Cu含量对一种新型Al-Mg-Si合金晶间腐蚀的影响

采用浸泡腐蚀实验和电化学实验研究了Cu含量变化和热处理条件对一种新型舰载飞机用Al-Mg-Si合金的耐腐蚀性能的影响.结果表明,添加Cu后,实验合金的 腐蚀方式由点蚀转变为晶间腐蚀,且腐蚀程度随Cu含量的增加而严重;与欠时效和过时效状态相比,T6态对晶间腐蚀较敏感,与晶界析出相的连续分布有关.电化学实验表明,所有实验合金均较快进入钝态;随Cu含量的增加,实验合金的自腐蚀电位向正向变化,腐蚀电流密度增加;随时效时间的延长,点蚀电位、晶间腐蚀的临界点位和自腐蚀电位逐渐向负向变化.而点蚀电位和自腐蚀电位随时效时间呈抛物线变化,晶间腐蚀的临界电位则呈直线变化.        

Significantly changed intergranular corrosion and exfoliation corrosion behavior of the ultra‐fine grained Al–5 mass% Cu alloy fabricated by ECAP

Significantly changed intergranular corrosion (IGC) and exfoliation corrosion (EFC) behaviors of the equal‐channel‐angular‐pressed (ECAPed) Al–Cu alloy were discovered through immersion test, electrochemical measurements, and microstructure observation. The ECAPed alloys with ultra‐fine grained (UFG) α(Al) matrix and extremely refined θ‐phase particles displayed obvious decreased IGC sensitivity, but deteriorated susceptibility to EFC. The decreased IGC sensitivity of ECAPed alloys presented decreased IGC propagation depths in immersion test in NaCl + H₂O₂ solutions and increased polarization resistance in electrochemical impedance spectrum test in MIL‐H‐600 solution. The reason for the decreased IGC sensitivity was the breakage of the net structure of θ phase during ECAP process, which destroys the continuity of IGC propagation channel. The deteriorated susceptibility to EFC of ECAPed alloys in EXCO solution presented gradual evolution from serious IGC attack into obvious lamellar EFC, and finally complete dissolution of surface grains. Meanwhile, the EFC propagation depths were sharply decreased with the increasing ECAP passes. This phenomenon was caused by the aspects ratio evolution of deformed grains and the gradually decreased IGC sensitivity of the ECAPed alloys.     

Corrosion behaviour of twin belt cast EN AW 7075 alloy

The corrosion behaviour of the twin belt cast EN AW 7075 alloy is governed by intermetallic phases, namely Al₁₂(Fe,Cr,Mn)₃Si, Mg₂Si and CuAl₂, and by Mg(Zn,Cu,Al)₂ precipitates. The former are responsible for pitting activities while the Mg(Zn,Cu,Al)₂ precipitates play a key role in intergranular corrosion. The very fine dispersion of Mg(Zn,Cu,Al)₂ precipitates in samples aged to peak hardness undergo coarsening, particularly along the grain boundaries, when the hot band samples are overaged. Overageing improves the resistance to intergranular corrosion while the samples in T6 temper suffer heavy attack along grain boundaries. While ageing treatments hardly produce any change in the features of the intermetallic particles, they nevertheless seem to impact the pitting response. This may be accounted for also by the precipitation activities which in turn, change the chemistry of the solid solution matrix. Overageing to the T73 temper implies a higher purity matrix and thus changes the microgalvanic effects when exposed to neutral chloride solutions.     

Exfoliation and intergranular corrosion resistance of the 2198 Al–Cu–Li alloy with different thermomechanical treatments

In this study, the resistance to exfoliation and intergranular corrosion (IGC) of the 2198 Al–Cu–Li alloy submitted to different thermomechanical treatments (T3, T8, and T851) was investigated. The tests were carried out following the standard practices, ASTM G34-18 and ASTM G110-15, respectively. All the tested alloys showed susceptibility to exfoliation and some alloys showed susceptibility to IGC, but the artificially aged alloys presented a higher tendency to exfoliation. The extensive hydrogen evolution reaction (HER) was observed on the surfaces of artificially aged alloys when immersed in the EXCO solution. The HER resulted in an increase in solution pH with the time of immersion. Also, the weight losses related to the artificially aged alloys were higher than that of the naturally aged ones. The T8 treatment was the only condition that resulted in susceptibility to both, intergranular and transgranular corrosion, whereas the T851 treatment did not show IGC susceptibility, only transgranular corrosion. Finally, the 2198-T3 condition showed the highest corrosion resistance among the thermomechanical treatments tested. The results of the 2198 alloy subjected to various treatments were compared with that of the 2024-T3 alloy. This last alloy showed higher resistance to exfoliation and IGC as compared with the 2198 alloy.     

Effect of artificial aging on intergranular corrosion of extruded AlMgSi alloy with small Cu content

The effect of artificial aging parameters on the corrosion performance of air cooled AlMgSi(Cu) model alloy extrusions was investigated. Accelerated corrosion test revealed that the extrusions were highly susceptible to intergranular corrosion (IGC) in the naturally aged condition. However, IGC susceptibility was reduced, and finally eliminated, by artificial aging. Overaging introduced slight pitting susceptibility. EDS X-ray mapping in FE-TEM revealed Mg₂Si and Q-phase (Al₄Cu₂Mg₈Si₇) grain boundary precipitates and a continuous Cu-enriched grain boundary film. IGC susceptibility was related to the Cu-enriched grain boundary film. Increased IGC resistance was caused by coarsening of the grain boundary film by aging. Pitting susceptibility by over aging evolved due to coarsening of the Q-phase particles in the grain bodies.     

Improving corrosion resistance of Al‐11mass%Si alloy through a large number of ECAP passes

Ultrafine‐grained (UFG) Al‐11mass%Si alloy, processed by multi‐pass equal‐channel angular pressing (ECAP) at 573 K, was investigated on corrosion behavior in 0.6 M NaCl solution. Potentiodynamic polarization tests and scanning electron microscopy observation showed that a large number of ECAP passes resulted in lower corrosion current density, more positive corrosion potential, and rather smooth corroded surface with shallow corrosion pits. The uniform distribution of fine secondary‐phase particles on UFG Al matrix weakened the susceptibility to pitting corrosion while inhibited general microgalvanic reactions. The present results indicate that grain refinement of aluminum matrix to the UFG state and uniform redistribution of broken particles (including eutectic silicon and secondary phases), via severe plastic deformation at elevated temperature undergoing dynamic recrystallization, can significantly improve the corrosion resistance of Al alloys, besides the known exceptional mechanical advantages. The simple and effective ECAP procedure makes UFG Al alloys more attractive for high strength structural application in corrosive environment.     

A comparative study on corrosion of Mg–Al–Si alloys

Corrosion behavior of various Mg–Al–Si alloys (AS11, AS21, AS41, AS61 and AS91 series), cast under the same cooling conditions and controlled alloying composition, was investigated systematically. Optical microscopy and scanning electron microscopy were used for microstructural examinations. The corrosion behavior was evaluated by immersion tests and potentiodynamic polarization measurements in 3.5% NaCl solution. The results from both immersion tests and the potentiodynamic polarization measurements showed that marginal improvement in corrosion resistance was observed with 2.0% Al (mass fraction) containing alloy (AS21) whereas Al addition above 2.0% (AS41, AS61 and AS91) deteriorated the corrosion resistance which was attributed to β phase, acting as cathode, and the interruption of continuity of the oxide film on the surface of the alloys owing to coarsened β and Mg₂Si phases.     

Corrosion and self‐healing behaviour of AZ91D magnesium alloy in ethylene glycol/water solutions

Corrosion behaviour of magnesium alloy‐based engine parts in cooling system is an urgent fundamental issue in automotive field where magnesium alloys are increasingly used. In the present work, the corrosion behaviour of AZ91D magnesium alloys in various ethylene glycol/water solutions was studied by electrochemical measurements and immersion tests at room temperature. The surfaces of the samples after immersion tests were examined using scanning electron microscope (SEM) and X‐ray diffraction (XRD). The results showed that the corrosion rates of AZ91D magnesium alloys decreased with the increase of ethylene glycol concentration in ethylene glycol/water solutions and the corrosion process was dominated by pitting corrosion. A continuous protective film transferred from corrosion products was formed on the corroded surface after sufficient immersion duration in ethylene glycol/water solutions, which is able to heal the corrosion pits. The self‐healing behaviour inhibited the further corrosion of AZ91D magnesium alloy.     

Stress corrosion behavior of 6082 aluminum alloy

Stress corrosion tests of 6082 aluminum alloy were carried out by using a three-point bending fixture while holding at 50% of yield strength state through different immersion times in 1.5% NaCl electrolyte solution. The electrochemical impedance spectra and dynamic electric potential polarization curves were measured to indicate the stress corrosion behavior of the alloy. Optical microscopy, scanning electron microscopy, and X-ray energy spectrum analysis were applied for microstructural investigations. The results show that all of the Nyquist electrochemical impedance spectra consisted of high- and low-frequency double capacitive arcs. However, an increase in immersion time while holding at 50% of yield stress resulted in a corresponding increase in the corrosion current density, leading to gradual corrosion depth growth, and a decrease in the corrosion resistance of the alloy. 6082 Aluminum alloy included AlMnFeSi, Mg₂Si, and Si secondary phases. The different secondary phases presented different stress corrosion behaviors. Stress corrosion cracks were generated at the boundaries of AlMnFeSi and matrix or within the AlMnFeSi phase. Crack direction is always perpendicular to the tensile stress applied. Mg₂Si secondary phase was self-corroded as its corrosion potential is lower than that of the matrix. As the electric potential of Si is higher than that of the matrix, corrosion occurred at the matrix side of the boundary between Si and matrix.     

电弧喷涂Al-Zn-Si-RE合金涂层在3.5%NaCl溶液中的电化学腐蚀行为(英文)

采用电弧喷涂方法在低碳钢表面获得高铝含量的Al-Zn-Si-RE涂层。通过测量Al-Zn-Si-RE涂层在3.5%NaCl溶液中的动电位极化曲线,腐蚀电位-时间曲线和电化学阻抗谱,系统地研究涂层的电化学腐蚀行为。通过将测量电化学阻抗谱拟合成等效电路图,研究涂层在3.5%NaCl溶液中浸泡不同时间的阻抗行为。结果表明:Al-Zn-Si-RE涂层与Zn-15Al涂层具有相似的极化行为,阳极极化曲线均无钝化特征,仅呈现出活性溶解,但其腐蚀性能优于Zn-15Al涂层。Al-Zn-Si-RE涂层可以给钢基体提供有效的牺牲阳极保护作用,且牺牲阳极保护作用在涂层腐蚀过程中占主导地位。此外,腐蚀电位-时间曲线和电化学阻抗谱结果表明:在浸泡过程中存在点蚀-溶解-再沉积、活化溶解、阴极保护、腐蚀产物引起的物理屏蔽和涂层失效五个腐蚀阶段。     

The effect of Ca on corrosion behavior of heat‐treated Mg–Al–Zn alloy

The effect of 0.5, 1.0, and 1.5 wt% Ca additions on the microstructure and corrosion resistance of the heat‐treated Mg–Al–Zn alloy was investigated. Addition of 0.5 wt% Ca did not form any new phase but suppressed the discontinuous precipitation of the β ‐Mg₁₇Al₁₂ phase by being dissolved in both the second phase and magnesium matrix. In the materials containing higher amounts of Ca, however, metallographic investigation shows that Ca added to Mg–Al–Zn can obviously decrease the size of β ‐Mg₁₇Al₁₂ and forms Al₄Ca intermetallic compounds in the shape of bone‐like morphology. The corrosion tests used include constant immersion technique, and potentiodynamic polarization experiments and salt spray test. Surface examination and analytical studies were carried out using optical and scanning electron microscopy, EDX, and XRD. The results of corrosion tests show that magnesium alloy Mg–Al–Zn with 1.0 wt% Ca addition has the best corrosion resistance behavior.     

2050铝锂合金薄板拉伸性能及晶间腐蚀与时效的相关性

采用拉伸性能测试、浸泡腐蚀及透射电镜(TEM)观察,研究了2050铝锂合金薄板T6及T8态时效时后的拉伸性能、晶间腐蚀(IGC)及微观组织。结果表明,T8态时效2050铝锂合金强度及伸长率均明显高于T6态时效。T6及T8态时效时,合金IGC敏感性随时效延长至峰时效阶段而逐渐降低;进一步延长至过时效阶段,IGC敏感性有所增加。另外,T8态时效时IGC敏感性明显低于T6态时效。基于提高强度、伸长率及降低IGC敏感性的综合考虑,2050铝锂合金薄板适宜的时效制度为T8态峰值时效,相应合金具有最高的强度(抗拉强度529 MPa)、良好的伸长率(10%)及最低的IGC敏感性。     

Rauschuntersuchungen zur Spaltkorrosion

Noise measurements on crevice corrosion The importance of Al‐Mg‐Si‐alloys as an alternative to Al‐Cu‐Mg‐alloys has continuously increased in aircraft industry over the recent years. Al‐Mg‐Si‐alloys are corrosion resistant under normal atmospheric conditions. However localised corrosion, especially crevice corrosion, can be very dangerous. Pitting or crevice corrosion can be divided into an initial state and a propagation state of corrosion. The transition of a corrosion system from the passive state into the initial state of localized corrosion is characterised by the small fluctuation of the current and the potential. The measurement of this fluctuation is the subject of the electrochemical noise analysis (ENA). Therefore ENA leads to extensive knowledge about the activity of the corrosion system already in the pre‐damaged state. With the help of ENA the influence of crevice condition, potential and time on the initial state of the crevice corrosion on AA 6013 can be demonstrated.     

Improving corrosion resistance of pure Al through ECAP

Abstract

Significant grain refinement and corrosion resistance improvement were achieved in industrial pure Al through equal channel angular pressing (ECAP). The effect of microstructure change on its corrosion resistance was investigated by optical/electron microscopy observation, constant immersion tests, polarisation tests and electrochemical impedance spectroscopy (EIS) in aqueous NaCl solution. The ultrafine grained (UFG) bulk pure Al (with grain sizes of 300–500 nm) has a higher pitting potential E_pit, a lower corrosion current density I_corr in polarisation tests and an increased polarisation resistance R_p from EIS plots, along with reduced corrosion damage in immersion tests, compared with the as cast material. It was found that the improved corrosion resistance resulted from the uniform distribution of fine Si containing impurities and the formation of a denser oxide film. The ECAPed samples with smaller Si containing impurities have lower microgalvanic currents and reduced susceptibilities of pitting corrosion, which is consistent with the classical ‘small cathode, large anode’ mechanism. The strain induced crystalline defects, for example, high angle grain boundaries and dislocations, appear to provide more nucleation sites for the formation of a denser and thicker oxide film, thus enhancing its corrosion resistance.     

Corrosion of twin belt and twin roll cast AlMg3Mn alloys

Corrosion of twin belt and twin roll cast AlMg3Mn sheet samples was investigated. The AlMg3Mn sheet samples submitted to immersion tests undergo alkaline pitting around Al–Fe and α_c-Al(Fe,Mn)Si intermetallic particles in the twin roll and twin belt cast samples respectively. The weight loss is higher in the latter and increases with increasing homogenisation temperature for both groups. The twin roll cast AlMg3Mn samples reveal very few and small alkaline corrosion pits and hence much less weight loss in the immersion tests. The pitting activity is governed in the immersion tests by the microgalvanic corrosion activities between the intermetallic particles and the matrix while the anodic particles were inactive.     

Study on localized corrosion mechanism of 2195 Al‐Li alloy in 4.0% NaCl solution (pH 6.5) using a three‐electrode coupling system

Localized corrosion morphologies of 2195 Al‐Li alloy with various heat treatment in 4.0% NaCl solution (pH 6.5) were investigated, and its corrosion mechanism was studied using a three‐electrode coupling system of α (Al) substituting for the precipitate‐free zone (PFZ), simulated bulk θ′ (Al₂Cu) and T1 (Al₂CuLi). θ′ acts as cathodic zone in the alloy. At the initial stage, T1 phase is active with respect to θ′ and α (Al), and endures the main anodic current, indicating that anodic dissolution occurs on T1. However, its potential moves to positive direction with immersion time, due to dealloying of Li from T1. As a result, the main anodic dissolution occurs on α (Al) at a later stage. At this stage, as only T1 and α (Al) are coupled, T1 is cathodic to α (Al). In real 2195 alloy, T1 phase is very tiny, and anodic dissolution of T1 and PFZ occurs alternately. These results show that its intergranular corrosion or intersubgranular corrosion is caused by alternate anodic dissolution of T1 phase and PFZ along grain and subgrain boundaries.     

Si和RE对热浸铝镀层耐盐水腐蚀性能的影响

对铝浴中添加Ｓｉ和ＲＥ后批量热浸铝镀层的组织及耐盐水腐蚀性能的研究结果表明，铝浴中添加１￣７％Ｓｉ和适量ＲＥ，明显提高镀层耐腐蚀性能，减少镀层腐蚀速度随溶液温度升高而增加的幅度，但加入过量稀土则降低镀层耐蚀性，文中探讨了合金元素提高镀层耐蚀性能的原因。     

Corrosion behavior of twinning‐induced plasticity (TWIP) steel

In this study, the corrosion behavior of twinning‐induced plasticity (TWIP) steel i.e. Fe‐Mn‐Al‐Si steel subjected to cold‐working (0, 20, and 35%), was examined in acidic (0.1 M H₂SO₄), alkaline (0.1 M NaOH) and chloride‐containing (3.5% NaCl) environments, using potentiodynamic polarization experiments. Interestingly, cold‐working did not show any significant change in the corrosion susceptibility of TWIP steel in all the three environments. However, TWIP steel showed the highest corrosion susceptibility in acidic environment and the lowest in alkaline environment. Scanning electron microscope analysis of the corroded TWIP steel samples revealed high‐localized attack in acidic environment and some pitting corrosion in chloride‐containing solution.     

Effects of coolant chemistry on corrosion of 3003 aluminum alloy in automotive cooling system

In this work, effects of coolant chemistry, including concentrations of chloride ions and ethylene glycol and addition of various ions, on corrosion of 3003 Al alloy were investigated by electrochemical impedance spectroscopy measurements and scanning electron microscopy characterization. In chloride‐free, ethylene glycol–water solution, a layer of Al‐alcohol film is proposed to form on the electrode surface. With the increase of ethylene glycol concentration, more Al‐alcohol film is formed, resulting in the increase in film resistance and charge‐transfer resistance. In the presence of Cl^? ions, they would be involved in the film formation, decreasing the stability of the film. In 50% ethylene glycol–water solution, the threshold value of Cl^? concentration for pitting initiation is within the range of 100 ppm to 0.01 M. When the ethylene glycol concentration increases to 70%, the threshold Cl^? concentration for pitting is from 0.01 to 0.1 M. In 100% ethylene glycol, there is no pitting of 3003 Al alloy even at 0.1 M of Cl^?. Even a trace amount of impurity cation could affect significantly the corrosion behavior of 3003 Al alloy in ethylene glycol–water solution. Addition of Zn²⁺ is capable of increasing the corrosion resistance of Al alloy electrode, while Cu²⁺ ions containing in the solution would enhance corrosion, especially pitting corrosion, of Al alloy. The effect of Mg²⁺ on Al alloy corrosion is only slight.     

Role of second phase particles in pitting corrosion of 3003 Al alloy in NaCl solution

The second phase particles in 3003 aluminum (Al) alloy were characterized by scanning electron microscope, energy‐dispersive X‐ray analysis and X‐ray diffraction techniques. The role of second phase particles in Al alloy pitting corrosion was investigated by cyclic polarization measurement, and scanning vibrating electrode technique. Results demonstrated that the second phase particles in 3003 Al alloy are mainly Al_x(Fe,Mn) intermetallics, with an average diameter of about 5 µm. The enrichment of Mn in second phase particles forms a galvanic cell effect relative to the adjacent Al alloy substrate. The initiation of pitting corrosion of 3003 Al alloy is the local dissolution of Al substrate around the second phase particles. When a sufficient amount of Al is dissolved away, the second phase particles drop off from the Al substrate, forming large pitting cavities that are usually linked each other.