This investigation studied the potential influence of different amounts of alloying element Cr (0.5, 1.2 and 2.1 wt%) on hydrogen-induced delayed fracture (HIDF) performance of V+Nb-microalloyed high-strength bolt steel with high temperature tempered martensitic microstructure. The HIDF performance was evaluated by slow strain rate tensile (SSRT) tests using pre-hydrogen-charged notched specimens. The results show that the size of re-precipitated plate-like nano-sized V-rich MC carbides slightly decreases with the increase in Cr content, and Cr-rich M7C3 carbides only exist in the steel containing 2.1 wt% Cr. The HIDF resistance represented by notch tensile strength decreases and the tendency to brittle intergranular fracture along notch root region increases with the increase in Cr content. The diffusible hydrogen contents obtained from both the pre-hydrogen-charged and the fractured SSRT specimens exhibit an increasing trend while the effective hydrogen diffusion coefficient decreases with increasing Cr content. The reasons for this adverse effect of increasing Cr content on HIDF performance are explained by the changes of microstructural characteristics and corresponding hydrogen trapping characteristics.
{"title":"Effect of Cr on hydrogen-induced delayed fracture of high-strength bolt steel","authors":"Boyang Fang, Weijun Hui, Zhuo Hua, Yixuan Xu, Yongjian Zhang, Xiaoli Zhao","doi":"10.1016/j.corsci.2025.113533","DOIUrl":"10.1016/j.corsci.2025.113533","url":null,"abstract":"<div><div>This investigation studied the potential influence of different amounts of alloying element Cr (0.5, 1.2 and 2.1 wt%) on hydrogen-induced delayed fracture (HIDF) performance of V+Nb-microalloyed high-strength bolt steel with high temperature tempered martensitic microstructure. The HIDF performance was evaluated by slow strain rate tensile (SSRT) tests using pre-hydrogen-charged notched specimens. The results show that the size of re-precipitated plate-like nano-sized V-rich MC carbides slightly decreases with the increase in Cr content, and Cr-rich M<sub>7</sub>C<sub>3</sub> carbides only exist in the steel containing 2.1 wt% Cr. The HIDF resistance represented by notch tensile strength decreases and the tendency to brittle intergranular fracture along notch root region increases with the increase in Cr content. The diffusible hydrogen contents obtained from both the pre-hydrogen-charged and the fractured SSRT specimens exhibit an increasing trend while the effective hydrogen diffusion coefficient decreases with increasing Cr content. The reasons for this adverse effect of increasing Cr content on HIDF performance are explained by the changes of microstructural characteristics and corresponding hydrogen trapping characteristics.</div></div>","PeriodicalId":290,"journal":{"name":"Corrosion Science","volume":"260 ","pages":"Article 113533"},"PeriodicalIF":7.4,"publicationDate":"2025-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145734286","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 : 2025-12-11DOI: 10.1016/j.corsci.2025.113549
L.Z. Kang, Y.H. Lu, Z.J. Shi, Y.M. Han, L. Xin
The effect of dissolved hydrogen (DH) on the fretting corrosion of Zr-alloy under different fretting regimes in high temperature pressurised water was investigated. The results indicated that the effect of DH on fretting corrosion of Zr-alloy depended on the fretting regime. Under partial slip regime (PSR) and mixed fretting regime (MFR), the main damage mechanism was fretting corrosion cracks, introduction of 2.5 ppm DH had a negligible effect on fretting corrosion behavior and did not change damage mechanism. Under gross slip regime (GSR), the main damage mechanisms without DH were adhesive wear, oxidation, and delamination. Introduction of 2.5 ppm DH caused a significant increase in wear volume and changed damage mechanisms to adhesive wear, oxidation and fretting corrosion cracks. Introduction of 2.5 ppm DH reduced the formation of NiCr2O4 and introduced a small amount of Cr2O3 in TBL, which resulted in less formation of the protective TBL under GSR and thereby promoted fretting corrosion.
{"title":"Influence of dissolved hydrogen on the fretting corrosion of zirconium alloy under different fretting regimes in high temperature pressurised water environment","authors":"L.Z. Kang, Y.H. Lu, Z.J. Shi, Y.M. Han, L. Xin","doi":"10.1016/j.corsci.2025.113549","DOIUrl":"10.1016/j.corsci.2025.113549","url":null,"abstract":"<div><div>The effect of dissolved hydrogen (DH) on the fretting corrosion of Zr-alloy under different fretting regimes in high temperature pressurised water was investigated. The results indicated that the effect of DH on fretting corrosion of Zr-alloy depended on the fretting regime. Under partial slip regime (PSR) and mixed fretting regime (MFR), the main damage mechanism was fretting corrosion cracks, introduction of 2.5 ppm DH had a negligible effect on fretting corrosion behavior and did not change damage mechanism. Under gross slip regime (GSR), the main damage mechanisms without DH were adhesive wear, oxidation, and delamination. Introduction of 2.5 ppm DH caused a significant increase in wear volume and changed damage mechanisms to adhesive wear, oxidation and fretting corrosion cracks. Introduction of 2.5 ppm DH reduced the formation of NiCr<sub>2</sub>O<sub>4</sub> and introduced a small amount of Cr<sub>2</sub>O<sub>3</sub> in TBL, which resulted in less formation of the protective TBL under GSR and thereby promoted fretting corrosion.</div></div>","PeriodicalId":290,"journal":{"name":"Corrosion Science","volume":"260 ","pages":"Article 113549"},"PeriodicalIF":7.4,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145734287","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}
The multi-layer oxides formed on surfaces of nickel-based single crystal superalloys are well-documented, yet their precise formation scenarios remain uncovered, since a fine time series of microstructural observations of their dynamic evolution in early-stage oxidation has never been accomplished. Here, we report a refined formation scenario of these oxide sub-layers in a second-generation nickel-based single crystal superalloy. Our findings demonstrate that there are actually 5 distinct oxide sub-layers formed on surface, which are identified respectively as the 1st (Ni0.9Co0.1)O, 2nd NiAl₂O₄, 3rd CoCr₂O₄, 4th CrTaO₄, and 5th Al₂O₃ sub-layers. However, their temporal formation sequence or scenario differs from their spatial formation sequence: the 5th secondary Al₂O₃ sub-layers appear before formation of the 2nd, 3rd and 4th oxide sub-layers. Notably, upon oxidation γ-phase areas act as preferential pathways for in-depth oxygen diffusion, facilitating the innermost 5th secondary Al₂O₃ sub-layer to form. Our study provides in-depth insights into a high-temperature oxidation mechanism of superalloys.
{"title":"A refined formation scenario of high-temperature oxide sub-layers in nickel-based single crystal superalloys","authors":"Zhiqiang Zhou , Pan Xie , Cuilan Wu , Jianghua Chen","doi":"10.1016/j.corsci.2025.113548","DOIUrl":"10.1016/j.corsci.2025.113548","url":null,"abstract":"<div><div>The multi-layer oxides formed on surfaces of nickel-based single crystal superalloys are well-documented, yet their precise formation scenarios remain uncovered, since a fine time series of microstructural observations of their dynamic evolution in early-stage oxidation has never been accomplished. Here, we report a refined formation scenario of these oxide sub-layers in a second-generation nickel-based single crystal superalloy. Our findings demonstrate that there are actually 5 distinct oxide sub-layers formed on surface, which are identified respectively as the 1st (Ni<sub>0.9</sub>Co<sub>0.1</sub>)O, 2nd NiAl₂O₄, 3rd CoCr₂O₄, 4th CrTaO₄, and 5th Al₂O₃ sub-layers. However, their temporal formation sequence or scenario differs from their spatial formation sequence: the 5th secondary Al₂O₃ sub-layers appear before formation of the 2nd, 3rd and 4th oxide sub-layers. Notably, upon oxidation γ-phase areas act as preferential pathways for in-depth oxygen diffusion, facilitating the innermost 5th secondary Al₂O₃ sub-layer to form. Our study provides in-depth insights into a high-temperature oxidation mechanism of superalloys.</div></div>","PeriodicalId":290,"journal":{"name":"Corrosion Science","volume":"260 ","pages":"Article 113548"},"PeriodicalIF":7.4,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145734288","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 : 2025-12-10DOI: 10.1016/j.corsci.2025.113546
Siyu Hu , Xin Zhong , Dong Fan , Xiao You , Du Hong , Liping Huang , Yaran Niu , Xuebin Zheng
Rare-earth disilicates (RE2Si2O7) environmental barrier coatings (EBCs) face the problem of insufficient resistance to high-temperature water vapor corrosion. In this study, a novel non-equimolar multiple-rare-earth disilicate, (Yb0.7Er0.1Tm0.1Ho0.1)2Si2O7 ((4RExi)2Si2O7), was developed to improve the corrosion resistance of RE2Si2O7. Bi-layer (4RExi)2Si2O7/Si and Yb2Si2O7/Si EBCs were prepared using atmospheric plasma spray (APS), and their corrosion behaviors under water vapor environment at 1400 °C were studied. The results show that (4RExi)2Si2O7 exhibits better corrosion resistance compared with Yb2Si2O7, which is attributed to the better structural stability and increased lattice distortion. Compared to the Yb2Si2O7/Si, the thermally grown oxide (TGO) layer thickness in the (4RExi)2Si2O7/Si system decreased by 23.8 %, and no significant interfacial crack was observed after 300 h of exposure. Molecular dynamics calculations further reveal that the oxygen diffusion coefficient in (4RExi)2Si2O7 is approximately 13.6 % lower than that in Yb2Si2O7. The enhanced corrosion resistance is therefore attributed to the improved structural stability and the suppressed oxygen-diffusion kinetics, providing an effective strategy for designing durable EBCs.
{"title":"Enhanced high-temperature water vapor corrosion resistance of RE2Si2O7 environmental barrier coatings via non-equimolar multi-rare-earth design","authors":"Siyu Hu , Xin Zhong , Dong Fan , Xiao You , Du Hong , Liping Huang , Yaran Niu , Xuebin Zheng","doi":"10.1016/j.corsci.2025.113546","DOIUrl":"10.1016/j.corsci.2025.113546","url":null,"abstract":"<div><div>Rare-earth disilicates (RE<sub>2</sub>Si<sub>2</sub>O<sub>7</sub>) environmental barrier coatings (EBCs) face the problem of insufficient resistance to high-temperature water vapor corrosion. In this study, a novel non-equimolar multiple-rare-earth disilicate, (Yb<sub>0.7</sub>Er<sub>0.1</sub>Tm<sub>0.1</sub>Ho<sub>0.1</sub>)<sub>2</sub>Si<sub>2</sub>O<sub>7</sub> ((4RE<sub><em>xi</em></sub>)<sub>2</sub>Si<sub>2</sub>O<sub>7</sub>), was developed to improve the corrosion resistance of RE<sub>2</sub>Si<sub>2</sub>O<sub>7</sub>. Bi-layer (4RE<sub><em>xi</em></sub>)<sub>2</sub>Si<sub>2</sub>O<sub>7</sub>/Si and Yb<sub>2</sub>Si<sub>2</sub>O<sub>7</sub>/Si EBCs were prepared using atmospheric plasma spray (APS), and their corrosion behaviors under water vapor environment at 1400 °C were studied. The results show that (4RE<sub><em>xi</em></sub>)<sub>2</sub>Si<sub>2</sub>O<sub>7</sub> exhibits better corrosion resistance compared with Yb<sub>2</sub>Si<sub>2</sub>O<sub>7</sub>, which is attributed to the better structural stability and increased lattice distortion. Compared to the Yb<sub>2</sub>Si<sub>2</sub>O<sub>7</sub>/Si, the thermally grown oxide (TGO) layer thickness in the (4RE<sub><em>xi</em></sub>)<sub>2</sub>Si<sub>2</sub>O<sub>7</sub>/Si system decreased by 23.8 %, and no significant interfacial crack was observed after 300 h of exposure. Molecular dynamics calculations further reveal that the oxygen diffusion coefficient in (4RE<sub><em>xi</em></sub>)<sub>2</sub>Si<sub>2</sub>O<sub>7</sub> is approximately 13.6 % lower than that in Yb<sub>2</sub>Si<sub>2</sub>O<sub>7</sub>. The enhanced corrosion resistance is therefore attributed to the improved structural stability and the suppressed oxygen-diffusion kinetics, providing an effective strategy for designing durable EBCs.</div></div>","PeriodicalId":290,"journal":{"name":"Corrosion Science","volume":"260 ","pages":"Article 113546"},"PeriodicalIF":7.4,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145734290","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 : 2025-12-09DOI: 10.1016/j.corsci.2025.113543
Huijun Liu , Chun Yu , Fangkun Xie , Fanghao Chen , Lingxu Yang , Liankui Wu , Chaoliu Zeng
To develop novel ceramic top-coat for thermal barrier coatings (TBCs) with excellent thermophysical properties and corrosion resistance, the optical basicity (OB) regulation and high-entropy strategy were innovatively proposed and adopted to prepare (10RE1/10)2Zr2O7 ceramics with high configuration entropy. The microstructure, thermophysical properties, and molten silicate environment deposits (CaO-MgO-Al2O3-SiO2, CMAS) corrosion behavior of the ceramic were also systematically characterized. The results show that the (10RE1/10)2Zr2O7 with a configuration entropy of 2.30 R exhibits excellent comprehensive performance such as a thermal conductivity as low as 1.54 W·m⁻1·K⁻1 (1000 °C), a moderate thermal expansion coefficient (CTE, 10.92 ×10⁻6 K⁻1, at 1200 °C), and excellent stability for anneling at 1500 °C for 200 h. Furthermore, the average corrosion rate of the ceramic after molten CMAS attack at 1300 °C for 50 h is only 0.8 μm·h−1, which is much lower than traditional (5RE1/5)2Zr2O7, indicating excellent CMAS corrosion resistance of (10RE1/10)2Zr2O7. The reason may be that on the one hand, the low OB of the selected rare-earth elements reduces the reactivity between the ceramic and CMAS, and on the other hand, the atomic disorder caused by the extremely high configurational entropy leads to sluggish diffusion effect of ions. The synergistic effect of the two significantly reducing the corrosion rate. Therefore, the OB regulation and high-entropy strategy can synergistically enhance the thermophysical properties and CMAS corrosion resistance of HE-REZs. This work provides important theoretical and experimental basis for the development of next-generation high-temperature and CMAS resistant TBC materials.
{"title":"Synergistic enhancement of CMAS corrosion resistance in rare-earth zirconate via optical basicity regulation and high-entropy strategy","authors":"Huijun Liu , Chun Yu , Fangkun Xie , Fanghao Chen , Lingxu Yang , Liankui Wu , Chaoliu Zeng","doi":"10.1016/j.corsci.2025.113543","DOIUrl":"10.1016/j.corsci.2025.113543","url":null,"abstract":"<div><div>To develop novel ceramic top-coat for thermal barrier coatings (TBCs) with excellent thermophysical properties and corrosion resistance, the optical basicity (OB) regulation and high-entropy strategy were innovatively proposed and adopted to prepare (10RE<sub>1/10</sub>)<sub>2</sub>Zr<sub>2</sub>O<sub>7</sub> ceramics with high configuration entropy. The microstructure, thermophysical properties, and molten silicate environment deposits (CaO-MgO-Al<sub>2</sub>O<sub>3</sub>-SiO<sub>2</sub>, CMAS) corrosion behavior of the ceramic were also systematically characterized. The results show that the (10RE<sub>1/10</sub>)<sub>2</sub>Zr<sub>2</sub>O<sub>7</sub> with a configuration entropy of 2.30 R exhibits excellent comprehensive performance such as a thermal conductivity as low as 1.54 W·m⁻<sup>1</sup>·K⁻<sup>1</sup> (1000 °C), a moderate thermal expansion coefficient (CTE, 10.92 ×10⁻<sup>6</sup> K⁻<sup>1</sup>, at 1200 °C), and excellent stability for anneling at 1500 °C for 200 h. Furthermore, the average corrosion rate of the ceramic after molten CMAS attack at 1300 °C for 50 h is only 0.8 μm·h<sup>−1</sup>, which is much lower than traditional (5RE<sub>1/5</sub>)<sub>2</sub>Zr<sub>2</sub>O<sub>7</sub>, indicating excellent CMAS corrosion resistance of (10RE<sub>1/10</sub>)<sub>2</sub>Zr<sub>2</sub>O<sub>7</sub>. The reason may be that on the one hand, the low OB of the selected rare-earth elements reduces the reactivity between the ceramic and CMAS, and on the other hand, the atomic disorder caused by the extremely high configurational entropy leads to sluggish diffusion effect of ions. The synergistic effect of the two significantly reducing the corrosion rate. Therefore, the OB regulation and high-entropy strategy can synergistically enhance the thermophysical properties and CMAS corrosion resistance of HE-REZs. This work provides important theoretical and experimental basis for the development of next-generation high-temperature and CMAS resistant TBC materials.</div></div>","PeriodicalId":290,"journal":{"name":"Corrosion Science","volume":"260 ","pages":"Article 113543"},"PeriodicalIF":7.4,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145734282","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 : 2025-12-09DOI: 10.1016/j.corsci.2025.113540
Jiaojiao Ma , Jie Tan , Xing Yin , Hui Wang , Xiujie He
This study investigates the corrosion behavior of 9Cr1Si ferritic/martensitic steel after pre-irradiation with 2.4 MeV Fe2 + ions at 550 ℃ and subsequent exposure to stagnant lead-bismuth eutectic (LBE) at 550 °C under low (10−7 wt% O2) and high (10−3 wt% O2) oxygen conditions. Pre-irradiation accelerates corrosion, leading to a thicker duplex oxide scale (outer Fe3O4 and inner Fe3-xCrxO4) and eliminating Cr-rich precipitate chains through M23C6 amorphization and subsequent Cr redistribution. Under oxygen-saturated LBE, defect-assisted oxygen transport and Si segregation promote formation of Si-rich oxides that impede outer layer growth; under oxygen-depleted LBE, pre-irradiation enhances intergranular oxidation and microcracking. These results demonstrate the distinct roles of pre-irradiation generated defects in altering diffusion pathways and oxide stability under variable oxygen potentials.
{"title":"Effect of pre-irradiation on corrosion resistance of 9Cr1Si ferritic/martensitic steels in oxygen saturated-depleted stagnant lead-bismuth eutectic at 550 °C","authors":"Jiaojiao Ma , Jie Tan , Xing Yin , Hui Wang , Xiujie He","doi":"10.1016/j.corsci.2025.113540","DOIUrl":"10.1016/j.corsci.2025.113540","url":null,"abstract":"<div><div>This study investigates the corrosion behavior of 9Cr1Si ferritic/martensitic steel after pre-irradiation with 2.4 MeV Fe<sup>2 +</sup> ions at 550 ℃ and subsequent exposure to stagnant lead-bismuth eutectic (LBE) at 550 °C under low (10<sup>−7</sup> wt% O<sub>2</sub>) and high (10<sup>−3</sup> wt% O<sub>2</sub>) oxygen conditions. Pre-irradiation accelerates corrosion, leading to a thicker duplex oxide scale (outer Fe<sub>3</sub>O<sub>4</sub> and inner Fe<sub>3-x</sub>Cr<sub>x</sub>O<sub>4</sub>) and eliminating Cr-rich precipitate chains through M<sub>23</sub>C<sub>6</sub> amorphization and subsequent Cr redistribution. Under oxygen-saturated LBE, defect-assisted oxygen transport and Si segregation promote formation of Si-rich oxides that impede outer layer growth; under oxygen-depleted LBE, pre-irradiation enhances intergranular oxidation and microcracking. These results demonstrate the distinct roles of pre-irradiation generated defects in altering diffusion pathways and oxide stability under variable oxygen potentials.</div></div>","PeriodicalId":290,"journal":{"name":"Corrosion Science","volume":"260 ","pages":"Article 113540"},"PeriodicalIF":7.4,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145734289","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 : 2025-12-08DOI: 10.1016/j.corsci.2025.113542
Xinglong Zhu , Lijing Yang , Tingting Zhu , Pingping Zhao , Zhengli Wu , Zhiwei Wang , Fangcai Li , Chengyue Zhu , Zhenlun Song
The inherent trade-off between strength and ductility in biodegradable Zn alloys has long hindered their clinical adoption as next-generation biomedical implants, while the corrosion rate needs further enhancement to reduce in vivo residence time for implant requirements. In this study, a novel gradient heterogeneous lamellar (GHL) structure was developed in Zn-0.45Mn-0.8Li (wt%) alloy via an integrated extrusion-rotary swaging deformation process. The special structure combines the advantages of gradient structure and heterogeneous lamellar (HL) structure, achieving synchronous strength and ductility improvement. The R70 alloy exhibited the highest ultimate tensile strength (UTS) of 494 MPa and elongation (EL) of 81 %. The synergistic interplay of grain refinement, hetero-deformation induced (HDI) strengthening, and plastic strain gradient leads to progressive enhancement of the strength-ductility synergy. The corrosion rate increased and the corrosion pattern tended towards uniform corrosion with the increase of deformation, which is attributed the uniform grain refinement and phases distribution, resulting in an increase in micro-electrochemical corrosion areas and non-uniformity of corrosion products between disordered textures after rotary-swaging. The R20 alloy presented an electrochemical corrosion rate of 188 μm/year, an immersion corrosion rate in the first 15 days of 134 μm/year, while the R70 alloy had corresponding values of 316 μm /year and 156 μm /year. The degradation products are non-toxic, and controlled release of bioactive ion (Zn2 +, Mn2+, Li+) synergistically promotes osteogenic differentiation. Therefore, the rotary-swaged Zn-0.45Mn-0.8Li alloy with GHL structure represented an ideal candidate for biodegradable medical implants, integrating excellent mechanical properties, controlled degradation kinetics, and osteogenic bioactivity.
{"title":"Gradient heterogeneous lamellar structure Zn-Mn-Li alloy: A biodegradable medical alloy with synergistic strengthening-toughening and regulated corrosion via integrated extrusion-rotary swaging","authors":"Xinglong Zhu , Lijing Yang , Tingting Zhu , Pingping Zhao , Zhengli Wu , Zhiwei Wang , Fangcai Li , Chengyue Zhu , Zhenlun Song","doi":"10.1016/j.corsci.2025.113542","DOIUrl":"10.1016/j.corsci.2025.113542","url":null,"abstract":"<div><div>The inherent trade-off between strength and ductility in biodegradable Zn alloys has long hindered their clinical adoption as next-generation biomedical implants, while the corrosion rate needs further enhancement to reduce in vivo residence time for implant requirements. In this study, a novel gradient heterogeneous lamellar (GHL) structure was developed in Zn-0.45Mn-0.8Li (wt%) alloy via an integrated extrusion-rotary swaging deformation process. The special structure combines the advantages of gradient structure and heterogeneous lamellar (HL) structure, achieving synchronous strength and ductility improvement. The R70 alloy exhibited the highest ultimate tensile strength (UTS) of 494 MPa and elongation (EL) of 81 %. The synergistic interplay of grain refinement, hetero-deformation induced (HDI) strengthening, and plastic strain gradient leads to progressive enhancement of the strength-ductility synergy. The corrosion rate increased and the corrosion pattern tended towards uniform corrosion with the increase of deformation, which is attributed the uniform grain refinement and phases distribution, resulting in an increase in micro-electrochemical corrosion areas and non-uniformity of corrosion products between disordered textures after rotary-swaging. The R20 alloy presented an electrochemical corrosion rate of 188 μm/year, an immersion corrosion rate in the first 15 days of 134 μm/year, while the R70 alloy had corresponding values of 316 μm /year and 156 μm /year. The degradation products are non-toxic, and controlled release of bioactive ion (Zn<sup>2 +</sup>, Mn<sup>2+</sup>, Li<sup>+</sup>) synergistically promotes osteogenic differentiation. Therefore, the rotary-swaged Zn-0.45Mn-0.8Li alloy with GHL structure represented an ideal candidate for biodegradable medical implants, integrating excellent mechanical properties, controlled degradation kinetics, and osteogenic bioactivity.</div></div>","PeriodicalId":290,"journal":{"name":"Corrosion Science","volume":"260 ","pages":"Article 113542"},"PeriodicalIF":7.4,"publicationDate":"2025-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145734281","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 : 2025-12-08DOI: 10.1016/j.corsci.2025.113539
Zihan Zhu , Rui Wang , Ning Li , Chenyang Lu , Shaoqiang Guo , Dichen Li , Qingyu Li , Sheng Huang
To ensure the long-term reliability of pressure vessels in lead-cooled fast reactors (LFRs) exposed to lead–bismuth eutectic (LBE) environments, developing corrosion-resistant materials with superior formability and LBE compatibility has become a critical research priority. In this study, 30 AlCrFeNi alloys with varying Al and Cr contents were prepared using directed energy deposition (DED) from elemental powders. The effects of alloy composition on formability, microstructure, and corrosion resistance were investigated. The results indicated that the FCC phase exhibited a preferential tendency toward corrosion, whereas the intergranular distribution of BCC/B2 phases can suppress dissolution within the FCC. The designed Al17.825Cr17FeNi alloy exhibited a relatively thin oxide layer, with a dense Al2O3–Cr2O3 passive layer formed on its surface. This work demonstrated a synergistic optimization of composition and properties in AlCrFeNi alloys, while additive manufacturing allows an effective increase in the thickness of corrosion-resistant layer, highlighting its potential for advanced nuclear structural materials.
{"title":"Additive manufacturing of AlCrFeNi alloys: Correlation between composition, formability, and corrosion resistance in lead-bismuth eutectic","authors":"Zihan Zhu , Rui Wang , Ning Li , Chenyang Lu , Shaoqiang Guo , Dichen Li , Qingyu Li , Sheng Huang","doi":"10.1016/j.corsci.2025.113539","DOIUrl":"10.1016/j.corsci.2025.113539","url":null,"abstract":"<div><div>To ensure the long-term reliability of pressure vessels in lead-cooled fast reactors (LFRs) exposed to lead–bismuth eutectic (LBE) environments, developing corrosion-resistant materials with superior formability and LBE compatibility has become a critical research priority. In this study, 30 AlCrFeNi alloys with varying Al and Cr contents were prepared using directed energy deposition (DED) from elemental powders. The effects of alloy composition on formability, microstructure, and corrosion resistance were investigated. The results indicated that the FCC phase exhibited a preferential tendency toward corrosion, whereas the intergranular distribution of BCC/B2 phases can suppress dissolution within the FCC. The designed Al<sub>17.825</sub>Cr<sub>17</sub>FeNi alloy exhibited a relatively thin oxide layer, with a dense Al<sub>2</sub>O<sub>3</sub>–Cr<sub>2</sub>O<sub>3</sub> passive layer formed on its surface. This work demonstrated a synergistic optimization of composition and properties in AlCrFeNi alloys, while additive manufacturing allows an effective increase in the thickness of corrosion-resistant layer, highlighting its potential for advanced nuclear structural materials.</div></div>","PeriodicalId":290,"journal":{"name":"Corrosion Science","volume":"260 ","pages":"Article 113539"},"PeriodicalIF":7.4,"publicationDate":"2025-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145734283","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}
The corrosion behavior of Inconel 625 in contact with LiF was compared with its behavior in NaF at 600°C in air. Thermodynamic calculations were carried out to determine the stability of metal fluorides in both conditions, confirming salt specific element depletion. TOF-SIMS was conducted to examine the lithium-ion behavior in the oxide and metal over short-term and long-term exposures. A redox mechanism is suggested where fluoride ion A redox mechanism is suggested where fluoride ion ingress into the alloy towards an inner anode is discussed coupled with an outer anode at the alloy surface. The diffusion of lithium ions is considered a passive process along cation diffusion paths. The suggested mechanism discusses also why the presence of fluorine gas in the corrosion process is not viable. The presented mechanism and energetic pathway are in full agreement with the experimental observations and can be easily transferred to other alkali fluoride experiments in literature.
{"title":"Redox mechanisms and metal fluoride stability in alkali fluoride corrosion -confirmed by experiment","authors":"Aida Nikbakht , Per Malmberg , Behnam Bahramian , Christine Geers","doi":"10.1016/j.corsci.2025.113538","DOIUrl":"10.1016/j.corsci.2025.113538","url":null,"abstract":"<div><div>The corrosion behavior of Inconel 625 in contact with LiF was compared with its behavior in NaF at 600°C in air. Thermodynamic calculations were carried out to determine the stability of metal fluorides in both conditions, confirming salt specific element depletion. TOF-SIMS was conducted to examine the lithium-ion behavior in the oxide and metal over short-term and long-term exposures. A redox mechanism is suggested where fluoride ion A redox mechanism is suggested where fluoride ion ingress into the alloy towards an inner anode is discussed coupled with an outer anode at the alloy surface. The diffusion of lithium ions is considered a passive process along cation diffusion paths. The suggested mechanism discusses also why the presence of fluorine gas in the corrosion process is not viable. The presented mechanism and energetic pathway are in full agreement with the experimental observations and can be easily transferred to other alkali fluoride experiments in literature.</div></div>","PeriodicalId":290,"journal":{"name":"Corrosion Science","volume":"260 ","pages":"Article 113538"},"PeriodicalIF":7.4,"publicationDate":"2025-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145734284","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 : 2025-12-08DOI: 10.1016/j.corsci.2025.113541
Yue Yang , Minghui Chen , Shasha Yang , Fuhui Wang
The fast growing of Cr2O3 scale via Cr outward diffusion upon most Cr-rich alloys or coatings during high-temperature oxidation inevitably leads to the formation of pores at interface, which induce scale spallation and accelerate oxidation. Reactive elements doping suppresses pores formation to some extent. But it has no effect on reducing the thermal stress generated by mismatch of thermo-physical properties between the coatings and the oxide scale. Scale rumpling occurs, and pores generate at interface because the uncoordinated deformation. In this study, a double-layered nanocrystalline nickel-based coating (MSO5) was prepared and subjected to isothermal oxidation at 800 °C for 100 h. The outer layer was deliberately incorporated with oxygen, resulting in the formation of Cr₂O₃ nano dispersoids exhibiting a specific crystallographic orientation relationship. After oxidation, the MSO5 coating demonstrated high oxidation resistance, exhibiting a mass gain of only 0.15 mg·cm⁻², which is 73 % lower than the arc ion plated coating. Crucially, interfacial pores are completely avoided and scale rumpling was suppressed. This performance is attributed to a dynamic "dissolution-diffusion-regeneration" process of the Cr₂O₃ dispersoids, which suppresses pores condensation. Furthermore, the bilayer structure facilitates stress dissipation through abnormal grain growth in the inner layer, preventing stress accumulation at the interface. It provides a novel strategy for the development of long-life high-temperature protective coatings.
{"title":"Suppressing interfacial pores and enhancing oxidation resistance of NiCoCr nanocrystalline coatings via oxygen doping","authors":"Yue Yang , Minghui Chen , Shasha Yang , Fuhui Wang","doi":"10.1016/j.corsci.2025.113541","DOIUrl":"10.1016/j.corsci.2025.113541","url":null,"abstract":"<div><div>The fast growing of Cr<sub>2</sub>O<sub>3</sub> scale <em>via</em> Cr outward diffusion upon most Cr-rich alloys or coatings during high-temperature oxidation inevitably leads to the formation of pores at interface, which induce scale spallation and accelerate oxidation. Reactive elements doping suppresses pores formation to some extent. But it has no effect on reducing the thermal stress generated by mismatch of thermo-physical properties between the coatings and the oxide scale. Scale rumpling occurs, and pores generate at interface because the uncoordinated deformation. In this study, a double-layered nanocrystalline nickel-based coating (MSO5) was prepared and subjected to isothermal oxidation at 800 °C for 100 h. The outer layer was deliberately incorporated with oxygen, resulting in the formation of Cr₂O₃ nano dispersoids exhibiting a specific crystallographic orientation relationship. After oxidation, the MSO5 coating demonstrated high oxidation resistance, exhibiting a mass gain of only 0.15 mg·cm⁻², which is 73 % lower than the arc ion plated coating. Crucially, interfacial pores are completely avoided and scale rumpling was suppressed. This performance is attributed to a dynamic \"dissolution-diffusion-regeneration\" process of the Cr₂O₃ dispersoids, which suppresses pores condensation. Furthermore, the bilayer structure facilitates stress dissipation through abnormal grain growth in the inner layer, preventing stress accumulation at the interface. It provides a novel strategy for the development of long-life high-temperature protective coatings.</div></div>","PeriodicalId":290,"journal":{"name":"Corrosion Science","volume":"260 ","pages":"Article 113541"},"PeriodicalIF":7.4,"publicationDate":"2025-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145734285","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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