CN110940691A - Method for comparing protection effects of different oxide films on metal matrix and application thereof - Google Patents

Method for comparing protection effects of different oxide films on metal matrix and application thereof Download PDF

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CN110940691A
CN110940691A CN201811110486.9A CN201811110486A CN110940691A CN 110940691 A CN110940691 A CN 110940691A CN 201811110486 A CN201811110486 A CN 201811110486A CN 110940691 A CN110940691 A CN 110940691A
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comparing
different
oxide films
metal
oxide film
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CN110940691B (en
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徐连勇
许有伟
荆洪阳
韩永典
赵雷
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Tianjin University
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    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
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    • G01N23/227—Measuring photoelectric effect, e.g. photoelectron emission microscopy [PEEM]
    • G01N23/2273—Measuring photoelectron spectrum, e.g. electron spectroscopy for chemical analysis [ESCA] or X-ray photoelectron spectroscopy [XPS]

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Abstract

The invention discloses a method for comparing the protection effects of different oxide films on a metal matrix and application thereof, wherein the comparison method comprises the following steps: step 1, XPS depth analysis is carried out on an oxide film on the surface of a sample, and an element which plays a decisive role in metal corrosion resistance is selected as a reference element; and 2, finding out the position where the reference element just appears in a metal state in the deep analysis process, and comparing the contents of Fe elements with different valence states, wherein the higher the content of Fe element with low valence state is, the better the protection capability of the oxide film is. The invention can accurately compare the protection effects of different oxide films on the metal matrix.

Description

Method for comparing protection effects of different oxide films on metal matrix and application thereof
Technical Field
The invention relates to the technical field of stress corrosion, in particular to a method for comparing the protection effects of different oxide films on a metal matrix and application thereof.
Background
The metal can form an oxide film in the oxidation process, and when the oxide film reaches a certain degree, the metal substrate has certain protection to the metal substrate, and the oxidation is retarded. The oxide film has different compositions and structures and different protection effects on the metal matrix. For example, CF8A austenitic stainless steel under different applied loads can form double-layer oxide films with different structures in a high-temperature water environment at 300 ℃. When the external load is less than the yield strength, the inner layer oxidation film is compact and continuous Cr2O3An oxide; when the applied load is greater than the yield strength, the inner layer oxide film is (Ni)xFe1-x)(CryFe1-y)2O4(x, y is less than or equal to 1) spinel structure oxide. The conventional techniques for analyzing the protective effect of the oxide film on the substrate include Transmission Electron Microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). TEM can only observe local features of a sample in the nanometer range, however, for a stainless steel oxide film with a thickness of up to several hundred nanometers, observation using TEM may be misled by local information. XPS is a surface analysis technique that can analyze a large area of hundreds of microns, thereby making up for limitations of TEM observations. Furthermore, XPS is a spectroscopic technique that provides information about the chemical composition of elements and the chemical environment.
However, when the protection effect of different oxide films on the metal substrate is analyzed by using XPS, the selection of the element valence state information acquisition position is very important in order to compare the distribution of the element valence state at different positions of the oxide film due to different oxide film thicknesses. The invention relates to a method for selecting characteristic positions when different oxidation films of Fe-Ni-Cr alloy are compared, so that the protection effects of the different oxidation films on a metal matrix can be accurately compared.
The oxide film formed by Fe-Ni-Cr alloy in corrosive environment can be divided into two kinds, the first is oxide which plays a decisive role in preventing metal corrosion, such as Cr2O3(ii) a The first is an oxide having little effect on preventing metal corrosion, such as Fe generated on the surface of stainless steel3O4And spinel oxides.
Disclosure of Invention
The invention aims to provide a method for comparing the protection effect of different oxide films on a metal matrix, aiming at the technical defects in the prior art.
The technical scheme adopted for realizing the purpose of the invention is as follows:
a method for comparing the protective effect of different oxide films on a metal substrate, comprising the steps of:
step 1, XPS depth analysis is carried out on an oxide film on the surface of a sample, and an element which plays a decisive role in metal corrosion resistance is selected as a reference element;
and 2, finding out the position where the reference element just appears in a metal state in the deep analysis process, and comparing the contents of Fe elements with different valence states, wherein the higher the content of Fe element with low valence state is, the better the protection capability of the oxide film is.
In the above technical solution, when the specimen is a stainless steel specimen, the reference element is Cr and/or Ni.
In the above technical solution, the XPS depth profiling process is as follows: the test samples measured by XPS were analyzed on an EASCAB 250X-ray photoelectron spectrometer, with monochromatic Al Ka radiation source HV 1486.6eV exciting photoelectron emission of 150 μ W, depth profile analysis was performed over a 2X 2mm area, and depth profile information was obtained by sputtering samples with 2keV scanning argon ions.
In another aspect of the invention, the application of the method for comparing the protection effect of different oxide films on the metal matrix in comparison of different oxide films of Fe-Ni-Cr alloy is also included.
Compared with the prior art, the invention has the beneficial effects that:
the method can compare different oxidation films of the Fe-Ni-Cr alloy, so that the protection effects of the different oxidation films on the metal matrix can be accurately compared.
Drawings
FIG. 1 depth-resolved Cr high resolution XPS peaks; wherein: (a) carrying a sample under constant load; (b) overload the sample.
FIG. 2 comparison of the valence states of the elements at the oxide film/substrate interface; (a) cr; (b) fe.
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The protective effect of a typical oxide film generated on the surface of CF8A SS under different load forms on a substrate was evaluated in a simulated PWR environment by the following examples.
To simulate a PWR environment, test solutions were prepared using high purity water with 2.2ppm Li (LiOH), 1200ppm B (H) added3BO3). 1.7L of the solution was charged to a 3.5L autoclave, which was heated to 300 ℃. The test solution was maintained at 5ppb with a continuous nitrogen (99.999%). The temperature fluctuation is within +/-1 ℃, and the heating speed is about 100 ℃/h.
Example 1
When the environment parameters of the simulated PWR are stable, a test for enabling the sample to be always under the constant load is carried out in the PWR environment, and specifically, the sample is 1 multiplied by 10-4s-1Is loaded to 150MPa (90% of the yield strength at 300 ℃ CF8A SS) and then held under constant load for 240 hours, yielding a constant load sample.
Example 2
When the simulated PWR environmental parameters were stable, the samples were at 1X 10-4s-1Is loaded to 150MPa (90% of the yield strength of CF8ASS at 300 ℃) and then kept under constant load for 120 hours, after which the test specimen is at 1X 10-3s-1The overload rate is 1.6, then the load is reduced to 150MPa and the corrosion is continued in PWR environment for 120 hours, and an overload sample is obtained.
XPS measurements were performed on the samples obtained in example 1 and example 2, and the test samples of the XPS measurements were performed on an eascb 250X radiation photoelectron spectrometer. Photoelectron emission of 150 μ W was excited with a monochromatic Al Ka radiation source (HV ═ 1486.6eV) and depth profiling was achieved over an area of 2 × 2 mm. Depth profile information was obtained by sputtering a sample with 2keV scanning argon ions.
After the XPS depth analysis is finished, making the peak of the high-resolution XPS spectrum of Cr into IIIDimension map, and then searching for the oxide film matrix interface, namely the position of the peak of the sample in the metallic state Cr just appeared in the XPS depth profiling process, as shown in FIG. 1, wherein (a) is the dead load sample obtained in example 1, and (b) is the overload sample obtained in example 2. Two Cr lines in FIG. 1(a) and FIG. 1(b)0The curves just appearing (the curves labeled oxide film/substrate in the figure) are compared to compare the content of elements of different valence states at the interface between the surface of the sample and the oxide film substrate under different sample conditions, as shown in fig. 2. FIG. 2a is a comparison of the valence states of Cr at the oxide film/substrate interface generated under constant load (example 1) and overload (example 2), from FIG. 2a it can be seen that the constant load and overload curves Cr0The peak intensity of (2p3/2) was the same, further demonstrating that both curves are Cr0The curves just presented, FIG. 2b is a comparison of the valence states of Fe at the oxide film/substrate interface generated under constant load and overload. It is evident that the oxide film formed under the overload condition is Fe at the interface of the oxide film substrate2+(in the figure, Fe is indicated2+Position of (2p3/2) and Fe in a metallic state (Fe is indicated in the figure)0Position of (2p3/2) content is low, i.e. the oxide film formed after the overload limits the out-diffusion of metal atoms, and the solution and O have poor out-diffusion capacity, i.e. the protection of the oxide film formed after the overload is poor.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (4)

1. A method for comparing the protective effects of different oxide films on a metal substrate, comprising the steps of:
step 1, XPS depth analysis is carried out on an oxide film on the surface of a sample, and an element which plays a decisive role in metal corrosion resistance is selected as a reference element;
and 2, finding out the position where the reference element just appears in a metal state in the deep analysis process, and comparing the contents of Fe elements with different valence states, wherein the higher the content of Fe element with low valence state is, the better the protection capability of the oxide film is.
2. The method for comparing the protective effects of different oxide films on metal substrates according to claim 1, wherein the reference elements are Cr and/or Ni when the test specimen is a stainless steel test specimen.
3. The method of claim 1, wherein the XPS depth profiling comprises: the test samples measured by XPS were analyzed on an EASCAB250X ray photoelectron spectrometer, with monochromatic Al Ka radiation source HV 1486.6eV exciting the photoelectron emission of 150 μ W, depth profile analysis was performed over a 2X 2mm area, and depth profile information was obtained by sputtering the samples with 2keV scanning argon ions.
4. Use of a method according to claim 1 for comparing the protective effect of different oxide films on a metal substrate in comparison with different oxide films of Fe-Ni-Cr alloys.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115060755A (en) * 2022-08-18 2022-09-16 季华实验室 Depth analysis method for unknown sample layer structure

Citations (3)

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Publication number Priority date Publication date Assignee Title
JP2000206065A (en) * 1999-01-11 2000-07-28 Oki Electric Ind Co Ltd Structure analysis method of film containing ga, as, and at least one type of element being different from ga and as and its surface oxide film
CN102952419A (en) * 2012-10-19 2013-03-06 山东科技大学 Preparation method of modified titanium oxide coating applied to metal matrix corrosive protection
CN105132870A (en) * 2015-08-13 2015-12-09 江苏科技大学 Composite oxide coating with high temperature conductivity and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000206065A (en) * 1999-01-11 2000-07-28 Oki Electric Ind Co Ltd Structure analysis method of film containing ga, as, and at least one type of element being different from ga and as and its surface oxide film
CN102952419A (en) * 2012-10-19 2013-03-06 山东科技大学 Preparation method of modified titanium oxide coating applied to metal matrix corrosive protection
CN105132870A (en) * 2015-08-13 2015-12-09 江苏科技大学 Composite oxide coating with high temperature conductivity and preparation method thereof

Non-Patent Citations (2)

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李惠: "双相不锈钢组织变化及腐蚀行为的研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 *
陈俊劼: "预形变不锈钢在模拟压水堆一回路水中的界面反应特征与应力腐蚀开裂行为", 《中国优秀博硕士学位论文全文数据库工程科技Ⅰ辑》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115060755A (en) * 2022-08-18 2022-09-16 季华实验室 Depth analysis method for unknown sample layer structure

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