<strong>DZ445</strong>镍基高温合金高温长时间氧化形成的多层膜结构

doi:10.11900/0412.1961.2021.00482

金属学报

2023, Vol. 59

Issue (3): 387-398 DOI: 10.11900/0412.1961.2021.00482

研究论文

本期目录 | 过刊浏览

DZ445镍基高温合金高温长时间氧化形成的多层膜结构

刘来娣¹^,², 丁彪¹^,²(

), 任维丽¹^,²(

), 钟云波¹^,², 王晖³, 王秋良³

1 上海大学材料科学与工程学院省部共建高品质特殊钢冶金与制备国家重点实验室上海 200444
2 上海大学上海市钢铁冶金新技术开发应用重点实验室上海 200444
3 中国科学院电工研究所北京 100190

Multilayer Structure of DZ445 Ni-Based Superalloy Formed by Long Time Oxidation at High Temperature

LIU Laidi¹^,², DING Biao¹^,²(

), REN Weili¹^,²(

), ZHONG Yunbo¹^,², WANG Hui³, WANG Qiuliang³

1 State Key Laboratory of Advanced Special Steel, School of Materials Science and Engineering, Shanghai University, Shanghai 200444, China
2 Shanghai Key Laboratory of Advanced Ferrometallurgy, Shanghai University, Shanghai 200444, China
3 Institute of Electrical Engineering, Chinese Academy of Sciences, Beijing 100190, China

引用本文:

刘来娣, 丁彪, 任维丽, 钟云波, 王晖, 王秋良. DZ445镍基高温合金高温长时间氧化形成的多层膜结构[J]. 金属学报, 2023, 59(3): 387-398.
Laidi LIU, Biao DING, Weili REN, Yunbo ZHONG, Hui WANG, Qiuliang WANG. Multilayer Structure of DZ445 Ni-Based Superalloy Formed by Long Time Oxidation at High Temperature[J]. Acta Metall Sin, 2023, 59(3): 387-398.

全文: PDF(3933 KB) HTML

摘要:

研究了高Cr / Al比和中Ta含量的DZ445镍基高温合金在900℃下300~2600 h的氧化行为。结果表明，900℃氧化≥ 500 h，氧化膜呈现多层结构，最外层氧化物相为NiCr₂O₄、Cr₂O₃和TiO₂，次外层为CrTaO₄和TiO₂，次内层为Al₂O₃、NiCr₂O₄和NiO，最内层主要是Al₂O₃。次外层和次内层的出现使得合金氧化速率降低，表现为动力学方程的指数大幅度增加和氧化速率常数急剧下降。这2层的出现也使得合金氧化机理发生转变，次外层形成后氧化过程由合金元素Cr、Ti、Ni向外扩散转变为由Al的向外扩散和O的向内扩散所控制；次内层形成后，氧化过程转变为Ni、Cr的向外扩散和O的向内扩散所控制。这种多层氧化膜结构使得DZ445合金表现出优异的抗氧化能力。

关键词 ：镍基高温合金, 氧化, 多层结构氧化膜

Abstract：

Nickel-based superalloys have been widely used in aero engines and gas turbines because of their excellent high-temperature strength and exceptional oxidation resistance. The oxidation resistance is obtained using the thermal barrier coatings and alloying elements. In the previous investigations, the oxidation time of the nickel-based superalloys has been focused on hundreds of hours. However, in practice, the superalloys last far longer. This study investigated the superalloy DZ445's oxidation behavior at 900^oC for 300-2600 h. An oxidation film with a four-layer structure is formed after oxidation at 900^oC for 500 h and above. The outermost layer is primarily composed of NiCr₂O₄, Cr₂O₃, and TiO₂. The subouter layer consists of CrTaO₄ and TiO₂, and the subinner layer consists of Al₂O₃, NiCr₂O₄, and NiO. The innermost layer is primarily Al₂O₃. The appearances of the subouter layer and subinner layer greatly reduce the oxidation rate of the alloy, which is represented by the dramatic increase in the oxidation kinetics equation exponent and a sharp reduction of the oxidation rate constant. The formation of subouter layer changes the oxidation mechanism from outward diffusion of alloy elements to O-inward diffusion. When the subinner layer is formed, the oxidation behavior is controlled using the outward diffusion of Ni and Cr and the O-inward diffusion. The multilayer structure gave the alloy an excellent oxidation resistance capacity.

Key words： Ni-based superalloy oxidation multi-layer structure oxide film

收稿日期: 2021-11-12

ZTFLH:

TG132.3

基金资助:国家自然科学基金项目(51871142);省部共建高品质特殊钢冶金与制备国家重点实验室、上海市钢铁冶金新技术开发应用重点实验室自主研发项目(SKLASS 2020-Z04);上海市科学技术委员会项目(19DZ2270200)

作者简介: 刘来娣，女，1994年生，硕士生

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表1 DZ445镍基高温合金的化学成分

图1 DZ445镍基高温合金在900℃氧化不同时间的XRD谱

图2 900℃下DZ445镍基高温合金氧化不同时间表面形貌的SEM像

表2 DZ445镍基高温合金在900℃氧化500 h后表面氧化膜不同区域的元素分布 (atomic fraction / %)

图3 DZ445镍基高温合金在900℃氧化不同时间横截面形貌的SEM像

表3 DZ445镍基高温合金在900℃氧化不同时间后的氧化膜各层元素分布的EDS分析 (atomic fraction / %)

图4 DZ445镍基高温合金在900℃氧化不同时间后各氧化层的厚度变化曲线

图5 DZ445镍基高温合金在不同温度下的恒温氧化动力学曲线

图6 DZ445镍基高温合金在不同温度下氧化增重的双对数曲线

图7 lnK和1 / T的关系图

表4 900℃下不同时段的氧化动力学方程指数(n)、恒温氧化速率常数(K)和氧化激活能(E)

表5 900℃下DZ445镍基高温合金元素氧化物生成的Gibbs自由能(ΔG)[17,21,23] (kJ·mol-1)

图8 CrTaO4、NiCr2O4、Cr2O3和Al2O3的晶体结构

图9 Al、Ni、Cr元素在氧化300和500 h时从最内层(或次内层)到基体的浓度梯度曲线

图10 氧化机理示意图

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