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Microstructural Evolution of Pre-oxidized T91 Steel During LBE Dissolution Corrosion 预氧化 T91 钢在 LBE 溶解腐蚀过程中的微观结构演变
IF 2.1 3区 材料科学 Q2 METALLURGY & METALLURGICAL ENGINEERING Pub Date : 2024-09-19 DOI: 10.1007/s11085-024-10309-z
Chao Liu, Tielong Shen, Le Qi, Zhiwei Ma, Hailong Chang, Zhiguang Wang

The microstructural evolution of T91 steel by pre-steam oxidation during liquid lead-bismuth eutectic (LBE) dissolution corrosion was investigated. A bi-layered pre-oxide film with Fe-rich outer layer and Cr-rich inner layer was formed on T91 steel, which was similar to the oxide film of T91 after oxidation corrosion in LBE. The pre-oxide film effectively protects the matrix from LBE corrosion at 620 °C. However, the composition and microstructure of the pre-oxide film changed dramatically. Unlike the original duplex structure, the pre-oxide film exposed to LBE undergoes a process of reduction of the outer layer and oxidative growth of the inner layer and changes into five layers, the loose and easily peeling outer Fe layer, the dense and intact inner layers successively consisting of Fe–Cr spinel layer, a transition layer of matrix and Cr-rich oxide, continuous Cr-rich oxide layer with tetragonal distorted spinel structure and amorphous SiO2 layer. The evolution mechanism of the pre-oxide film during LBE dissolution corrosion is discussed.

研究了 T91 钢在液态铅铋共晶(LBE)溶解腐蚀过程中通过预氧化作用产生的微观结构演变。在 T91 钢上形成了外层富含铁、内层富含铬的双层预氧化膜,这与 T91 在 LBE 中氧化腐蚀后的氧化膜相似。在 620 °C 下,预氧化膜有效地保护了基体免受 LBE 腐蚀。然而,预氧化膜的成分和微观结构发生了显著变化。与原来的双相结构不同,暴露在 LBE 中的预氧化膜经历了外层还原和内层氧化生长的过程,变为五层,即疏松易剥离的外层铁层、致密完整的内层铁铬尖晶石层、基体和富铬氧化物的过渡层、具有四方扭曲尖晶石结构的连续富铬氧化物层和无定形 SiO2 层。讨论了 LBE 溶解腐蚀过程中预氧化膜的演变机理。
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引用次数: 0
Comparison of Isothermal Oxidation Performance of IN939 Produced by Casting and Additive Manufacturing 通过铸造和增材制造生产的 IN939 等温氧化性能比较
IF 2.1 3区 材料科学 Q2 METALLURGY & METALLURGICAL ENGINEERING Pub Date : 2024-09-16 DOI: 10.1007/s11085-024-10305-3
Batuhan Basbozkurt, Cevat Sarioglu

The focus of this study was to compare the isothermal oxidation behavior of IN 939 nickel-based superalloys produced by selective laser melting and casting. Oxidation experiments were performed on both heat-treated and non-heat-treated, as cast and additively manufactured samples, to reveal the role of heat treatment and manufacturing methods on oxidation behavior. As cast samples underwent a two-step aging at 1080 and 843 °C, while a one-step aging was carried out for additively manufactured samples at 845 °C. The microstructure of the as cast IN 939 exhibited a dendritic structure with gamma prime precipitates. Following the heat treatment, primary and secondary gamma prime precipitates were formed. Additively manufactured IN 939 exhibited clearly visible melt pools and no trace of gamma prime precipitates. After heat treatment the melt pools disappeared, and gamma prime precipitates formed. Oxidation experiments were performed at 800, 900 and 1000 °C. All samples exhibited similar weight gain characteristics and obeyed a parabolic rate law. Spallation did not occur at 800 and 900 °C, whereas at 1000 °C all samples experienced spallation. The activation energies of all samples, calculated for three temperatures (800, 900, and 1000 °C), were similar, ranging between 260.99 and 287.51 kJ/mole. XRD and EDS analyses indicated that the oxide scale formed on all IN 939 samples was mainly Cr2O3 and TiO2 in rutile form. The internal oxidation and nitridation zones were investigated using SEM and image analysis. The results showed that at 1000 °C, internal oxidation and nitridation extended deeper into the bulk material for additively manufactured samples due to the finer and columnar grains along the building direction which contained extensive amounts of precipitates compared to cast microstructure.

本研究的重点是比较通过选择性激光熔化和铸造生产的 IN 939 镍基超级合金的等温氧化行为。对经过热处理和未经过热处理的铸造样品和添加剂制造样品进行了氧化实验,以揭示热处理和制造方法对氧化行为的影响。铸造样品在 1080 ℃ 和 843 ℃ 下进行了两步时效处理,而添加制造样品则在 845 ℃ 下进行了一步时效处理。铸件 IN 939 的微观结构呈现出带有伽马质沉淀的树枝状结构。热处理后,形成了原生和次生伽马原生析出物。添加剂制造的 IN 939 显示出清晰可见的熔池,没有伽马原质沉淀物的痕迹。热处理后,熔池消失,伽马原质析出物形成。氧化实验在 800、900 和 1000 °C 温度下进行。所有样品都表现出相似的增重特性,并遵循抛物线速率规律。在 800 和 900 ℃ 时没有发生剥落,而在 1000 ℃ 时所有样品都发生了剥落。在三个温度(800、900 和 1000 °C)下计算得出的所有样品的活化能相似,介于 260.99 和 287.51 kJ/mole 之间。XRD 和 EDS 分析表明,所有 IN 939 样品上形成的氧化鳞主要是金红石型的 Cr2O3 和 TiO2。利用扫描电镜和图像分析对内部氧化和氮化区进行了研究。结果表明,在 1000 °C时,添加剂制造的样品的内部氧化和氮化扩展到了块状材料的更深处,这是因为与铸造微观结构相比,沿着构建方向的晶粒更细且呈柱状,其中含有大量析出物。
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引用次数: 0
Improved Oxidation Resistance and Cr Retention of Coated AISI441 for SOC Application 用于 SOC 应用的涂层 AISI441 的抗氧化性和铬保持率得到改善
IF 2.1 3区 材料科学 Q2 METALLURGY & METALLURGICAL ENGINEERING Pub Date : 2024-09-16 DOI: 10.1007/s11085-024-10301-7
Karine Couturier, Nathalie Giacometti, Pierre Hanoux, Sakina Yahiaoui, Thomas David, Thanh-Loan Lai, Théo Dejob, Jolan Bestautte, Mathilde Bouvier, Fabien Rouillard

Durability is still a critical factor that limits solid oxide cell (SOC) technology industrialization. In order to maintain a good level of performance for the overall targeted lifetime of about 40 kh, the oxidation of the interconnects made of ferritic stainless steel and Cr volatilization from this material to the cell electrodes have to be restricted. CeCo-based coatings were applied by PVD HiPIMS on AISI441 alloy. Their ability to reduce the thickness of the poorly conductive formed oxide and improve Cr retention was studied at sample scale by measurements of weight gain and Cr content by ICP-OES after 5000 h of exposure in ambient air at 700 and 800 °C. In the testing conditions, post-test characterization by SEM/EDX showed that oxide scale thickness was reduced when coatings were applied compared to bare AISI441 steel. Moreover, the strong oxide scale spallation observed at 800 °C with bare AISI441 steel was avoided. Cr volatilization was also strongly decreased. Post-test SEM/EDX and ToF–SIMS characterization of a short stack integrating coatings on the air side in some repeat units (RU) confirmed the limited Cr diffusion in the strontium doped lanthanum manganite (LSM) contact layer when the coating is present after 5200 h of solid oxide electrolysis cell operation (SOEC).

耐久性仍然是限制固体氧化物电池(SOC)技术产业化的关键因素。为了在约 40 kh 的总目标寿命内保持良好的性能水平,必须限制铁素体不锈钢制成的互连器件的氧化以及从这种材料到电池电极的铬挥发。通过 PVD HiPIMS 在 AISI441 合金上涂覆钴基涂层。在 700 和 800 °C 的环境空气中暴露 5000 小时后,通过 ICP-OES 测量增重和铬含量,研究了涂层在样品尺度上减少导电性差的氧化物厚度和提高铬保留率的能力。在测试条件下,通过 SEM/EDX 进行的测试后表征表明,与 AISI441 裸钢相比,涂覆涂层后氧化鳞厚度减小。此外,裸 AISI441 钢在 800 ℃ 时出现的强烈氧化鳞剥落现象也得以避免。铬的挥发也大大减少。对一些重复单元 (RU) 中空气侧集成涂层的短堆栈进行的测试后 SEM/EDX 和 ToF-SIMS 表征证实,在固体氧化物电解槽 (SOEC) 运行 5200 小时后,当涂层存在时,掺锶镧锰矿 (LSM) 接触层中的铬扩散有限。
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引用次数: 0
Understanding the Corrosion Behavior of P92 Steel in CO2 Using In Situ Monitoring Technology I: Mechanism of Carbon Migration and Transformation 利用原位监测技术了解 P92 钢在二氧化碳中的腐蚀行为 I:碳迁移和转化机制
IF 2.1 3区 材料科学 Q2 METALLURGY & METALLURGICAL ENGINEERING Pub Date : 2024-09-14 DOI: 10.1007/s11085-024-10306-2
Tingshan Guo, Zhiyuan Liang, Qinxin Zhao

Carbon migration and subsurface transformation, among the corrosion processes of P92 steel in high-temperature CO2 were investigated using in situ monitoring technology. During monitoring reaction intermediate CO was used to distinguish between the oxidation and carbonization reactions. The CO generation rate on P92 steel at 550 °C and 600 °C reached the highest value after 80 min and 100 min, respectively. Honeycomb pores in Fe3O4 oxide scale were observed as the main channels for CO2 and CO gas diffusion and carbon deposition. The deposited carbon gradually diffused into the matrix in an ionic state and transformed into carbides.

利用原位监测技术研究了 P92 钢在高温 CO2 中的腐蚀过程中的碳迁移和地下转化。在监测反应过程中,使用中间 CO 来区分氧化反应和碳化反应。P92 钢在 550 °C 和 600 °C 下的 CO 生成率分别在 80 分钟和 100 分钟后达到最高值。观察发现,Fe3O4 氧化物鳞片上的蜂窝状孔隙是 CO2 和 CO 气体扩散和碳沉积的主要通道。沉积的碳以离子状态逐渐扩散到基体中,并转化为碳化物。
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引用次数: 0
Understanding and Modeling CMAS and Thermal Barrier Coating Interaction Under Thermal Gradients 了解 CMAS 和隔热涂层在热梯度下的相互作用并建立模型
IF 2.1 3区 材料科学 Q2 METALLURGY & METALLURGICAL ENGINEERING Pub Date : 2024-09-14 DOI: 10.1007/s11085-024-10299-y
T. Brunet, T. Archer, A. Dolmaire, M. Vilasi

When operating at very high temperatures (starting from 1200 °C), thermal barrier coatings (TBCs) start interacting with oxide particles such as CMAS (CaO-MgO-Al2O3-SiO2), found in sand or volcanic ashes. Namely, CMAS can infiltrate the TBC and tamper the thermal and mechanical properties of said TBC, leading to its deterioration. This study aimed to understand the interaction between yttria partially stabilized zirconia (YSZ) TBCs and CMAS particles under a thermal gradient. The TBC was made through an EB-PVD process. The experimental study was conducted with a laser rig. TBC samples were heated up to 1200 °C and exposed to a cylinder-shaped CAS (CaO-Al2O3-SiO2) deposit for different durations. The study was conducted in presence of a through-thickness thermal gradient of up to 150 °C in the sample. It was observed that the infiltration is a rather quick phenomenon; while, the dissolution of the TBC and the precipitation of the crystalline phases worked on a longer timeline. Both phenomena can then be considered uncoupled under these test conditions and modeled as such. A heat transfer model was implemented as to better understand the different phenomena happening. The model was fitted to experimental data through a test-calculation dialog.

在超高温(1200 °C以上)条件下工作时,隔热涂层(TBC)开始与沙子或火山灰中的氧化物颗粒(如CMAS(CaO-MgO-Al2O3-SiO2))发生相互作用。也就是说,CMAS 会渗入 TBC,破坏 TBC 的热性能和机械性能,导致其老化。本研究旨在了解钇部分稳定氧化锆(YSZ)TBC 与 CMAS 粒子在热梯度下的相互作用。TBC 是通过 EB-PVD 工艺制成的。实验研究使用激光设备进行。将 TBC 样品加热至 1200 °C,并在不同的持续时间内暴露于圆柱形 CAS(CaO-Al2O3-SiO2)沉积物。研究是在样品厚度热梯度高达 150 °C 的情况下进行的。研究发现,渗透是一种相当快速的现象;而 TBC 的溶解和结晶相的沉淀则需要较长的时间。因此,在这些测试条件下,这两种现象可以被认为是不耦合的,并以此为模型。为了更好地理解所发生的不同现象,我们建立了一个传热模型。该模型通过测试计算对话框与实验数据相匹配。
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引用次数: 0
Evaluation of Environmental Behavior of Pure Iron in an Ammonia Atmosphere by Using a Hydrogen and an Oxygen Sensor 使用氢气和氧气传感器评估纯铁在氨气环境中的环境行为
IF 2.1 3区 材料科学 Q2 METALLURGY & METALLURGICAL ENGINEERING Pub Date : 2024-09-13 DOI: 10.1007/s11085-024-10308-0
Michihisa Fukumoto, Hiroki Takahashi, Laure Martinelli, Sophie Bosonnet, Clara Desgranges

As ammonia does not emit greenhouse gases when burned, it is considered a fuel instead of fossil fuels. However, there are few reports on the corrosion behavior of materials when ammonia is used as fuel. Therefore, this study measured the hydrogen produced by the reaction between ammonia and iron using a hydrogen sensor containing a proton conductor. As a result, the amount of hydrogen produced by the decomposition of ammonia was small at low temperatures but increased at high temperatures. Also, when the ammonia content was low, oxidation of iron occurred preferentially. This way, the relationship between the amount of hydrogen generated and corrosion behavior could be clarified.

由于氨在燃烧时不会排放温室气体,因此被认为是一种替代化石燃料的燃料。然而,有关使用氨作为燃料时材料腐蚀行为的报道却很少。因此,本研究使用含有质子导体的氢传感器测量氨和铁反应产生的氢。结果发现,氨分解产生的氢气量在低温时很少,但在高温时却有所增加。此外,当氨含量较低时,铁的氧化作用优先发生。这样,产生的氢量与腐蚀行为之间的关系就可以得到澄清。
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引用次数: 0
Design of Oxidation-Resistant Alloys Using Combinatorial Approaches with Chemically Graded Materials 利用化学级配材料的组合方法设计抗氧化合金
IF 2.1 3区 材料科学 Q2 METALLURGY & METALLURGICAL ENGINEERING Pub Date : 2024-08-28 DOI: 10.1007/s11085-024-10284-5
Sabrina Ghanes, Mikael Perrut, Enrica Epifano, Matthieu Degeiter, Thomas Vaubois, Yohan Cosquer, Daniel Monceau

This work introduces a new high-throughput method to characterize the oxidation behavior of chemically graded Ni-based alloys in order to feed databases destined to numerical metallurgy approaches. A Ni–wCr–3Al (w ∈ [0, 30]) chemically graded material was obtained from two homogeneous samples by a diffusion couple method at 1300 °C for 100 h. The composition range was selected in order to observe the three types of oxidation behavior identified in the reference work of Giggins and Pettit (Giggins and Pettit in Journal of The Electrochemical Society 118:1782, 1971). The excellent agreement between simulated and experimental diffusion profiles validated the experimental method used to manufacture the chemically graded material (CGM). The CGM was then oxidized at 1200 °C in air. Surface and cross-section characterization was conducted by SEM/EDS and Raman spectroscopy to identify the oxides formed on the CGM. To accelerate the Raman characterization treatment, a method linking principal component analysis and K-means unsupervised clustering algorithm was developed. It allowed for the identification of the oxide type without peak indexation issues and is well suited for CGM. These results show that results similar to well-recognized reference experiments (Giggins and Pettit in Journal of The Electrochemical Society 118:1782, 1971) can be achieved using only one CGM.

本研究介绍了一种新的高通量方法来表征化学分级镍基合金的氧化行为,以便为数值冶金方法的数据库提供数据。选择该成分范围是为了观察 Giggins 和 Pettit 的参考文献(Giggins 和 Pettit 发表于 Journal of The Electrochemical Society 118:1782,1971 年)中确定的三种氧化行为。模拟和实验扩散曲线之间的极佳一致性验证了用于制造化学分级材料 (CGM) 的实验方法。然后,在 1200 °C 的空气中对 CGM 进行氧化。通过 SEM/EDS 和拉曼光谱进行表面和横截面表征,以确定 CGM 上形成的氧化物。为了加速拉曼表征处理,开发了一种将主成分分析和 K-means 无监督聚类算法联系起来的方法。这种方法可以识别氧化物类型,而不存在峰值索引问题,非常适合 CGM。这些结果表明,只需使用一个 CGM,就能获得与公认的参考实验(Giggins 和 Pettit,载于《电化学学会杂志》118:1782,1971 年)类似的结果。
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引用次数: 0
Effect of Electrodeposited Nickel Coatings on the High Temperature Degradation and Electrical Performance of Steel SOEC Interconnects 电沉积镍涂层对钢质 SOEC 互联器高温降解和电气性能的影响
IF 2.1 3区 材料科学 Q2 METALLURGY & METALLURGICAL ENGINEERING Pub Date : 2024-08-27 DOI: 10.1007/s11085-024-10295-2
Louis Boccaccini, Fabien Rouillard, Fernando Pedraza

The performance of solid oxide electrolyzer cells (SOEC) can be improved through the development of coatings applied to the surface of ferritic steel interconnects in view of mitigating chromium evaporation and reducing the growth rate of low conductive oxides in oxidizing environments. This work investigated the oxidation and area specific resistance (ASR) of two electrodeposited nickel coatings on preoxidized and non-preoxidized AISI 441 ferritic stainless steel substrates. The nickel coating effectively restricted the outward diffusion of chromium after 100 h of exposure at 700 °C in air but led to nickel/iron interdiffusion between the substrate and coating forming an iron-nickel-rich spinel on the surface, with NiO underneath and Cr2O3 at the coating-substrate interface and at the coating grain boundaries. The application of a LSM ((La0.80Sr0.20)0.95MnO3−x) coating on top of the Ni electrodeposited coatings resulted in the same type of oxides but the oxidation kinetics were slower. Interdiffusion continued with the exposure at 700 °C for 2400 h resulting in the growth of a thick iron-rich oxide layer on top of Cr2O3, steadily raising the interconnect ASR to 25 mΩ cm2. The addition of a preoxidation step before the electrodeposit of nickel helped to limit iron-nickel interdiffusion, leading to the formation of a thicker NiO layer on a Cr2O3 layer between substrate and coating. While the ASR was higher than without preoxidation at the beginning of the test, it stabilized at about 33 mΩ cm2 after 1750 h. Despite displaying a higher electrical resistance, the coatings effectively limited the outward chromium diffusion throughout exposure compared to the bare substrate.

铁素体钢互连器件表面涂层的开发可改善固体氧化物电解槽(SOEC)的性能,从而减轻铬蒸发并降低氧化环境中低导电氧化物的增长速度。这项研究调查了两种电沉积镍涂层在预氧化和非预氧化 AISI 441 铁素体不锈钢基底上的氧化和面积比电阻 (ASR)。镍镀层在空气中 700 °C 暴露 100 小时后,有效地限制了铬的向外扩散,但导致基体和镀层之间的镍/铁相互扩散,在表面形成富含铁-镍的尖晶石,其下为 NiO,镀层-基体界面和镀层晶界为 Cr2O3。在镍电沉积涂层上涂覆 LSM((La0.80Sr0.20)0.95MnO3-x)涂层也会产生相同类型的氧化物,但氧化动力学较慢。在 700 °C 下暴露 2400 小时后,相互扩散继续进行,在 Cr2O3 上生长出一层厚厚的富铁氧化物层,使互联 ASR 稳步上升到 25 mΩ cm2。在电沉积镍之前增加预氧化步骤有助于限制铁-镍相互扩散,从而在基底和镀层之间的 Cr2O3 层上形成更厚的氧化镍层。与裸基底相比,尽管镀层显示出更高的电阻,但在整个暴露过程中有效地限制了铬的向外扩散。
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引用次数: 0
Editorial on the Influence of Additive Manufacturing on the High-Temperature Corrosion Behaviour of Alloys 关于增材制造对合金高温腐蚀行为的影响的社论
IF 2.1 3区 材料科学 Q2 METALLURGY & METALLURGICAL ENGINEERING Pub Date : 2024-08-27 DOI: 10.1007/s11085-024-10293-4
Laurence Latu‑Romain, Jérôme Favergeon, Bruce Pint, Daniel Monceau, Clara Desgranges, Stéphane Mathieu, Fernando Pedraza
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引用次数: 0
Oxidation Behavior of a Novel Nickel-Based Alloy in Air and Steam at 1273 K for the Oxygen–Hydrogen Combustion Chamber 新型镍基合金在 1273 K 氧氢燃烧室空气和蒸汽中的氧化行为
IF 2.1 3区 材料科学 Q2 METALLURGY & METALLURGICAL ENGINEERING Pub Date : 2024-08-27 DOI: 10.1007/s11085-024-10303-5
Abdul Latif, Mitsutoshi Ueda, Masao Takeyama

As part of advancing oxygen–hydrogen combustion power generation technology, a study was carried out to evaluate the oxidation behavior of a novel developed Ni–Cr–W alloy as the structural material candidate. Tungsten is utilized in the alloy as a solid solution-strengthened element and as an α2-W precipitate former. The examination involved exposing the developed alloy and commercial alloys, Hastelloy X and Nimonic 263, to air and steam environments at 1273 K. The results show a different oxidation behavior of the developed alloy. Considering the air oxidation kinetics, the performance of the developed alloy was on par with that of Hastelloy X and superior to Nimonic 263. A single outer chromia scale was established with an intergranular oxide. Whereas steam exposure resulted in the formation of outer and inner chromia scales with a deeper intergranular oxide penetration. Thicker chromia formation with a lower mass gain indicates the evaporation of chromia under a steam atmosphere.

作为推进氢氧燃烧发电技术的一部分,一项研究对作为候选结构材料的新型 Ni-Cr-W 合金的氧化行为进行了评估。钨作为固溶强化元素和α2-W沉淀前体用于合金中。测试包括将开发的合金和商用合金(哈氏合金 X 和尼莫克 263)暴露在 1273 K 的空气和蒸汽环境中。考虑到空气氧化动力学,所开发合金的性能与哈氏合金 X 相当,而优于 Nimonic 263。形成了单一的外铬垢和晶间氧化物。而蒸汽暴露会形成内外铬鳞,晶间氧化物渗透更深。铬鳞形成较厚,但质量增加较少,这表明铬在蒸汽环境下蒸发。
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引用次数: 0
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Oxidation of Metals
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