纳米化对Fe-20Cr合金在[Cl<sup>-</sup>]=0.1 mol/L硼酸缓冲溶液中Cl<sup>-</sup>吸附行为的影响*

doi:10.11901/1005.3093.2015.345

材料研究学报

2016, Vol. 30

Issue (1): 6-9 DOI: 10.11901/1005.3093.2015.345

研究论文

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纳米化对Fe-20Cr合金在[Cl^-]=0.1 mol/L硼酸缓冲溶液中Cl^-吸附行为的影响*

张滨^1,², 刘莉²(

), 李天书², 李瑛², 雷鸣凯¹, 王福会²

1. 大连理工大学大连 116024
2. 中国科学院金属研究所沈阳 110016

Influence of Nanocrystallization on Adsorption Behavior of Cl^- on Fe20Cr Alloy in 0.1 mol/L Cl^- Borate Buffer Solution

ZHANG Bin^1,², LIU Li^2,^**(

), LI Tianshu², LI Ying², LEI Mingkai¹, WANG Fuhui²

1. Dalian University of Technology, Dalian 116024, China
2. Institute of metal research, Chinese Academy of Sciences, Shenyang 110016, China

引用本文:

张滨, 刘莉, 李天书, 李瑛, 雷鸣凯, 王福会. 纳米化对Fe-20Cr合金在[Cl^-]=0.1 mol/L硼酸缓冲溶液中Cl^-吸附行为的影响*[J]. 材料研究学报, 2016, 30(1): 6-9.
Bin ZHANG, Li LIU, Tianshu LI, Ying LI, Mingkai LEI, Fuhui WANG. Influence of Nanocrystallization on Adsorption Behavior of Cl^- on Fe20Cr Alloy in 0.1 mol/L Cl^- Borate Buffer Solution[J]. Chinese Journal of Materials Research, 2016, 30(1): 6-9.

全文: PDF(4857 KB) HTML

摘要:

应用X射线光电子能谱(XPS)和第一性原理计算的方法研究了纳米化对Fe20Cr合金在Cl^-浓度为0.1 mol/L的硼酸缓冲溶液中Cl^-吸附行为的影响。结果表明, Cr对Cl^-吸附行为有两方面的影响: 根据理论计算结果, 随着界面处Cr元素含量的增加Cl^-的吸附能逐步降低, 易于Cl^-的吸附; 但是在实际环境中Cr含量的增大导致合金更易于形成Cr氧化物的钝化膜, 从而阻止Cl^-的吸附行为。纳米化加速了Cr元素的扩散行为, 导致Cr元素在钝化膜内及钝化膜/金属界面的富集。由此可见, 纳米化抑制了Cl^-吸附及在钝化膜内的扩散行为, 提高了钝化膜的耐蚀能力。

关键词 ：金属材料, 纳米化, XPS, 第一性原理计算, Fe20Cr合金, Cl-吸附

Abstract：

The effect of nanocrystallization on the adsorption of Cl^-on Fe20Cr alloy in [Cl^-] =0.1 mol/L borate buffer solution was investigated by means of X-ray photoelectron spectrum(XPS) and calculations per the first-principles. The results show that the influence of Cr on Cl^- adsorption behavior could be described as the following two aspects : the one, in view of the calculation per the first-principles, is that the adsorption energy decrease with the increasing Cr content at the interface of passive film/alloy, which is conducive to the adsorption of Cl^-; the other is that the Cr enrichment may also facilitate the formation of passivation film, which inhibit the Cl^- adsorption. Nanocrystallization may enhance the diffusivity of Cr, which leads to the enrichment of Cr within the passive film as well as at the interface of passive film/alloy. Thus, nanocrystallization can inhibit the adsorption and the inward migration of Cl^-, and finally enhance the corrosion resistance of the alloy.

Key words： metallic materials nanocrystallization XPS first-principles calculation Fe20Cr alloy Cl- adsorption

收稿日期: 2015-06-15

基金资助:* 国家自然科学基金50801063、51271187和国家重点基础研究发展规划2014CB643303资助项目

作者简介: 刘莉, 研究员

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表1 Fe20Cr合金成分

图1 Fe20Cr铸态合金的光学金相照片

图2 溅射纳米晶薄膜的透射电镜照片

图3 Fe-20Cr溅射纳米晶的截面形貌

图4 Fe20Cr合金及其溅射纳米晶薄膜的XRD谱图

图5 Fe-20Cr合金及其溅射纳米晶薄膜在0.15 M B(OH)3 + 0.075 M Na2B4O710H2O+0.1M NaCl缓冲体系中的动电位极化曲线

图6 铸态Fe20Cr合金及其溅射纳米晶薄膜在0.15 M B(OH)3 + 0.075 M Na2B4O710H2O+0.1M NaCl溶液中Mott-Schottky曲线及拟合结果

图7 恒电位极化后Fe-20Cr合金表面的XPS全谱扫描

图8 铸态和溅射纳米晶薄膜表面Cl2p谱线沿深度变化图

图9 铸态和溅射纳米晶薄膜Cl含量沿深度的变化

表2 对于 XPS测试得到的Fe2p3、Cr2p3谱线的拟合原则

	$C r ox F e ox + C r ox$	$C r 0 + F e 0 Cr + Fe$
Nano thin film	0.949	0.598
Cast alloy	0.813	0.518

表3 钝化膜内Cr富集程度和钝化膜厚度表

图10 在恒电位0.2 V下钝化300 s后的铸态和溅射纳米晶薄膜表面Fe2p3谱线及拟合结果

图11 在恒电位0.2 V下钝化300 s后的铸态和溅射纳米晶薄膜表面Cr2p3谱线及拟合结果

图12 Fe (110) (7层)上搭建1 nm的真空层的结构图

Surface	Position	E_ads(eV)	$d C l -$ (nm)
(100)	T	-0.48	0.218
	H	-0.48	0.225
	B	-0.67	0.163
(110)	T	-0.27	0.219
	H	-0.73	0.163
	B	-0.30	0.216

表4 Cl-吸附在Fe (100)和(110)T、H、B不同位置上的吸附能(Eads)和吸附距离(dCl-)

图13 Cl-处于稳定的B位置Fe (100) (7 层原子, 2×2)及上表面Cr含量为25%时, a、b、c、d四个不同的取代位置结构图

图14 Cr取代最上层Fe的不同含量的俯视图

	E_t(eV)	$d C l -$ (nm)
25%Cr	-26280.00	0.195
50%Cr	-27878.18	0.191
75%Cr	-29481.56	0.185

表5 界面处Cr含量改变对于Cl-吸附在Fe (100) B(bridge)位置上的总能(Et)和吸附距离(dCl-)的影响

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