Summary of corrosion parameters for some metallic glasses and its crystalline alloys from literature reports.
Metallic glasses exhibit excellent corrosion resistance and electrocatalytic properties, and present extensive potential applications as anticorrosion, antiwearing, and catalysis materials in many industries. The effects of minor alloying element, microstructure, and service environment on the corrosion resistance, pitting corrosion, and electrocatalytic efficiency of metallic glasses are reviewed. Some scarcities in corrosion behaviors, pitting mechanism, and eletrocatalytic reactive activity for hydrogen are discussed. It is hoped that the overview is beneficial for some researcher paying attention to metallic glasses.
- metallic glass
- corrosion resistance
- pitting corrosion
- electrocatalytic property
Except for high compression strength, microhardness, electrical resistivity, and good soft magnetic properties, most metallic glasses exhibit excellent corrosion resistance. The excellent corrosion resistances of metallic glasses are mainly attributed to the homogeneous single glass phase, the alloy chemistry, and the presence of metalloids [1–3]. No grain boundaries, dislocations, and other defects where corrosion can occur preferentially are expected to allow the growth of a uniform protective film. The chemical homogeneity is believed for rapid cooling rates required to produce full amorphous structure since no enough time is available for solid-state diffusion, that is, it is impossible for the formation of second phases, precipitation, and segregations. The homogeneity in chemical composition and microstructure promotes amorphous oxide formation on the surface which retards ionic transport. The improvement of corrosion resistance is also considered to link to the ability of these metastable alloys to form supersaturated solid solution in one or more alloying elements. The alloying element available in solid solution may be incorporated into the oxide film to enhance its passivity. Thus, the effect of the amorphous structure, chemical and structural homogeneity, and the possibility of forming unique chemical composition not typical of near-equilibrium crystalline alloys are mostly considered as factors that can affect the corrosion properties of metallic glass.
In order to estimate the corrosion resistance, immersion test is one of method to calculate the average corrosion rate in one year, while the electronic chemistry methods such as the potentiodynamic polarization are applied in most researches, where the considerable information on the electrode processes can be attained, such as corrosion potential (
While for the susceptibility of pitting corrosion, the cyclic-anodic-polarization is usually measured, and some parameters and typical characteristics with regard to pitting corrosion susceptibility are defined in the schematic polarization curves of Figure 2 . A potential scan is started below the corrosion potential,
2. Corrosion resistances of nonferrous metallic glasses
Metallic glass is comparatively newcomer to the amorphous material group, which is fabricated from a cooled liquid without crystallization under a rapid cooling rate. As the first metallic glass of Au80Si20 was discovered in 1960 by Duwez and coworkers , a series of metallic glasses such as Zr-, Ti-, Pd-, Cu-, Fe-, and Mg-based alloys are successfully fabricated by the method of melt quenching. In order to extend the industrial application of metallic glasses, the corrosion behaviors of metallic glass have been of great interest. The corrosion resistance of nonferrous metallic glass of Cu-, Ti-, Zr-, and Mg-based alloys will be discussed in the following part.
2.1. Effect of composition
Among of nonferrous metallic glasses, Zr-based metallic glass (Zr-MG) is investigated abroad in corrosion resistances. Addition of minor element such as Ag, Cu, Y, Ti, Ni, and Nb has been utilized to enhance the glass forming ability and resistance to general and local corrosion. Inoue and coworkers [6–10] have investigated the effect of Ni on the corrosion resistance of Zr-Ni-Cu-Al alloy. Zr-MG without Ni shows lowest corrosion potential and no obvious passivation region, but pitting directly can be observed as potential rises. Zr-MG with Ni is spontaneously passivated with current density around 10−3 A/m2 before the occurrence of pitting corrosion in chloride solution. Since the Cu element in the Zr-MG is easily dissolved in chloride solutions, thus leads to a low corrosion resistance. The additional Ni inhibits the formation of soluble Cu-Cl films and facilitates forming the protective surface films with a high concentration of Zr cation, leading to a denser, thicker, and more pitting resistance ZrO2 passive film. Zhang and coworkers [11, 12] reported that partial substitution of Ni and Co by Ag was effective in improving the corrosion resistance of Zr-MG, as the Ag addition increases the concentration of Zr and decreases the concentration of Al in the surface passive films, while Liu and coworkers  found that the addition of Ag could promote the formation of Al2O3 but slightly suppressed the formation of ZrO2. The cast Zr56Al16Co28−
Compared to Zr-MG, Cu-based metallic glasses with their superiority in price and mechanical properties possess great potential applications in the fields, such as bipolar plate materials, biomedical instruments, and microdevices. The investigations about corrosion resistance have been carried extensively. Small addition of Nb, Cr, Ta, and Mo has proved to be effective in improving the corrosion resistance [19–21]. Asami et al.  investigated the effect of small addition of Nb, Mo, and Ta to Cu60Zr30Ti10 at% metallic glass in 1 M HCl, HNO3, NaOH, and 0.5 M NaCl solutions. The results demonstrate that Nb element is most effective in decreasing the corrosion rate in all of the solutions, moreover, the corrosion rate decreases with increasing the Nb content. The minor element addition can enhance the stability of passive film enriched in ZrO2 and TiO2. Except the minor addition Mentioned above, some rare metal element additions of In, Y, Ce, and Ln to Cu-MG are effective to improve the corrosion resistance [22–25]. The results demonstrate that the dissolution of rare element is favorable to forming continuous Zr-, Ti-rich protective oxide film and alleviates the local corrosion and propagation at the initial corrosion stage. The Ln addition can increase the nearest neighbor atomic distance affecting the topological instability, which is attributed to the improvement of corrosion resistance.
As conventional titanium alloy, Ti-based metallic glass with high yield strength, low Young’s modulus, high corrosion resistance can be applied as biomaterial , and mostly possesses higher corrosion resistance than Ti-6Al-4V alloy in a simulated body fluid environment. The minor element addition of Zr, Nb, and Cu will change the corrosion behavior of Ti-MG [27–29]. Nb addition can enhance the pitting resistance due to an improvement of the passive layer properties for near-homogenous alloys. Small addition of Zr promotes the corrosion potential and decreases the corrosion current density. The addition of Cu can shift the beginning of polarization reaction to a positive voltage level, while provokes severe Cu-induced selective dissolution under the higher applied voltage levels, resulting continuous pitting and the depletion of Ti and Zr in the alloy. With increase of (Ti + Zr)/Cu ratio, the pitting corrosion resistance is greatly enhanced due to the formation of surface film mainly composed of TiO2 and ZrO2.
As well known, magnesium alloy is also one of biomaterials. Recently, the corrosion behavior of Mg-based metallic glass is investigated. Wang et al.  reported that the Mn addition can promote the formation of a dense passive film, which delays the corrosion of the matrix. The Zn addition provokes the formation of Zn(HO)2 and Mg(OH)2, and the evolution of the corrosion process of the MgZnCa glass is schematically illustrated in Figure 4 . When Mg-MG is immersed in body fluid, the anodic dissolution of magnesium occurs and the magnesium hydroxide layer well is formed on the surface of the sample. The attack of Cl− occurs at the weak sites of the magnesium hydroxide layer and transforms the magnesium hydroxide into soluble magnesium chloride. The fresh substrate, exposed to the medium directly, suffers further corrosion, and results in the releasing of Mg2+ and Zn2+, as shown Figure 4(a). As immersion prolonged, the Zn2+ concentration is increasing due to the continuous dissolution of Zn. The Zn(OH)2 precipitates preferentially, compared to that of Mg(OH)2 (Figure 4(b)), the Zn(OH)2 precipitations will repair the defects in the surface layer, and then forms a continuous and uniform layer. With the corrosion proceeding, the corrosion product layer will be thickened and Zn(OH)2 precipitation spreads, which are evidently depicted in Figure 4(c). Meanwhile, the undissolved Mg(OH)2 and Zn(OH)2 precipitation can provide favorable sites for apatite nucleation. With Ti addition, the protective film of Mg(OH)2 will enrich Ti, improving the stability .
2.2. Effect of microstructure
The microstructure and composition homogeneities are destroyed with the crystallization, which is necessary to deteriorate the corrosion resistance of metallic glasses. Zr56Al16Co28 metallic glass exhibits a decrease of passivation potential and an increasing of penetration rate with increasing heating temperature in Ringer’s simulated body fluid at room temperature . The corrosion parameters of some metallic glasses are summarized in the Table 1 [34–39]. It can be attained that the corrosion resistance of most metallic glasses after crystallized will decrease, as shown that the corrosion potential decreases and the corrosion current density increases relatively, suggesting that the passive films formed on the surface of the glassy alloy in the anodic process are protective and denser than those on the crystal alloys. However, another metallic glasses exhibit more positive corrosion potential and low corrosion current density after crystallized, meaning that the crystalline alloy possesses excellent corrosion resistance, compared to metallic glass with same composition, since the nanocrystal phase such as a-Ti, CuZr precipitation or the reduction of the free volume in amorphous state that in turn reduces the average atomic distance.
|Composition||State||Ecorr (mV)||Icorr (A/cm2)||Epit (mV)||Epit−Ecorr (mV)||Ipass (A/cm2)||CPR (um/y)||Temp (K)||Solution|
|Zr62.3Cu22.5Fe4.9Al6.8Ag3.5 ||Am.||−290||5.5 × 10−8||−22||268||---||1.5||310||PBS|
|Cry.||−305||7.7 × 10−8||−45||160||---||0.9||310||PBS|
|Ti40Zr10Cu38Pd12 ||Am.||−31||4.6 × 10−7||---||---||---||---||---||HBSS|
|Cry.||−61||2.0 × 10−8||---||---||---||---||---||HBSS|
|Ti42Zr40Si15Ta3 ||Am.||−455||4.9 × 10−8||113||---||2.9 × 10−6||---||310||SBF|
|Cry.||−321||8.7 × 10−8||176||---||4.0 × 10−6||---||310||SBF|
|Zr60Cu20Al10Fe5Ti5 ||Am.||−214||3.0 × 10−4||---||---||---||---||310||SBF|
|Relx||−43||8.8 × 10−6||39||83||---||---||310||SBF|
|Cry.||−22||1.4 × 10−6||407||429||---||---||310||SBF|
|Zr2Ni ||Am.||−354||1.3 × 10−7||82||---||1.1 × 10−6||---||300||0.1 M NaCl|
|Cry.||−369||1.4 × 10−7||76||---||9.3 × 10−7||---||300||0.1 M NaCl|
|Cu47.5Zr47.5Al5 ||Am.||−760||1.2 × 10−7||110||870||5.2 × 10−7||---||300||ASS|
|Cry.||−460||5.0 × 10−8||110||570||1.6 × 19−6||---||300||ASS|
Wang et al. [40, 41] reported that the corrosion resistance of Mg-MGs was slightly reduced when the in situ second phase or reinforcement phase were induced into metallic glass. It is believed, when corrosion is developing, the continuous distribution of glass matrix might be able to prevent corrosion from spreading from one a grain to another a grain directly across the glass matrix. Then corrosion is stopped after the crystalline phases dissolves and a continuous glass matrix is exposed to solution. If the crystalline phase is nanoparticle and presents high chemical potential, the corrosion resistance of metallic glass composite will not reduce, even increase for some metallic glass alloy [39, 42].
When bulk metallic glass is fabricated into metallic glass coating, the corrosion resistance of metallic glass coating is affected not only by the composition, but also by the surface and porosity of the metallic glass coating . The effect of porosity on corrosion resistance for Ti-MG evaluated with potentiodynamic polarization is shown in Figure 5 . The metastable current transition of different magnitude can be observed for the porous bulk metallic glass. Although rapid increase in anodic current due to pitting is not observed, anodic current density slightly increases, indicating that some of metastable pitting occur within the pore at the same time and afterward are stabilized by the pore wall during the anodic polarization process. Undoubtedly, the existing of pores would result in crevice corrosion, where potentiodynamic polarization curve exhibits a slow increase of current density in the anodic polarization part. Gebert et al.  reported that the state of surface finishing of Zr-based metallic glass remarkably influences its corrosion and passivity. It is considered that the smoothness, homogeneity, and the modification of surface chemistry such as Cu concentration on the surface of Zr-MG are modified after polished with different polishing materials.
Besides chemical and physical defects of glassy alloy, the mechanically generated defects can enhance the corrosion susceptibility. Gebert et al.  reported that a slight improvement of spontaneous passivity but a decrease of resistance against chloride-induce pitting were detected when Zr-based bulk metallic glass was shot-peened with long time, and the corrosion damage evolution was governed by the nature of the mechanically generated defects, such as craters, cracks of scratches and their surrounding stress fields. The effect of shear bands breaking through a sample surface on corrosion processes in acidic environments is investigated. The preferential sites for corrosion initiation and propagation are formed along the shear bands, as shown Figure 6 . The local chemical and structural changes in the close vicinity of the shear band zone are mainly predisposing factor. An et al.  found that the Cu-MG after tensioned exhibited more negative corrosion potential and larger corrosion current density in chloride solution, which indicated the deterioration of corrosion resistance of Cu-MG tensioned, compared with as-cast.
2.3. Effect of environment
Though the microstructure and chemical composition of nonferrous affect the corrosion resistance, it is evident from Table 2 that the environment is also a significant factor in the corrosion properties. Table 2 provides corrosion parameters for some nonferrous metallic glass in various electrolytes. Pourgashti et al.  found that Zr-MG exhibited excellent corrosion resistance in 3.5% NaCl solution, and showed better corrosion resistance than 316L in HNO3 and H2SO4 solutions. It can be seen from Table 2 that the tendency of corrosion current density
|Composition||Ecorr (mV)||Icorr (A/cm2)||Epit (mV)||Epit−Ecorr (mV)||Ipass (A/cm2)||CPR (um/y)||Temp (K)||Solution|
|Zr41.2Ti13.8Ni10Cu12.5Be22.5 ||−469||6.7 × 10−7||97||---||---||10||298||3.5% NaCl|
|−428||9.0 × 10−7||---||---||---||80||298||1 M HNO3|
|−491||5.4 × 10−7||---||---||---||620||298||0.5M H1SO4|
|−322||1.4 × 10−6||---||---||---||260||298||1 M HCl|
|Zr55Cu30Al10Ni5 ||---||---||450||---||---||---||298||0.001 M NaCl|
|---||---||50||---||---||---||423||0.001 M NaCl|
|---||---||−100||---||---||---||523||0.001 M NaCl|
|Zr59Ti3Cu20Al10Ni8 ||603||2.3 × 10−8||1450||---||1.1 × 10−7||---||298||1 M HNO3|
|357||5.6 × 10−7||1370||---||2.2 × 10−6||---||298||6M HNO3|
|818||3.4 × 10−6||1200||---||9.8 × 10−5||---||298||11.5M HNO3|
|Cu55Zr35T10 ||18.9||2.4 × 10−4||---||---||---||33.2||298||0.005M HCl|
|−10.2||1.2 × 10−4||---||---||---||82.5||298||0.01 M HCl|
|−119.6||2.0 × 10−4||---||---||---||342||298||0.5M HCl|
|−322.9||1.2 × 10−3||---||---||---||702||298||1 M HCl|
|164.9||2.7 × 10−5||---||---||---||2.6||298||0.005M NaCl|
|−21.1||2.3 × 10−5||---||---||---||7.7||298||0.01 M NaCl|
|−58.0||1.8 × 10−4||---||---||---||37.6||298||0.5M NaCl|
|−87.6||6.4 × 10−5||---||---||---||79.2||298||1 M NaCl|
|Ti46Cu27.5Zr11.5Co7Sn3Si1Ag4 ||−270.8||2.7 × 10−4||---||---||---||---||310||PBS|
|−151.7||2.0 × 10−4||---||---||---||---||298||0.9 wt% NaCl|
|−289.8||1.6 × 10−4||---||---||---||---||298||1 M HCl|
|−345.6||1.4 × 10−3||---||---||---||---||298||1 M NaOH|
As similar to Zr-MG, Cu60Zr20T20 metallic glass during the potentiodynamic polarization exhibits the active dissolution state in the whole anodic region in different solutions . The current density increases to a very high value after the
3. Corrosion resistance of Fe-based metallic glass
Due to its high strength, good soft magnetic properties, excellent corrosion resistance, and low producing cost, Fe-based metallic glass is attended extensively to the researchers in material science and technology fields around the world. Besides the glass forming ability, strength, and soft magnetic properties, the investigation on corrosion resistance is interesting for the industrial application of Fe-based metallic glasses.
3.1. Enhance of minor element addition
The effects of the addition of a small amount of metallic elements such as Cr, Mo, Nb, W, Ni, Ta, Y, Al, Co, and Mn on the corrosion resistance of Fe-MGs are investigated by means of electrochemical polarization and weight loss measurements. It is well known that chromium is an effective element enhancing corrosion resistance of Fe-MGs. In Fe-Co-B-Si-Nb metallic glass , the corrosion rate decreases from 0.7 mm/year for Cr-free alloy to 6 × 10−2 mm/year for the alloy with 4 at% Cr in 0.5 M NaCl solution at 298 K. For the Fe73.5Si13.5B9Nb3Cu1 metallic glass in marine environments, the corrosion rate is 14 times lower for the material with 2 at% Cr and 88 times lower for the material with 4 and 6 at% Cr as compared with the material in amorphous state without Cr . Though increasing Cr concentration up to 8 at% Cr tends to stabilize the passive layer, the corrosion rate remains very high. The addition of 8 at% is not sufficient to the formation of a stable passive layer, and the materials are dissolved or undergo severe attack in 1, 2, and 5 M H2SO4 . In 9.7 M H2SO4 solution at 70°C, the Fe63.1C7.1Si4.4B6.5P8.6Cr8.3Al2.0 metallic glass exhibits high corrosion rate of 13 mm/year that is five times lower than that of AISI304L . The crack width on the corrosion product layer after potentiostatic polarization measurement decreases with increase of content as shown in Figure 7(a) and (b), the pitting morphology occurs on the surface of metallic glass with 6.3 at% Cr, as showed in Figure 7(c), however, a homogenous surface without cracks or pitting is formed for the alloys with Cr content exceeding 8.3 at% as shown in Figure 7(d) and (e), due to the formation of Cr-enrich passive film on the surface.
With minor addition of Y, not only glass forming ability, but also corrosion resistance is increasing evidently. The dependence of the electrochemical parameters upon the yttrium content is shown in Figure 8 . The corrosion current density
|Composition||Elem. X||Content (at%)||Ecorr (mV)||Icorr (A/cm2)||Epit (mV)||Ipass (A/cm2)||CPR (um/y)||Temp (K)||Solution|
|FeBSiNbX ||Ni||0||−626||4.5 × 10−6||---||---||897||298||0.5M NaCl|
|0.2||−426||3.2 × 10−7||---||7.9 × 10−6||1.8|
|0.4||−367||1.2 × 10−7||---||4.1 × 10−6||< 1|
|0||−936||5.9 × 10−6||---||---||978||0.5M NaOH|
|0.2||−677||9.9 × 10−7||---||1.6 × 10−5||56|
|0.4||−647||7.0 × 10−7||---||1.1 × 10−5||32|
|0||−404||7.0 × 10−5||---||9.3 × 10−3||2106||0.5M H2SO4|
|0.2||−356||3.4 × 10−6||---||1.9 × 10−3||787|
|0.4||−334||1.1 × 10−6||---||1.0 × 10−3||674|
|FeBCuX ||Nb, Zr||3.5, 3.5||---||---||−170||---||---||298||NaCl+NaOH (pH13)|
|Nb, Mo||3.5, 3.5||---||---||−270||---||---|
|Zr. Mo||3.5, 3.5||---||---||−310||---||---|
|FeCrMoBCX ||Nb||0||−169||---||715||2.5 × 10−6||---||310||RS(pH6)|
|3||−45||---||876||2.0 × 10−7||---|
|4||122||---||1299||3.8 × 10−8||---|
|FeBCrX ||Mo, Nb||0||---||---||---||2.8 × 10−3*||---||289||0.1 M H2SO4|
|Mo,Nb||0.3, 0||---||---||---||1.4 × 10−3*||---|
|Mo,Nb||0, 0.3||---||---||---||1.0 × 10−3*||---|
|Mp,Nb||0.15, 0.15||---||---||---||4.5 × 10−4*||---|
|FeCSiBPAlMoCoX ||Cr||0||−304||6.5 × 10−6||---||1.2 × 10−2||---||298||0.5M H2SO4|
|2.3||−279||2.3 × 10−6||---||1.9 × 10−4||---|
|12.3||−235||7.0 × 10−7||---||2.9 × 10−5||---|
|0||−311||4.5 × 10−6||---||7.9 × 10−3||---||1 M HCl|
|2.3||290||1.9 × 10−6||---||2.8 × 10−4||---|
|12.3||220||8.0 × 10−7||---||1.7 × 10−5||---|
|FeCrNiX ||Si||20||−200||1.9 × 10−6||---||---||---||298||0.01 M HCl|
|P||20||−800||1.5 × 10−7||---||---||---|
|FeCrMoCX ||B||4||---||---||---||---||5~30||298||1 M HCl|
Besides the metal elements, the metalloids element addition of B, Si, P, S, Ni, and C are also important to the corrosion resistance. The Fe50−
3.2. Effects of microstructure homogeneity
Since metallic glasses are metastable and can be transformed into stable crystalline phase by heat treatment or mechanical working, the structural change can also affect corrosion resistance for metallic glasses. A comparison of passive current density
|Composition||State||Ecorr (mV)||Ipass (A/cm2)||CPR (um/y)||Temp (K)||Solution|
|FeCrMoCBY ||Amor||77||3.0 × 10−5||---||298||1 M HCl|
|200||6.0 × 10−5||---||6M HCl|
|Cryst||29||1.0 × 10−4||---||1 M HCl|
|FeSiB ||Amor||−735||---||---||298||0.5M NaCl|
|FeSiBNbCu ||Amor||−605||---||120||298||0.5M NaCl|
|FeZrB ||Amor||−520*||1.9 × 10−3||---||298||0.5M H2O4|
|Cryst||−463*||2.2 × 10−2||---|
|FeNbZrBCu ||Amor||−860*||1.0 × 10−3||---||298||0.5M H2O4|
|Cryst||−685*||1.3 × 10−2||---|
|FeNbB ||Amor||−1070*||7.5 × 10−4||---||298||0.5M H2O4|
|Cryst||−850*||1.0 × 10−2||---|
The decrease of corrosion resistance in crystalline alloys obtained by the isothermal heat treatment of Fe-M-B (M = Nb, Zr) metallic glasses is explained by the formation of the α-Fe crystalline phase that has greater corrosion susceptibility in compared to that of the amorphous phase . Long et al. thought the galvanic effects between adjacent phases with different composition were resulted in the deterioration of corrosion resistance for Fe-Co-B-Si-Nb metallic glass . A comparison of BF-TEM morphologies for amorphous and devitrified SAM 1651  is shown in Figure 9. It indicates that the lacier morphologies for devitrified SAM 1651 mean the degradation in the corrosion resistance. However, the abrupt increase in the corrosion potential for crystalline alloy is attributed to the decrease of the residual stress during densification, and the surface atom electrochemically active site . Since atom at a glassy metal surface are in nonequilibrium configuration and may effectively sit on higher energy wells than that corresponding to atoms on an equilibrium configuration. Moreover, the faster migration of silicon ions to the surface in the crystalline structure promotes the SiO2 film formation, which enhances the corrosion properties .
During the fabrication processing of bulk metallic glass and metallic glass coating, the porosity is not avoided due to rapid cooling. The effect of porosity on the corrosion resistance is investigated in some literatures [75–77].The corrosion resistance of coating 1 with the porosity of 0.04% is better than that of another two coatings with the porosity of 0.2% and 0.5%, respectively . When the porosity decreases form 1.89% of low deposition rate to 1.22% of high deposition rate, the corrosion resistance of FeCrMoCBY amorphous coating increases evidently due to the elimination of through pores . However, when the porosity is lower than 1.22%, the corrosion resistance seems more sensitive to the amorphous phase content. If the thickness of the coating decreases, the number of through-porosity in coating increases, which affects the corrosion resistance, as shown in Figure 10 . It indicates that through-porosity is much more detrimental to the corrosion resistance of the coated material compared with nonthrough porosity.
In some bulk metallic glass or metallic glass coating, the crystallize particles such as WC, TiN, SUS316, NbC, TiO2, and Al2O3 are induced [78–83]. It is obvious that the crystallized particles are deteriorated the structural homogeneity. However, little investigations are done about the influence of crystalline particle on the corrosion resistance, which is important for the potential application of Fe-based metallic glass as anticorrosion and antiwearing materials.
3.3. Effects of service environment
The corrosion behaviors of Fe-based metallic glasses are affected by environmental factors. Intuitively, the stronger the aggressiveness of the solution is, the weaker the corrosion resistance of metallic glass exhibits. The results  attained in immersion experiments for Fe48Cr16Mo16C8B4 glassy alloy in 1, 6, and 12 M HCl solutions exhibit, as expected, that the corrosion rate increases as the increase in concentration of HCl solution. The alloy occurs pitting on the surface after 168 h of immersion in the 12 M HCl solution at room temperature. FeCrMoCBP alloy is spontaneously passivated with a passive current density of about 10−1 A/m2 and a wide passive region in 1 M HCl solution, however, its passive film is not stable by anodic polarization, as an anodic current density increases with increasing potential in 6 M HCl solution, and no passive film seems formed on the surface with rapid increasing of current density in 12 M HCl solution . Fe54.2Cr18.3Mo13.7Mn2.0W6.0B3.3C1.1Si1.4 (wt%) alloy can passivate spontaneously in the H2SO4 solution, and the passive current density is changed from 1 × 10−5 A/cm2 with 0.4 M to 2 × 10−5 A/cm2 with 0.1 M . The corrosion penetration rates of Fe48Cr15Mo14Er2C15B6 metallic glass  are 39.9, 27.5, and 3 mm/year in 1 M HCl, 1 M NaOH, and 0.6 M NaCl with pH 7 solutions, respectively. The critical passivation potential
The corrosion rate of FeNiB metallic glass is only 70 μm/year in 3.5 wt% NaCl solution , while the corrosion rate increases to 130,000 μm/year in 1 M HNO3 solution, near two thousand times larger than that in sodium chloride solution, as shown in Table 5. In Table 5, it is attained that more negative corrosion potential is obtained with increase of pH value, and the corrosion current density decreases. As the acidic ion or hydroxyl ion concentration increase, the corrosion potential becomes more negative and the corrosion current density increases generally. That is, the corrosion resistance decreases with increase of acidic ion concentration and hydroxyl ion content. When the concentration of hydrogen ion is same, the existence of chloride ion will deteriorate the corrosion resistance. In a word, the corrosion resistance of Fe-based metallic glass decreases as the solution aggressiveness increases.
|Composition||Ecorr (mV)||Icorr (A/cm2)||Epit (mV)||Ipass (A/cm2)||CPR (um/y)||Temp (K)||Solution|
|FeNiB ||---||1.5 × 10−2||---||---||130,000||298||1 M HNO3|
|---||1.5 × 10−3||---||---||14,900||---||1 M NaOH|
|---||8.0 × 10−5||---||---||70||---||3.5 wt% NaCl|
|---||1.3 × 10−4||---||---||1140||---||1 M HCl|
|FeNiBAiNb ||−367||1.2 × 10−7||---||1.1 × 10−6||<1||298||0.5 M NaCl|
|−647||7.0 × 10−7||---||1.1 × 10−5||32||298||0.5 M NaOH|
|−334||1.1 × 10−6||---||1.0 × 10−3||674||298||0.5 M H2SO4|
|FeCSiBPCrAlMo ||−264||9.0 × 10−7||---||---||---||298||0.5 M H2SO5|
|−283||4.1 × 10−6||---||---||---||298||1 M HCl|
|FeCoCrMoCBY ||−269||2.4 × 10−7||1090||---||---||298||Hank’s|
|−315||4.8 × 10−8||1200||---||---||298||Saliva|
|FeCrMoCBY ||−614||2.0 × 10−6||988||1.3 × 10-3||---||298||3.5wt% NaCl|
|−414||1.1 × 10−5||904||1.7 × 10−3||---||298||1 M HCl|
|−377||4.6 × 10−6||879||5.5 × 10−4||---||298||1 M H2SO4|
|FeCoCrMoCBY ||---||---||---||---||0.12||298||1 M HCl|
|---||---||---||---||0.12||298||1 M HNO3|
|---||---||---||---||0.13||298||1 M NaOH|
|---||---||---||---||0.07||298||3.5 wt% NaCl|
|FeCrMnMoWBCSi ||−367||---||---||---||---||298||0.25 M H2SO4|
|−219||---||---||---||---||298||0.25 M Na2SO4|
|−455||---||---||---||---||298||0.5 M HCl|
|49||---||---||---||---||298||0.5 M NaCl|
|FeCoCrMoCBY ||−257||4.7 × 10−8||715||---||---||298||Acid rain|
|−378||7.5 × 10−8||1033||---||---||298||3.5 wt% NaCl|
|FeBNb ||−458||1.5 × 10−5||---||---||---||298||NaCl+H2SO4pH1.0|
|−700||1.5 × 10−5||---||---||---||298||NaCl pH5.5|
|−637||7.0 × 10−6||---||---||---||298||NaCl+NaOH pH10|
|FeCoBSiNb ||−381||1.5 × 10−5||---||---||---||298||NaCl+H2SO4 pH1.0|
|−550||2.0 × 10−6||---||---||---||298||NaCl pH5.5|
|−509||1.5 × 10−6||---||---||---||298||NaCl+NaOH pH10|
|FeCrNiB ||−192||6.0 × 10−8||---||---||---||298||NaCl+H2SO4 pH1.0|
|−128||1.5 × 10−8||---||---||---||298||NaCl pH5.5|
|−209||2.0 × 10−8||---||---||---||298||NaCl +NaOH pH10|
4. Pitting corrosion of metallic glasses
Though metallic glass exhibits excellent general corrosion resistance, it is also susceptible to pitting corrosion in aggressive solutions, especially containing Cl− ion . Since the surface film is not stable during the anodic polarization, many pits are observed on the surface of FeCrMoCB metallic glass with 4 at% B immersed in 12 M HCl solution for 168 h . During potentiodynamic polarization in 1.7 M HCl solution, many peaks of current density occur for FeCrMB (M = Mo, Nb) metallic glass, which is attributed from pitting corrosion. Moreover, the morphologies of pits are confirmed by SEM analysis after the immersion test . Fe52Mn10Mo14Cr4B6C14 metallic glass is susceptible to pitting corrosion, although presents good corrosion resistance characterized by a low passivating current in 0.6 M NaCl solution . Fe48Cr15Mo14B6C15Y2 metallic glass, as known SAM1651, exhibits hysteresis loop during cyclic potentiodynamic polarization in 4 M NaCl solution at 373 K, which indicates the formation of localized corrosion . Pardo et al. [58, 59] found that FeSiNbBCuCr metallic glass was immune to pitting corrosion in simulated industrial environments, since the current density decreased when the potential scan direction is reversed and it is identified that no pit formed on surface after immersion test. Though no hysteresis loop is observed and
Gostin et al.  considers that no pitting propagation is attributed from the high repassivation ability due to the high content of the beneficial Mo in its composition, although the yttrium oxide particle provides a favorable location for pit formation and local dissolution is initiated at their interface with the glassy matrix. However, Gostin et al.  also found that a pitting-like process occurred for the glassy alloy with high concentration of C, as the initial breakdown of passive film caused by the sudden direct exposure of the alloy surface to the electrolyte subsequent to local rupturing of the C-rich layer by growing CO2 bubbles. Liu and coworkers  reported the pitting was initiated since the formation of a nanoscale Cr-depleted zone near the intersplat due to oxidation effect during thermal spraying, as shown in Figure 12. Paillier et al.  reported that Cu-rich nanocrystals of 5–10 nm were formed inside the corrosion pits during the corrosion process, as shown in Figure 13. The corrosion mechanisms of is feasible that elements like Zr, Ti, and Al mainly dissolve in solution whereas Cu and probably Ni is prone to form nanocrystals on the surface covered by a passive oxide layer, as in Figure 13(a), the structure vanishes with the complete removing of the surface oxide by HF (Figure 13(b)). On the bare surface alloy without native oxide layer, the small pits develop first with the bow-like morphology, and then, because the corrosion appears to proceed quicker in the vertical direction, and goes along with the canyon-like morphology. Very deep trenches are indeed hollowed leading to a canyon aspect, as shown in Figure 13(c).
5. Electrocatalytic properties of metallic glasses
Metallic glasses have gained considerable attention in catalysis research due to their unique structural and chemical properties , such as the unique atomic structure with a short-range ordering of the constituents, the large flexibility in their chemical composition compared to that of crystalline alloys, the structural and chemical homogeneity, the high reactivity due to their metastable structure, and the excellent conductivity for electricity and heat. Some investigations about the electrocatalytic activity of metallic glasses for the hydrogen evolution reaction or oxygen reduction reaction, such as Co- [108, 109], Zr- [110, 111], Ni- , Cu- , Pt- [115, 116], and Au-based  metallic glasses, are done in last few decades. However, Fe-based metallic glasses are the most attractive as catalytic material. Since the first catalytic materials of Fe-based metallic glass were reported in 1981 , a larger number of investigations have be done [118–123], such as the Fe82.7B17.8 amorphous ribbon used as a catalyst for the Fischer-Tropsch-type reaction of CO + H2 , amorphous Fe-Zr precursor for ammonia synthesis , amorphous FeNiCrPB alloy as catalysts for acetylene hydrogenation  and hydrogen evolution [122,123]. The chromium effect on the catalytic activity for FeNiCrPB metallic glass is shown in Figure 14. It can be seen that the catalytic activity is strongly affected by Cr presence, while catalytic efficiency is independent of Cr content.
The famous composition of Fe60Co20Si10B10 (G14)  is firstly reported in 1988, exhibiting good electrocatalytic activity for hydrogen evolution reaction (HER) comparable with Pt. A comparison of kinetics parameters between G14 and pure Fe, vit.7505, pure Pt is illustrated in Table 6. With increasing temperature the exchange current densities
|Electrode||T (K)||i0 (A/cm2)||b (−mV)|
|Fe (poly)||298||1.0 × 10−5||135|
|323||3.3 × 10−5||140|
|348||4.0 × 10−5||150|
|Fe78Si11B11||298||1.0 × 10−6||140|
|323||5.0 × 10−5||150|
|348||1.6 × 10−4||155|
|Fe60Co20Si10B10||298||1.0 × 10−6||95|
|323||4.8 × 10−5||140|
|348||2.7 × 10−4||150|
|Pt (poly)||298||2.4 × 10−5||120|
|323||4.8 × 10−5||150|
|348||3.3 × 10−4||170|
The electrocatalytic properties are affected not only by the composition of alloy, but also by the surface composition and/or surface area by chemical pretreatment. The catalytic studies  on the hydrogenation of carbon monoxide by Fe-based alloy indicated that the activity is augmented by a treatment in HNO3 solution. Guczi et al.  thought that the surface composition and valence state determined in depth were related to the catalytic activity and selectivity revealed in CO + H2 reaction. An increased number of nickel and iron sites by removing of the prevailing boron oxide, iron oxide, and iron oxide layer after HCl treatment was responsible for the enhanced catalytic activity, as shown in Figure 15, that is, the activity of the FeB sample in as-received state was about twice that observed for the FeNiB sample, on the other hand, comparing the HCl etched samples, the activity of the FeNiB alloy was about 30 times higher than that of the FeB ribbon.
The electrocatalytic activity of Fe40Ni40P14B6 metallic glass  is improved for HER by acid pretreatment with 1 M HF or HNO3 for 10 min, since a porous structure with highly roughed and numerous small craters resulted from the selectively leachability of phosphorous from the surface of Fe40Ni40P14B6 metallic glass enhanced the electrode surface area in comparison to the as-polished surface.
The mechanism of hydrogen evolution reaction at the metal electrode in alkaline solution is based on three-step reactions as following:
Electronation of water with adsorption of hydrogen—Volmer reaction is shown in Eq. (1):
Electrochemical desorption of H2—Heyrouvsky reaction is shown in Eq. (2):
Chemical desorption—Tafel reaction is shown in Eq. (3):
Due to involving the transfer of electron from the electrode surface, the density of electrons close to the energy level of metal surface is an important parameter governing electrocatalytic reaction activity. However, it is difficult to estimate during HER, so the efficiency is usually evaluated with overpotential
Some Fe-based metallic glasses with high electrocatalytic efficiency are reported, such as a low overpotential
The investigation of corrosion resistance of metallic glass is attractive for allover researchers in materials science and engineering, since the unique structure and properties, extensive potential application. Most researches are focus on the effects of element addition and nanocrystallization on the general and local corrosion resistance in various environments. Certain elements are identified are quite effective in improving the corrosion resistance. And the crystallization of metallic glass is usually deleterious for the corrosion resistance. In general, the decreasing is the corrosion resistance of metallic glasses, the increasing is the solution aggressiveness, especial for the chloride ion concentration. Unfortunately, the mechanism of pitting corrosion of metallic glass is not clear, as that of conventional materials such as stainless steel. As practical application of the metallic glasses in industrial field, some metallic glasses such as Fe-based metallic glass are used as anticorrosion or antiwearing materials. The coating is one of effective methods. During the coating processing, some inclusion, oxidation, crystallization, and even second particle as reinforcement phase in the coat layer is inevitable. However, the effect of these particles on the general and pitting corrosion resistance is seldom reported. Therefore, further investigation about the pitting corrosion is necessary to the industrial application of metallic glass.
The work was supported by the National Natural Science Foundation of China (51461031) and the Department of Education Fund of Jiangxi (GJJ150733). Thanks for their understanding and support of my wife, Yanmei Zhang, and my son, Bob.
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