Pub Date : 2025-12-10DOI: 10.1016/j.corsci.2025.113547
Qian Du , Zelin Ma , Jie Qiu , Di Yun , Long Gu , Zhangjian Zhou , Shaoqiang Guo
This paper aims to investigate the oxidation mechanisms of Al/Si-doped Fe-Cr ODS steels exposed to liquid lead containing 10⁻6 wt% oxygen at 600 °C. To achieve this, the oxide scales of 12Cr1.5Si2Al0.5Zr-ODS and 9Cr0.5Si4.5Al0.6Zr-ODS steels after 5000 h of exposure were systematically characterized using a state-of-the-art characterization approach that combines synchrotron transmission micro-X-ray diffraction (TμXRD) and site-specific transmission electron microscopy (TEM). In 12Cr1.5Si2Al0.5Zr-ODS steel, the oxide scale consisted of a thin, multilayered structure, accompanied by pronounced intergranular oxidation (∼30 μm). This severe oxidation was attributed to the formation of discontinuous amorphous Al2O3 and SiO2 layers, which were insufficient to block inward oxygen diffusion. Additionally, nano-cavities within the intergranular amorphous SiO2 layer acted as rapid diffusion pathways, further accelerating oxygen ingress and exacerbating intergranular attack. In contrast, 9Cr0.5Si4.5Al0.6Zr-ODS steel developed a similar thin, multilayered structure, but it included a continuous, low-crystallinity Al2O3 layer that acted as an effective diffusion barrier, resulting in stable passivation. Moreover, the formation mechanisms of these complex oxide scales were further interpreted through oxidation thermodynamics and the internal-to-external oxidation transition theory.
{"title":"Mechanistic understanding of intergranular oxidation and passivation in Si/Al-doped Fe–Cr ODS steels exposed to liquid Pb via advanced characterization","authors":"Qian Du , Zelin Ma , Jie Qiu , Di Yun , Long Gu , Zhangjian Zhou , Shaoqiang Guo","doi":"10.1016/j.corsci.2025.113547","DOIUrl":"10.1016/j.corsci.2025.113547","url":null,"abstract":"<div><div>This paper aims to investigate the oxidation mechanisms of Al/Si-doped Fe-Cr ODS steels exposed to liquid lead containing 10⁻<sup>6</sup> wt% oxygen at 600 °C. To achieve this, the oxide scales of 12Cr1.5Si2Al0.5Zr-ODS and 9Cr0.5Si4.5Al0.6Zr-ODS steels after 5000 h of exposure were systematically characterized using a state-of-the-art characterization approach that combines synchrotron transmission micro-X-ray diffraction (TμXRD) and site-specific transmission electron microscopy (TEM). In 12Cr1.5Si2Al0.5Zr-ODS steel, the oxide scale consisted of a thin, multilayered structure, accompanied by pronounced intergranular oxidation (∼30 μm). This severe oxidation was attributed to the formation of discontinuous amorphous Al<sub>2</sub>O<sub>3</sub> and SiO<sub>2</sub> layers, which were insufficient to block inward oxygen diffusion. Additionally, nano-cavities within the intergranular amorphous SiO<sub>2</sub> layer acted as rapid diffusion pathways, further accelerating oxygen ingress and exacerbating intergranular attack. In contrast, 9Cr0.5Si4.5Al0.6Zr-ODS steel developed a similar thin, multilayered structure, but it included a continuous, low-crystallinity Al<sub>2</sub>O<sub>3</sub> layer that acted as an effective diffusion barrier, resulting in stable passivation. Moreover, the formation mechanisms of these complex oxide scales were further interpreted through oxidation thermodynamics and the internal-to-external oxidation transition theory.</div></div>","PeriodicalId":290,"journal":{"name":"Corrosion Science","volume":"260 ","pages":"Article 113547"},"PeriodicalIF":7.4,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145787147","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}
Pub Date : 2025-12-05DOI: 10.1016/j.corsci.2025.113537
J.M. Duan, C.Y. Si, Z.N. Jiang, Sarfaraz Khan, S.Y. Tian, R.Y. Xue, G.A. Zhang
In this work, a new corrosion-resistant refractory high entropy alloy (RHEA, Ti28Zr28Hf14Nb22Al8) with a combination of extraordinary corrosion resistance and mechanical properties was designed. Microstructural analyses confirm the single-phase BCC structure of RHEA. Electrochemical tests indicate that Ti28Zr28Hf14Nb22Al8 RHEA has extraordinary corrosion resistance with ultra-low corrosion current densities (0.369 μA/cm2 in 0.5 M H2SO4 at 25°C) and widely passive regions (>3 VSCE). The exceptional corrosion resistance of Ti28Zr28Hf14Nb22Al8 RHEA can be attributed to the outstanding protective property of the formed passive film with low donor density. The cross-sectional TEM further indicates that this dual-layer passive film is rich in Ti, Hf and Zr, with a thickness of approximately 10 nm. Moreover, atomic-scale AIMD simulations reveal that this passive film acts as a robust physical barrier to resist to the attack of corrosive species (sulfuric acid molecules). DFT calculations further verify that the passivation of the RHEA is dominated by Ti, Hf and Zr. Meanwhile, Ti28Zr28Hf14Nb22Al8 RHEA exhibits exceptional mechanical properties with a high ductility (fracture elongation > 50 %) while maintaining a yield strength of approximately 908 MPa. This work provides valuable guidance for the design of RHEAs with exceptional corrosion resistance and mechanical properties.
{"title":"Decoding the exceptional corrosion resistance of a new refractory high entropy alloy Ti28Zr28Hf14Nb22Al8: Integrated experimental approaches and AIMD simulations","authors":"J.M. Duan, C.Y. Si, Z.N. Jiang, Sarfaraz Khan, S.Y. Tian, R.Y. Xue, G.A. Zhang","doi":"10.1016/j.corsci.2025.113537","DOIUrl":"10.1016/j.corsci.2025.113537","url":null,"abstract":"<div><div>In this work, a new corrosion-resistant refractory high entropy alloy (RHEA, Ti<sub>28</sub>Zr<sub>28</sub>Hf<sub>14</sub>Nb<sub>22</sub>Al<sub>8</sub>) with a combination of extraordinary corrosion resistance and mechanical properties was designed. Microstructural analyses confirm the single-phase BCC structure of RHEA. Electrochemical tests indicate that Ti<sub>28</sub>Zr<sub>28</sub>Hf<sub>14</sub>Nb<sub>22</sub>Al<sub>8</sub> RHEA has extraordinary corrosion resistance with ultra-low corrosion current densities (0.369 μA/cm<sup>2</sup> in 0.5 M H<sub>2</sub>SO<sub>4</sub> at 25°C) and widely passive regions (>3 V<sub>SCE</sub>). The exceptional corrosion resistance of Ti<sub>28</sub>Zr<sub>28</sub>Hf<sub>14</sub>Nb<sub>22</sub>Al<sub>8</sub> RHEA can be attributed to the outstanding protective property of the formed passive film with low donor density. The cross-sectional TEM further indicates that this dual-layer passive film is rich in Ti, Hf and Zr, with a thickness of approximately 10 nm. Moreover, atomic-scale AIMD simulations reveal that this passive film acts as a robust physical barrier to resist to the attack of corrosive species (sulfuric acid molecules). DFT calculations further verify that the passivation of the RHEA is dominated by Ti, Hf and Zr. Meanwhile, Ti<sub>28</sub>Zr<sub>28</sub>Hf<sub>14</sub>Nb<sub>22</sub>Al<sub>8</sub> RHEA exhibits exceptional mechanical properties with a high ductility (fracture elongation > 50 %) while maintaining a yield strength of approximately 908 MPa. This work provides valuable guidance for the design of RHEAs with exceptional corrosion resistance and mechanical properties.</div></div>","PeriodicalId":290,"journal":{"name":"Corrosion Science","volume":"260 ","pages":"Article 113537"},"PeriodicalIF":7.4,"publicationDate":"2025-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145682996","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 : 2025-12-05DOI: 10.1016/j.corsci.2025.113536
Zhangwei Guo , Tingyu Ye , Qun Feng , Na Guo , Jinlong Yang , Xiao Liang , Tao Liu
Microbially Induced Calcite Precipitation (MICP) plays a significant role in corrosion prevention, yet its regulatory mechanisms remain poorly understood, severely limiting its practical applications. This study investigates the influence of the flagellar gene fliP on MICP and the resulting anti-corrosion efficacy on marine steel EH36, using wild-type Pseudoalteromonas marina (WT) and its flagellin mutant strain (ΔfliP) as model systems. By comparing the growth metabolism, motility and adhesion capacity, biofilm formation characteristics, as well as corrosion behavior and biomineralization layer structure on steel surfaces, we found that while no significant differences were observed in growth curves or metabolic levels between WT and ΔfliP, the absence of flagella in ΔfliP impaired motility, altered adhesion patterns, and hindered the formation of a uniform and dense biofilm. Although both strains significantly reduced the general corrosion rate of steel through mineralization, localized pitting occurred on the steel surface in the ΔfliP group, where the biomineralization layer was discontinuous and defective, facilitating the formation of oxygen concentration ce lls. In contrast, the WT group formed a homogeneous and compact biomineralization layer that effectively suppressed localized corrosion. These results demonstrate that the flagellar system plays a crucial role in determining the protective performance of microbial biomineralization layers by regulating the spatial distribution and uniformity of biofilms. This study provides a theoretical foundation for further exploitation of MICP technology to inhibit metal corrosion.
{"title":"Effects and mechanisms of the flagellar gene (fliP) on the anticorrosion function of Pseudoalteromonas marina","authors":"Zhangwei Guo , Tingyu Ye , Qun Feng , Na Guo , Jinlong Yang , Xiao Liang , Tao Liu","doi":"10.1016/j.corsci.2025.113536","DOIUrl":"10.1016/j.corsci.2025.113536","url":null,"abstract":"<div><div>Microbially Induced Calcite Precipitation (MICP) plays a significant role in corrosion prevention, yet its regulatory mechanisms remain poorly understood, severely limiting its practical applications. This study investigates the influence of the flagellar gene <em>fli</em>P on MICP and the resulting anti-corrosion efficacy on marine steel EH36, using wild-type <em>Pseudoalteromonas marina</em> (WT) and its flagellin mutant strain (Δ<em>fli</em>P) as model systems. By comparing the growth metabolism, motility and adhesion capacity, biofilm formation characteristics, as well as corrosion behavior and biomineralization layer structure on steel surfaces, we found that while no significant differences were observed in growth curves or metabolic levels between WT and Δ<em>fli</em>P, the absence of flagella in Δ<em>fli</em>P impaired motility, altered adhesion patterns, and hindered the formation of a uniform and dense biofilm. Although both strains significantly reduced the general corrosion rate of steel through mineralization, localized pitting occurred on the steel surface in the Δ<em>fli</em>P group, where the biomineralization layer was discontinuous and defective, facilitating the formation of oxygen concentration ce lls. In contrast, the WT group formed a homogeneous and compact biomineralization layer that effectively suppressed localized corrosion. These results demonstrate that the flagellar system plays a crucial role in determining the protective performance of microbial biomineralization layers by regulating the spatial distribution and uniformity of biofilms. This study provides a theoretical foundation for further exploitation of MICP technology to inhibit metal corrosion.</div></div>","PeriodicalId":290,"journal":{"name":"Corrosion Science","volume":"260 ","pages":"Article 113536"},"PeriodicalIF":7.4,"publicationDate":"2025-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145682995","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 : 2025-12-04DOI: 10.1016/j.corsci.2025.113523
Yizhen Yan , León Zendejas Medina , Yihan Zhang , Akinsanmi Oluwatosin Fowowe , Ibrahim Hotan Alsohaimi , Jinshan Pan , Fan Zhang
This study investigates the combination of dopamine (DA) and tyrosinase (TYR) for corrosion protection of carbon steel in acidic conditions, focusing on corrosion protection behavior and film formation mechanisms. Confocal Raman microscopy analysis demonstrated that DA forms a thin protective film on carbon steel through complexation with Fe ions, preferably at defect sites, thereby transforming mixed Fe oxides to Fe(catechol)3, while TYR promotes DA oxidation and enhances the complexation. Surface coverage of Fe(catechol)3 increases from 37 % at 10 min to 89 % at 60 min of exposure in the DA/TYR solution. Inductively coupled plasma-optical emission spectroscopy (ICP-OES) measurements showed a 25 % reduction in Fe release after 48 h in the DA/TYR solution. X-ray photoelectron spectroscopy (XPS) analysis revealed that TYR promotes oxidation from Fe2+ to Fe3+ at the surface, resulting in a thinner yet more protective DA-Fe complexation film. The DA/TYR system increased corrosion resistance by 47 % after 24 h, primarily attributed to the rapid and extensive formation of Fe(catechol)3 complexes between DA and Fe ions released from the substrate, further strengthened by TYR. This bio-inspired and green corrosion inhibitor strategy, combining DA’s metal-binding affinity with TYR’s enzymatic oxidation capability, provides a scalable and non-toxic strategy for effective corrosion protection.
{"title":"Combination of dopamine and tyrosinase as a green corrosion inhibitor for carbon steel","authors":"Yizhen Yan , León Zendejas Medina , Yihan Zhang , Akinsanmi Oluwatosin Fowowe , Ibrahim Hotan Alsohaimi , Jinshan Pan , Fan Zhang","doi":"10.1016/j.corsci.2025.113523","DOIUrl":"10.1016/j.corsci.2025.113523","url":null,"abstract":"<div><div>This study investigates the combination of dopamine (DA) and tyrosinase (TYR) for corrosion protection of carbon steel in acidic conditions, focusing on corrosion protection behavior and film formation mechanisms. Confocal Raman microscopy analysis demonstrated that DA forms a thin protective film on carbon steel through complexation with Fe ions, preferably at defect sites, thereby transforming mixed Fe oxides to Fe(catechol)<sub>3</sub>, while TYR promotes DA oxidation and enhances the complexation. Surface coverage of Fe(catechol)<sub>3</sub> increases from 37 % at 10 min to 89 % at 60 min of exposure in the DA/TYR solution. Inductively coupled plasma-optical emission spectroscopy (ICP-OES) measurements showed a 25 % reduction in Fe release after 48 h in the DA/TYR solution. X-ray photoelectron spectroscopy (XPS) analysis revealed that TYR promotes oxidation from Fe<sup>2+</sup> to Fe<sup>3+</sup> at the surface, resulting in a thinner yet more protective DA-Fe complexation film. The DA/TYR system increased corrosion resistance by 47 % after 24 h, primarily attributed to the rapid and extensive formation of Fe(catechol)<sub>3</sub> complexes between DA and Fe ions released from the substrate, further strengthened by TYR. This bio-inspired and green corrosion inhibitor strategy, combining DA’s metal-binding affinity with TYR’s enzymatic oxidation capability, provides a scalable and non-toxic strategy for effective corrosion protection.</div></div>","PeriodicalId":290,"journal":{"name":"Corrosion Science","volume":"260 ","pages":"Article 113523"},"PeriodicalIF":7.4,"publicationDate":"2025-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145682999","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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