一种新型镍基合金在超临界多种离子共存环境下的腐蚀行为<sup>*</sup>

doi:10.11900/0412.1961.2016.00113

金属学报

2016, Vol. 52

Issue (12): 1557-1564 DOI: 10.11900/0412.1961.2016.00113

本期目录 | 过刊浏览

一种新型镍基合金在超临界多种离子共存环境下的腐蚀行为^*

欧美琼^1,²,刘扬³,查向东¹,马颖澈^1,⁴(

),程乐明³,刘奎¹

1 中国科学院金属研究所, 沈阳 110016
2 中国科学技术大学材料科学与工程学院, 合肥 230026
3 新奥科技发展有限公司煤基低碳能源国家重点实验室, 廊坊 065001
4 江苏图南合金股份有限公司, 丹阳 212352

CORROSION BEHAVIOR OF A NEW NICKEL BASE ALLOY IN SUPERCRITICAL WATERCONTAINING DIVERSE IONS

Meiqiong OU^1,²,Yang LIU³,Xiangdong ZHA¹,Yingche MA^1,⁴(

),Leming CHENG³,Kui LIU¹

1 Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China
2 School of Materials Science and Engineering, University of Science and Technology of China, Hefei 230026, China
3 State Key Laboratory of Coal-Based Low Carbon Energy, ENN Science and Technology Development Co., Ltd. Langfang 065001, China
4 Jiangsu Toland Alloy Co., Danyang 212352, China

引用本文:

欧美琼,刘扬,查向东,马颖澈,程乐明,刘奎. 一种新型镍基合金在超临界多种离子共存环境下的腐蚀行为^*[J]. 金属学报, 2016, 52(12): 1557-1564.
Meiqiong OU, Yang LIU, Xiangdong ZHA, Yingche MA, Leming CHENG, Kui LIU. CORROSION BEHAVIOR OF A NEW NICKEL BASE ALLOY IN SUPERCRITICAL WATERCONTAINING DIVERSE IONS[J]. Acta Metall Sin, 2016, 52(12): 1557-1564.

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摘要:

研究一种新型镍基合金X-1#在550 ℃, 23 MPa含PO₄^3-, Cl^-和SO₄^2-超临界水中分别腐蚀72, 159, 248, 429和537 h的腐蚀特性. 结合SEM, EDS, XRD和XPS等分析测试方法研究了X-1#合金氧化膜和反应釜沉积物的形貌、物相组成和元素成分分布等. 结果表明, X-1#合金在该环境下形成了均匀和完整的氧化膜, 氧化膜由疏松外层和致密内层组成, 外层主要包含NiO, Ni(OH)₂和磷酸盐, 内层由NiCr₂O₄和Cr₂O₃组成. 腐蚀初始阶段腐蚀速率较快, 248 h后腐蚀速率明显下降, 这是由于氧化膜内层稳定性好且连续致密分布, 有利于X-1#合金抗高温氧化腐蚀.

关键词 ：镍基合金,, 超临界水氧化,, 氧化膜,, 磷酸盐

Abstract：

The productivity of municipal sewage sludge is difficult to treat by traditional methods. Supercritical water oxidation (SCWO) is an attractive municipal sewage sludge treatment technology. However, the process of SCWO must be carried out in a reactor which will resist not only high temperature (above 374.15 ℃) and high pressure (above 22.1 MPa) conditions but also a corrosive environment. Thus, the material used in the equipment is referred to be a key factor that restricts the application of the SCWO technology. Many materials have been selected for corrosion test under corrosive environments with SCWO, including austenitic stainless steel, nickel base alloys, titanium alloys and zirconium alloys. At present, in order to treat rich phosphorous sewage sludge, a new corrosion resistant nickel base alloy X-1# alloy has been developed to apply to the reactor of SCWO process. X-1# alloy has excellent corrosion-resistance and oxidation-resistance properties in supercritical water containing PO₄^3-, Cl^- and SO₄^2-. The corrosion behaviors of X-1# alloy exposed to 550 ℃, 23 MPa supercritical water containing PO4^3-, Cl^- and SO₄^2- were investigated in this research. The exposed time was 72, 159, 248, 429 and 537 h. Morphologies, microstructures and chemical composition of oxide films in X-1# alloy and deposit sediment in reaction were studied using grazing incidence XRD, XPS and SEM equipped with EDS. The XRD, EDS and XPS analysis of X-1# alloy was performed to identify the composition of oxide layers, which were identified as NiCr₂O₄, Cr₂O₃, NiO, Ni₃(PO₄)₂, CrPO₄ and Na₃PO₄. In addition, it was founded that continuous and uniform oxide films were formed in supercritical water. The oxide film was a duplex-layer structure, the loose outer layer was NiO, Ni(OH)₂ and phosphates, including Ni₃(PO₄)₂, CrPO₄ and Na₃PO₄, while the compact inner layer consisted of NiCr₂O₄ and Cr₂O₃. X-1# alloy showed a high corrosion rate in the initial stage and the corrosion rate decreased obviously after exposed to 248 h, the reason of which was that the compact inner layer of oxide films had good stability and benefited to the corrosion behavior of X-1# alloy. In order to explain the corrosion behavior of X-1# alloy, the oxide films growth mechanical, metal ions and oxygen ions dissolution mechanism and phosphates precipitation mechanism will be discussed in this research.

Key words： nickel base alloy, supercritical water oxidation (SCWO), oxide film, phosphate

收稿日期: 2016-04-01

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https://www.ams.org.cn/CN/10.11900/0412.1961.2016.00113 或 https://www.ams.org.cn/CN/Y2016/V52/I12/1557

图1 X-1#合金腐蚀537 h的氧化膜的XRD谱

图2 X-1#合金腐蚀72, 159, 248, 429 和537 h 的氧化膜表面形貌的SEM像

表1 X-1#合金表面氧化膜的EDS分析结果

图3 反应釜沉积物表面形貌的SEM像

表2 反应釜沉积物的EDS分析结果

图4 反应釜中沉积物的XPS分析

图5 X-1#合金腐蚀72, 159, 248, 429和537 h试样的氧化膜截面形貌的SEM像

图6 X-1#合金腐蚀159和248 h试样的氧化膜截面成分分布

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