Method for evaluating hydrogen electric drive removal rate in metal

Abstract

The invention discloses a method for evaluating the hydrogen electric drive removal rate in metal. The method comprises the following steps: obtaining two pieces of metal with the same deuterium content by adopting an isotopic tracer method; the method comprises the following steps: carrying out electric driving treatment on a piece of deuterium-containing metal at room temperature, and removing deuterium in the metal to obtain the metal subjected to electric driving treatment; respectively carrying out temperature programming desorption treatment on the metal subjected to electric driving treatment and another deuterium-containing metal which is not subjected to electric driving treatment, so that deuterium in the metal is completely desorbed, detecting the desorbed deuterium content through mass spectrometry, and recording the desorbed deuterium content as a first total desorption amount and a second total desorption amount; and according to the first total desorption amount and the second total desorption amount, the hydrogen electric drive removal rate in the metal at the room temperature is evaluated. According to the method, the air background hydrogen signal interference can be eliminated by adopting an isotopic tracing experiment method in which hydrogen is replaced by deuterium, mass-to-charge ratio analysis is carried out on substance molecules through mass spectrometry, and a deuterium desorption signal can be accurately detected, so that the accuracy of room-temperature electrically-driven removal rate evaluation is ensured.

Description

Technical Field

[0001] The invention relates to the field of hydrogen embrittlement, and in particular to a method for evaluating the electrically driven removal rate of hydrogen in metals. Background Art

[0002] Hydrogen is widely present in nature in various forms such as water, hydrogen gas, and organic molecules. Due to its small atomic size, easy diffusion, and extremely active chemical properties, hydrogen has a significant affinity with metal atoms. During the preparation, processing, and use of metal materials, hydrogen tends to penetrate into the metal and remain in defects such as lattice gaps, dislocations, grain boundaries, and vacancies. This retention of hydrogen not only causes cracks and hydrogen embrittlement in the metal, destroying the integrity of metal components, but also aggravates the degree of corrosion of the metal during use. Therefore, effectively removing hydrogen from metals is crucial to preventing hydrogen-induced metal damage.

[0003] At present, the traditional method of removing hydrogen is mainly high-temperature thermal desorption, but this method is prone to cause phase change, oxidation and structural deformation of metals. To avoid these problems, it is necessary to find a method of removing hydrogen at relatively low temperatures or even at room temperature. Experiments have found that the electric drive method can achieve the effect of removing hydrogen from metals at room temperature.

[0004] For the measurement of hydrogen content in metals, oxygen, nitrogen and hydrogen analyzers are usually used. This method has problems such as strong interference from the background signal of environmental hydrogen and large measurement errors, which leads to inaccurate evaluation of the effect of electrically driven hydrogen removal. Therefore, although electrically driven technology in solution is expected to achieve room temperature hydrogen removal, we still cannot accurately evaluate the hydrogen removal rate due to the lack of highly sensitive detection methods.

[0005] Therefore, it is necessary to develop non-high-temperature hydrogen removal technologies with excellent effects and to explore methods to more accurately evaluate the hydrogen removal effects. Summary of the invention

[0006] The present invention aims to solve the problem in the prior art that the oxygen, nitrogen and hydrogen analyzer has a large error in detecting hydrogen elements, resulting in inaccurate evaluation of the electric-driven hydrogen removal effect. The present invention can accurately detect the deuterium content by adopting hydrogen isotope tracing, programmed temperature desorption and mass spectrometry detection experimental methods, thereby ensuring the accuracy of evaluating the electric-driven hydrogen removal rate.

[0007] The technical method of the present invention is as follows:

[0008] A method for evaluating the electric drive removal rate of hydrogen in metal, the method comprising: A1. using an isotope tracer method to obtain two pieces of metal with the same deuterium content; A2. at room temperature, electrically driving a piece of deuterium-containing metal to remove deuterium from the metal to obtain the metal after the electric drive treatment; A3. performing a programmed temperature desorption treatment on the metal after the electric drive treatment to completely desorb the deuterium in the metal, and detecting the desorbed deuterium content by mass spectrometry, which is recorded as the first desorption total amount S1; A4. performing a programmed temperature desorption treatment on another piece of deuterium-containing metal that has not been electrically driven to completely desorb the deuterium in the metal, and detecting the desorbed deuterium content by mass spectrometry to record it as the second desorption total amount S2; A5. evaluating the electric drive removal rate of hydrogen in the metal at room temperature based on the first desorption total amount S1 and the second desorption total amount S2. Here, since hydrogen and deuterium have the same electric drive response behavior, deuterium is used to evaluate the hydrogen removal rate.

[0009] Specifically, step A3 includes: heating the metal after the electric drive treatment from room temperature to 700-880°C to completely desorb the deuterium in the metal, and detecting the desorbed deuterium content by mass spectrometry; drawing a desorption curve based on the deuterium desorption intensity data corresponding to different temperatures, and calculating the first desorption total amount S1.

[0010] In step A3, the heating rate from room temperature to 700-880° C. is 2-15° C. / min, and the heating time is 50-415 min.

[0011] Specifically, the electric drive process includes: using a deuterium-containing metal as an anode; placing the anode and a cathode in an electrolyte; applying a voltage between the anode and the cathode to remove deuterium from the metal.

[0012] Furthermore, the electrolyte includes a liquid electrolyte, a solid electrolyte or a gel electrolyte.

[0013] Furthermore, the applied voltage is 0.3 to 1.2 V; and the voltage is applied for 0.5 to 48 h.

[0014] Furthermore, the material of the cathode includes one or more of platinum, palladium, nickel, titanium, molybdenum, silver or their alloys, carbon materials or their composite materials.

[0015] Specifically, step A4 includes: heating another piece of deuterium-containing metal that has not been electrically driven from room temperature to 700-880°C to desorb deuterium from the metal, and detecting the desorbed deuterium content by mass spectrometry; drawing a desorption curve based on the deuterium desorption intensity data corresponding to different temperatures, and calculating the second desorption total amount S2.

[0016] In step A4, the heating rate from room temperature to 700-880° C. is 2-15° C. / min, and the heating time is 50-415 min.

[0017] Specifically, step A5 includes: calculating the deuterium removal rate by formula (1) to evaluate the hydrogen electric driven removal rate in the metal;

[0018] S = (S2 - S1) / S2 * 100% (1).

[0019] Compared with the prior art, the present invention has the following beneficial effects: the method of the present invention includes isotope tracing of deuterium replacing hydrogen, accurately measuring the deuterium content in the electrically driven treated metal and the metal not electrically driven treated by programmed temperature desorption and mass spectrometry detection methods, calculating the first desorption total amount S1 corresponding to the metal after the electrically driven deuterium removal and the second desorption total amount S2 corresponding to the deuterium-containing metal not electrically driven, calculating the deuterium removal rate based on the first desorption total amount S1 and the second desorption total amount S2 to evaluate the electrically driven removal rate of hydrogen in the metal, and since hydrogen is widely present in water vapor and hydrogen in the air, the isotope tracing experimental method of replacing hydrogen with deuterium can eliminate the interference of the air background hydrogen signal, and then performing mass-to-charge ratio analysis of the material molecules by mass spectrometry can accurately detect the signal of the desorbed deuterium in real time, thereby ensuring the accuracy of the room temperature electrically driven removal rate evaluation. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 The programmed temperature thermal desorption spectrum of Example 1 shown in the embodiment of the present invention;

[0021] Figure 2 The programmed temperature thermal desorption spectrum of Example 2 shown as an example of the present invention. DETAILED DESCRIPTION

[0022] The technical solution of the present invention is described clearly and completely below in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0023] In the description of the present invention, the terms “first” and “second” are only used for descriptive purposes and should not be understood as indicating or implying relative importance.

[0024] In addition, the technical features involved in the different embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0025] In one exemplary embodiment, a method for evaluating electrically driven removal of hydrogen from a metal is provided, the method comprising:

[0026] A1. Use the isotope tracer method to obtain two pieces of metal with the same deuterium content.

[0027] The metal includes one or more of iron, steel, stainless steel, nickel, cobalt, aluminum, magnesium, zirconium, tungsten, titanium, molybdenum, tantalum, niobium, rare earth metals or their alloys.

[0028] The two pieces of deuterium-containing metal have the same size and the method of introducing deuterium is the same.

[0029] Specifically, the steps of the isotope tracer method include: placing the metal in a cavity, evacuating the cavity, introducing deuterium, heating the cavity, and finally cooling the cavity to obtain a deuterated metal. Here, the evacuation pressure is less than 1×10 -3 Pa. The pressure of deuterium introduced is 10-500KPa. The heating temperature is 50-130℃ and the heating time is 20-28h.

[0030] Optionally, the cooling is natural cooling, and the cooling time may be 20 to 24 hours.

[0031] A2. At room temperature, a piece of deuterium-containing metal is electrically driven to remove deuterium from the metal and obtain the electrically driven metal.

[0032] Among them, the high-temperature driven removal of hydrogen in the prior art easily leads to problems such as metal structure deformation and chemical composition changes. However, the normal temperature electric drive method is used to remove hydrogen, ensuring that the metal structure and chemical composition do not change. At the same time, electric drive removal of hydrogen at room temperature can reduce energy consumption. Here, by controlling and optimizing parameters such as voltage and solution, the ideal hydrogen removal effect can be achieved.

[0033] Specifically, the electric drive process includes: using a deuterium-containing metal as an anode; placing the anode and a cathode in an electrolyte; applying a voltage between the anode and the cathode to remove deuterium from the metal.

[0034] Among them, the electrolyte includes a liquid electrolyte, a solid electrolyte or a gel electrolyte. Here, the liquid electrolyte includes an aqueous electrolyte or an oily electrolyte. The liquid electrolyte is an acidic electrolyte, an alkaline electrolyte or a neutral electrolyte. The acidic electrolyte includes a sulfuric acid solution or a polymer electrolyte. The alkaline solution includes a sodium hydroxide solution or a polymer electrolyte. The neutral solution includes a sodium chloride solution or a polymer electrolyte. The solid electrolyte is Nafion. The gel electrolyte is PVA / KOH. Here, the liquid electrolyte can be applied to scenarios where hydrogen problems occur in liquid environments, such as nuclear power plants, pipelines in oil and gas exploration, etc. The solid electrolyte can be applied to various metal parts exposed to hydrogen isotope environments. The gel electrolyte is located between the solid phase and the liquid phase, has good flexibility, and can fit metals of different shapes. Here, the shape may include regular shapes and irregular shapes.

[0035] Under the combined action of electrolyte and voltage, the present invention diffuses strongly adsorbed hydrogen in the metal to the metal surface and into the solution, significantly improving the hydrogen dehydrogenation rate. Here, strongly adsorbed hydrogen refers to hydrogen retained in the lattice gap and accumulated in defects such as dislocations, grain boundaries, and vacancies.

[0036] Here, the voltage can promote the hydrogen in the metal to leave the metal and enter the solution through oxidation reaction. The applied voltage is 0.3 to 1.2V; the applied voltage time is 0.5 to 48 hours. For example, the voltage is 0.4V, 0.6V, 0.8V, 1.0V. The applied voltage time can be 5h, 15h, 20h.

[0037] Among them, hydrogen in the metal can be removed by continuously applying a voltage of 0.3 to 1.2 V for 0.5 to 48 hours.

[0038] The cathode is one or more of platinum, palladium, nickel, titanium, molybdenum, silver or their alloys, carbon materials or their composite materials. These metals have good chemical stability and corrosion resistance, and can ensure that they do not react in the electrolyte.

[0039] Here, since hydrogen, deuterium and tritium are isotopes and have the same electrically driven response behavior, the electrically driven hydrogen removal method is also applicable to deuterium and tritium.

[0040] A3. Performing a programmed temperature desorption treatment on the metal after the electric drive treatment to completely desorb the deuterium in the metal, and detecting the desorbed deuterium content by mass spectrometry, which is recorded as the first desorption total amount S1.

[0041] Specifically, step A3 includes: heating the metal after the electric drive treatment from room temperature to 700-880°C to completely desorb the deuterium in the metal, and detecting the desorbed deuterium content by mass spectrometry; drawing a desorption curve according to the deuterium desorption intensity data corresponding to different temperatures, and calculating the first desorption total amount S1. Here, the desorption curve is drawn for the deuterium desorption intensity data corresponding to different temperatures, and the area is integrated to calculate the first desorption total amount S1.

[0042] In step A3, the heating rate from room temperature to 700-880°C is 2-15°C / min, and the heating time is 50-415min. For example, the heating rate may be 4°C / min, 10°C / min, or 11°C / min. The heating time may be 85min, 200min, or 300min.

[0043] Specifically, from room temperature to 600°C, the remaining deuterium in the metal after the electric drive treatment will gradually be removed from the metal. From 600°C to 700°C or even higher temperatures such as 880°C, no deuterium is desorbed from the metal. Therefore, the temperature desorption from room temperature to 700-880°C ensures that deuterium is completely separated from the metal. At the same time, the desorption amount is measured in real time by mass spectrometry, thereby ensuring that the measured first desorption amount is accurate. Furthermore, the mass spectrometer is a highly sensitive and high-precision mass spectrometer.

[0044] The deuterium-containing metal is evacuated to a pressure less than 5×10 -5 Pa, and then perform programmed temperature desorption treatment.

[0045] Optionally, compared to the oxygen, nitrogen and hydrogen analyzer in the prior art, which detects deuterium elements but cannot distinguish between hydrogen and deuterium signals, there are problems such as strong background interference and signal superposition that lead to huge measurement errors. The present invention adopts programmed temperature removal mass spectrometry detection technology, which can accurately distinguish hydrogen and deuterium elements based on molecular mass differences, reduce measurement errors and improve detection sensitivity. Compared with the hydrogen content detection line of 1appm measured by the oxygen, nitrogen and hydrogen analyzer in the prior art, the hydrogen content detection line of this method is 0.02appm, and the detection accuracy performance is high.

[0046] A4. Perform a programmed temperature desorption process on another piece of deuterium-containing metal that has not been electrically driven to completely desorb the deuterium in the metal, and detect the desorbed deuterium content by mass spectrometry to record it as the second desorption total amount S2.

[0047] Specifically, step A4 includes: heating another piece of deuterium-containing metal that has not been electrically driven from room temperature to 700-880°C to desorb deuterium from the metal, and detecting the desorbed deuterium content by mass spectrometry; drawing a desorption curve based on the deuterium desorption intensity data corresponding to different temperatures, and calculating the second desorption total amount S2. Here, the desorption curve is drawn for the deuterium desorption intensity data corresponding to different temperatures, and the area is integrated to calculate the first desorption total amount S2.

[0048] Specifically, from room temperature to 600°C, deuterium will gradually come out of the metal, and from 600°C to 700-880°C, no deuterium will be desorbed from the metal. Therefore, the programmed temperature desorption from room temperature to 700-880°C ensures that deuterium is completely separated from the metal, thereby ensuring that the second total desorption amount measured is accurate. At the same time, the desorption amount is measured in real time by mass spectrometry, thereby ensuring that the second total desorption amount measured is accurate. Further, the mass spectrometer is a highly sensitive and high-precision mass spectrometer.

[0049] In step A4, the heating rate from room temperature to 700-880°C is 2-15°C / min, and the heating time is 50-415min. For example, the heating rate may be 4°C / min, 10°C / min, or 11°C / min. The heating time may be 85min, 200min, or 300min.

[0050] A5. Based on the first desorption amount and the second desorption amount, the electrically driven removal rate of hydrogen in the metal at room temperature is evaluated.

[0051] Step A5 includes: calculating the deuterium removal rate by formula (1) to evaluate the hydrogen electrically driven removal rate in the metal.

[0052] S=(S2-S1) / S2*100% (1)

[0053] Here, since hydrogen and deuterium have the same electrical drive response behavior, the calculated deuterium removal rate is the hydrogen removal rate.

[0054] At the same time, by accurately measuring the first desorption amount and the second desorption amount, the deuterium removal rate can be guaranteed to be accurate. Here, the deuterium removal rate is an indicator for evaluating the ability of electrically driven hydrogen removal (here, it refers to the electrically driven removal rate of hydrogen in metals).

[0055] The method of the present invention comprises isotope tracing of replacing hydrogen with deuterium, accurately measuring the deuterium content in the metal treated by electric drive and the metal not treated by electric drive, and then measuring the deuterium content by programmed temperature desorption treatment, calculating a first desorption total amount S1 corresponding to the metal after the deuterium is removed by electric drive and a second desorption total amount S2 corresponding to the deuterium-containing metal not treated by electric drive, and calculating the deuterium removal rate according to the first desorption total amount S1 and the second desorption total amount S2 to evaluate the electric drive removal rate of hydrogen in the metal. Since hydrogen is widely present in water vapor and hydrogen in the air, the isotope tracing experimental method of replacing hydrogen with deuterium can eliminate the interference of air background hydrogen signal, and then the mass-to-charge ratio analysis of the material molecule is performed by mass spectrometry, so that the signal of the desorbed deuterium can be accurately detected in real time, so that the calculated first desorption amount and the second desorption amount are accurate, thereby ensuring the accuracy of the evaluation of the room temperature electric drive removal rate.

[0056] In order to better understand the present invention, the content of the present invention is further explained below with reference to the accompanying drawings and examples, but the content of the present invention is not limited to the following embodiments.

[0057] Example 1

[0058] Step 1: Place two pieces of metal iron samples on a 1×10 -3 500KPa deuterium gas is introduced into the small Pa cavity, heated to 100℃ and kept constant for 24 hours, and two iron samples with the same deuterium content are obtained. Here, the deuterium gas diffuses into the metallic iron sample and is retained.

[0059] Step 2: Based on the programmed temperature thermal desorption technique, a piece of deuterated iron sample from step 1 was placed in a vacuum chamber with a degree of vacuum less than 5×10 -5 The Pa cavity heating stage is heated from 30°C to 880°C at 10°C / min. Deuterium desorbs the sample during the heating process and is detected by a quantitatively calibrated mass spectrometer to obtain a programmed temperature thermal desorption spectrum. The area of ​​the programmed temperature thermal desorption spectrum is integrated to obtain the first total desorption amount.

[0060] Step 3: Use another deuterated iron sample from step 1 as an anode and a platinum sheet as a cathode, immerse the anode and cathode in a sodium hydroxide solution, set a voltage of 0.6 V, and remove hydrogen for 4 hours. The deuterium in the deuterated iron sample diffuses and releases outward, and obtains an electrically driven deuterated iron sample;

[0061] Step 4: Based on the programmed temperature thermal desorption technique, the deuterated iron sample treated by electric drive was placed in a vacuum chamber with a degree of less than 5×10 -5 The Pa cavity heating stage is heated from 30°C to 880°C at 10°C / min. Deuterium desorbs the sample during the heating process and is detected by a quantitatively calibrated mass spectrometer to obtain a programmed temperature thermal desorption spectrum. The area of ​​the programmed temperature thermal desorption spectrum is integrated to obtain the second desorption total amount. 1#-The desorption total amount of the sample after the electric drive treatment; 2#-The desorption total amount of the sample without the electric drive treatment is referenced Figure 1 ;

[0062] Step 5: Based on the first desorption amount and the second desorption amount, using formula (1), it is estimated that the hydrogen electrically driven removal efficiency in the metal is 76.5%.

[0063] Example 2

[0064] Step 1: Place two pieces of zirconium-niobium alloy on a 1×10 -3 500KPa deuterium gas was introduced into the small Pa cavity, heated to 100℃ and kept at a constant temperature for 24 hours, and two zirconium-niobium alloy samples with the same deuterium content were obtained. Here, the deuterium gas diffused into the metallic iron sample and was retained.

[0065] Step 2: Based on the programmed temperature thermal desorption technology, a piece of deuterium-containing zirconium-niobium alloy sample from step 1 is placed in a vacuum chamber with a degree of less than 5×10 -5 The Pa cavity heating stage is heated from 30°C to 880°C at 10°C / min. Deuterium desorbs the sample during the heating process and is detected by a quantitatively calibrated mass spectrometer to obtain a programmed temperature thermal desorption spectrum. The area of ​​the programmed temperature thermal desorption spectrum is integrated to obtain the first total desorption amount.

[0066] Step 3: another deuterium-containing zirconium-niobium alloy sample in step 1 is used as an anode, and a platinum sheet is used as a cathode. The anode and the cathode are immersed in a sodium hydroxide solution, and a voltage of 0.6 V is set. The deuterium removal working time is 4 hours. The deuterium in the deuterium-containing zirconium-niobium alloy sample diffuses and releases outward, and a deuterium-containing zirconium-niobium alloy sample treated by electric drive is obtained;

[0067] Step 4: Based on the programmed temperature thermal desorption technology, the deuterium-containing zirconium-niobium alloy sample treated by electric drive is placed in a vacuum of less than 5×10 -5 The Pa cavity heating stage is heated from 30°C to 880°C at 10°C / min. Deuterium desorbs the sample during the heating process and is detected by a quantitatively calibrated mass spectrometer to obtain a programmed temperature thermal desorption spectrum. The area of ​​the programmed temperature thermal desorption spectrum is integrated to obtain the second desorption total amount; 1#-the desorption total amount of the sample after the electric drive treatment; 2#-the desorption total amount of the sample without the electric drive treatment is referenced Figure 2 .

[0068] Step 5: Based on the first desorption amount and the second desorption amount, using formula (1), it is estimated that the hydrogen electric driven removal efficiency in the metal is 68.8%.

[0069] Comparative Example 1

[0070] Step 1: Place two pieces of metal iron samples on a 1×10 -3 500KPa deuterium gas is introduced into the small Pa cavity, heated to 100℃ and kept constant for 24 hours, and two iron samples with the same deuterium content are obtained. Here, the deuterium gas diffuses into the metallic iron sample and is retained.

[0071] Step 2: Based on the programmed temperature thermal desorption technique, a piece of deuterated iron sample from step 1 was placed in a vacuum chamber with a degree of vacuum less than 5×10 -5 The Pa cavity heating stage is heated from 30°C to 880°C at 10°C / min. Deuterium desorbs the sample during the heating process and is detected by a quantitatively calibrated mass spectrometer to obtain a programmed temperature thermal desorption spectrum. The area of ​​the programmed temperature thermal desorption spectrum is integrated to obtain the first total desorption amount.

[0072] Step 3: Use another deuterated iron sample from step 1 as an anode and a platinum sheet as a cathode, immerse the anode and cathode in a sodium hydroxide solution, set a voltage of 0.1 V, and remove hydrogen for 4 hours. The deuterium in the deuterated iron sample diffuses and releases outward, and obtains an electrically driven deuterated iron sample;

[0073] Step 4: Based on the programmed temperature thermal desorption technique, the deuterated iron sample treated by electric drive was placed in a vacuum chamber with a degree of less than 5×10 -5 The Pa cavity heating stage is heated from 30°C to 880°C at 10°C / min. Deuterium desorbs the sample during the heating process and is detected by a quantitatively calibrated mass spectrometer to obtain a programmed temperature thermal desorption spectrum. The area of ​​the programmed temperature thermal desorption spectrum is integrated to obtain the second desorption total amount.

[0074] Step 5: Based on the first desorption amount and the second desorption amount, using formula (1), it is estimated that the hydrogen electrically driven removal rate in the metal is 0.0%.

[0075] Comparative Example 2

[0076] Step 1: Place two pieces of metal iron samples on a 1×10 -3 500KPa deuterium gas is introduced into the small Pa cavity, heated to 100℃ and kept constant for 24 hours, and two iron samples with the same deuterium content are obtained. Here, the deuterium gas diffuses into the metallic iron sample and is retained.

[0077] Step 2: Use an oxygen, nitrogen and hydrogen analyzer to detect a piece of deuterated iron sample from step 1. Since it is impossible to distinguish isotopes of hydrogen and deuterium, and there is a lot of hydrogen in the sample and the detection environment, the test result is the total hydrogen and deuterium content of the deuterated iron sample.

[0078] Step 3: Use another deuterated iron sample from step 1 as an anode and a platinum sheet as a cathode, immerse the anode and cathode in a sodium hydroxide solution, set a voltage of 0.6 V, and remove hydrogen for 4 hours. The deuterium in the deuterated iron sample diffuses and releases outward, and obtains an electrically driven deuterated iron sample;

[0079] Step 4: Use an oxygen, nitrogen and hydrogen analyzer to analyze the content. Since the oxygen, nitrogen and hydrogen analyzer cannot distinguish between hydrogen and deuterium, and there is a lot of hydrogen in the sample and the detection environment, the test result obtains the total hydrogen and deuterium content of the deuterium-containing iron sample treated by electric drive. Therefore, it is evaluated that the electric drive removal rate of hydrogen in the metal is 68.3%.

[0080] The deuterium contents and hydrogen removal rates of Examples 1-2 and Comparative Examples 1-2 are shown in Table 1.

[0081]

[0082]

[0083] As shown in Table 1:

[0084] It can be seen from Comparative Example 1 and Example 1 that the voltages are different, and no electric drive reaction occurs when the voltage is lower than 0.3 V. At the same time, Example 1 also shows that the dehydrogenation effect of the present invention is best when the voltage is 0.3-1.2 V.

[0085] It can be seen from Example 2 and Example 1 that both zirconium-niobium alloy and iron can achieve electrically driven dehydrogenation efficiency.

[0086] It can be seen from Comparative Example 3 and Example 1 that the oxygen, nitrogen and hydrogen analyzer is greatly interfered by the hydrogen signal when measuring deuterium, resulting in low measurement accuracy; if the isotope tracer method is not used and only hydrogen is monitored, the background signal is large due to the widespread existence of hydrogen, and the detection limit can only reach 1 appm. The oxygen, nitrogen and hydrogen analyzer shows a clear disadvantage when detecting samples with low hydrogen and deuterium content, while the isotope tracer combined with thermal desorption mass spectrometry detection technology used in the present invention has a detection limit of 0.02 appm, which is 50 times better than the performance.

[0087] The above specific implementation methods are detailed descriptions of the present invention. It cannot be determined that the specific implementation methods of the present invention are limited to these descriptions. For ordinary technicians in the technical field to which the present invention belongs, several simple deductions and substitutions can be made without departing from the concept of the present invention, which should be regarded as belonging to the protection scope of the present invention.

Claims

1. A method for evaluating the electro-driven removal of hydrogen from a metal, characterized in that: The method comprises: A1. Use the isotope tracer method to obtain two pieces of metal with the same deuterium content; A2. At room temperature, a piece of deuterium-containing metal is electrically driven to remove deuterium from the metal to obtain an electrically driven metal; A3. performing a programmed temperature desorption process on the metal after the electric drive treatment to completely desorb the deuterium in the metal, and detecting the desorbed deuterium content by mass spectrometry, which is recorded as the first desorption total amount S1; A4. performing a programmed temperature desorption process on another piece of deuterium-containing metal that has not been electrically driven to completely desorb the deuterium in the metal, and detecting the desorbed deuterium content by mass spectrometry as the second desorption total amount S2; A5. Based on the first desorption amount S1 and the second desorption amount S2, the electrically driven removal rate of hydrogen in the metal at room temperature is evaluated.

2. The method according to claim 1, characterized in that Step A3 includes: The metal after the electric drive treatment is heated from room temperature to 700-880°C to completely desorb the deuterium in the metal, and the desorbed deuterium content is detected by mass spectrometry; A desorption curve is drawn according to the deuterium desorption intensity data corresponding to different temperatures, and the first desorption total amount S1 is calculated.

3. The method according to claim 2, characterized in that In step A3, the heating rate from room temperature to 700-880° C. is 2-15° C. / min, and the heating time is 50-415 min.

4. The method according to claim 1, characterized in that: Electric drive processing includes: Using a deuterium-containing metal as an anode; placing the anode and cathode in an electrolyte; A voltage is applied between the anode and cathode and deuterium is removed from the metal.

5. The method according to claim 4, characterized in that The electrolyte includes a liquid electrolyte, a solid electrolyte or a gel electrolyte.

6. The method according to claim 4, characterized in that The applied voltage is 0.3 to 1.2 V; the applied voltage time is 0.5 to 48 h.

7. The method according to claim 4, characterized in that The material of the cathode includes one or more of platinum, palladium, nickel, titanium, molybdenum, silver or alloys thereof, carbon materials or composite materials thereof.

8. The method according to claim 1, characterized in that A4 steps include: Another piece of deuterium-containing metal that has not been electrically driven is heated from room temperature to 700-880°C to desorb deuterium from the metal, and the desorbed deuterium content is detected by mass spectrometry; A desorption curve is drawn according to the deuterium desorption intensity data corresponding to different temperatures, and the second desorption total amount S2 is calculated.

9. The method according to claim 8, characterized in that In step A4, the heating rate from room temperature to 700-880° C. is 2-15° C. / min, and the heating time is 50-415 min.

10. The method according to claim 1, characterized in that A5 steps include: The deuterium removal rate was calculated by formula (1) to evaluate the hydrogen electrically driven removal rate in metals; S = (S2 - S1) / S2 * 100% (1).

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