Pub Date : 2026-01-06DOI: 10.1016/j.corsci.2026.113606
Naizhi Liu , Chengze Liu , Jinping Wu , Jianping Xu , Yi Liu , Zhonglin Shen , Lai-Chang Zhang , Yusheng Zhang
To mitigate stress corrosion cracking (SCC) and improve the breakdown resistance of Zr alloys in high-temperature nitric acid, we developed a series of Zr-Ti alloys with varying Ti contents. Their mechanical and electrochemical properties were evaluated by slow strain rate tensile (SSRT) tests in 6 M HNO3 at 95 °C under both open-circuit potential (OCP) and a constant potential of 1.5 V conditions. While pure Zr exhibited brittle fracture and significant oxide thickening (∼96 μm) with severe cracking at 1.5 V, Zr702L (Zr-6Ti) maintained superior strength and ductility, forming only a nanoscale, crack-free oxide film. We found that the addition of Ti facilitated the formation of a dense hybrid oxide film composed of nanocrystalline ZrO2/TiO2 and an amorphous phase. Compared with other works, this composite structure ensured the preservation of the alloy's mechanical integrity while concurrently inhibited crack initiation and blocked the invasion of corrosive species. Our results highlight the critical role of Ti in stabilizing the oxide film and enhancing the SCC resistance of Zr alloys under aggressive electrochemical conditions.
为了减轻Zr合金在高温硝酸中的应力腐蚀开裂（SCC），提高其抗击穿性能，我们研制了一系列不同Ti含量的Zr-Ti合金。在开路电位（OCP）和恒电位1.5 V条件下，在95°C 6 M HNO3中进行慢应变速率拉伸（SSRT）试验，评价了它们的力学和电化学性能。纯Zr表现为脆性断裂和明显的氧化增厚（~ 96 μm），在1.5 V时严重开裂，而Zr702L （Zr- 6ti）保持了优异的强度和延展性，仅形成纳米级无裂纹的氧化膜。我们发现，Ti的加入有利于形成由纳米晶ZrO2/TiO2和非晶相组成的致密杂化氧化膜。与其他作品相比，这种复合结构既保证了合金的力学完整性，又抑制了裂纹的萌生，阻断了腐蚀物质的侵入。我们的研究结果强调了Ti在稳定氧化膜和增强Zr合金在侵略性电化学条件下的抗SCC能力方面的关键作用。
{"title":"Ti-induced amorphous/nanocrystalline oxide films enabling high-potential SCC immunity to zirconium alloys in nitric acid","authors":"Naizhi Liu , Chengze Liu , Jinping Wu , Jianping Xu , Yi Liu , Zhonglin Shen , Lai-Chang Zhang , Yusheng Zhang","doi":"10.1016/j.corsci.2026.113606","DOIUrl":"10.1016/j.corsci.2026.113606","url":null,"abstract":"<div><div>To mitigate stress corrosion cracking (SCC) and improve the breakdown resistance of Zr alloys in high-temperature nitric acid, we developed a series of Zr-Ti alloys with varying Ti contents. Their mechanical and electrochemical properties were evaluated by slow strain rate tensile (SSRT) tests in 6 M HNO<sub>3</sub> at 95 °C under both open-circuit potential (OCP) and a constant potential of 1.5 V conditions. While pure Zr exhibited brittle fracture and significant oxide thickening (∼96 μm) with severe cracking at 1.5 V, Zr702L (Zr-6Ti) maintained superior strength and ductility, forming only a nanoscale, crack-free oxide film. We found that the addition of Ti facilitated the formation of a dense hybrid oxide film composed of nanocrystalline ZrO<sub>2</sub>/TiO<sub>2</sub> and an amorphous phase. Compared with other works, this composite structure ensured the preservation of the alloy's mechanical integrity while concurrently inhibited crack initiation and blocked the invasion of corrosive species. Our results highlight the critical role of Ti in stabilizing the oxide film and enhancing the SCC resistance of Zr alloys under aggressive electrochemical conditions.</div></div>","PeriodicalId":290,"journal":{"name":"Corrosion Science","volume":"261 ","pages":"Article 113606"},"PeriodicalIF":7.4,"publicationDate":"2026-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145923725","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-06DOI: 10.1016/j.corsci.2026.113603
Zhumin Li , Yuan Li , Jiansheng Li , Yusheng Li , Yuehong Zheng , Wei Jiang , Ao Meng , Qingzhong Mao , Yonghao Zhao
The development of advanced copper alloys with excellent oxidation resistance and high thermal stability is crucial for the application of key hot-end components. Herein, we systematically investigate the effects of the co-addition of Cr and Zr on the microstructure and oxidation behavior of coherent γ' phase-strengthened Cu-Ni-Al alloys. Through comprehensive microstructural characterization, thermodynamic calculations, and first-principles calculation, their microstructural evolution and oxidation resistance mechanisms were elucidated. The results indicate that the strong negative mixing enthalpies of Cr-Ni (ΔHNi-Cr = −7 kJ/mol) and Zr-Ni (ΔHNi-Zr = −49 kJ/mol) facilitate the complete solid solution of Cr and Zr in the γ and γ′ phases of the Cu49.66 alloy. With increasing Cu content, the volume fraction and size of the γ′ phase decreases, and excess Cr and Zr precipitate predominantly as BCC-Cr and Ni5Zr phases. When the Cu content is ≤ 86.66 at%, the alloys exhibit outstanding oxidation resistance, with mass gains of only 0.22–3.54 mg/cm2 at 850 ℃. This behavior is attributed to: (1) Cr promotes the formation of Al2O3 layer and healing its micro-defects via rapid diffusion, suppressing cation/anion interdiffusion; (2) Zr possesses a pronounced tendency for grain boundary segregation, effectively impeding oxygen diffusion along grain boundaries. (3) BCC-Cr and Ni5Zr phases exhibiting high oxygen adsorption energies (−8.79 eV and −7.62 eV, respectively), which enhance surface oxygen adsorption and promote the formation of a protective oxide scale. This study provides both theoretical and experimental foundations for the composition design and oxidation protection of high-temperature-resistant copper alloys.
开发具有优异抗氧化性和高热稳定性的高级铜合金，对于关键热端部件的应用至关重要。本文系统地研究了Cr和Zr共添加对共格γ′相强化Cu-Ni-Al合金显微组织和氧化行为的影响。通过综合的微观结构表征、热力学计算和第一性原理计算，阐明了它们的微观结构演变和抗氧化机理。结果表明：Cr- ni （ΔHNi-Cr =−7 kJ/mol）和Zr- ni （ΔHNi-Zr =−49 kJ/mol）较强的负混合焓有利于Cr和Zr在Cu49.66合金的γ和γ′相中完全固溶；随着Cu含量的增加，γ′相的体积分数和尺寸减小，过量的Cr和Zr主要以BCC-Cr和Ni5Zr相析出。当Cu含量≤ 86.66 at%时，合金表现出优异的抗氧化性能，850℃下的质量增益仅为0.22 ~ 3.54 mg/cm2。这是由于：(1)Cr通过快速扩散促进了Al2O3层的形成并修复其微缺陷，抑制了正离子/阴离子的相互扩散；(2) Zr具有明显的晶界偏析倾向，有效地阻碍了氧沿晶界扩散。(3) BCC-Cr和Ni5Zr相表现出较高的氧吸附能（分别为- 8.79 eV和- 7.62 eV），增强了表面氧吸附，促进了保护氧化层的形成。本研究为耐高温铜合金的成分设计和抗氧化提供了理论和实验依据。
{"title":"Microstructural characteristics and oxidation behaviors of heat-resistant Cu-Ni-Al alloys with co-addition of Cr and Zr","authors":"Zhumin Li , Yuan Li , Jiansheng Li , Yusheng Li , Yuehong Zheng , Wei Jiang , Ao Meng , Qingzhong Mao , Yonghao Zhao","doi":"10.1016/j.corsci.2026.113603","DOIUrl":"10.1016/j.corsci.2026.113603","url":null,"abstract":"<div><div>The development of advanced copper alloys with excellent oxidation resistance and high thermal stability is crucial for the application of key hot-end components. Herein, we systematically investigate the effects of the co-addition of Cr and Zr on the microstructure and oxidation behavior of coherent γ' phase-strengthened Cu-Ni-Al alloys. Through comprehensive microstructural characterization, thermodynamic calculations, and first-principles calculation, their microstructural evolution and oxidation resistance mechanisms were elucidated. The results indicate that the strong negative mixing enthalpies of Cr-Ni (Δ<em>H</em><sub>Ni-Cr</sub> = −7 kJ/mol) and Zr-Ni (Δ<em>H</em><sub>Ni-Zr</sub> = −49 kJ/mol) facilitate the complete solid solution of Cr and Zr in the γ and γ′ phases of the Cu<sub>49.66</sub> alloy. With increasing Cu content, the volume fraction and size of the γ′ phase decreases, and excess Cr and Zr precipitate predominantly as BCC-Cr and Ni<sub>5</sub>Zr phases. When the Cu content is ≤ 86.66 at%, the alloys exhibit outstanding oxidation resistance, with mass gains of only 0.22–3.54 mg/cm<sup>2</sup> at 850 ℃. This behavior is attributed to: (1) Cr promotes the formation of Al<sub>2</sub>O<sub>3</sub> layer and healing its micro-defects via rapid diffusion, suppressing cation/anion interdiffusion; (2) Zr possesses a pronounced tendency for grain boundary segregation, effectively impeding oxygen diffusion along grain boundaries. (3) BCC-Cr and Ni<sub>5</sub>Zr phases exhibiting high oxygen adsorption energies (−8.79 eV and −7.62 eV, respectively), which enhance surface oxygen adsorption and promote the formation of a protective oxide scale. This study provides both theoretical and experimental foundations for the composition design and oxidation protection of high-temperature-resistant copper alloys.</div></div>","PeriodicalId":290,"journal":{"name":"Corrosion Science","volume":"261 ","pages":"Article 113603"},"PeriodicalIF":7.4,"publicationDate":"2026-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145923647","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-05DOI: 10.1016/j.corsci.2026.113598
Yeonggeun Cho , Hyung-Jun Cho , Jinheung Park , Sung-Joon Kim
The present study investigated the microstructure-driven mechanisms governing hydrogen embrittlement (HE) in low-Ni austenitic stainless steels, by integrating multi-scale experimental analysis with crystal plasticity and hydrogen transport simulations. The results revealed that while α’ martensite increases susceptibility to HE, grain-size heterogeneity and intragranular nanoscale carbides play critical roles in local H distribution and H-induced cracking. Grain refinement enhanced strength and decreased H uptake; however, simulations demonstrated that inevitable grain-size deviations induced stress heterogeneity between fine and coarse grains. H segregation along high-angle grain boundaries, coupled with stress heterogeneity, promoted localized H-induced cracking in highly deformed regions to deteriorate HE resistance. Increased carbon content for strengthening facilitated the precipitation of nanoscale Cr23C6 carbides within austenite grains, but these carbides increased the uptake of diffusible H. Their interfaces acted as preferential crack initiation sites in central regions, and the cracks propagated toward the surface during deformation. Surface H-induced cracks generated additional stress concentrations in the interior, which synergized negatively with central cracking to accelerate premature fracture of the steel.
{"title":"Hydrogen embrittlement in low-Ni austenitic stainless steel: Microstructure-driven mechanisms revealed by experimental and simulation study","authors":"Yeonggeun Cho , Hyung-Jun Cho , Jinheung Park , Sung-Joon Kim","doi":"10.1016/j.corsci.2026.113598","DOIUrl":"10.1016/j.corsci.2026.113598","url":null,"abstract":"<div><div>The present study investigated the microstructure-driven mechanisms governing hydrogen embrittlement (HE) in low-Ni austenitic stainless steels, by integrating multi-scale experimental analysis with crystal plasticity and hydrogen transport simulations. The results revealed that while α’ martensite increases susceptibility to HE, grain-size heterogeneity and intragranular nanoscale carbides play critical roles in local H distribution and H-induced cracking. Grain refinement enhanced strength and decreased H uptake; however<strong>,</strong> simulations demonstrated that inevitable grain-size deviations induced stress heterogeneity between fine and coarse grains. H segregation along high-angle grain boundaries, coupled with stress heterogeneity, promoted localized H-induced cracking in highly deformed regions to deteriorate HE resistance. Increased carbon content for strengthening facilitated the precipitation of nanoscale Cr<sub>23</sub>C<sub>6</sub> carbides within austenite grains, but these carbides increased the uptake of diffusible H. Their interfaces acted as preferential crack initiation sites in central regions, and the cracks propagated toward the surface during deformation. Surface H-induced cracks generated additional stress concentrations in the interior, which synergized negatively with central cracking to accelerate premature fracture of the steel.</div></div>","PeriodicalId":290,"journal":{"name":"Corrosion Science","volume":"261 ","pages":"Article 113598"},"PeriodicalIF":7.4,"publicationDate":"2026-01-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145923723","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-05DOI: 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 (Epit), higher corrosion potential (Ecorr), and lower corrosion current density (icorr). 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.
{"title":"Chemically complex ordered alloy enables electrochemically stable passivation for superior corrosion resistance","authors":"J.Y. Zhang , Y.H. Zhou , T.H. Chou , J.H. Luan , H. Luo , Y.L. Zhao , T. Yang","doi":"10.1016/j.corsci.2026.113597","DOIUrl":"10.1016/j.corsci.2026.113597","url":null,"abstract":"<div><div>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 L1<sub>2</sub> 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 (<em>E</em><sub>pit</sub>), higher corrosion potential (<em>E</em><sub>corr</sub>), and lower corrosion current density (<em>i</em><sub>corr</sub>). This performance stems from the rapid formation of a ∼3.7 nm thick, non-stoichiometric amorphous passive film comprising multiple stable oxides (primarily Al<sub>2</sub>O<sub>3</sub>, TiO<sub>2</sub>, Ta<sub>2</sub>O<sub>5</sub>, Co<sub>3</sub>O<sub>4</sub>, and minor V<sub>2</sub>O<sub>5</sub>, Co(OH)<sub>2</sub>, Ni(OH)<sub>2</sub>). 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.</div></div>","PeriodicalId":290,"journal":{"name":"Corrosion Science","volume":"261 ","pages":"Article 113597"},"PeriodicalIF":7.4,"publicationDate":"2026-01-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145923720","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-05DOI: 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.
{"title":"Effects of Cu content and Ga addition on suppressing intergranular corrosion of copper substrate in stainless steel/copper vacuum brazed joints","authors":"Guoqian Mu , Dongping Gao , Wenqing Qu , Xiaohong Li , Yanhua Zhang , Hongshou Zhuang","doi":"10.1016/j.corsci.2026.113605","DOIUrl":"10.1016/j.corsci.2026.113605","url":null,"abstract":"<div><div>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.</div></div>","PeriodicalId":290,"journal":{"name":"Corrosion Science","volume":"261 ","pages":"Article 113605"},"PeriodicalIF":7.4,"publicationDate":"2026-01-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145923721","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-05DOI: 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.
{"title":"Superior hydrogen embrittlement resistance of WAAM Ti-6Al-4V compared to wrought alloy under gaseous hydrogen charging","authors":"Soobin Kim , Yuanjiu Huang , Dong-Hyuck Kam , Jin-Yoo Suh , Kee-Ahn Lee","doi":"10.1016/j.corsci.2025.113591","DOIUrl":"10.1016/j.corsci.2025.113591","url":null,"abstract":"<div><div>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.</div></div>","PeriodicalId":290,"journal":{"name":"Corrosion Science","volume":"261 ","pages":"Article 113591"},"PeriodicalIF":7.4,"publicationDate":"2026-01-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145923727","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
This study modifies the texture and precipitation phases of titanium-free maraging steel by adjusting the heat treatment process, thereby enhancing its resistance to hydrogen embrittlement and toughness without compromising the steel's strength. The results revealed three key advancements: (i) ω-precipitates and reversed austenite acted as hydrogen traps, delaying hydrogen diffusion; the subsequent formation of the Laves phase further enhanced this effect, significantly reducing the hydrogen diffusion coefficient by 71.3 %; (ii) incomplete recrystallization of austenite before quenching inhibited the formation of martensite variants, resulting in a pronounced < 110 > //RD fiber texture that effectively altered the crack propagation path—a texture mechanism previously overlooked in hydrogen embrittlement studies; (iii) analysis of the crack path and thermal desorption spectra of SLLA-480 demonstrated that reversed austenite served as a hydrogen trap, inhibiting hydrogen diffusion, while dispersed reversed austenite had limited capacity to impede crack propagation in high-strength maraging steel. Due to these synergistic mechanisms, the SLLA-480 process reduced hydrogen embrittlement sensitivity by 17 % without compromising strength. This work deepens our understanding of the hydrogen embrittlement mechanism in maraging steel and proposes a microstructure design strategy based on the synergistic control of nanoprecipitates and crystal texture—a strategy particularly important for titanium-free maraging steel systems.
{"title":"Texture and nano-precipitates synergistically suppress hydrogen embrittlement susceptibility in titanium-free maraging steel","authors":"Xin Liu , Kaiyu Zhang , Wanliang Zhang , Jinrong Wu , Kehang Wu , Chengshuang Zhou , Lin Zhang , Jinyang Zheng","doi":"10.1016/j.corsci.2026.113599","DOIUrl":"10.1016/j.corsci.2026.113599","url":null,"abstract":"<div><div>This study modifies the texture and precipitation phases of titanium-free maraging steel by adjusting the heat treatment process, thereby enhancing its resistance to hydrogen embrittlement and toughness without compromising the steel's strength. The results revealed three key advancements: (i) ω-precipitates and reversed austenite acted as hydrogen traps, delaying hydrogen diffusion; the subsequent formation of the Laves phase further enhanced this effect, significantly reducing the hydrogen diffusion coefficient by 71.3 %; (ii) incomplete recrystallization of austenite before quenching inhibited the formation of martensite variants, resulting in a pronounced < 110 > //RD fiber texture that effectively altered the crack propagation path—a texture mechanism previously overlooked in hydrogen embrittlement studies; (iii) analysis of the crack path and thermal desorption spectra of SLLA-480 demonstrated that reversed austenite served as a hydrogen trap, inhibiting hydrogen diffusion, while dispersed reversed austenite had limited capacity to impede crack propagation in high-strength maraging steel. Due to these synergistic mechanisms, the SLLA-480 process reduced hydrogen embrittlement sensitivity by 17 % without compromising strength. This work deepens our understanding of the hydrogen embrittlement mechanism in maraging steel and proposes a microstructure design strategy based on the synergistic control of nanoprecipitates and crystal texture—a strategy particularly important for titanium-free maraging steel systems.</div></div>","PeriodicalId":290,"journal":{"name":"Corrosion Science","volume":"261 ","pages":"Article 113599"},"PeriodicalIF":7.4,"publicationDate":"2026-01-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145923718","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-05DOI: 10.1016/j.corsci.2026.113602
Jun Fan , Hongwei Yao , Kai Xu , Gang Liu , Jibin Pu
Corrosion is the primary challenge for metallic materials serving in marine environments, and the pursuit of lower corrosion rate and more stable passivation remains perpetual. However, these two key properties are difficult to simultaneously optimize for traditional metallic materials. Oxygen, typically treated as an impurity during the smelting process of metallic materials, requires strict control. In contrast, oxygen in marine environments can promote the formation of dense passive films on metal surfaces. In this work, in-situ incorporation of oxygen into a novel CrNbTiZr multi-principal element coating was implemented to achieve the synergistic regulation of corrosion rate and passivation behavior. In NaCl solution, the self-corrosion current density of the coating was reduced by approximately two orders of magnitude compared to traditional 304 stainless steel and its passivation potential even outperformed that of titanium alloys. The excellent corrosion resistance originates from the microstructural transformation of CrNbTiZr from BCC to amorphous state induced by controlled oxygen content. The collapsed BCC phase enables more uniform distribution of Nb/Ti passivating elements within the amorphous phase. Additionally, the formation of local (covalent) bonds between oxygen and metal atoms reduces the element dissolution rate, facilitating the formation of a uniform-thickness and dense double-layer passive film across different phases on the surface of the coating. The high-quality passive film and dense intrinsic structure of coatings significantly enhance the resistance of Cl⁻ attack, endowing the coating with potential applications in marine engineering. This work highlights the beneficial effect of in-situ oxygen incorporation on the corrosion resistance of metallic materials, providing a new strategy for the design of metallic materials with high corrosion resistance in harsh environments.
{"title":"Robust corrosion resistance enabled by in-situ oxygen-tailored microstructure of CrNbTiZr multi-principal element coating","authors":"Jun Fan , Hongwei Yao , Kai Xu , Gang Liu , Jibin Pu","doi":"10.1016/j.corsci.2026.113602","DOIUrl":"10.1016/j.corsci.2026.113602","url":null,"abstract":"<div><div>Corrosion is the primary challenge for metallic materials serving in marine environments, and the pursuit of lower corrosion rate and more stable passivation remains perpetual. However, these two key properties are difficult to simultaneously optimize for traditional metallic materials. Oxygen, typically treated as an impurity during the smelting process of metallic materials, requires strict control. In contrast, oxygen in marine environments can promote the formation of dense passive films on metal surfaces. In this work, in-situ incorporation of oxygen into a novel CrNbTiZr multi-principal element coating was implemented to achieve the synergistic regulation of corrosion rate and passivation behavior. In NaCl solution, the self-corrosion current density of the coating was reduced by approximately two orders of magnitude compared to traditional 304 stainless steel and its passivation potential even outperformed that of titanium alloys. The excellent corrosion resistance originates from the microstructural transformation of CrNbTiZr from BCC to amorphous state induced by controlled oxygen content. The collapsed BCC phase enables more uniform distribution of Nb/Ti passivating elements within the amorphous phase. Additionally, the formation of local (covalent) bonds between oxygen and metal atoms reduces the element dissolution rate, facilitating the formation of a uniform-thickness and dense double-layer passive film across different phases on the surface of the coating. The high-quality passive film and dense intrinsic structure of coatings significantly enhance the resistance of Cl⁻ attack, endowing the coating with potential applications in marine engineering. This work highlights the beneficial effect of in-situ oxygen incorporation on the corrosion resistance of metallic materials, providing a new strategy for the design of metallic materials with high corrosion resistance in harsh environments.</div></div>","PeriodicalId":290,"journal":{"name":"Corrosion Science","volume":"261 ","pages":"Article 113602"},"PeriodicalIF":7.4,"publicationDate":"2026-01-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145923653","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-05DOI: 10.1016/j.corsci.2026.113596
Lili Liu , Haiyang Jiang , Quan Shan , Junlei Zhang , Xiang Chen , Zulai Li , Dawei Wang , Guangsheng Huang
This study systematically investigated, through a combination of experimental characterization and first-principles calculations, the influence of pre-deformation modes on the microstructural evolution and corrosion behavior of AM60 magnesium alloy. The results indicated that basal slip was the dominant mechanism during pre-tension, leading to significant dislocation multiplication. In contrast, pre-compression activated extensive twinning, which resulted in grain refinement and a reorientation of the grain c-axis by ∼86.5°. Mechanical testing indicated that pre-deformation improved the alloy's strength at the expense of ductility; the yield strength increased by ∼50 MPa, and the elongation reduced by ∼1.6 % (pre-tension) and ∼5.2 % (pre-compression). Corrosion results revealed that the corrosion rates of the pre-tensioned and pre-compressed samples increased to 2.01 and 1.19 times that of the initial state, respectively. The high-density dislocations generated by pre-tension formed preferential corrosion channels, which promoted cracking of the surface product film, thereby accelerating localized corrosion. Conversely, the twins introduced by pre-compression refined the grain structure, which effectively alleviated the tensile stress within the product film and facilitated the formation of a dense protective layer. First-principles calculations further revealed the dual role of extension twins. Although their high interfacial energy (90.4 mJ/m2) decreased atomic stability, the high-density twin distribution in the pre-compressed specimen reduced its surface energy (1.431 J/cm2) compared to the pre-tensioned specimen (1.465 J/cm2), while simultaneously diminishing the energy differences among grains. The synergistic effect between surface energy optimization and grain refinement collectively contributes to the superior corrosion resistance of pre-compressed specimens over pre-tensioned ones.
{"title":"The influence of pre-compression/tension induced deformation mechanisms on the corrosion behavior of AM60 Mg alloy","authors":"Lili Liu , Haiyang Jiang , Quan Shan , Junlei Zhang , Xiang Chen , Zulai Li , Dawei Wang , Guangsheng Huang","doi":"10.1016/j.corsci.2026.113596","DOIUrl":"10.1016/j.corsci.2026.113596","url":null,"abstract":"<div><div>This study systematically investigated, through a combination of experimental characterization and first-principles calculations, the influence of pre-deformation modes on the microstructural evolution and corrosion behavior of AM60 magnesium alloy. The results indicated that basal slip was the dominant mechanism during pre-tension, leading to significant dislocation multiplication. In contrast, pre-compression activated extensive twinning, which resulted in grain refinement and a reorientation of the grain c-axis by ∼86.5°. Mechanical testing indicated that pre-deformation improved the alloy's strength at the expense of ductility; the yield strength increased by ∼50 MPa, and the elongation reduced by ∼1.6 % (pre-tension) and ∼5.2 % (pre-compression). Corrosion results revealed that the corrosion rates of the pre-tensioned and pre-compressed samples increased to 2.01 and 1.19 times that of the initial state, respectively. The high-density dislocations generated by pre-tension formed preferential corrosion channels, which promoted cracking of the surface product film, thereby accelerating localized corrosion. Conversely, the twins introduced by pre-compression refined the grain structure, which effectively alleviated the tensile stress within the product film and facilitated the formation of a dense protective layer. First-principles calculations further revealed the dual role of <span><math><mrow><mspace></mspace><mo>{</mo><mn>10</mn><mover><mrow><mn>1</mn></mrow><mo>̅</mo></mover><mn>2</mn><mo>}</mo></mrow></math></span> extension twins. Although their high interfacial energy (90.4 mJ/m<sup>2</sup>) decreased atomic stability, the high-density twin distribution in the pre-compressed specimen reduced its surface energy (1.431 J/cm<sup>2</sup>) compared to the pre-tensioned specimen (1.465 J/cm<sup>2</sup>), while simultaneously diminishing the energy differences among grains. The synergistic effect between surface energy optimization and grain refinement collectively contributes to the superior corrosion resistance of pre-compressed specimens over pre-tensioned ones.</div></div>","PeriodicalId":290,"journal":{"name":"Corrosion Science","volume":"261 ","pages":"Article 113596"},"PeriodicalIF":7.4,"publicationDate":"2026-01-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145923729","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-03DOI: 10.1016/j.corsci.2026.113595
Wang Diao , Junwei Wang , Li Lu , Bo Li , Leyang Dai , Jun Cheng , Haifeng Liao , Xiangning Wang , Zhenjie Wang , Zhilong Xu
The anti-tribocorrosion mechanisms of CoCrFeNiTix (x = 0.0, 0.1, 0.3, 0.5, 1.0) in simulated seawater were investigated quantitatively. At low Ti content (Ti0.1), corrosion-promoted wear (ΔWc) is pronounced due to rapid repassivation, resulting in a high tribocorrosion rate. At higher Ti contents (Ti0.5 and Ti1.0), the Laves phase (L-phase) delaminates after the R phase (HCP structure similar to Ni3Fe) is corroded, also leading to a high tribocorrosion rate. The Ti0.3 alloy exhibits outstanding tribocorrosion resistance (4.35 × 10−6 mm³/(N·m)) due to the anodic protection by the R phase. Improving wear resistance and reducing the L phase are beneficial for enhancing its tribocorrosion resistance.
{"title":"Tribocorrosion resistance of high entropy alloy CoCrFeNiTix in simulated seawater","authors":"Wang Diao , Junwei Wang , Li Lu , Bo Li , Leyang Dai , Jun Cheng , Haifeng Liao , Xiangning Wang , Zhenjie Wang , Zhilong Xu","doi":"10.1016/j.corsci.2026.113595","DOIUrl":"10.1016/j.corsci.2026.113595","url":null,"abstract":"<div><div>The anti-tribocorrosion mechanisms of CoCrFeNiTi<sub>x</sub> (<em>x</em> = 0.0, 0.1, 0.3, 0.5, 1.0) in simulated seawater were investigated quantitatively. At low Ti content (Ti<sub>0.1</sub>), corrosion-promoted wear (Δ<em>W</em><sub>c</sub>) is pronounced due to rapid repassivation, resulting in a high tribocorrosion rate. At higher Ti contents (Ti<sub>0.5</sub> and Ti<sub>1.0</sub>), the Laves phase (<span>L</span>-phase) delaminates after the R phase (HCP structure similar to Ni<sub>3</sub>Fe) is corroded, also leading to a high tribocorrosion rate. The Ti<sub>0.3</sub> alloy exhibits outstanding tribocorrosion resistance (4.35 × 10<sup>−6</sup> mm³/(N·m)) due to the anodic protection by the R phase. Improving wear resistance and reducing the L phase are beneficial for enhancing its tribocorrosion resistance.</div></div>","PeriodicalId":290,"journal":{"name":"Corrosion Science","volume":"261 ","pages":"Article 113595"},"PeriodicalIF":7.4,"publicationDate":"2026-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145897958","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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