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金属学报, 2026, 62(3): 458-466 DOI: 10.11900/0412.1961.2024.00168

研究论文

Cr对FeWB块体金属玻璃热稳定性和耐腐蚀性能的影响

肖思明1, 刘天豪2, 苏辰1, 郭胜锋,1

1.西南大学 材料与能源学院 重庆 400715

2.重庆川仪自动化股份有限公司 重庆 401121

Effect of Chromium on Thermal Stability and Corrosion Resistance in FeWB Bulk Metallic Glasses

XIAO Siming1, LIU Tianhao2, SU Chen1, GUO Shengfeng,1

1.School of Materials and Energy, Southwest University, Chongqing 400715, China

2.Chongqing Chuanyi Automation Co. Ltd., Chongqing 401121, China

通讯作者: 郭胜锋，sfguo@swu.edu.cn，主要从事非晶合金、高熵合金研究

责任编辑: 李海兰

收稿日期: 2024-05-17   修回日期: 2024-09-09  

基金资助: 国家自然科学基金项目(52071276)

Corresponding authors: GUO Shengfeng, professor, Tel: 13500330725, E-mail:sfguo@swu.edu.cn

Received: 2024-05-17   Revised: 2024-09-09  

Fund supported: National Natural Science Foundation of China(52071276)

作者简介 About authors

肖思明，男，1995年生，博士生

摘要

块体金属玻璃属于热力学亚稳态合金，其非晶结构在环境温度超过玻璃转变温度时易失稳，从而导致其优异性能退化。提高非晶合金的热稳定性对于维持其综合性能至关重要。本工作在Fe59W23B18 (原子分数，%)块体金属玻璃基础上，引入Cr元素，制备了一系列(Fe1 - x Cr x )59W23B18 (x = 0、0.05、0.1、0.15、0.2、0.25)块体金属玻璃。结果表明，Cr元素显著提高了该块体金属玻璃的热稳定性，其中(Fe0.9Cr0.1)59W23B18金属玻璃的玻璃转变温度为954 K，晶化起始温度为994 K，极高的热稳定性主要源于Cr的引入使得体系更容易形成强过渡金属-类金属共价键(Cr—B键)，增强了原子间的相互作用。此外，大量类Fe23B6的中程序结构也进一步提高了体系的稳定性。Cr元素进一步降低了该金属玻璃体系的自腐蚀电流密度，这主要得益于Cr促进了合金表面稳定钝化膜的形成。然而，Cr2O3的抗点蚀能力弱于WO3，导致合金的抗点蚀能力有所下降。

关键词： 铁基块体金属玻璃; 热稳定性; 耐腐蚀性能

Abstract

Bulk metallic glasses are thermodynamically metastable alloys with an amorphous structure that becomes increasingly unstable at temperatures above their glass transition temperature, leading to degradation of their advantageous properties. Thus, enhancing the thermal stability of bulk metallic glasses is critical for preserving their exceptional characteristics. Recently, our team successfully synthesized a Fe59W23B18 (atomic fraction, %) bulk metallic glass that exhibits high thermal stability and further developed a series of (Fe1 - x Cr x )59W23B18 (x = 0, 0.05, 0.1, 0.15, 0.2, 0.25) bulk metallic glasses by incorporating Cr in this study. Results show that Cr addition notably enhanced the thermal stability of FeWB bulk metallic glasses, with (Fe0.9Cr0.1)59W23B18 achieving a glass transition temperature of 954 K and an crystallization onset temperature of 994 K. This substantial increase in thermal stability is primarily attributed to Cr playing a role in the formation of strong metal-metalloid covalent bonds (Cr—B bonds), which enhance interatomic interactions. Additionally, the substantial presence of an Fe23B6-like medium-range order structure further stabilized the system. Furthermore, the corrosion resistance of the FeWB bulk metallic glass system was considerably improved by Cr addition, as indicated by an approximately 10-fold reduction in the corrosion current density. This enhancement can be primarily attributed to the formation of a dense Cr2O3 passivation layer on the alloy surface. However, the reduced pitting potential of Cr2O3 relative to WO3 led to a slight decrease in the pitting corrosion resistance of the FeCrWB alloys.

Keywords： Fe-based bulk metallic glass; thermal stability; corrosion resistance

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本文引用格式

肖思明, 刘天豪, 苏辰, 郭胜锋. Cr对FeWB块体金属玻璃热稳定性和耐腐蚀性能的影响[J]. 金属学报, 2026, 62(3): 458-466 DOI:10.11900/0412.1961.2024.00168

XIAO Siming, LIU Tianhao, SU Chen, GUO Shengfeng. Effect of Chromium on Thermal Stability and Corrosion Resistance in FeWB Bulk Metallic Glasses[J]. Acta Metallurgica Sinica, 2026, 62(3): 458-466 DOI:10.11900/0412.1961.2024.00168

块体金属玻璃(bulk metallic glass，BMG)[1]，又称块体非晶合金，因其长程无序、短程有序的原子排列特征，通常展现出独特的力学、物理和化学性质。然而，在一些条件严苛的服役环境中，如高温、强腐蚀、强辐照等，由于其在能量上处于亚稳态，非晶结构往往容易遭到破坏，因而其热力学稳定性至关重要[2~5]。近年来，科研人员成功开发出具有超高热稳定性、高玻璃转变温度(Tg > 1000 K)和耐王水腐蚀的IrNiTa(B)系金属玻璃[6]，但Ir价格昂贵，其规模化工业应用受限。因此，开发低成本的高热稳定性金属玻璃体系成为当前研究热点。

在众多已开发的金属玻璃体系中，铁基金属玻璃因其高强度、高硬度、良好的耐腐蚀性能和低廉的原料成本受到了人们的广泛关注[7~9]。但与一些难熔金属基块体金属玻璃相比，铁基块体金属玻璃的热稳定性还需进一步提高。研究[10]表明，在铁基金属玻璃体系(FeC(B)基、FeB基及FeP(C)基)中，FeB基体系通常具有较高的强度和热稳定性。本课题组[11]近期开发出了具有高热稳定性的三元Fe59W23B18 (原子分数，%，下同)块体金属玻璃，其Tg = 923 K，晶化起始温度Tx = 974 K。为了进一步提高合金的Tg和耐腐蚀性能，采用了微合金化策略[12]，添加高熔点Cr (1907 ℃)[13]、Nb (2477 ℃)[14]、Mo (2623 ℃)[15]、Ta (3017 ℃)[16]、W (3422 ℃)[17]等元素增强合金原子间的结合力，常常可以获得高热稳定性的金属玻璃。其中，Cr与Fe性质类似，具有比Fe (1538 ℃)更高的熔点，能在一定程度上保证金属玻璃形成能力的同时，使合金表现出更好的热稳定性。此外，Cr常作为一种耐腐蚀元素用来调控合金的耐腐蚀性能，但在FeWB这类高W含量的非晶合金中，Cr与W的协同作用尚不明确。

为此，本工作研究了Cr含量对Fe59W23B18块体金属玻璃热稳定性和在3.5%NaCl (质量分数)溶液中腐蚀行为的影响，制备了具有高热稳定性的新型(Fe1 - x Cr x )59W23B18块体金属玻璃，为进一步拓宽铁基块体金属玻璃在极端环境下的应用提供参考。

1 实验方法

采用电弧熔炼铜模吸铸法制备(Fe1 - x Cr x )59W23B18 (x = 0、0.05、0.1、0.15、0.2、0.25，后文中分别记为Cr0、Cr0.05、Cr0.1、Cr0.15、Cr0.2、Cr0.25合金)，原料用纯Fe (99.8%)、纯W (99.9%)、纯Cr (99.9%)、纯B (99.5%)。采用海绵钛吸附炉体内的杂质气体，吸铸合金棒状样品直径分别为1和1.5 mm。利用XRD-6100 X射线衍射仪(XRD)对不同Cr含量的合金样品进行分析，扫描范围30°~90°，扫描速率4°/min。利用Sigma 500场发射扫描电子显微镜(FESEM)和Talos F200S透射电子显微镜(TEM)分析合金的微观组织。利用PIPS Ⅱ 695氩离子减薄仪制备TEM样品，减薄过程中先用高电压高角度进行短时间减薄，观察到出现孔洞时降低电压和角度继续减薄，以此类推，最终得到理想薄区。利用PerkinElmer STA8000型差热分析仪(DTA)分析合金的热稳定性，升温速率20 K/min，样品质量约为100 mg，测试过程通入高纯Ar气防止样品氧化。通过HVS 1000A型显微硬度仪测量合金的Vickers硬度，载荷4.9 N，保压10 s，每个样品至少测量7个点，取平均值，样品经砂纸逐级打磨至3000号后，利用金刚石抛光膏抛光至镜面。利用Corrtest CS310电化学工作站进行电化学腐蚀实验，采用三电极体系，以直径1 mm的合金为工作电极(样品镶嵌于环氧树脂中，金属裸露面积为0.785 mm2)，Pt电极为辅助电极，饱和甘汞电极(SCE)为参比电极，电解液为3.5%NaCl溶液。在静置20 min确保体系稳定后，测试合金样品的电化学阻抗谱(EIS，测量频率为10-2~105 Hz)和动电位极化曲线(扫描速率为0.33 mV/s)。选取0.8 V恒定电位，对Cr0和Cr0.1样品进行恒电位极化5000 s，以生成稳定钝化膜。Mott-Schottky测试范围为0.5~1.5 V，实验中所有电位均相对于饱和甘汞电极。利用ESCALAB 250Xi型X射线光电子能谱仪(XPS，AlKα )分析合金表面钝化膜的元素价态，利用Avantage软件对实验数据进行拟合，采用C1s (284.8 eV)校准XPS谱。

2 实验结果与分析

2.1 显微结构

图1a和b为直径1 mm的Cr0~Cr0.25合金棒材XRD谱。可以看出，Cr0、Cr0.05、Cr0.1合金的衍射峰为漫散射峰，说明样品在XRD有效分辨率内为典型的非晶态结构。Cr0.15、Cr0.2、Cr0.25合金在具有漫散射峰的同时，也包含明显的晶态峰。通过标准PDF卡片比对，析出的晶态相主要为Fe23B6相、FeWB相以及Fe7W6相，这说明随着Cr含量的增加，FeCrWB合金的玻璃形成能力逐渐减弱。为了判断合金是否为完全非晶态结构，对Cr0.1合金进行背散射电子像分析，如图1c所示，图中没有明显的衬度变化和晶体结构。高分辨TEM像和选区电子衍射(SAED)花样如图1d所示。SAED花样中未观察到任何的晶格条纹，SAED花样中只出现了非晶的晕环，没有晶体相的衍射斑点，说明Cr0.1合金确为完全非晶态结构。

图1

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图1   不同Cr含量(Fe1 - x Cr x )59W23B18合金棒材(直径1 mm)的XRD谱，及Cr0.1合金的背散射电子像、高分辨TEM像和选区电子衍射花样

Fig.1   XRD patterns of (Fe1 - x Cr x )59W23B18 (x = 0, 0.05, 0.1, 0.15, 0.2, and 0.25; atomic fraction, %. The corresponding samples are marked by Cr0, Cr0.05, Cr0.1, Cr0.15, Cr0.2, and Cr0.25, respectively) alloy rods with 1 mm diameter (a, b); backscattered electron image (c) and HRTEM image and selected area electron diffraction pattern (inset) (d) of Cr0.1 alloy rod


为了进一步澄清该体系的非晶相与晶化相的竞争关系，分析了直径为1.5 mm的Cr0和Cr0.05合金棒材XRD谱，结果见图2。可以看出，随着样品尺寸增大，即合金熔体冷速的降低，二者均有Fe23B6相和FeWB相析出。需要说明的是，1.5 mm直径Cr0合金的漫散射峰基本消失，而1.5 mm直径的Cr0.05合金XRD谱表现为漫散射峰上叠加少量的FeWB和Fe23B6的晶态峰，意味着微量的Cr可以提高FeWB系非晶合金形成能力，这主要源自Cr的添加引起合金体系的原子错配度和混合熵的增加。但Cr与体系的主要元素Fe和W的混合焓均为+1 kJ/mol[18]，体系的熵和焓相互竞争，随着Cr含量的增加，焓逐渐成为主导因素引起液相自由能升高。同时，正混合焓促进了不均匀结构的形成，更多的不均匀结构可能成为异质形核位点，导致晶核的形成和长大。此外，Cr (1.66)还具有比Fe (1.83)更低的电负性，从而减小原子堆垛密度，形成更弱键的原子对，这会破坏过冷液体的稳定性[19]。

图2

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图2   直径为1.5 mm的Cr0和Cr0.05合金的XRD谱

Fig.2   XRD patterns of Cr0 and Cr0.05 alloy rods with 1.5 mm diameter


2.2 热稳定性

添加高熔点Cr的目的之一是为了进一步提高合金的热稳定性。图3a为Cr0、Cr0.05和Cr0.1三组样品的DTA曲线。可以看出，Cr的加入使得Tg和Tx均有了明显提升，Tg从初始Cr0合金的923 K提高到Cr0.1合金的954 K，Tx则从974 K提升至994 K，合金体系热稳定性有了显著增加。相关热稳定性参数见表1。图3b[11,20~36]总结了FeC(B)基、FeB基和FeP(C)基三类金属玻璃典型的Tg和Tx。可以看出，本工作所制备的FeCrWB块体金属玻璃的热稳定性在已报道的铁基金属玻璃体系中处于极高水平。

图3

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图3   不同Cr含量FeCrWB合金的DTA曲线及典型铁基块体金属玻璃的玻璃转变温度(Tg)和结晶起始温度(Tx)[11,20~36]

Fig.3   DTA curves of FeCrWB alloys with different Cr contents (a), and the Tg and Tx of typical Fe-based bulk metallic glasses (BMGs) previously report-ed[11,20-36] (b) (Tg—glass transition temperature, Tx—crystallization onset temperature)


表1   不同Cr含量FeCrWB合金的热稳定性参数和显微硬度

Table 1  Thermal stability parameters and microhardnesses of FeCrWB alloys with different Cr contents

AlloyTg / KTx / KΔTx / KHv / HV
Cr0923974511381 ± 13
Cr0.05938987491410 ± 20
Cr0.1954994401514 ± 17

Note: ΔTx = Tx - Tg, Hv—Vickers hardness

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一方面，Cr (1.66)具有比W (2.36)、B (2.04)、Fe (1.83)更低的电负性，较大的电负性差异有利于原子间强键的形成，Cr的最外层电子为4s1，而Fe的最外层电子为4s2，Cr替换Fe更容易形成s-d杂化键，即更容易引入强过渡金属-类金属共价键(Cr—B键)，增强了原子间的相互作用，原子的排列更加紧密，增大了晶化过程的阻力，使得非晶结构更加稳定。

其次，研究[37]表明，金属玻璃原子尺度的不均匀结构同样对其稳定性有重要影响。随着Cr的增加，大量的Fe23B6和少量的FeWB相从熔体中析出，这意味着非晶结构中包含与竞争晶化相相似的局域原子结构。Fe23B6具有类十次准晶结构，其中包含了大量类二十面体结构，这与液体结构之间存在紧密的关联。同时，Fe23B6的晶格常数为a = b = 1.076 nm，c = 0.100 nm，其中包含了92个Fe原子和24个B原子，复杂的晶体结构使得合金晶化阻力更高，需要大量原子之间协同扩散，这增加了长程原子重排的难度。此外，Fe23B6具有大的晶胞结构，这也意味着该非晶体系中所包含的大量类Fe23B6结构单元也具有大的空间结构，表明该非晶体系中具有高含量的比短程序更为稳定的中程序结构，从而提升了体系的稳定性[38]。同时，Tg会随着合金组元的平均熔点和摩尔汽化焓的增加而增加，利用Cr (熔点1907 ℃，摩尔汽化焓339 kJ/mol)替换Fe (熔点1538 ℃，摩尔汽化焓347 kJ/mol)，虽然摩尔汽化焓差异不大，但是熔点得到了很大的提升，这也使得体系的热稳定性得到进一步提升。

2.3 显微硬度

为了评估Cr对合金体系热稳定性与显微硬度的关联，对FeCrWB合金的硬度进行了分析，结果列于表1。可见，Cr含量的增加使得合金硬度有了很大提升，从Cr0合金的(1381 ± 13) HV提高到Cr0.1合金的(1514 ± 17) HV。在铁基金属玻璃体系之中，FeCrWB合金在硬度上同样有着优异的表现，如图4a[9,11,33,36,37,39~42]所示。Cr作为硬度最高的金属，其添加量的增大使得合金整体的硬度不断增大。此外，如前所述，Cr的添加引入了强Cr—B键，增强了原子间的相互作用，原子的排列更加紧密，从而也使得体系的硬度进一步提高。研究[39]表明，金属玻璃的Tg与其断裂强度(σ)之间存在线性关系：

σ=C0Tg3/2 / Vm

式中，C0为常数，C0 = 1.1 GPa·mm3/K3/2；Vm为合金的摩尔体积。如图4b[43,44]所示，按照此经验公式对Cr0和Cr0.1合金进行预估，其断裂强度分别约为3.8和4.0 GPa。

图4

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图4   不同铁基块体金属玻璃的显微硬度[9,11,33,36,37,39~42]，及不同金属玻璃Tg3/2 / Vm与σ的关系[43,44] (Vm为合金的摩尔体积，σ为断裂强度)

Fig.4   Microhardnesses of different Fe-based BM-Gs[9,11,33,36,37,39-42] (a), and the relationship between Tg3/2 / Vm and σ of different metallic glasses[43,44] (b) (Vm—molar volume of alloy, σ—fracture strength, C0—constant)


2.4 电化学腐蚀

图5所示为FeCrWB样品在3.5%NaCl溶液中的EIS以及等效电路图。由图5a Nyquist图可以看出，随着Cr含量的增加，合金的阻抗环半径随之增大，说明合金耐腐蚀性能不断提高。除Cr0.15合金外，其余成分的Nyquist图主要由高频电容弧与低频范围表示扩散行为的45°直线构成，表明该合金的极化过程主要受电荷转移与扩散共同控制；而Cr0.15合金则是由高频电容弧与低频电容弧组成，体现了其较强的钝化行为。从相位角-频率关系(图5b)可以看出，高频峰值也是Cr含量多的合金高，Cr0.15与Cr0.1合金的峰值相当，这可能是存在部分晶态相所导致。根据相位角结果来看，随着Cr含量增加，合金发生电荷转移的难度明显升高。从模值-频率关系(图5c)也可以看出，随着Cr含量增加，低频时的模值明显提高。建立了等效电路图(图5d)并对阻抗进行了拟合，相关参数的拟合值见表2。对于Cr0、Cr0.05、Cr0.1合金，其等效电路主要由溶液电阻(R1)、双电荷层非理想电容的常相位角原件(CPE)、电荷转移电阻(R2)以及扩散过程中的Weber电阻(Ws)组成。而对于含有少量晶体相的Cr0.15合金，其等效电路主要由R1、局部腐蚀区域的双电荷层电容(CPE1)和R2、表面钝化相关的双电荷层电容(CPE2)和钝化膜电阻(R3)构成。R2随着Cr的增加而增加，表明Cr增加了电荷转移的难度，从而使腐蚀更难进行。虽然Cr0.15合金的R2不大，但R3却很大，表明钝化膜具有极强的保护作用，因此具有最佳的耐腐蚀性能。Cr0、Cr0.05、Cr0.1合金的Ws也随着Cr含量的增加而增加，此时扩散过程难以进行。即对于受电荷转移与扩散共同控制的腐蚀过程来说，Cr同时增加了这2个过程进行的难度，进而有效提高了合金体系的耐腐蚀性能。

图5

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图5   不同Cr含量FeCrWB合金在3.5%NaCl溶液中的电化学阻抗谱(EIS)以及等效电路图

Fig.5   Nyquist plots (Inset is a locally enlarged riew) (a), Bode phase plots (b), Bode plots (c), and equivalent circuit diagram (d) of FeCrWB alloys in 3.5%NaCl solution (Z'—real part of impedance; Z"—imaginary part of impedance; |Z|—modulus of impedance; R1—solution resistance; R2—charge transfer resistance; R3—passive film resistance; Ws—Weber resistance; CPE, CPE1, and CPE2—constant phase elements)


表2   FeCrWB合金在3.5%NaCl溶液中的相关电化学参数

Table 2  Electrochemical corrosion properties of FeCrWB alloys with different Cr in 3.5%NaCl solution

AlloyEcorrVicorrA·cm-2R2Ω·cm2R3Ω·cm2WsΩ·cm2

Cr0

Cr0.05

Cr0.1

Cr0.15

-0.76

-0.66

-0.47

-0.41

3.06 × 10-5

1.25 × 10-5

7.52 × 10-6

3.91 × 10-6

451.54

840.92

3621.90

1200.40

-

-

-

14638

1955

1918

10182

-

Note:Ecorr—corrosion potential, icorr—corrosion current density

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图6a为FeCrWB金属玻璃合金在3.5%NaCl溶液中的动电位极化曲线。随着Cr含量的增加，合金极化曲线逐渐向电位更高、电流密度更低的方向移动，合金的自腐蚀电位从Cr0合金的-0.76 V提高到Cr0.15合金的-0.41 V，合金的自腐蚀电流密度(icorr)从Cr0合金的3.06 × 10-5 A/cm2降至Cr0.15合金的3.91 × 10-6 A/cm2，icorr降低至1/10左右，具体电化学腐蚀参数见表2。需要注意的是，即使存在部分晶态相的Cr0.15合金，其icorr仍是该系列合金中最低的，说明该类材料的腐蚀行为很大程度上取决于其化学元素组成。图6a中方框区域为Cr0合金腐蚀中的活化过程，由于元素标准电极电位Fe < Cr < W，在腐蚀过程中Fe最先溶解，合金表面生成附着物Fe(OH)ad，随着腐蚀电位的增大，电流密度迅速增大到最大值。由于Cr元素的添加，使得合金表面迅速形成稳定的Cr2O3钝化膜，合金的溶解和钝化快速达到动态平衡，从而提高了合金的耐腐蚀性能。

图6

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图6   不同Cr含量FeCrWB合金在3.5%NaCl溶液中的动电位极化曲线，及Cr0和Cr0.1合金在0.8 V恒电位下电流密度与时间的关系、电流密度与时间的双对数曲线、空间电荷电容与电位之间的关系

Fig.6   Potentiodynamic polarization curves of FeCrWB alloys with different Cr contents in 3.5%NaCl solution (a); plots of current density and time (b), double-lg plots of current density and time (c), and the correlation between space charge capacitance (C) and potential (E) of Cr0 and Cr0.1 alloys (d) (k—slope)


在稳定的钝化区间，取0.8 V的恒定电位，对同为纯非晶态的Cr0和Cr0.1样品进行恒电位极化，生成稳定的钝化膜。从图6b可以看出，Cr0.1合金的电流密度迅速减少直至稳定，最终稳定在8.6 × 10-6 mA/cm2，展现出很好的钝化性能。而Cr0合金的电流密度最终稳定在2.1 × 10-5 mA/cm2，高于Cr0.1合金。在恒电位极化形成钝化膜的过程中，瞬态电流密度的降低与钝化膜的增长有关。电流密度(i)随时间(t)的变化可表示为以下公式[45]：

lgi=lgA – klgt

式中，A为常数，取决于外加电位和电解质；k表示钝化膜的生长速率和致密度，由电流密度随时间的双对数图的斜率给出，通常，k = 0表示主动腐蚀过程，k = 0.5表示通过扩散控制生长机制形成多孔膜，k = 1表示形成致密的钝化膜[45]。由图6c可以看出，Cr0.1合金的钝化过程中斜率更大，代表了材料越容易发生钝化，钝化膜也越稳定。而Cr0合金的斜率更小，表示其钝化膜形成速率/钝化膜溶解速率的比值较低，代表了钝化过程进行得越缓慢。此外，可以看到Cr0.1合金在更短的时间内出现上升(d点)，代表了点蚀的萌生，此时钝化膜溶解速率加快。

为了分析FeCrWB合金耐腐蚀性能优异的原因，进行了Mott-Schottky测试，以确定钝化膜半导体的类型、点缺陷密度等，结果如图6d所示。在Mott-Schottky理论[46]中，假设Helmholtz层的电容可以忽略不计，并且测量的电容等于空间电荷电容。根据点缺陷模型，钝化膜的性质取决于其主要缺陷，即氧空位、金属间隙和金属空位。钝化膜的n型特性是通过间隙扩散的阳离子传输或通过阴离子扩散到金属中而产生的，而p型特性则归因于钝化膜中金属离子的缺乏或阳离子空位的过量。根据Mott-Schottky理论[46]：

C-2=2(E-Efb-kbT / e) / (εε0eND)
C-2=-2(E-Efb+kbT / e) / (εε0eNA)

式中，C为空间电荷电容；ε为钝化膜的介电常数，此处取15.6[47]；ε0为真空的介电常数(8.854 × 10-14 F/cm)；e为电子电荷(1.602 × 10-19 C)；ND为n型半导体的施主密度(cm-3)；NA为p型半导体的受体密度(cm-3)；E为施加的电势(V (vs SCE))；Efb为平带电势(V (vs SCE))；kb为Boltzmann常数(8.16 × 10-5 eV/K)；T为热力学温度(K)。由图6d可以看出，2种合金的斜率都为正，表明其半导体类型相同，均为n型半导体。计算结果显示，Cr0.1合金的ND为2.09 × 1019 cm-3，Cr0合金的ND为8.38 × 1019 cm-3。这表明在Cr0.1合金的钝化膜中，点缺陷数量减少，其钝化膜与Cr0合金相比更为致密，能有效地阻止电解质的扩散和阳离子向溶液的溶解，从而提高了合金的耐腐蚀性能。

对于含Cr的金属材料，其良好的耐腐蚀性能主要归因于Cr元素能够生成稳定且致密的Cr2O3钝化膜，可以有效阻止腐蚀介质的扩散[48]。为分析W对合金耐腐蚀性能的影响，利用XPS对Cr0和Cr0.1合金的钝化膜进行了分析，结果如图7所示。合金钝化膜中，W的氧化物为WO2和WO3，其中以WO3为主，且Cr0和Cr0.1合金钝化膜中W6+的原子分数分别占W的氧化物的66.7%和60.3%。WO3相较于Cr2O3具有更高的点蚀电位，能有效提升合金的抗点蚀能力[42]。因而，Cr0、Cr0.05、Cr0.1合金分别在图6a中点a (1.55 V)、b (1.34 V)、c (1.26 V)处首次出现钝化膜的溶解。分析认为，在FeWB金属玻璃中添加Cr后，在电流密度较低时，样品表面很容易生成具有保护性的Cr2O3，有效地抑制了Fe的溶解，促进了表面钝化膜的形成，使得合金表面迅速进入稳定的钝化区，提升了合金的耐腐蚀性能。在高电位下，WO3的存在保证了合金优异的耐点蚀能力，随着Cr含量的增加，Cr2O3钝化膜优先溶解，从而使得合金的耐点蚀能力下降。图8列举了不同成分铁基金属玻璃以及316L不锈钢在3.5%NaCl溶液中的点蚀电位和钝化区间[42,49~52]。可以看出，FeCrWB合金拥有更高的点蚀电位和更宽的钝化区间，意味着FeCrWB金属玻璃具有更为优异的耐腐蚀性能，能更好地满足极端环境下的安全服役。

图7

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图7   Cr0和Cr0.1合金钝化膜中的W4f XPS

Fig.7   XPS of W4f of the passive films formed on the Cr0 (a) and Cr0.1 (b) alloys


图8

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图8   典型铁基金属玻璃和不锈钢在3.5%NaCl溶液中的点蚀电位和钝化区间[42,49~52]

Fig.8   Pitting potentials and passivation intervals of typical Fe-based metallic glasses and 316L stainless steel in 3.5%NaCl[42,49-52]


3 结论

在Fe59W23B18三元块体金属玻璃的基础上，通过添加Cr，制备了(Fe1 - x Cr x )59W23B18 (x = 0、0.05、0.1、0.15、0.2、0.25)新型铁基块体金属玻璃。Cr显著提高了FeWB金属玻璃的热稳定性，其中(Fe0.9Cr0.1)59W23B18的Tg达到954 K，Tx高达994 K，展现出优异的热稳定性。同时，Cr的引入使得合金在3.5%NaCl溶液中的腐蚀电流密度从Fe59W23B18的3.06 × 10-5 A/cm2降低至(Fe0.9Cr0.1)59W23B18的7.52 × 10-6 A/cm2，这表明合金在NaCl溶液中的耐腐蚀性能得到了明显提升，但是在高电位下的耐点蚀能力有所下降。

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