CN114323909A - Method for improving pre-hydrogen filling speed of metal sample in hydrogen embrittlement test - Google Patents
Method for improving pre-hydrogen filling speed of metal sample in hydrogen embrittlement test Download PDFInfo
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Abstract
The invention belongs to the technical field of metal materials, and relates to a method for improving the pre-hydrogen charging speed of a metal sample in a hydrogen embrittlement test, which comprises the following steps: forming a hydrogen storage alloy film on the surface of the metal sample to obtain a pre-hydrogen filling sample; and placing the pre-hydrogen filling sample in a hydrogen filling device for pre-filling. In the invention, the hydrogen storage alloy film has the catalytic action of accelerating the dissociation of hydrogen molecules into hydrogen atoms, so that the surface hydrogen atom concentration of the pre-filled hydrogen sample is high, and meanwhile, the hydrogen storage alloy film has the action of absorbing the hydrogen atoms, and the diffusion speed of the hydrogen atoms in the hydrogen storage alloy film is extremely high. Therefore, the high-pressure hydrogen introduced into the hydrogen charging device can be rapidly decomposed into hydrogen atoms under the action of the hydrogen storage alloy film and can enter the matrix of the metal sample through the interface diffusion of the hydrogen storage alloy film and the metal sample, so that the pre-charging speed of the metal sample is effectively improved, and the pre-charging time is shortened.
Description
Technical Field
The invention relates to the technical field of metal materials, in particular to a method for improving the pre-charging hydrogen speed of a metal sample in a hydrogen embrittlement test.
Background
The most important challenge in the development of hydrogen energy is the storage and transportation of hydrogen energy, and the safe, economic, efficient and feasible storage and transportation mode is found as the key to the full life cycle application of hydrogen energy. At present, hydrogen storage in a high-pressure container is a main hydrogen storage mode, the hydrogen pressure grade is generally 35MPa or 70MPa, but the high-pressure container can be subjected to hydrogen embrittlement after being exposed in a high-pressure hydrogen environment for a long time, so that the high-pressure container is cracked.
Therefore, it is important to perform hydrogen embrittlement tests on materials for high pressure vessels, and it is most critical to provide an actual hydrogen service environment for the materials. However, a large amount of time cost and working cost are required for directly simulating a high-pressure hydrogen storage and transportation environment for a long time, which is not beneficial to research on hydrogen embrittlement behaviors caused by the high-pressure hydrogen environment, so that a hydrogen pre-charging method needs to be designed, which can be used for simulating a real working environment approximately and reducing the time for charging hydrogen into a material.
The conventional hydrogen pre-charging method for the hydrogen embrittlement test is roughly divided into three methods:
(1) electrolyzing and charging hydrogen in aqueous solution: graphite plates or platinum wires are used as anodes, materials are used as cathodes, and hydrogen is charged in acid-containing or alkali-containing solution in an electrolytic mode, and the final hydrogen content in the materials depends on factors such as current density, electrolyte variety and time and temperature of hydrogen charging. Although electrolytic hydrogen charging is the simplest and most common hydrogen charging mode at present, the method only ensures a certain hydrogen ion concentration and cannot truly simulate the service state of the material in the actual high-pressure hydrogen environment. In addition, the electrolytic charging of hydrogen in aqueous solution can generate high hydrogen fugacity on the surface of the material, which leads to cracking or phase change on the surface of the material.
(2) High-temperature gas-phase hydrogen filling: increasing the temperature can expand the gas to produce high pressure hydrogen gas according to the gas equation of state, but relying only on increasing the temperature to achieve increased pressure, the required heating temperature is often quite high, for example: when the hydrogen pressure of 10MPa at 25 ℃ is increased to 40MPa, the temperature needs to be heated to about 920 ℃, and when the hydrogen pressure is increased to 70MPa, the temperature needs to be heated to 1820 ℃, and the traditional high-temperature and high-pressure hydrogen charging device cannot bear the pressure. In addition, the high temperature environment may have destructive effects on the material itself, such as thermal stress cracking.
(3) Mechanical pressurization and hydrogen charging: the material is placed in a hydrogen charging device, high-pressure hydrogen is provided for the hydrogen charging device by using a compressor after the material is sealed, and pre-charging is carried out under the mild condition of room temperature or below 150 ℃.
Disclosure of Invention
In view of the above, there is a need to provide a method for increasing the pre-hydrogen charging speed of a metal sample in a hydrogen embrittlement test, which can effectively increase the pre-hydrogen charging speed of the metal sample and shorten the pre-hydrogen charging time.
A method for improving the pre-hydrogen charging speed of a metal sample in a hydrogen embrittlement test comprises the following steps:
forming a hydrogen storage alloy film on the surface of the metal sample to obtain a pre-hydrogen filling sample; and
and placing the pre-hydrogen filling sample in a hydrogen filling device for pre-filling.
In one embodiment, the hydrogen storage alloy thin film has a thickness of 10nm to 30 nm.
In one embodiment, the hydrogen storage alloy film is a continuous film, or alternatively, the hydrogen storage alloy film is a discontinuous film.
In one embodiment, the hydrogen storage alloy thin film is selected from at least one of a rare earth-based hydrogen storage alloy thin film and a titanium-based hydrogen storage alloy thin film.
In one embodiment, the rare-earth hydrogen storage alloy in the rare-earth hydrogen storage alloy film has a general formula of RTxWherein R is selected from at least one of rare earth elements, T is selected from at least one of transition metals, and x is more than or equal to 4.5 and less than or equal to 5.5.
In one embodiment, the general formula of the titanium hydrogen storage alloy in the titanium hydrogen storage alloy film is MTyWherein M is selected from Ti or Ti and Zr, T is selected from at least one of Fe, Ni, V, Cr and Mn, and y is more than or equal to 0.8 and less than or equal to 1.2, or y is more than or equal to 1.8 and less than or equal to 2.4.
In one embodiment, the hydrogen storage alloy film is formed on the surface of the metal sample by deposition or coating.
In one embodiment, the hydrogen storage alloy film is formed on the surface of the metal sample by deposition by a magnetron sputtering method or a thermal plasma physical vapor deposition method.
In one embodiment, before the hydrogen storage alloy film is formed on the surface of the metal sample, the metal sample is subjected to a pretreatment, and the pretreatment comprises sanding and/or ultrasonic cleaning.
In one embodiment, the pre-charging step is performed under vacuum, and high-pressure hydrogen gas of 30MPa to 70MPa is introduced, and the pressure is maintained at 25 ℃ to 200 ℃ for 50 hours to 200 hours.
According to the invention, the hydrogen storage alloy film is formed on the surface of the metal sample to serve as the pre-hydrogen charging sample, and then the pre-hydrogen charging sample is placed in the hydrogen charging device for pre-hydrogen charging, so that on one hand, the hydrogen storage alloy film has a catalytic action of accelerating hydrogen molecules to be dissociated into hydrogen atoms, so that the surface hydrogen atom concentration of the pre-hydrogen charging sample is high, and on the other hand, the hydrogen storage alloy film has an action of absorbing the hydrogen atoms, and the diffusion speed of the hydrogen atoms in the hydrogen storage alloy film is extremely high. Therefore, the high-pressure hydrogen introduced into the hydrogen charging device can be more rapidly decomposed into hydrogen atoms under the action of the hydrogen storage alloy film and can be diffused into the matrix of the metal sample through the interface of the hydrogen storage alloy film and the metal sample, so that the pre-charging speed of the metal sample is effectively improved, and the pre-charging time is shortened.
Detailed Description
The method for increasing the pre-charging hydrogen rate of the metal sample in the hydrogen embrittlement test provided by the invention is further described below.
When the traditional mechanical pressurization hydrogen charging method is adopted, the reason that the hydrogen charging time is longer is mainly as follows: during the process of pre-charging the metal sample by the high-pressure hydrogen introduced into the charging device, gaseous hydrogen molecules firstly collide with the surface of the metal sample and are partially adsorbed on the surface of the metal sample, and then the adsorbed hydrogen molecules are slowly decomposed into hydrogen atoms on the surface of the metal sample and gradually diffused into the matrix of the metal sample. It can be seen that the decomposition of hydrogen molecules into hydrogen atoms on the surface of the metal sample is a control step of the whole pre-hydrogen charging process, but it is difficult to dissociate hydrogen molecules into hydrogen atoms on the surface of the metal sample which is generally used, and the dissociation rate of hydrogen molecules is extremely slow even in a high-pressure hydrogen gas environment.
Therefore, the method for improving the pre-charging hydrogen speed of the metal sample in the hydrogen embrittlement test comprises the following steps:
s1, forming a hydrogen storage alloy film on the surface of the metal sample to obtain a pre-filled hydrogen sample;
and S2, placing the pre-hydrogen filling sample in a hydrogen filling device for pre-filling hydrogen.
According to the invention, the hydrogen storage alloy film is formed on the surface of the metal sample, and the metal sample and the hydrogen storage alloy film are jointly used as the pre-hydrogen charging sample for pre-charging hydrogen, so that on one hand, the hydrogen storage alloy film has a catalytic action of accelerating hydrogen molecules to be dissociated into hydrogen atoms, so that the surface hydrogen atom concentration of the pre-hydrogen charging sample is high, and on the other hand, the hydrogen storage alloy film has an action of absorbing the hydrogen atoms, and the diffusion speed of the hydrogen atoms in the hydrogen storage alloy film is extremely high. Therefore, the high-pressure hydrogen introduced into the hydrogen charging device can be more rapidly decomposed into hydrogen atoms under the action of the hydrogen storage alloy film and can enter the matrix of the metal sample through the interface diffusion of the hydrogen storage alloy film and the metal sample, and further, the invention can effectively improve the pre-charging speed of the metal sample and shorten the pre-charging time.
The hydrogen storage alloy film formed on the surface of the metal sample according to the present invention may be a continuous film or a discontinuous film, that is, the hydrogen storage alloy film may completely cover the metal sample or partially cover the metal sample, and expose a part of the surface of the metal sample. In order to more effectively increase the pre-hydrogen charging speed of the metal sample and shorten the pre-hydrogen charging time, the hydrogen storage alloy film is preferably a continuous film.
In order to make the hydrogen storage alloy film capable of catalyzing the decomposition of hydrogen molecules into hydrogen atoms more rapidly and, at the same time, ensure that the hydrogen atoms are absorbed by the hydrogen storage alloy film and rapidly diffuse into the matrix of the metal sample, the thickness of the hydrogen storage alloy film is preferably 10nm to 30 nm.
The hydrogen storage alloy is classified into a titanium-based hydrogen storage alloy, a zirconium-based hydrogen storage alloy, an iron-based hydrogen storage alloy, a rare earth-based hydrogen storage alloy, and the like, and in the present invention, the hydrogen storage alloy thin film is preferably at least one of a rare earth-based hydrogen storage alloy thin film and a titanium-based hydrogen storage alloy thin film.
Specifically, the general formula of the rare earth hydrogen storage alloy in the rare earth hydrogen storage alloy film is RTxWherein R is selected from at least one of rare earth elements, T is selected from at least one of transition metals, x is more than or equal to 4.5 and less than or equal to 5.5, such as: the rare earth-based hydrogen storage alloy is selected from LaNi5、CeNi5Or PrNi5.3And the like. The general formula of the titanium hydrogen storage alloy in the titanium hydrogen storage alloy film is MTyWherein M is selected from Ti or Ti and Zr, T is selected from at least one of Fe, Ni, V, Cr and Mn, y is more than or equal to 0.8 and less than or equal to 1.2, or y is more than or equal to 1.8 and less than or equal to 2.4, such as: the titanium-based hydrogen storage alloy is selected from TiNi and Ti (MnCr)2、TiFe、TiFe0.83Or Ti0.9Zr0.1Cr1.2Mn0.8And the like.
In step S1, the hydrogen storage alloy thin film may be formed on the surface of the metal sample by deposition or coating.
Furthermore, the invention preferably adopts a magnetron sputtering method or a thermal plasma physical vapor deposition method to deposit on the surface of the metal sample to form the hydrogen storage alloy film.
In the specific deposition process of the magnetron sputtering method, a smelting method can be adopted to prepare the single element into the hydrogen storage alloy, and then the hydrogen storage alloy is taken as a target material to deposit on the surface of the metal sample to obtain a hydrogen storage alloy film; or, the simple substance element metal is directly used as the target material, in the magnetron sputtering process, the simple substance element firstly forms hydrogen storage alloy, and the hydrogen storage alloy is deposited on the surface of the metal sample to obtain the hydrogen storage alloy film.
Such as: when the hydrogen storage alloy is used as a target material and an ultrahigh vacuum multi-target magnetron sputtering system is adopted to deposit a hydrogen storage alloy film, a smelting method is firstly adopted to prepare TiNi and Ti (MnCr)2、TiFe、CeNi5、LaNi5After hydrogen storage alloy is used as a target material, the target material is placed in a target material base, and TiNi and Ti (MnCr) with the thickness of 10nm-30nm are obtained through deposition2、TiFe、CeNi5、LaNi5And the like.
When the hydrogen storage alloy film is deposited by using the ultrahigh vacuum multi-target magnetron sputtering system by taking elemental metal as a target material, the elemental metal such as Ti, Ni, Ti, Mn, Cr, Ti, Fe, Ce, Ni, La, Ni and the like is directly and respectively taken as the target material to be placed in a target material base, and TiNi and Ti (MnCr) with the thickness of 10nm-30nm are obtained by deposition2、TiFe、CeNi5、LaNi5And the like.
In the specific deposition process of the thermal plasma physical vapor deposition method, a smelting method can be adopted to prepare the single element into the hydrogen storage alloy, then the hydrogen storage alloy is crushed into powder, the hydrogen storage alloy powder is taken as the raw material of the thermal plasma physical vapor deposition, and the hydrogen storage alloy film is obtained by deposition on the surface of the metal sample; or, the simple substance element metal is directly used as the raw material, in the thermal plasma physical vapor deposition process, the simple substance element firstly forms the hydrogen storage alloy, and the hydrogen storage alloy is deposited on the surface of the metal sample to obtain the hydrogen storage alloy film.
Such as: when the hydrogen storage alloy is used as a raw material and a thermal plasma physical vapor deposition hydrogen storage alloy film is adopted, a smelting method is firstly adopted to prepare TiNi and Ti (MnCr)2、TiFe、CeNi5、LaNi5The hydrogen storage alloy is crushed into powder by adopting a ball milling method, the hydrogen storage alloy powder is taken as a raw material for thermal plasma physical vapor deposition, and Ar-H is carried out2Depositing hydrogen storage alloy on the surface of the metal sample by thermal plasma physical vapor deposition method to obtain TiNi and Ti (MnCr) with the thickness of 10nm-30nm2、TiFe、CeNi5、LaNi5And the like.
When the hydrogen storage alloy film is subjected to physical vapor deposition by adopting thermal plasma, elemental metal powders such as Ti powder, Ni powder, Ti powder, Mn powder, Cr powder, Ti powder, Fe powder, Ce powder, Ni powder, La powder, Ni powder and the like are directly used as raw material powders, and Ar-H is introduced into the raw material powders2Forming hydrogen storage alloy in the thermal plasma region, and depositing the hydrogen storage alloy on the surface of the metal sample to obtain TiNi and Ti (MnCr) with the thickness of 10-30 nm2、TiFe、CeNi5、LaNi5And the like.
In addition, the surface of the metal sample is easily contaminated by oxides generated by oxidation or other substances, and a high barrier is formed for hydrogen atoms to enter the inside of the matrix of the metal sample, so that the oxidation layer and the contamination layer also prevent the hydrogen atoms from diffusing from the surface of the metal sample to enter the inside of the matrix.
Therefore, before the hydrogen storage alloy film is formed on the surface of the metal sample, the method also comprises the step of pretreating the metal sample, wherein the pretreatment method comprises sanding and/or ultrasonic cleaning to remove an oxidation layer and a pollution layer, so that the oxidation layer and the pollution layer are prevented from hindering hydrogen atoms from diffusing from the surface of the metal sample to enter the matrix, the pre-hydrogen filling speed of the metal sample can be further improved, and the pre-hydrogen filling time is shortened.
In one embodiment, the surface of the metal sample is sequentially sanded and ultrasonically cleaned, and then a hydrogen storage alloy film is formed on the surface of the metal sample, so as to obtain a pre-hydrogen-filled sample.
Optionally, during ultrasonic cleaning, the metal sample is subjected to ultrasonic cleaning for 20min by using acetone and ethanol, and then is dried.
In step S2, in the step of pre-charging the pre-charged hydrogen sample in the hydrogen charging device, the pre-charged hydrogen sample is first placed in the hydrogen charging device, sealed and then pumped to vacuum, for example, 10%-2Pa, removing impurity gas in the hydrogen filling device, then introducing high-pressure hydrogen of 30MPa-70MPa, and keeping the pressure at the temperature of 25-200 ℃ for 50-200 hours.
It will be appreciated that the high pressure hydrogen of from 30MPa to 70MPa may be provided by a compressor.
Therefore, the method of the invention can effectively improve the pre-hydrogen filling speed of the metal sample, shorten the pre-hydrogen filling time and basically not damage the metal sample.
Hereinafter, the method for increasing the pre-charging hydrogen rate of the metal sample in the hydrogen embrittlement test will be further described by the following specific examples.
Example 1:
processing S304 stainless steel into a sample with the diameter of 10mm and the thickness of 2mm, removing machining pollutants on the surface of the sample by using sand paper, then ultrasonically cleaning the sample by using acetone and ethanol for 20min, drying the sample, and putting the sample into a vacuum chamber of a magnetron sputtering system after drying.
Method for preparing CeNi by smelting5Hydrogen storage alloy, and preparing into alloy target material, and then placing the target material in a target material base.
Adopting high-purity argon with the volume fraction of 99.999 percent as working atmosphere to deposit CeNi on the surface of a sample5Depositing hydrogen storing alloy film for 30min with CeNi5The thickness of the hydrogen storage alloy film was 12nm, and a hydrogen pre-charging sample was obtained.
Placing the sample without the deposited hydrogen storage alloy film and the pre-hydrogen-charging sample with the deposited hydrogen storage alloy film in a hydrogen charging device at the same time, sealing and vacuumizing to 10 DEG-2Pa, removing impurity gas in the cavity of the hydrogen charging device, introducing 50MPa high-pressure hydrogen through a compressor, and maintaining the pressure at 150 ℃ for 120 hours.
And (3) carrying out thermal desorption spectrum test on the sample subjected to hydrogen pre-charging and the pre-charged hydrogen sample, wherein the results are as follows: the hydrogen content in the hydrogen pre-charging sample deposited with the hydrogen storage alloy film is improved by 21 percent compared with the sample without the hydrogen storage alloy film. Therefore, the hydrogen storage alloy film is deposited and formed on the surface of the metal sample, so that the pre-hydrogen charging speed of the metal sample can be effectively improved, and the pre-hydrogen charging time is shortened.
Example 2:
processing S316 stainless steel into a sample with the diameter of 10mm and the thickness of 2mm, removing mechanical processing pollutants on the surface of the sample by using sand paper, then performing ultrasonic cleaning on the sample by using acetone and ethanol for 20min, and drying the sample.
And (3) putting the sample into a vacuum chamber of a magnetron sputtering system, and simultaneously, respectively putting the sample into two target material bases by using metal Ti and metal Ni as target materials.
And (3) depositing a TiNi hydrogen storage alloy film on the surface of the sample by using high-purity argon with the volume fraction of 99.999% as a working atmosphere, wherein the deposition time is 40min, and the thickness of the TiNi hydrogen storage alloy film is 15nm to obtain a pre-hydrogen charging sample.
Placing the hydrogen pre-charging sample deposited with the hydrogen storage alloy film in a hydrogen charging device, sealing, and vacuumizing to 10 DEG-2Pa, removing impurity gas in the cavity of the hydrogen charging device, introducing 50MPa high-pressure hydrogen through a compressor, and maintaining the pressure at 150 ℃ for 90 hours.
And (3) carrying out thermal desorption spectrum test on the pre-filled hydrogen sample after pre-filled hydrogen is completed, wherein the result is as follows: the hydrogen content in the hydrogen pre-charged sample was substantially close to that of the sample of example 1 in which the hydrogen storage alloy thin film was not deposited after charging for 120 hours. It can be seen that the hydrogen charging time of the hydrogen pre-charged sample on which the hydrogen storage alloy thin film is deposited is shortened by 30 hours.
Example 3:
processing S30408 stainless steel into a sample with a diameter of 10mm and a thickness of 2mm, removing mechanical processing pollutants of the sample by using sand paper, then performing ultrasonic cleaning on the sample by using acetone and ethanol for 20min, and drying the sample.
Preparation of Ti by smelting method0.9Zr0.1Cr1.2Mn0.8Hydrogen storing alloy, ball milling to obtain powder, and mixing with Ti0.9Zr0.1Cr1.2Mn0.8The hydrogen storage alloy powder is a raw material for thermal plasma physical vapor deposition by Ar-H2Thermal plasma physical vapor deposition method for depositing Ti0.9Zr0.1Cr1.2Mn0.8The hydrogen storage alloy is deposited on the surface of the sample for 1 minute, Ti0.9Zr0.1Cr1.2Mn0.8The thickness of the hydrogen absorbing alloy was 19nm, and a hydrogen pre-charged sample was obtained.
Placing the sample without the deposited hydrogen storage alloy film and the pre-hydrogen-charging sample with the deposited hydrogen storage alloy film in a hydrogen charging device at the same time, sealing and vacuumizing to 10 DEG-2Pa, removing impurity gas in the cavity of the hydrogen charging device, introducing 60MPa high-pressure hydrogen through a compressor, and maintaining the pressure at 120 ℃ for 100 hours.
And (3) carrying out thermal desorption spectrum test on the sample subjected to hydrogen pre-charging and the pre-charged hydrogen sample, wherein the results are as follows: the hydrogen content in the hydrogen pre-charging sample deposited with the hydrogen storage alloy film is improved by 23 percent compared with the sample without the hydrogen storage alloy film. Therefore, the hydrogen storage alloy film is deposited and formed on the surface of the metal sample, so that the pre-hydrogen charging speed of the metal sample can be effectively improved, and the pre-hydrogen charging time is shortened.
Example 4:
s310 stainless steel is processed into a sample with the diameter of 10mm and the thickness of 2mm, mechanical processing pollutants of the sample are removed by sand paper, then the sample is subjected to ultrasonic cleaning for 20min by acetone and ethanol, and then the sample is dried.
Simultaneously adopts Ti powder and Fe powder as raw materials for thermal plasma physical vapor deposition through Ar-H2Forming a TiFe hydrogen storage alloy by a thermal plasma physical vapor deposition method and depositing the TiFe hydrogen storage alloy on the surface of the sample, wherein the deposition time is 1 minute, and the thickness of the TiFe hydrogen storage alloy film is 15nm to obtain a pre-hydrogen-filled sample.
Placing the hydrogen pre-charging sample deposited with the hydrogen storage alloy film in a hydrogen charging device, sealing, and vacuumizing to 10 DEG-2Pa, removing impurity gas in the cavity of the hydrogen charging device, introducing 60MPa high-pressure hydrogen through a compressor, and maintaining the pressure at 120 ℃ for 75 hours.
And (3) carrying out thermal desorption spectrum test on the pre-filled hydrogen sample after the pre-filled hydrogen is completed, wherein the result is as follows: the hydrogen content in the hydrogen pre-charged sample was substantially close to that of the sample of example 3 in which the hydrogen storage alloy thin film was not deposited after charging hydrogen for 100 hours. It can be seen that the hydrogen charging time of the hydrogen pre-charged sample on which the hydrogen storage alloy thin film is deposited is shortened by 25 hours.
Example 5:
processing S304 stainless steel into a sample with the diameter of 10mm and the thickness of 2mm, removing machining pollutants on the surface of the sample by using sand paper, then ultrasonically cleaning the sample by using acetone and ethanol for 20min, drying the sample, and putting the sample into a vacuum chamber of a magnetron sputtering system after drying.
PrNi is prepared by adopting a smelting method5.3Hydrogen-absorbing alloy and TiFe0.83Hydrogen storage alloy, and preparing into alloy target materials, and placing the two target materials in different target material bases respectively.
Adopting high-purity argon with the volume fraction of 99.999 percent as working atmosphere to deposit PrNi on the surface of a sample5.3/TiFe0.83The deposition time of the hydrogen storage alloy film is 20min, PrNi5.3/TiFe0.83The thickness of the hydrogen storage alloy film was 21nm, and a hydrogen precharge sample was obtained.
Placing the sample without the deposited hydrogen storage alloy film and the pre-hydrogen-charging sample with the deposited hydrogen storage alloy film in a hydrogen charging device at the same time, sealing and vacuumizing to 10 DEG-2Pa, removing impurity gas in the cavity of the hydrogen charging device, introducing 70MPa high-pressure hydrogen through a compressor, and maintaining the pressure at 100 ℃ for 90 hours.
And (3) carrying out thermal desorption spectrum test on the sample subjected to hydrogen pre-charging and the pre-charged hydrogen sample, wherein the results are as follows: the hydrogen content in the hydrogen pre-charging sample deposited with the hydrogen storage alloy film is improved by 27 percent compared with the sample without the hydrogen storage alloy film. Therefore, the hydrogen storage alloy film is deposited and formed on the surface of the metal sample, so that the pre-hydrogen charging speed of the metal sample can be effectively improved, and the pre-hydrogen charging time is shortened.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A method for improving the pre-hydrogen filling speed of a metal sample in a hydrogen embrittlement test is characterized by comprising the following steps:
forming a hydrogen storage alloy film on the surface of the metal sample to obtain a pre-hydrogen filling sample; and
and placing the pre-hydrogen filling sample in a hydrogen filling device for pre-filling.
2. The method for increasing the pre-charging hydrogen rate of a metal sample in the hydrogen embrittlement test according to claim 1, wherein the thickness of the hydrogen storage alloy thin film is 10nm to 30 nm.
3. The method for increasing the pre-charging hydrogen rate of a metal sample in the hydrogen embrittlement test according to claim 1, wherein the hydrogen storage alloy thin film is a continuous thin film, or the hydrogen storage alloy thin film is a discontinuous thin film.
4. The method for increasing the pre-charging hydrogen rate of a metal sample in the hydrogen embrittlement test according to claim 1, wherein the hydrogen storage alloy thin film is at least one selected from a rare earth-based hydrogen storage alloy thin film and a titanium-based hydrogen storage alloy thin film.
5. The method for increasing the pre-hydrogen charging rate of a metal sample in the hydrogen embrittlement test according to claim 4, wherein the general formula of the rare earth hydrogen storage alloy in the rare earth hydrogen storage alloy thin film is RTxWherein R is selected from at least one of rare earth elements, T is selected from at least one of transition metals, and x is more than or equal to 4.5 and less than or equal to 5.5.
6. The method for increasing the pre-charging hydrogen rate of the metal sample in the hydrogen embrittlement test according to claim 4, wherein the general formula of the titanium-based hydrogen storage alloy in the titanium-based hydrogen storage alloy film is MTyWherein M is selected from Ti or Ti and Zr, T is selected from at least one of Fe, Ni, V, Cr and Mn, and y is more than or equal to 0.8 and less than or equal to 1.2, or y is more than or equal to 1.8 and less than or equal to 2.4.
7. The method for increasing the pre-charging hydrogen rate of a metal sample in the hydrogen embrittlement test according to any one of claims 1 to 6, wherein the hydrogen storage alloy thin film is formed on the surface of the metal sample by deposition or coating.
8. The method for increasing the pre-charging hydrogen rate of the metal sample in the hydrogen embrittlement test according to claim 7, wherein the hydrogen storage alloy film is formed by depositing on the surface of the metal sample by a magnetron sputtering method or a thermal plasma physical vapor deposition method.
9. The method for increasing the pre-charging hydrogen rate of a metal sample in the hydrogen embrittlement test according to claim 7, further comprising performing a pre-treatment on the metal sample before the hydrogen storage alloy thin film is formed on the surface of the metal sample, wherein the pre-treatment comprises sanding and/or ultrasonic cleaning.
10. The method for increasing the pre-charging hydrogen rate of the metal sample in the hydrogen embrittlement test according to any one of claims 1 to 6, wherein the pre-charging hydrogen step is performed under vacuum, high pressure hydrogen gas of 30MPa to 70MPa is introduced, and pressure is maintained at a temperature of 25 ℃ to 200 ℃ for 50 hours to 200 hours.
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