Corrosion Science最新文献_第7页

A generalized model of corrosion inhibition efficiency for multilayer adsorption 多层吸附缓蚀效率的广义模型

IF 7.4 1区材料科学 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY

Corrosion Science

Pub Date : 2026-04-01 Epub Date: 2026-01-12 DOI: 10.1016/j.corsci.2026.113626

Anton Kokalj

In a recent study (Kokalj, 2026), a model was developed to map multilayer surface coverage to inhibition efficiency (

η

). In that model, the corrosion protectiveness of adsorbed molecular layers beyond the first was postulated to follow a Langmuir-like dependence on the number of layers. In the present work, this model is generalized by leveraging an experimental observation that the polarization resistance of Langmuir–Blodgett monolayers increases linearly with the number of deposited monolayers beyond the first. It is shown that the previously developed model is a special case of the more general formulation presented here. Both models predict a characteristic hallmark shape in the

c / η

versus

c

plot — where

c

is the inhibitor concentration — featuring a bent, arching profile above the

c / η = c

line at low concentrations, followed by a linear regime at higher concentrations. The generalized model, however, provides further insight, indicating that the extent of this curvature increases when the contribution of the subsequent layers to inhibition efficiency is strong, or when the first adsorbed layer contributes weakly, a behavior that is consistently reproduced when the model is applied to experimental inhibition efficiency data from the literature. Yet under many conditions, the curvature remains too subtle to allow unambiguous identification of multilayer adsorption based on

c / η

versus

c

plots alone.

在最近的一项研究中（Kokalj, 2026），开发了一个模型，将多层表面覆盖映射到抑制效率（η）。在该模型中，被吸附的分子层的防腐性被假设遵循朗缪尔式的依赖于层数。在目前的工作中，通过利用实验观察，该模型得到了推广，即Langmuir-Blodgett单层膜的极化电阻随着沉积的单层膜数量的增加而线性增加。结果表明，先前开发的模型是此处提出的更一般公式的一个特例。两种模型都预测了c/η与c曲线的特征标志形状——其中c为抑制剂浓度——在低浓度时，在c/η=c曲线上方呈现弯曲的拱形轮廓，在高浓度时呈现线性曲线。然而，广义模型提供了进一步的见解，表明当后续层对抑制效率的贡献较大时，或者当第一层吸附层对抑制效率的贡献较弱时，这种曲率的程度会增加，当模型应用于文献中的实验抑制效率数据时，这种行为会得到一致的再现。然而，在许多条件下，曲率仍然太微妙，无法明确地识别基于c/η和单独的c图的多层吸附。

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引用次数: 0

Comparing the oxidation behaviour of three generations of single crystal nickel-based superalloys at an intermediate service temperature 比较三代单晶镍基高温合金在中等使用温度下的氧化行为

IF 7.4 1区材料科学 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY

Corrosion Science

Pub Date : 2026-04-01 Epub Date: 2025-12-26 DOI: 10.1016/j.corsci.2025.113582

Joseph C. Doyle , Edward A. Saunders , Jane M. Woolrich , Mark E. Light , Nong Gao , Philippa A.S. Reed

The oxidation behaviours of three different generations of single crystal Ni-based superalloys (SRR-99 – 1st generation, CMSX-4 – 2nd generation, and CMSX-10N – 3rd generation) have been investigated and compared at 550 °C. Isothermal oxidation tests were carried out at various exposure times ranging from 2 h up to 1000 h and it was found that oxide morphology and development showed noticeable differences between the alloys. Scanning electron microscopy (SEM), 3D imaging reconstruction, energy-dispersive X-ray spectroscopy (EDS) and X-ray diffraction (XRD) were employed to characterise the oxide scales. The external and internal oxides were studied through high-resolution imaging, measurements from which revealed the oxidation kinetics of CMSX-4 and CMSX-10N followed a near-parabolic law whilst a logarithmic law better described the kinetics behaviour of SRR-99. Thermodynamic modelling was used to predict the species and composition of oxides formed in each alloy and compared to measured EDS and XRD results. From the experimental results and modelling, it was found that the mechanism and oxide products formed for CMSX-4 and CMSX-10N are very similar, as NiO initially formed externally over the γ channels and the γ’ precipitates were preferentially oxidised internally at the γ/γ’ interface.

研究了三代单晶镍基高温合金（第一代SRR-99、第二代CMSX-4和第三代CMSX-10N）在550℃下的氧化行为。在2 h到1000 h的不同暴露时间下进行等温氧化试验，发现合金之间的氧化物形态和发育有明显的差异。采用扫描电镜（SEM）、三维成像重建、能量色散x射线能谱（EDS）和x射线衍射（XRD）对氧化鳞片进行表征。通过高分辨率成像研究了外部和内部氧化物，测量结果显示CMSX-4和CMSX-10N的氧化动力学遵循近抛物线定律，而对数定律更好地描述了SRR-99的动力学行为。利用热力学模型预测了每种合金中形成的氧化物的种类和组成，并与EDS和XRD的测量结果进行了比较。从实验结果和模拟结果来看，CMSX-4和CMSX-10N的氧化机制和氧化产物非常相似，NiO最初是在γ通道上形成的，而γ′沉淀在γ/γ′界面上优先被氧化。

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引用次数: 0

Synergistic effects of dissolved oxygen and subcooled nucleate boiling on CRUD deposition and zirconium alloy corrosion 溶解氧和过冷核沸腾对CRUD沉积和锆合金腐蚀的协同作用

IF 7.4 1区材料科学 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY

Corrosion Science

Pub Date : 2026-04-01 Epub Date: 2026-01-15 DOI: 10.1016/j.corsci.2026.113635

Qingdong Liu , Qifeng Zeng , Yang Liu , Lefu Zhang , Huilong Yang , Jianfeng Gu , Hiroaki Abe

Chalk River Unidentified Deposits (CRUD) pose a significant threat to zirconium alloy fuel cladding in water-cooled Small Modular Reactors (WC-SMRs) with potential dissolved oxygen (DO). This study investigates the microstructural interplay between CRUD and the underlying oxide on Zr-4 and SZA-4 alloys under simulated WC-SMR conditions. Results demonstrate that porous, Fe₂O₃ (hematite)-dominated CRUD forms even without subcooled nucleate boiling (SNB). Zr-4 forms a locally aggregated coarser deposit, whereas SZA-4 develops a uniform denser layer of fine particles, mainly attributed to the higher thermal resistance of the thicker ZrO₂ on SZA-4. Zr-4 exhibits a thinner oxide (∼1.29μm) than SZA-4 (∼1.65μm) under identical conditions, demonstrating its superior resistance and confirming the detrimental effect of DO on Nb-containing alloys. The CRUD chemistry is confirmed by XPS combined with SAED and XRD to be predominantly Fe^3 + in Fe₂O₃ phase, accompanying by Sn clustering in Zr-4’s CRUD and discrete Cr₂O₃ formation at the SZA-4’s CRUD/ZrO₂(C/O) interface. Porous CRUD, formed via particulate accumulation and solute redeposition, can locally impede heat transfer and alter water chemistry. This, combined with stress concentration, induces microcracking and ZrO₂ dissolution, as a precursor to CRUD-Induced Localized Corrosion (CILC). These findings underscore that prevailing Nb-containing zirconium alloys require revised mitigation strategies for DO-rich WC-SMRs environments, and future CRUD models must integrate deposit porosity, thermal-chemical coupling and interface stress effects.

白垩河未识别沉积物（CRUD）对水冷小型模块堆（WC-SMRs）中具有潜在溶解氧（DO）的锆合金燃料包壳构成重大威胁。本研究在模拟WC-SMR条件下，研究了Zr-4和SZA-4合金中CRUD与底层氧化物之间的微观组织相互作用。结果表明，即使没有过冷核沸腾（SNB），以Fe2O3（赤铁矿）为主的多孔CRUD也会形成。Zr-4形成局部聚集的粗颗粒沉积，而SZA-4形成均匀致密的细颗粒层，这主要是由于ZrO2较厚在SZA-4上的热阻较高。在相同的条件下，Zr-4的氧化层（~ 1.29μm）比SZA-4的氧化层（~ 1.65μm）薄，这表明Zr-4具有更强的电阻性，也证实了DO对含铌合金的有害影响。通过XPS、SAED和XRD分析，证实了crd的化学性质以Fe3 +为主，并伴有Sn在Zr-4的CRUD中聚集，SZA-4的CRUD/ZrO2（C/O）界面上形成离散的Cr2O3。多孔CRUD通过颗粒积聚和溶质再沉积形成，可以局部阻碍传热并改变水的化学性质。这与应力集中相结合，诱发微裂纹和ZrO2溶解，作为原油诱导局部腐蚀（CILC）的前兆。这些研究结果表明，对于富do的wc - smr环境，目前流行的含铌锆合金需要修改缓解策略，未来的CRUD模型必须考虑沉积层孔隙度、热化学耦合和界面应力效应。

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引用次数: 0

Type II hot corrosion of the polycrystalline nickel-based superalloy AD730 in presence of Na2SO4 and Na2SO4-MgSO4 deposits Na2SO4和Na2SO4- mgso4沉积存在下多晶镍基高温合金AD730的II型热腐蚀

IF 7.4 1区材料科学 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY

Corrosion Science

Pub Date : 2026-04-01 Epub Date: 2026-01-02 DOI: 10.1016/j.corsci.2026.113592

D. Diomande, P-J. Panteix, S. Migot, J. Ghanbaja, L. Aranda, C. Clément, M. Vilasi, S. Mathieu

The type II corrosion resistance of AD730 was studied at 650 °C and 700 °C in air + 400 ppm SO₂ (g), in the presence of Na₂SO₄ and Na₂SO₄-MgSO₄ deposits. At 650°C, the pit-like attacks were of similar depth for both salts and less severe than those observed at 700°C. Although the sulfate mixture (Na₂SO₄-MgSO₄) was liquid at 700°C from the beginning of the exposure, it proved to be less aggressive than Na₂SO₄. Wavelength dispersive spectrometry characterization of the pits revealed the systematic stratification of the oxides from the alloy-corrosion products interface toward the corrosion products-gas interface across the pit corrosion products, i.e. the establishment of a gradient of oxygen ions activity. High resolution transmission electron microscopy highlighted a high level of porosity, sulfur enrichment as well as the presence of the WS₂ sulfide, with an anisotropic bidimensional structure, located at the alloy-oxide interface. Sulfation tests carried out on nickel oxide and cobalt oxide in the presence of Na₂SO₄ and Na₂SO₄-MgSO₄ showed little sulfation with the magnesium-containing salt, thus demonstrating how MgSO₄ contributes to limit the corrosion at 700°C. The results demonstrated that the severe hot corrosion attacks are not only related to the formation of a liquid phase, but also to its chemical composition.

研究了AD730在650℃和700℃空气+ 400 ppm SO2 (g)、Na2SO4和Na2SO4- mgso4沉积条件下的II型耐蚀性。在650°C时，两种盐的坑状腐蚀深度相似，并且比在700°C时观察到的严重。虽然硫酸盐混合物（Na2SO4- mgso4）在700°C时是液态的，但它的侵蚀性比Na2SO4小。波长色散光谱表征表明，氧化物从合金-腐蚀产物界面向腐蚀产物-气体界面跨坑腐蚀产物有系统的分层，即氧离子活性梯度的建立。在高分辨率透射电镜下，发现了高孔隙度、硫富集以及位于合金-氧化物界面的WS2硫化物的存在，具有各向异性的二维结构。在Na2SO4和Na2SO4-MgSO4存在下对氧化镍和氧化钴进行的磺化试验表明，含镁盐几乎没有磺化作用，从而证明了MgSO4如何有助于限制700°C下的腐蚀。结果表明，严重的热腐蚀不仅与液相的形成有关，而且与其化学成分有关。

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引用次数: 0

Chemically complex ordered alloy enables electrochemically stable passivation for superior corrosion resistance 化学复杂有序合金使电化学稳定钝化，具有优异的耐腐蚀性

IF 7.4 1区材料科学 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY

Corrosion Science

Pub Date : 2026-04-01 Epub Date: 2026-01-05 DOI: 10.1016/j.corsci.2026.113597

J.Y. Zhang , Y.H. Zhou , T.H. Chou , J.H. Luan , H. Luo , Y.L. Zhao , T. Yang

The nanoscale passive film on the alloy surface critically governs the corrosion resistance of alloys. An ideal passive film is expected to act as a protective barrier layer to effectively protect the alloy matrix by impeding the charge transfer reactions and diffusion of corrosive ions. Most traditional intermetallic alloys, however, face serious challenges when it comes to passivation or forming stable passive films in harsh/reactive environments. This is primarily due to limited elemental choices and single-atom occupancy tendencies, resulting in unsatisfactory aqueous corrosion resistance. Here, we develop a novel chemically complex intermetallic alloy (CCIMA) with a near-single-phase L1₂ structure, where tailored sublattice occupancy enables Co and Ni to occupy face-center sites and Al, V, Ta, and Ti to occupy corner sites. Electrochemical tests in 3.5 wt% NaCl solution demonstrate the superior comprehensive corrosion performance of CCIMA compared to most traditional intermetallic alloys, as evidenced by the higher pitting potential (E_pit), higher corrosion potential (E_corr), and lower corrosion current density (i_corr). This performance stems from the rapid formation of a ∼3.7 nm thick, non-stoichiometric amorphous passive film comprising multiple stable oxides (primarily Al₂O₃, TiO₂, Ta₂O₅, Co₃O₄, and minor V₂O₅, Co(OH)₂, Ni(OH)₂). Our work provides in-depth insights into the targeted design of passive films with desired properties towards better corrosion resistance and opens a new pathway for the optimization of damage-tolerant intermetallic alloys.

合金表面的纳米级钝化膜对合金的耐蚀性起着至关重要的作用。理想的钝化膜可以作为一种保护屏障层，通过阻止电荷转移反应和腐蚀离子的扩散，有效地保护合金基体。然而，大多数传统的金属间合金在恶劣/反应环境下的钝化或形成稳定的钝化膜时面临着严峻的挑战。这主要是由于有限的元素选择和单原子占用倾向，导致不满意的耐水性腐蚀。在这里，我们开发了一种具有近单相L12结构的新型化学复杂金属间合金（CCIMA），其中定制的亚晶格占用使Co和Ni占据面中心位置，Al， V， Ta和Ti占据角位置。在3.5 wt% NaCl溶液中的电化学测试表明，与大多数传统金属间合金相比，CCIMA具有更高的点蚀电位（Epit）、更高的腐蚀电位（Ecorr）和更低的腐蚀电流密度（icorr），具有更好的综合腐蚀性能。这种性能源于快速形成的~ 3.7 nm厚的非化学计量非晶钝化膜，包含多种稳定的氧化物(主要是Al2O3， TiO2, Ta2O5, Co3O4，以及少量的V2O5， Co（OH)2, Ni(OH)2）。我们的工作为钝化膜的目标设计提供了深入的见解，这些钝化膜具有更好的耐腐蚀性，并为优化耐损伤金属间合金开辟了新的途径。

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引用次数: 0

Effects of Cu content and Ga addition on suppressing intergranular corrosion of copper substrate in stainless steel/copper vacuum brazed joints Cu含量和Ga对抑制不锈钢/铜真空钎焊接头中铜基体晶间腐蚀的影响

IF 7.4 1区材料科学 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY

Corrosion Science

Pub Date : 2026-04-01 Epub Date: 2026-01-05 DOI: 10.1016/j.corsci.2026.113605

Guoqian Mu , Dongping Gao , Wenqing Qu , Xiaohong Li , Yanhua Zhang , Hongshou Zhuang

The intergranular corrosion of copper substrates caused by molten Ag-Cu based brazing alloys during the vacuum brazing of copper/stainless steel joints significantly compromises the structural integrity of assemblies in microwave vacuum electronic devices. This study presents a metallurgical approach to suppress intergranular liquid filler corrosion by modifying brazing alloy chemistry. It was found that both increasing the Cu content and adding Ga to Ag-Cu28-Ni0.75 brazing alloys effectively inhibit intergranular corrosion. A higher Cu content promotes the formation of a saturated liquid phase, thereby reducing the thermodynamic driving force for dissolution of solid copper. Meanwhile, the addition of Ga alters the composition and properties of the interfacial copper solid solution layer. Gallium facilitates uniform dissolution of the solid copper substrate rather than localized intergranular attack, thereby enhancing the mutual solubility between the solid and liquid. Based on these mechanisms, new quaternary Ag-Cu-Ni-Ga alloys were designed. The optimized Ag-Cu45-Ni-Ga9 and Ag-Cu50-Ni-Ga10 alloys completely suppressed intergranular corrosion at a brazing temperature of 870 ℃, producing sound joints free of cracks and pores. These newly developed brazing alloys consist of blocky copper solid solution and Ag-rich eutectic structure, with moderate hardness and good processability, without intermetallic compounds or liquid phase separation. The solidus and liquidus temperatures are 732–839 ℃ for Ag-Cu45-Ni-Ga9, and 734–847 ℃ for Ag-Cu50-Ni-Ga10. These results confirm that the intergranular corrosion of copper substrates is fundamentally associated with the grain boundary dissolution of solid copper.

微波真空电子器件中铜/不锈钢接头真空钎焊过程中，银铜基钎焊合金熔液对铜衬底造成晶间腐蚀，严重影响组件的结构完整性。本文提出了一种通过改变钎焊合金的化学性质来抑制晶间液体填料腐蚀的冶金方法。结果表明，在Ag-Cu28-Ni0.75钎焊合金中增加Cu含量和添加Ga均能有效抑制晶间腐蚀。较高的Cu含量促进了饱和液相的形成，从而降低了固体铜溶解的热力学驱动力。同时，Ga的加入改变了界面铜固溶层的组成和性能。镓有利于固体铜底物的均匀溶解，而不是局部的晶间攻击，从而增强了固液之间的相互溶解度。基于这些机理，设计了新型四元合金Ag-Cu-Ni-Ga。优化后的Ag-Cu45-Ni-Ga9和Ag-Cu50-Ni-Ga10合金在870℃的钎焊温度下完全抑制了晶间腐蚀，产生了无裂纹和气孔的良好接头。这些新开发的钎焊合金由块状铜固溶体和富银共晶组织组成，具有中等硬度和良好的加工性能，无金属间化合物和液相分离。Ag-Cu45-Ni-Ga9固相温度为732 ~ 839℃，Ag-Cu50-Ni-Ga10固相温度为734 ~ 847℃。这些结果证实了铜基体的晶间腐蚀从根本上与固体铜的晶界溶解有关。

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引用次数: 0

Superior hydrogen embrittlement resistance of WAAM Ti-6Al-4V compared to wrought alloy under gaseous hydrogen charging 在气体充氢条件下，WAAM Ti-6Al-4V合金的抗氢脆性能优于变形合金

IF 7.4 1区材料科学 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY

Corrosion Science

Pub Date : 2026-04-01 Epub Date: 2026-01-05 DOI: 10.1016/j.corsci.2025.113591

Soobin Kim , Yuanjiu Huang , Dong-Hyuck Kam , Jin-Yoo Suh , Kee-Ahn Lee

This study demonstrates the superior hydrogen embrittlement (HE) resistance of Ti-6Al-4V fabricated by wire arc additive manufacturing (WAAM) compared with its wrought counterpart under high-pressure gaseous hydrogen charging (300 °C, 15 MPa, 72 h). After hydrogen exposure, both alloys exhibited increased strength; however, their ductility responses differed significantly. The WAAM specimen retained stable tensile properties, with elongation decreasing from 9.33 % to 8.91 %, corresponding to a HE index (HEI) of only 4.5 %. In contrast, the wrought specimen showed a substantial ductility reduction, from 10.42 % to 7.73 %, resulting in an HEI of 25.8 % and indicating much higher susceptibility to embrittlement. Microstructural and crystallographic analyses revealed that the continuous α/β lamellar structure in WAAM activated hydrogen-enhanced localized plasticity (HELP) in a spatially distributed manner across multiple interfaces in conjunction with dual hydrogen-trapping states. Such interfacial dislocation activity facilitated slip transfer and alleviated strain localization, thereby enabling a more uniform macroscopic deformation response. Conversely, the wrought alloy exhibited highly localized HELP together with hydrogen-enhanced decohesion (HEDE) within the β phase, associated with a single deep trapping state that accelerated premature cracking. These results highlight that the unique interfacial network generated by WAAM mitigates hydrogen-induced damage and preserves ductility, underscoring its potential as a titanium structural material suitable for hydrogen-containing environments.

在高压气体充氢（300°C, 15 MPa, 72 h）条件下，采用电弧增材制造（WAAM）法制备的Ti-6Al-4V合金具有较好的抗氢脆（HE）性能。氢暴露后，两种合金的强度均有所提高；然而，它们的延性反应有显著差异。WAAM试样保持了稳定的拉伸性能，伸长率从9.33 %下降到8.91 %，HE指数（HEI）仅为4.5 %。相比之下，变形后的试样显示出明显的塑性降低，从10.42 %降至7.73 %，导致HEI为25.8 %，表明脆性敏感性更高。显微组织和晶体学分析表明，WAAM激活氢增强局部塑性（HELP）的连续α/β片层结构在多个界面上以空间分布的方式分布，并伴有双氢俘获态。这种界面位错活动促进了滑移传递，缓解了应变局部化，从而使宏观变形响应更加均匀。相反，变形后的合金在β相中表现出高度局域化的HELP和氢增强脱粘（HEDE），与单一深俘获态相关，加速了过早开裂。这些结果强调了WAAM产生的独特界面网络减轻了氢引起的损伤并保持了延展性，强调了其作为适合含氢环境的钛结构材料的潜力。

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引用次数: 0

Microstructures and high-temperature oxidation behavior of MoSi2-MoAlB composites MoSi2-MoAlB复合材料的显微组织和高温氧化行为

IF 7.4 1区材料科学 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY

Corrosion Science

Pub Date : 2026-04-01 Epub Date: 2026-01-16 DOI: 10.1016/j.corsci.2026.113639

Xiang-An Bei, Guo-Hua Zhang

In this study, MoAlB was introduced as a reactive precursor in MoSi₂-based ceramics. During spark plasma sintering, MoAlB underwent in-situ decomposition, forming MoB and Al₂O₃ phases. These phases were distributed uniformly within the MoSi₂ matrix as reinforcing phases. This resulted in significant improvements in hardness and toughness, with the peak flexural strength obtained for 10 vol% MoAlB addition. Oxidation tests from 900 to 1500 ℃ revealed a temperature-dependent oxidation behavior. At 1500 ℃, volatilization of MoO₃ and B₂O₃ destabilized the oxide scale, while the 5 vol% MoAlB composite offered excellent protection at intermediate temperatures (900–1200 ℃). The formation of a stable SiO₂-B₂O₃-Al₂O₃ self-healing glass provided effective protection in this critical temperature range. These findings demonstrate MoAlB’s effectiveness in designing MoSi₂-based ceramics for intermediate temperature applications.

在本研究中，MoAlB作为反应前驱体被引入到mosi2基陶瓷中。在放电等离子烧结过程中，MoAlB发生原位分解，形成MoB相和Al2O3相。这些相作为增强相均匀分布在MoSi2基体内。这导致了硬度和韧性的显著提高，当添加10 vol% MoAlB时，获得了最大的弯曲强度。900 ~ 1500℃的氧化试验表明，氧化行为与温度有关。在1500℃时，MoO3和B2O3的挥发使氧化垢失稳，而5 vol% MoAlB复合材料在900-1200℃时具有良好的保护作用。形成稳定的SiO2-B2O3-Al2O3自愈玻璃，在这个临界温度范围内提供了有效的保护。这些发现证明了MoAlB在设计中温应用的mosi2基陶瓷方面的有效性。

引用次数: 0

Effect of cold rolling on corrosion behavior of IN625 alloy in hydrofluoric acid solution 冷轧对IN625合金氢氟酸腐蚀行为的影响

IF 7.4 1区材料科学 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY

Corrosion Science

Pub Date : 2026-04-01 Epub Date: 2026-01-06 DOI: 10.1016/j.corsci.2026.113601

Rongrong Shang , Xiaoxuan Dong , Mengxia Chen , Yang Liu , Lu Liu , Jianwei Teng , Biaobiao Yang , Yunping Li

Corrosion behaviors of IN625 alloy after cold rolling to reduction rates of 20%, 50% and 80% were investigated by immersion in hydrofluoric acid (HF) solution. In contrast to the negligible influence on the anti-corrosive alloys IN600 and C276, significantly deteriorated corrosion resistance of alloy IN625 was observed after cold rolling. This can be partly ascribed to the extremely low stacking fault energy (SFE) of IN625 alloy, which is characterized by exceptionally high mean dislocation density and extremely high lattice distortions locally around the carbide, grain boundaries (GB), annealing twinning boundaries (ATB) and planar slipping bands (SB). The high-defect areas around the carbide, GBs, ATB and SB after cold rolling demonstrate enhanced anodic activity and consequently lower electrode potentials. The thermodynamic potential difference between defect-rich and defect-free regions drives the generation of microcurrents, accelerating the local corrosion process, and ultimately leading to a decreased overall corrosion resistance of alloy. This greatly lowered the passiveness of alloy by enhancing the dissolution of alloying elements and accelerated the internal penetration of F ions into alloy matrix through the high defect channels, carbide, GB, ATB and SB.

采用氢氟酸（HF）溶液浸泡的方法，研究了冷轧后IN625合金在还原率为20%、50%和80%时的腐蚀行为。冷轧对耐腐蚀合金IN600和C276的影响可以忽略，而冷轧后IN625的耐腐蚀性能明显下降。这可以部分归因于IN625合金极低的层错能（SFE），其特征是异常高的平均位错密度和在碳化物、晶界（GB）、退火孪晶界（ATB）和平面滑移带（SB）周围的极高的局部晶格畸变。冷轧后碳化物、GBs、ATB和SB周围的高缺陷区域阳极活性增强，电极电位降低。富缺陷区和无缺陷区之间的热力学电位差驱动微电流的产生，加速了局部腐蚀过程，最终导致合金的整体耐蚀性下降。这通过增强合金元素的溶解，大大降低了合金的钝化性，加速了F离子通过高缺陷通道、碳化物、GB、ATB和SB向合金基体内部渗透。

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引用次数: 0

Ultraviolet catalysis assisted chemical mechanical polishing of cobalt: Mechanism of corrosion inhibition and atomic-level planarization 紫外光催化辅助钴的化学机械抛光：缓蚀和原子水平平整化机理

IF 7.4 1区材料科学 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY

Corrosion Science

Pub Date : 2026-04-01 Epub Date: 2026-01-16 DOI: 10.1016/j.corsci.2026.113638

Lifei Zhang , Jialei Zhang , Xinchun Lu

As the feature sizes of integrated circuits shrink to 5 nm node and below, interconnection fabrication is approaching atomic-level precision requirements. Cobalt (Co) has emerged as a key interconnection material to replace copper due to its superior electrical property. However, achieving an atomically smooth Co surface remains challenging. This work modifies the conventional chemical mechanical polishing (CMP) process by introducing ultraviolet catalysis (UV-CMP). The approach precisely controls the oxidation process of the Co surface via UV irradiation, enabling the formation of a protective passive layer that effectively inhibits corrosion. Experiments demonstrate that UV irradiation catalytically activates H2O2 to generate highly reactive hydroxyl radical (·OH), facilitating the rapid formation of a dense and protective Co3O4 passivation layer on Co surface. Under the optimized condition, the in-situ formed passivation layer effectively suppresses corrosive dissolution and yields an atomically smooth surface with a roughness as low as 0.15 nm, representing a nearly 50 % reduction compared to the non-UV-irradiated case. Electrochemical measurements confirm the highest charge transfer resistance under the optimal condition, corroborating the exceptional surface protection capability of the passivation layer. Density functional theory (DFT) calculations reveal that ·OH exhibits a much stronger electron-withdrawing capability than H₂O₂ on various Co surfaces, promoting substantial electron transfer from Co and thereby driving the surface to a higher oxidation state. This work elucidates the mechanism of photocatalytic passivation in the CMP of Co, thereby providing both theoretical insights and technical support for the atomic-level precision surface fabrication of Co interconnects at advanced technology nodes.

随着集成电路的特征尺寸缩小到5 nm节点及以下，互连制造正接近原子级精度要求。钴（Co）因其优越的电学性能而成为取代铜的关键互连材料。然而，实现原子光滑的钴表面仍然具有挑战性。本工作通过引入紫外线催化（UV-CMP）对传统化学机械抛光（CMP）工艺进行了改进。该方法通过紫外线照射精确控制Co表面的氧化过程，从而形成有效抑制腐蚀的保护性被动层。实验表明，紫外辐射可催化活化H2O2生成高活性的羟基自由基（·OH），促进Co表面快速形成致密的保护性Co3O4钝化层。在优化的条件下，原位形成的钝化层有效地抑制了腐蚀溶解，并产生了原子光滑的表面，粗糙度低至0.15 nm，与未紫外线照射的情况相比，降低了近50% %。电化学测量证实了在最佳条件下的最高电荷转移电阻，证实了钝化层卓越的表面保护能力。密度泛函理论（DFT）计算表明，·OH在各种Co表面表现出比H₂O₂更强的吸电子能力，促进Co表面大量电子转移，从而驱动表面达到更高的氧化态。本研究阐明了Co在CMP中的光催化钝化机理，从而为在先进技术节点上原子级精密表面制备Co互连提供理论见解和技术支持。

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