alloys was evaluated using gravimetric measurements. The results were compared with the data obtained for the same alloys immersed in Madrid tap water. The corrosion rates of AZ alloys increased with the RH and temperature and were influenced by the aluminium content and alloy microstructure for RH values above 90%. The initiation of corrosion was localised around the Al–Mn inclusions in the AZ31 alloy and at the centre of the α‐Mg phase in the AZ80 and AZ91D alloys. The β‐Mg₁₇Al₁₂ phase acted as a barrier against corrosion.     

Effect of Gd on microstructure and stress corrosion cracking of the AZ91-extruded magnesium alloy

AZ91 and AZ91–xGd (x = 0.5, 1.0, 1.5 wt%) magnesium alloys are extruded into plates. The addition of Gd promotes the formation of Al₂Gd, effectively reducing the volume fraction of the β-Mg₁₇Al₁₂ phase and making the banded structures of the extruded magnesium alloys thinner. The corrosion weight loss tests and electrochemistry analyses demonstrate that Gd significantly improves the pitting resistance of the AZ91 in 3.5-wt% NaCl solution saturated with Mg(OH)₂. Slow strain rate tensile tests show that in a corrosive environment, compared with AZ91, the elongation to failure of the AZ91–1.0Gd alloy is increased by 47%, and the alloy exhibits excellent stress corrosion resistance in this study. The fracture mode of AZ91 is changed from typical intergranular fracture to a mixture of transgranular and intergranular fracture in the corrosion solution by adding Gd. The mechanism of Gd to improve the stress corrosion resistance of the AZ91 magnesium alloy is that Gd increases the corrosion resistance, especially the pitting of AZ91.     

Corrosion Behavior of AZ31 Magnesium Alloy in Highly Alkaline Environment

Industrial components made with a magnesium-aluminum alloy AZ31 are often used in diverse engineering applications where component weight,strength,and durability are critical.Similarly as other Mg alloys,however,the AZ31 is susceptible to corrosion in alkaline environments.In this work,corrosion of commercial grade AZ31 alloy plate was examined in potassium hydroxide(KOH) using immersion and potentiodynamic studies.The results suggest that the concentration of Al and Mn in the alloy may govern the kinetics of micro-galvanic corrosion and the initiation of corrosion pits.Further,trace amounts of Ni in the AZ31 alloy were seen to enable formation of Ni(OH)2 surface layer,which may have further accelerated alloy corrosion due to its cracking and void coalescence.The effect of pH on the corrosion behavior of AZ31 was studied with reference to Pourbaix diagrams.     

Mg合金AZ91D在城市大气环境中的腐蚀行为

用扫描电镜、X射线衍射方法对Mg合金AZ91D在城市大气中的腐蚀层形貌,腐蚀产物进行了分析和研究。结果表明:腐蚀初期在材料表面生成一层Mg(OH)_2薄膜,随着腐蚀的不断进行,膜增厚并开裂,最终形成网状结构,在裂纹处水蒸气容易凝聚,腐蚀性气体及盐粒容易吸附,且裂纹或缝隙为氧的扩散提供了通道,造成Mg合金局部腐蚀严重,生成的腐蚀产物主要为Mg(OH)_2,Al(OH)_3,Mg_2CO_3(OH)_2·3H_2O和Mg_2(OH)_3Cl-4H_2O,这些微溶的腐蚀产物对基体起到了一定的保护作用,从而在后期降低了Mg合金的腐蚀速率。     

AZ91D镁合金电偶腐蚀的扫描Kelvin探针研究

利用扫描Kelvin探针技术(SKP)研究AZ91D镁合金与316L不锈钢偶接件在盐雾试验中电偶腐蚀规律。通过在中性盐雾试验不同周期的表面腐蚀形貌的观察和伏打电位分布图的测量结果分析表明,AZ91D镁合金电偶腐蚀效应与偶接阴阳极的伏打电位差密切相关,AZ91D镁合金与316L不锈钢偶接件存在较大的电位差(约为–1.28V),其电偶腐蚀效应非常显著。在盐雾试验初始阶段,腐蚀主要发生在偶接界面AZ91D镁合金一侧,该腐蚀区域的伏打电位增加幅度较大,而316L不锈钢受到保护没有发生明显腐蚀。随着盐雾试验时间的延长,AZ91D镁合金腐蚀加快,腐蚀产物覆盖区域不断扩大,24h盐雾试验后,偶接件的平均伏打单位差由原始的–1.29V增加到–1.53V,AZ91D镁合金的电偶腐蚀效应加大。由于AZ91D镁合金在盐雾中生成的腐蚀产物对基体具有一定的保护作用,当腐蚀产物不断增加并覆盖表面,偶接件的电位差减小导致AZ91D镁合金的电偶腐蚀效应降低。     

AZ31镁合金摩擦搅拌焊在慢拉伸应力腐蚀过程中的组织演化和氢致延迟开裂

研究AZ31镁合金摩擦搅拌焊组织的演化,包括织构和断口变化。利用中子衍射仪测量织构。利用光学显微镜和扫描电子显微镜观察应力腐蚀开裂（SCC）样品的金相及断口形貌。利用X射线衍射仪研究SCC样品的断口表面结构。结果表明,在母材表面形成了明显的基面织构。然而,搅拌区晶粒发生了基面旋转,大多数晶粒的基面沿着焊接方向倾斜25°。在慢拉伸应力作用下,在空气和侵蚀性溶液中分别形成了羽毛状孪晶和氢化物。在溶液中,穿晶裂纹扩展,最终断裂在回转侧。在断口表面存在的氢化物表明镁合金应力腐蚀可能存在氢致延迟开裂机制。