Recently deepened insights regarding Mg corrosion and advanced engineering applications of Mg alloys

This review summarizes recent insights into the Mg corrosion mechanism, clarifies many critical controversial points regarding the Mg corrosion behaviour, and updates some efforts made to extend the industrial application of Mg alloys. Based on the new understandings gained so far, future research directions are also suggested in the review. This review has the following logic. The first section "1. Scope"is a consolidation of the new understandings or developments regarding the Mg corrosion mechanism and the new applications for Mg alloys. It also highlights some key points for the review. The second section "2. Widely accepted knowledge" briefly summarizes the general understanding of Mg corrosion gained so far, which acts as the foundation for the following sections. The third section "3. Recently deepened insights" mainly briefs on some new insights into Mg corrosion phenomena based on recent findings. Different interpretations on the corrosion behaviours are comprehensively discussed in the fourth section "4. Controversial points" and the conclusions are drawn in the subsection"4.5 Clarified points". Apart from the fundamental understandings, various efforts in the application of Mg alloys are presented in the fifth section "5. New applications". Following the research tendency as indicated in the review, prioritized research areas are suggested in "6.Future directions". The review is concluded with "7. Concluding remarks" at last.

Self-repairing functionality and corrosion resistance of in-situ Mg-Al LDH film on Al-alloyed AZ31 surface

A novel Mg-Al LDH film was in-situ prepared hydrothermally in an alkaline aqueous solution on an Al-alloyed AZ31 substrate.The structural,chemical and functional characteristics of the film were explored by means of scanning electron microscope(SEM),X-ray diffraction(XRD),energy dispersive spectrometer(EDS),polarization curve,AC impedance and salt immersion tests,respectively.The anti-corrosion results indicated that the Mg-Al LDH film on the Al-alloyed AZ31 surface could effectively protect the AZ31 from corrosion attack even after 90 days of immersion in 3.5 wt.%NaCl solution.The protection performance is surprisingly better than most of the reported coatings on Mg alloys.More interestingly,when the Mg-Al LDH film was scratched,the exposed Al-alloyed surface might gradually release metal ions and re-generate dense LDH nano-sheets in the corrosive environment to inhibit the further corrosion there,exhibiting a self-repairing behavior.The combination of the benign long-term protection and desirable self-repairing performance in this new process of surface-alloying and LDH-formation may significantly extend the practical application of magnesium alloys.

The anodically polarized Mg surface products and accelerated hydrogen evolution

To clarify the anodic dissolution mechanism of Mg,the hydrogen evolution from pure Mg in acidic solutions under galvanostatic conditions were systematically measured.With increasing anodic current density,the cathodic hydrogen evolution rate decreased,and the anodic hydrogen evolution became faster while some surface area on the Mg was becoming dark under anodic polarization.Based on the surface analysis results and the generally accepted basic electrochemical equations,the evolution kinetics of hydrogen from Mg was deduced,and the most possible surface intermediate active species that could facilitate the anodic Mg dissolution and anodic hydrogen evolution were proposed.This paper further develops the model of incomplete film Mg^(+) dissolution,explains many reported experimental phenomena,and clarifies misunderstandings of current mechanism.

Bio-inhibitive effect of an algal symbiotic bacterium on corrosion of magnesium in marine environment

It is a longstanding and challenging task to develop sustainable environment-friendly and cost-effective corrosion-protection technologies for Mg alloys, especially under marine conditions in which corrosion can normally be significantly accelerated by bacterial activity. However,this paper reports on the corrosion of highly active Mg interestingly inhibited by an algal-symbiotic bacterium Bacillus altitudinis. The corrosion of Mg in the presence of the bacterium drastically reduced by one order of magnitude after 14 days of immersion. This means that the algal-symbiotic bacterium widely available in natural ocean environments may be employed as a green and sustainable inhibitor in the marine industry. Based on electrochemical measurements, surface analyses and microbe experiments, a combined inhibition mechanism is proposed in the paper to interpret the interesting corrosion behavior of Mg.

A Mg alloy with no hydrogen evolution during dissolution

Hydrogen evolution is normally associated with the corrosion or dissolution of Mg alloys in aqueous solutions.This work studied the corrosion behavior of sputtered pure Mg,Mg82Zn18(at.%),Mg64Zn36(at.%),and pure Zn in 3.5%Na Cl solution.Mg64Zn36had(ⅰ)an amorphous microstructure with some nano-scale grains,(ⅱ)a corrosion rate substantially lower than that of pure Mg,and(ⅲ)no hydrogen evolution during corrosion or anodic dissolution,because the positive corrosion potential retarded the cathodic hydrogen evolution.This is a new route to prevent hydrogen evolution during Mg corrosion,which has never previously been realized.

Advances in Mg corrosion and research suggestions

Recent research is summarised with an emphasis on the use of Mg alloys for biodegradable medical applications.Mg melt purification using Zr has been shown to provide the opportunity to produce ultra-high-purity Mg alloys,which could lead to stainless Mg.Nor's solution may be a good starting model for the study of Mg for biodegradable medical implant applications.A systematic laboratory investigation is needed to elucidate the details of how the corrosion behaviour is controlled by the various constituents of the body fluids.In the evaluation of the Mg corrosion mechanism there is a critical lack of understanding of(i)the amount of hydrogen dissolved in the Mg metal during corrosion,and during anodic polarisation,and(ii)the size film-free area where corrosion occurs,and how to measure this area.In the evaluation of the apparent valence of Mg using an applied anodic current density,for reliable values,it is important to apply a sufficiently large applied current density.The available data are consistent with the slightly modified uni-positive Mg^(+)ion mechanism,which maintains that(i)the surface of Mg is covered by a partially protective film,and the film-free area increases as the potential becomes more positive(i.e.a catalytic activation process),(ii)corrosion occurs preferentially at breaks in the partial protective film,(iii)corrosion at the breaks in the partially protective film involves the uni-positive Mg ion,(iv)undermining of particles occurs when Mg is severely dissolved,and(v)there may be some self-corrosion not covered by these four processes,which may be associated with crevice-like features on a severely corroded surface or hydride dissolution at relatively negative potentials.Self-corrosion might also be possible under condition of essentially uniform corrosion.Mg^(+)has not been experimentally observed.Its existence is postulated as an extremely-short lifetime intermediate in the reaction sequence between metallic Mg and the equilibrium ion Mg^(++).There has been no direct experimental examination of this sequence,and a key challenge remains to devise an experimental approach to study the details of this reaction sequence and the intermediate steps.The apparent valence of Mg continues to be a critical question.If defendable values of effective valence for Mg less than 1.0 were measured,this would indicate that some phenomena contribute to these low values that are not currently accounted for in the uni-positive Mg^(+)corrosion mechanism.The most likely candidate would be self-corrosion.

Microstructure modification and corrosion resistance enhancement of die-cast Mg-Al-Re alloy by Sr alloying

The effects of Sr additions on the microstructure and corrosion performance of a Mg-Al-RE alloy in 3.5 wt.%Na Cl saturated with Mg(OH)_(2) have been investigated.Microstructure examination reveals that the Sr addition introduces additional intermetallic phases,refines intermetallic networks and dendritic grains,and improves the network continuity.More Al and rare earth elements can be identified in the intermetallics and grain boundaries or inter-dendrite regions under a transmission electron microscope and secondary electron microscope,respectively.On the Sr-containing intermetallic phases and the refined microstructure,the oxide films become more protective,resulting in more corrosion resistant boundary areas and thus dendrite grain grooves.Hence,the presence of large amounts of intermetallics and boundaries can enhance the corrosion performance of the Mg-Al-RE alloy containing Sr.

Review of Mg alloy corrosion rates

A review of the literature confirmed that the intrinsic corrosion rate of high-purity Mg as measured by weight-loss is 0.3mm/y in a concentrated chloride solution.Atmospheric corrosion of Mg alloys has produced corrosion rates of Mg-Al alloys an order of magnitude lower than the intrinsic corrosion rate of Mg in a concentrated chloride solution of 0.3 mm/y.The only successful strategy to produce a Mg alloy with a corrosion rate in a concentrated chloride solution substantially less than the intrinsic corrosion rate as measured by weight loss of Mg of 0.3 mm/y has been to improve the protectiveness of the corrosion product film.

不同电位下极化后的纯钛表面生物污损行为

钛及其合金作为常用工程材料,虽已广泛应用于海洋环境中,但同时面临着严重的生物污损威胁,因此有必要研究钛表面氧化膜在海水中的电化学行为和生物亲和性的关系,以寻找降低污损的有效表面处理技术。本工作在人工海水中对TA2纯钛直接施加阴极电位-0.8 V_(SCE)和钝化电位0.5 V_(SCE)进行恒电位极化处理,制备两种不同状态的表面膜,进而跟踪监测纯钛在含小新月菱形藻/舟形藻培养基和天然海水/灭菌天然海水中的电化学行为,并以小新月菱形藻和藤壶幼虫为目标生物,初步探究不同电位下极化后的纯钛表面的生物粘附规律。

Corrosivity of haze constituents to pure Mg

The corrosion behavior of pure Magnesium(Mg)in a Mg(OH)2-saturated solution containing different individual constituents of PM2.5 in haze were studied by hydrogen evolution,weight loss and electrochemical experiments.The results indicated that the corrosivity of these constituents to pure Mg decreased in the following order:(NH4)2SO4>Haze-contaminated-solution>NH4NO3>NH4Cl>NaCl≈KCl≈Na2SO4≈MgCl2≈CaSO4>Mg(OH)2(basic solution)>Ca(NO3)2.Possible mechanisms behind the different corrosion behaviors of Mg in response to these constituents were also briefly discussed in this paper.

Conversion of magnetron-sputtered sacrificial intermediate layer into a stable FeCo-LDH catalyst for oxygen evolution reaction

Controllable and scalable preparation of electrocatalyst materials holds significant importance for their practical application.Magnetron sputtering is a highly effective synthesis method,known for its producing uniform films and allowing easy control of component compositions.In this paper,we propose an in-situ synthesis method for layered double hydroxide(LDH)electrocatalysts through sacrificing magnetron sputtered films.The resulting FeCo-LDH catalyst demonstrated a low overpotential of only 300 mV at 10 mA·cm^(-2).Furthermore,we conducted spectroscopic analysis to investigate the surface changes of the catalysts during the oxygen evolution reaction(OER)process.Our findings indicated that the formation of Co oxyhydroxides plays a beneficial role in enhancing the catalytical performance of the FeCo-LDH for OER reaction.This restructuring strategy of converting a magnetron-sputtered sacrificial film into a catalytical LDH introduces a new avenue to the synthesis of transition metal-based electrocatalysts.

A corrosion-reconstructed and stabilized economical Fe-based catalyst for oxygen evolution

The anode activity can to a great degree limit the cathodic hydrogen evolution efficiency in an electrolyte cell.Thus,cost-efficient electrocatalysts with good water oxidation performance and stability are highly desired in widespread implementation of the hydrogen production from water splitting.This paper proposes a facile corrosion-reconstruction strategy to transform Fe surface into a Fe-Co hydroxide layer to improve the oxygen evolution activity.The as-prepared catalyst was measured to have an over-potentential as low as 320 mV at 100 mA·cm^(−2),and its stability even exceeded 600 h.Surface and Raman spectroscopy analyses indicated that the catalyst experienced chemical changes from hydroxides to oxyhydroxides and Co^(2+)to Co^(3+)during oxygen evolution reaction(OER).The corrosion-reconstruction is not only an economical method to synthesize a highly efficient,stable and durable Fe-based catalysts,it also converses the detrimental corrosion into a beneficial catalyst fabrication process.

Selection and Characterization for Corrosion Control

In a recent study by the National Association of Corrosion Engineers （NACE）, the global cost of corrosion was estimated to be US$ 2.5 trillion, equivalent to 3.4% of the global Gross Domestic Product [htto：//imtacact.nace.org/]. The prevention practices could save between study found that implementing the best corrosion 15%-35% of the cost of damage. One of the important measures to reduce the corrosion damage is using an appropriate material. Selection of a suitable material according to corrosivity of the service environment is essentially important in battle against industrial corrosion. Corrosion detection, damage characterization and surface analysis are critical approaches to fundamental understanding of the root cause and detailed mechanism of corrosion. They lay a foundation for prevention and mitigation of material corrosion in service environments. A technical breakthrough in these fields may result in significantly widened applications of traditional and emerging materials.

Review of the atmospheric corrosion of magnesium alloys

Mg atmospheric corrosion is induced by a thin surface aqueous layer. Controlling factors are microgalvanic acceleration between different phases, protection by a continuous second phase distribution, protection by corrosion products, and degradation of protective layers by aggressive species such as chloride ions. The Mg atmospheric corrosion rate increases with relative humidity (RH) and concentrations of aggressive species. Temperature increases the corrosion rate unless a protective film causes a decrease.O2, SO2 and NO2 accelerate the atmospheric corrosion rate, whereas the corrosion rate is decreased by CO2. The traditional gravimetric method can evaluate effectively the corrosion behavior of Mg alloys.

Galvanic Effect Between Galvanized Steel and Carbon Fiber Reinforced Polymers

The galvanic corrosion behavior of carbon fiber reinforced polymers （CFRPs） GM-CFRP and Tepex-CFRP in contact with a Zn-coated DP590 steel in solution containing 0.9 wt% NaCl＋ 0.1 wt% CaCl2 ＋ 0.075 wt% NaHCO3 was investigated. The results showed that the GM-CFRP/steel couple was initially more resistant to galvanic corrosion, but its galvanic corrosion activity gradually became higher than the Tepex-CFRP/steel couple. The different galvanic behaviors of these two couples were discussed based on the electrochemical performance of GM-CFRP, Tepex-CFRP and DP590 coupons in the testing solution.

What activates the Mg surface——A comparison of Mg dissolution mechanisms

Several mechanisms have been proposed to interpret the widely reported phenomenon of Mg corrosion that the hydrogen evolution rate increases with increasing anodic potential or anodic current density. This paper critically analyzed the two main mechanisms,(1) "the incomplete film univalent Mg+ion mechanism" and(2) "the enhanced catalytic activity mechanism", aiming to clarify the current understanding of the Mg corrosion mechanism and to provide a profound insight into the Mg characteristic electrochemical behavior, anodic polarization accelerating both hydrogen evolution and Mg dissolution. It is expected that the deepened fundamental understanding from this comprehensive mechanistic review will provide a basis of practical applications for Mg alloys and open up a new way to the control of corrosion of Mg alloys in practice.

A state-of-the-art review on passivation and biofouling of Ti and its alloys in marine environments

High strength-to-weight ratio, commendable biocompatibility and excellent corrosion resistance make Ti alloys widely applicable in aerospace, medical and marine industries. However, these alloys suffer from serious biofouling, and may become vulnerable to corrosion attack under some extreme marine conditions. The passivating and biofouling performance of Ti alloys can be attributed to their compact, stable and protective films. This paper comprehensively reviews the passivating and biofouling behavior, as well as their mechanisms, for typical Ti alloys in various marine environments. This review aims to help extend applications of Ti alloys in extremely harsh marine conditions.

基于可牺牲中间层制备大规模、可控双金属氢氧化物膜的协同策略

层状双金属氢氧化物(LDHs)作为一种类水滑石薄膜,以其优异的特性在许多领域中具有广泛的应用.然而,现有的LDH膜制备路线具有大规模生长受限和不可控等问题.本文中,我们受一种草本植物“落地生根”(Bryophyllum Pinnatum)具有肆意生长特性的启发,首次引入可牺牲的共溅射锌-铝中间层作为“植物种子”,通过“局部溶解”和“溶液渗透”的结构转化机制在任意形状、大小及材质的基底材料上实现大规模、厚度可控的LDH膜制备.通过调控中间膜的成分、结构和表面形貌,设计具有不同特性的LDH转化膜.实验结果表明,所制备的LDH膜具有较大的厚度和多级微观结构的特性,在严苛的磨损条件下仍能实现良好的机械稳定性.另外,我们设计了一系列基于锌-铝单金属中间层的电偶模拟实验对LDH膜的化学转化机理进行了深入探究,解决了传统复杂水热过程中实时监测困难的问题.本工作不仅开发了一种制备具有多尺度特性的LDH转化膜的新策略,同时揭示了复杂的LDH原位转化机理,为拓宽LDH材料在先进智能材料上的实际应用提供了新的发展思路.

Localized Corrosion of Binary Mg-Ca Alloy in 0.9 wt%Sodium Chloride Solution

To further understand the localized corrosion of magnesium alloy, various in situ electrochemical techmques and ex situ electron microprobe analysis and SEM were used to monitor the corrosion process of Mg-l.0Ca alloy in 0.9 wt% sodium chloride solution. The results indicated that the localized corrosion was accompanied by the formation and thickening of a corrosion product film on the Mg-l.0Ca alloy. A localized corrosion of the alloy initiated selectively on the eutectic micro-constituent zones, then enhanced with the exposure, developed in depth with ring-shaped corrosion products accumulated around and finally formed a volcanic-like pitting. Based on the measurements, an electrochemical corrosion model was proposed accordingly to describe the formation mechanism of the volcanic-like pitting on the alloy in 0.9 wt% sodium chloride solution.

Biocorrosion induced by red-tide alga-bacterium symbiosis and the biofouling induced by dissolved iron for carbon steel in marine environment

The assemblages of unicellular microalgae and bacteria in phytoplankton communities can generally result in biodeterioration of metals in marine environment.In this study,the self-promoted biofouling mechanism underneath red-tide alga Phaeodactylum tricornutum and its symbiotic bacterium Bacillus altitudinis was systematically revealed.The mutualistic interaction of the bacteria and algae quadrupled the corrosion rate in comparison to the individual effect of the bacterium or algal strain alone.Reversely,the corroded metal appeared to be an accelerator that can stimulate the activity of the P.tricornutum and aggravate the biological pollution based on the result of 62.3%up-regulation of the key photosynthesis genes.The corrosion-biofouling-accelerated corrosion-deteriorated biofouling formed a vicious cycle.