CN116953291A - Quantitative detection method for hydrogen distribution on surface of metal material based on SKPFM and TDS interactive use - Google Patents
Quantitative detection method for hydrogen distribution on surface of metal material based on SKPFM and TDS interactive use Download PDFInfo
- Publication number
- CN116953291A CN116953291A CN202310777727.XA CN202310777727A CN116953291A CN 116953291 A CN116953291 A CN 116953291A CN 202310777727 A CN202310777727 A CN 202310777727A CN 116953291 A CN116953291 A CN 116953291A
- Authority
- CN
- China
- Prior art keywords
- hydrogen
- sample
- potential difference
- metal material
- distribution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000001257 hydrogen Substances 0.000 title claims abstract description 115
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 115
- 238000009826 distribution Methods 0.000 title claims abstract description 48
- 239000007769 metal material Substances 0.000 title claims abstract description 42
- 238000001514 detection method Methods 0.000 title claims abstract description 10
- 230000002452 interceptive effect Effects 0.000 title claims abstract description 8
- 125000004435 hydrogen atom Chemical class [H]* 0.000 title description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 76
- 238000000034 method Methods 0.000 claims abstract description 46
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 38
- 238000012360 testing method Methods 0.000 claims abstract description 36
- 239000002184 metal Substances 0.000 claims abstract description 31
- 229910052751 metal Inorganic materials 0.000 claims abstract description 31
- 230000008859 change Effects 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 16
- 238000004090 dissolution Methods 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 6
- 239000000523 sample Substances 0.000 claims description 58
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 238000005259 measurement Methods 0.000 claims description 10
- 238000012545 processing Methods 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 101150037468 CPD1 gene Proteins 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 101100108853 Mus musculus Anp32e gene Proteins 0.000 claims description 6
- 101100221809 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cpd-7 gene Proteins 0.000 claims description 6
- 101100165815 Oryza sativa subsp. japonica CYP90A3 gene Proteins 0.000 claims description 6
- 101100490727 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) AIF1 gene Proteins 0.000 claims description 6
- 101150025236 dmaW gene Proteins 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 238000003860 storage Methods 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- ODZHLDRQCZXQFQ-UHFFFAOYSA-N chlorferron Chemical compound C1=C(O)C=CC2=C1OC(=O)C(Cl)=C2C ODZHLDRQCZXQFQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- 238000010998 test method Methods 0.000 claims description 3
- 238000013075 data extraction Methods 0.000 claims description 2
- 244000137852 Petrea volubilis Species 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 9
- 238000009659 non-destructive testing Methods 0.000 abstract description 2
- 239000012300 argon atmosphere Substances 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001004 secondary ion mass spectrometry Methods 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000012611 container material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000004147 desorption mass spectrometry Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01Q—SCANNING-PROBE TECHNIQUES OR APPARATUS; APPLICATIONS OF SCANNING-PROBE TECHNIQUES, e.g. SCANNING PROBE MICROSCOPY [SPM]
- G01Q60/00—Particular types of SPM [Scanning Probe Microscopy] or microscopes; Essential components thereof
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01Q—SCANNING-PROBE TECHNIQUES OR APPARATUS; APPLICATIONS OF SCANNING-PROBE TECHNIQUES, e.g. SCANNING PROBE MICROSCOPY [SPM]
- G01Q30/00—Auxiliary means serving to assist or improve the scanning probe techniques or apparatus, e.g. display or data processing devices
- G01Q30/20—Sample handling devices or methods
Landscapes
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Radiology & Medical Imaging (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating And Analyzing Materials By Characteristic Methods (AREA)
Abstract
The invention relates to the field of hydrogen energy utilization, and aims to provide a quantitative detection method for hydrogen distribution on the surface of a metal material based on SKPFM and TDS interactive use. According to the invention, SKPFM and TDS methods are utilized, firstly, the change value of the surface contact potential difference caused by hydrogen dissolution and the overall average hydrogen concentration corresponding to the change value are respectively measured for the hydrogen-charged metal material with the same chemical composition and heat treatment state as the metal material to be measured, and different hydrogen charging conditions are set to obtain the corresponding relation curve of the two. And scanning the change value of the surface contact potential difference of the metal surface to be detected caused by hydrogen dissolution through SKPFM, and directly and quantitatively obtaining the hydrogen distribution in the material. The invention has the advantages of nondestructive testing of SKPFM, time resolution, wide applicable material range, high inter-wide resolution, lower testing cost and the like, and the quantitative testing capability of TDS; the method can effectively eliminate the influence of high temperature, high pressure and other factors in the hydrogen charging process on the surface performance of the material, and improve the accuracy of measuring the potential difference change value.
Description
Technical Field
The invention belongs to the field of hydrogen energy utilization, and particularly relates to a quantitative detection method for hydrogen distribution on the surface of a metal material based on SKPFM and TDS interactive use.
Background
The hydrogen energy high-pressure storage and transportation equipment works in a high-pressure and high-purity hydrogen environment for a long time, and generally suffers from the problems of rapid crack growth speed, reduced fracture toughness and the like of materials caused by high-pressure hydrogen embrittlement. At present, hydrogen embrittlement theory is numerous, but the action mechanism of high-pressure hydrogen is not uniformly known; it is generally accepted that when the hydrogen concentration near the crack tip reaches a certain critical value, crack propagation will be promoted, and the higher the hydrogen concentration, the more severe the hydrogen embrittlement. Therefore, the quantitative measurement of the hydrogen distribution on the surface of the material is beneficial to the deeper understanding of the nature of high-pressure hydrogen embrittlement, and simultaneously, the method can provide technical support for the establishment of the service performance prediction method of the hydrogen energy storage and transportation equipment.
Currently common hydrogen distribution detection methods include three-dimensional Atom Probe (APT), hydrogen Microprinting Technology (HMT), scanning Kelvin Probe Force Microscope (SKPFM), thermal desorption mass spectrometry (TDS), secondary Ion Mass Spectrometry (SIMS), and the like. Wherein, the APT adopts a needle-shaped sample with the diameter of nm, the preparation difficulty is high, and hydrogen easily escapes from the sample; HMT can only qualitatively give out hydrogen distribution information at a certain moment, and cannot display the evolution process of hydrogen concentration along with time; the SKPFM can qualitatively analyze the hydrogen distribution and the evolution thereof, but cannot quantitatively detect the hydrogen distribution data due to the lack of the hydrogen concentration corresponding to the potential difference; the TDS spatial resolution is low, and only the average hydrogen content of the whole sample can be obtained; similar to the APT and the TDS, the SIMS needs to be vacuumized, the time cost is high, and the equipment is complex and expensive; in addition, all the other methods except SKPFM need to separate hydrogen from materials, and the detection process has no time resolution and no damage.
In summary, the existing methods have certain limitations in measuring the hydrogen distribution on the surface of the metal material. Therefore, there is a need for a method that can directly, quantitatively and flexibly detect the hydrogen distribution on the surface of a metal material.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and providing a quantitative detection method for hydrogen distribution on the surface of a metal material based on the interactive use of SKPFM and TDS.
In order to solve the technical problems, the invention adopts the following technical scheme:
the method for quantitatively detecting the hydrogen distribution on the surface of the metal material based on the interactive use of SKPFM and TDS comprises the following steps:
(1) Preparing a test metal material in the same production batch as the metal material to be detected, wherein the chemical components and the heat treatment state of the test metal material are consistent, but the test metal material does not contain hydrogen; processing a metal material for test into a sheet shape, and dividing the sheet shape according to the same size specification to obtain batch samples for test;
(2) Taking 3 samples from the batch, wherein the samples are respectively numbered as sample No. 1, sample No. 2 and sample No. 3; simultaneously placing the samples 1# and 2# in a gas-phase thermal hydrogen charging reaction kettle, introducing high-temperature high-pressure hydrogen according to preset test conditions, and keeping for a certain time to obtain hydrogen charging samples with the same hydrogen concentration; placing sample 3# in an argon environment, and processing according to the same temperature, pressure and holding time;
(3) Measuring contact potential difference distribution of the surfaces of the sample 1# and the sample 3# respectively by adopting an SKPFM method, and drawing a contact potential difference distribution map according to a measurement result; randomly selecting a plurality of points on the graph to obtain an average value, and recording the average value as delta V CPD1 And V CPD3 The method comprises the steps of carrying out a first treatment on the surface of the The change value of the surface contact potential difference of the sample due to hydrogen dissolution is calculated as follows: phi CPD ＝ΔV CPD1 -V CPD3 ；
(4) Measuring the overall average hydrogen concentration of sample No. 2 by using a TDS method, and marking the overall average hydrogen concentration as C; obtaining phi under the specific hydrogen charging condition of the group CPD Correspondence with C;
(5) Repeating the operations of steps (2) to (4) to obtain at least 5 phi by changing the temperature, pressure and holding time CPD Data points corresponding to C; on the basis, phi is fitted CPD A corresponding relation curve with C;
(6) Measuring the contact potential difference distribution of the metal surface to be measured by adopting an SKPFM method, and measuring the contact potential difference distribution of the metal surface to be measured again after hydrogen in the metal surface to be measured completely escapes;
(7) Subtracting the contact potential differences obtained by the two measurements in the step (6) at the same position of the metal surface to be measured to obtain phi of the metal surface to be measured CPD Distribution; and (3) obtaining quantitative data of hydrogen distribution on the surface of the metal material according to the fitting relation curve in the step (5).
In the step (1), the sheet metal material is polished to have a smooth surface by using 2000-mesh silicon carbide waterproof abrasive paper, segmented, ultrasonically washed for 3min by using ethanol solution, and then dried and stored.
In the preferred embodiment of the present invention, in the step (1), the processed and divided sample is square, the side length is not more than 10mm, and the thickness is not more than 1mm.
As a preferable mode of the invention, in the step (2), the heating temperature in the gas phase hot charging is less than or equal to 200 ℃.
In the step (2), the sample treated by hydrogen and argon is taken out and then directly put into liquid nitrogen for storage for standby.
As a preferred embodiment of the present invention, in the step (3), when the SKPFM method is used to measure the distribution of the contact potential difference, two scans are used: firstly, scanning for the first time to obtain the surface morphology of a sample; then the probe is lifted by 50nm, and a second reverse scanning is carried out to obtain the contact potential difference distribution.
As a preferred embodiment of the present invention, in the step (3), at least 10 data extraction points are randomly selected using a random function on the contact potential difference distribution map.
As a preferable scheme of the invention, in the step (5), the temperature, pressure and time in the sample treatment process are adjusted according to a hydrogen concentration prediction formula in annex E of Standard ANSI/CSA CHMC 1-2014 (Test methods for evaluating material compatibility in compressed hydrogen applications-Metals).
In the step (6), the temperature of the metal to be measured is ensured to be the same when the contact potential difference distribution of the surface of the metal to be measured is measured twice.
In the preferred embodiment of the present invention, in the step (6), the temperature may be increased appropriately to accelerate the hydrogen to escape, but the temperature should not be higher than 200 ℃, and an excessive temperature may cause the original stress state, plastic deformation, dislocation, etc. of the surface of the metal to be measured to be changed, and may cause carbide precipitation, which may cause interference to the measurement result.
Description of the inventive principles:
according to the invention, SKPFM and TDS methods are utilized, firstly, the change value of the surface contact potential difference caused by hydrogen dissolution and the overall average hydrogen concentration corresponding to the change value are respectively measured for the hydrogen-charged metal material with the same chemical composition and heat treatment state as the metal material to be measured, and different hydrogen charging conditions are set to obtain the corresponding relation curve of the two. And scanning the change value of the surface contact potential difference of the metal surface to be detected caused by hydrogen dissolution through SKPFM, and directly and quantitatively obtaining the hydrogen distribution in the material.
The dissolution of hydrogen atoms into the interior of the metal material weakens the cohesion between the metal atoms, reducing the energy of electrons escaping from the atoms and therefore the work function of the metal surface after charging. In addition, dissolution of hydrogen will cause lattice expansion of the metallic material, and the resulting mechanical stress will also lower the work function. And the contact potential difference has the following relation with work function:
in the middle ofAnd->Work functions of the probe tip and the sample surface, respectively, and e is electron charge.
Thus, as the concentration of hydrogen in the metallic material increases, the contact potential difference across the surface of the material also increases.
Based on the principle, the invention prepares the test metal materials with the same chemical composition and heat treatment state as the metal materials to be tested into batch samples, groups 3 samples from the batch samples, firstly carries out high-temperature high-pressure hydrogen charging treatment on two samples in the same group, and places a third sample in an argon environment with the same temperature and pressure for the same time. Then, measuring the overall average hydrogen concentration in the sample by adopting a TDS method, and measuring the change value of the surface contact potential difference of the sample due to hydrogen dissolution by adopting SKPFM (respectively scanning the sample after hydrogen and argon atmosphere treatment, taking the difference value of the two test results as the change value of the surface contact potential difference, and actually, the change of the surface work function only caused by hydrogen dissolution, so that the influence of factors such as high temperature, high pressure and the like on the surface performance of the material in the hydrogen charging process can be eliminated); therefore, after the same group of samples are charged with hydrogen, the corresponding relation between the change value of the surface contact potential difference caused by hydrogen dissolution and the overall average hydrogen concentration can be established; and finally, changing the hydrogen charging condition, and fitting a relation curve of the contact potential difference change value and the hydrogen concentration of the surface of the metal material for test. Since the metal material for test is the same as the metal material to be tested, the hydrogen distribution in the material can be directly and quantitatively obtained only by scanning the change value of the surface contact potential difference of the metal to be tested caused by hydrogen dissolution through SKPFM and consulting the fitting relation curve.
Compared with the prior art, the invention has the beneficial effects that:
1. the quantitative measurement of the hydrogen distribution on the surface of the material is realized by adopting a SKPFM and TDS combined method, and the evolution of the hydrogen distribution along with time can be observed. The method has the advantages of nondestructive testing of SKPFM, time resolution, wide applicable material range, high inter-wide resolution, lower testing cost and the like, and the quantitative testing capability of TDS.
2. The test sample treated by the high-temperature high-pressure argon atmosphere is subjected to comparison test, so that the influence of factors such as high temperature and high pressure in the hydrogen charging process on the surface performance of the material can be effectively eliminated, and the accuracy of measuring the potential difference change value is further improved.
3. The sample size is reasonable in design, the processing is simple and convenient, and the problems that a large amount of hydrogen escapes in the sample processing process and the initial morphology of the metal to be detected is greatly destroyed are avoided.
Drawings
FIG. 1 is a flow chart of the detection method of the present invention.
Detailed Description
The following describes specific embodiments of the present invention with reference to the drawings.
As shown in FIG. 1, the quantitative detection method for the hydrogen distribution on the surface of the metal material based on the interactive use of SKPFM and TDS comprises the following 4 steps.
1. Sample preparation
In order to quantitatively detect the hydrogen distribution on the surface of the metal material, it is necessary to prepare a test metal material having the same production lot as the metal material to be detected, and the chemical composition and the heat treatment state of both are identical, but the latter does not contain hydrogen.
The test metal material is processed into flake, and polished with 2000 mesh silicon carbide waterproof abrasive paper to obtain a smooth surface. After being divided into equal size specifications, the polished sample was subjected to ultrasonic washing with an ethanol solution for 3 minutes. And drying and storing the samples to obtain batch samples for test.
For example, the test pieces in this example are square sheets having a side length of 10mm and a thickness of 1mm, and the number of the sheets is at least 30. The test was performed by randomly dividing 3 specimens per group into 10 test groups (redundant specimens were used). Before each group of test, 3 samples in the group are respectively numbered as No. 1, no. 2 and No. 3.
2. Comparative charging
The hydrogen concentration interval between different test groups is defined, and the equilibrium hydrogen concentration value of each test group is preliminarily set. And predicting hydrogen charging conditions (hydrogen pressure, temperature and hydrogen charging time) corresponding to different equilibrium hydrogen concentration values according to thermodynamic relation in annex E of standard ANSI/CSA CHMC 1-2014 Test methods for evaluating material compatibility in compressed hydrogen applications-Metals. According to the calculation result, the charging conditions of each group are set. For each test group, placing samples 1# and 2# in the group into a high-temperature high-pressure gas-phase hot-charging reaction kettle for charging hydrogen to obtain two hydrogen-charging samples with the same hydrogen concentration in the same test group; the heating temperature is less than or equal to 200 ℃ when the gas phase is thermally charged with hydrogen, so that the precipitation of carbide in the metal caused by the overhigh temperature can be prevented. Sample 3# in this group was placed in an argon atmosphere under the same pressure and temperature conditions as in the hydrogen charging section of this group, and incubated for the same period of time. Then, samples 1#,2#,3# taken out of the reaction kettle were all immediately placed in liquid nitrogen at-200 ℃ for low-temperature storage.
3. Fitting a relation curve
(1) For each test group, samples 1# and 3# were measured by the SKPFM method, respectively, to obtain the variation of the contact potential difference due to only hydrogen dissolution, which was noted as Φ CPD The method comprises the steps of carrying out a first treatment on the surface of the Each group phi CPD The measurement process of (2) mainly comprises the following 4 steps:
(a) And (3) installing a sample: fixing sample No. 1 on a sample holder, and adsorbing the sample holder on a magnetic sample disk;
(b) Focusing the sample: moving the probe tip to the sample 1# surface, adjusting the optical focal length until the sample 1# surface is seen;
(c) Scanning an image: adopting a twice scanning method, and obtaining the surface morphology of the sample No. 1 through the first scanning; then the probe is lifted by 50nm, and a second reverse scanning is carried out to obtain a contact potential difference distribution image of the 1# surface of the sample.
Referring to the operation contents of steps (a) to (c), a sample 3# surface contact potential difference distribution image is obtained.
(d) Calculating phi CPD : on the contact potential difference distribution images of samples 1# and 3#, 10 points are randomly selected respectively by using a random function; calculate the average of the 10 point contact potential differences, recorded as DeltaV CPD1 And DeltaV CPD3 The method comprises the steps of carrying out a first treatment on the surface of the The contact potential difference change value of the sample due to hydrogen dissolution is: phi CPD ＝ΔV CPD1 -V CPD3 。
(2) Sample 2# was measured by the TDS method to obtain the overall average hydrogen concentration, designated C.
(3) Obtaining phi for each of the 10 test groups CPD Corresponding relation with C, removing abnormal points, and fitting phi of the metal material for test on the basis CPD And C is a corresponding relation curve.
4. Measuring hydrogen distribution
(1) Measuring contact potential difference distribution of the metal surface to be measured by adopting an SKPFM method according to the previous operation content, and measuring the contact potential difference distribution of the metal surface to be measured again after hydrogen in the metal surface to be measured completely escapes; in this process, it is ensured that the temperature of the metal to be measured is the same in both measurements.
The hydrogen escape is carried out at the temperature of less than or equal to 200 ℃, and specific operation can refer to a scheme recorded in the publication of the application research progress of thermal desorption spectrum technology in the research of hydrogen traps of hydrogen storage container materials.
(2) Subtracting the contact potential differences obtained by the two measurements at the same position of the metal surface to be measured to obtain phi of the metal surface to be measured CPD Distribution;
(3) And (3) obtaining hydrogen distribution quantitative data of the surface of the metal material according to the fitting relation curve in the step (3).
Finally, it should be noted that the above list is only specific embodiments of the present invention. The invention is not limited to the above embodiments, but many variations are possible. All modifications, equivalents, and improvements therein may occur to those skilled in the art from the present disclosure without departing from the spirit and principles of the present invention.
Claims (10)
1. The quantitative detection method for the hydrogen distribution on the surface of the metal material based on the interactive use of SKPFM and TDS is characterized by comprising the following steps:
(1) Preparing a test metal material in the same production batch as the metal material to be detected, wherein the chemical components and the heat treatment state of the test metal material are consistent, but the test metal material does not contain hydrogen; processing a metal material for test into a sheet shape, and dividing the sheet shape according to the same size specification to obtain batch samples for test;
(2) Taking 3 samples from the batch, wherein the samples are respectively numbered as sample No. 1, sample No. 2 and sample No. 3; simultaneously placing the samples 1# and 2# in a gas-phase thermal hydrogen charging reaction kettle, introducing high-temperature high-pressure hydrogen according to preset test conditions, and keeping for a certain time to obtain hydrogen charging samples with the same hydrogen concentration; placing sample 3# in an argon environment, and processing according to the same temperature, pressure and holding time;
(3) Measuring contact potential difference distribution of the surfaces of the sample 1# and the sample 3# respectively by adopting an SKPFM method, and drawing a contact potential difference distribution map according to a measurement result; randomly selecting a plurality of points on the graph to obtain an average value, and recording the average value as delta V CPD1 And DeltaV CPD3 The method comprises the steps of carrying out a first treatment on the surface of the The change value of the surface contact potential difference of the sample due to hydrogen dissolution is calculated as follows: phi CPD ＝ΔV CPD1 -ΔV CPD3 ；
(4) Measuring the overall average hydrogen concentration of sample No. 2 by using a TDS method, and marking the overall average hydrogen concentration as C; obtaining phi under the specific hydrogen charging condition of the group CPD Correspondence with C;
(5) Repeating the operations of steps (2) to (4) to obtain at least 5 phi by changing the temperature, pressure and holding time CPD Data points corresponding to C; on the basis, phi is fitted CPD A corresponding relation curve with C;
(6) Measuring the contact potential difference distribution of the metal surface to be measured by adopting an SKPFM method, and measuring the contact potential difference distribution of the metal surface to be measured again after hydrogen in the metal surface to be measured completely escapes;
(7) Subtracting the contact potential differences obtained by the two measurements in the step (6) at the same position of the metal surface to be measured to obtain phi of the metal surface to be measured CPD Distribution; and (3) obtaining quantitative data of hydrogen distribution on the surface of the metal material according to the fitting relation curve in the step (5).
2. The method according to claim 1, wherein in the step (1), the sheet-like metal material is polished to a smooth surface by using 2000 mesh silicon carbide waterproof sand paper, divided, ultrasonically washed for 3min by using ethanol solution, and then dried and stored.
3. The method according to claim 1, wherein in the step (1), the processed and divided sample is square, the side length is 10mm or less and the thickness is 1mm or less.
4. The method according to claim 1, wherein in the step (2), the heating temperature at the time of the gas phase hot charging is 200 ℃ or less.
5. The method according to claim 1, wherein in the step (2), the sample treated with hydrogen and argon is taken out and then directly put into liquid nitrogen for storage.
6. The method according to claim 1, wherein in the step (3), the SKPFM method is used to measure the distribution of the contact potential difference by two scans: firstly, scanning for the first time to obtain the surface morphology of a sample; then the probe is lifted by 50nm, and a second reverse scanning is carried out to obtain the contact potential difference distribution.
7. The method of claim 1, wherein in step (3), at least 10 data extraction points are randomly selected on the contact potential difference profile using a random function.
8. The method according to claim 1, wherein in the step (5), the temperature, pressure and time during the sample processing are adjusted according to the hydrogen concentration prediction formula in annex E of standard ANSI/CSA CHMC 1-2014 Test methods for evaluating material compatibility in compressed hydrogen applications-Metals.
9. The method according to claim 1, wherein in the step (6), it is ensured that the temperature of the metal to be measured is the same when the distribution of the contact potential difference of the surface of the metal to be measured is measured twice.
10. The method according to claim 1, wherein in the step (6), the hydrogen evolution is carried out at a temperature of 200 ℃ or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310777727.XA CN116953291A (en) | 2023-06-29 | 2023-06-29 | Quantitative detection method for hydrogen distribution on surface of metal material based on SKPFM and TDS interactive use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310777727.XA CN116953291A (en) | 2023-06-29 | 2023-06-29 | Quantitative detection method for hydrogen distribution on surface of metal material based on SKPFM and TDS interactive use |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116953291A true CN116953291A (en) | 2023-10-27 |
Family
ID=88452062
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310777727.XA Pending CN116953291A (en) | 2023-06-29 | 2023-06-29 | Quantitative detection method for hydrogen distribution on surface of metal material based on SKPFM and TDS interactive use |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116953291A (en) |
-
2023
- 2023-06-29 CN CN202310777727.XA patent/CN116953291A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100573181C (en) | Utilize the method for ferromagnetic materials surface stray magnetic field signal monitoring fatigue damage | |
| Merzlikin et al. | Ultra high vacuum high precision low background setup with temperature control for thermal desorption mass spectroscopy (TDA-MS) of hydrogen in metals | |
| CN112525735A (en) | Replica method for detecting fatigue small crack condition | |
| CN104777046A (en) | Fatigue crack propagation mechanism testing method based on small time scale | |
| Anunmana et al. | Residual stress in glass: Indentation crack and fractography approaches | |
| CN111426722A (en) | Device and method for rapidly determining recrystallization temperature of metal material | |
| CN111537534B (en) | Analysis method for nucleation of metal hydride containing surface oxide layer | |
| CN114184628B (en) | Method for rapidly preparing massive ceramic EBSD sample | |
| Shrivastava et al. | Determination of diffusion coefficients of hydrogen and deuterium in Zr–2.5% Nb pressure tube material using hot vacuum extraction-quadrupole mass spectrometry | |
| CN116953291A (en) | Quantitative detection method for hydrogen distribution on surface of metal material based on SKPFM and TDS interactive use | |
| Frazer et al. | Evaluation of the mechanical properties of TRISO particles using nanoindentation and ring compression testing | |
| Kreider et al. | Sputtered amorphous carbon nitride films | |
| Yeung et al. | Assessment of backside processes through die strength evaluation | |
| Graebner et al. | Thermal conductivity of amorphous germanium at low temperatures | |
| CN116518839A (en) | Method, system and equipment for measuring carburized layer thickness of furnace tube in radiation section of cracking furnace | |
| Kamerman et al. | Formation and characterization of hydride rim structures in Zircaloy-4 nuclear fuel cladding tubes | |
| CN109142041A (en) | A method of detection sample sliding and bending deformation | |
| CN114544476A (en) | Method for detecting uniform corrosion resistance of stainless steel | |
| CN115078086A (en) | Method for measuring bonding force between metal matrix and oxide film by using SEM (scanning electron microscope) in-situ tensile instrument | |
| Sun et al. | Analysis of the mechanical properties of Q345R steel in deep-regulating units by the spherical indentation method | |
| CN209342508U (en) | A kind of material strain original position EBSD observation test fixture | |
| CN105044145A (en) | Method for measuring bainite transformation temperature in solid phase transformation process | |
| JPH0674951A (en) | Creep damage evaluating method for ferrite heat resistant steel | |
| CN111175325B (en) | Method and special device for preparing thin-wall pipe flattening texture test sample | |
| CN109571302A (en) | A kind of characterizing method of the semi-consolidated abrasive polishing tools interfaces bond strength based on tensile strength |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |