Determination method and detection system for content of hydrogen element in zirconium and hafnium materials

Abstract

The invention discloses a determination method and a detection system for the content of hydrogen elements in zirconium and hafnium materials, and the determination method comprises the following steps: firstly, deoiling and cleaning a zirconium / hafnium material sample, drying, and weighing the mass m1 of the zirconium / hafnium material sample; meanwhile, weighing the mass m2 of the zirconium-based hydrogen sponge block which is not filled with hydrogen; then carrying out leak detection test on the whole test system, and carrying out vacuumizing treatment after the leak detection is qualified; then heating the high-temperature container in which the zirconium / hafnium material sample is placed, cooling the low-temperature container in which the zirconium-based hydrogen sponge block which is not filled with hydrogen is placed until the pressure in the high-temperature container is increased to a certain value and is stable, communicating the high-temperature container with the low-temperature container until the pressures in the high-temperature container and the low-temperature container are consistent and do not change any more, and stopping the test; weighing the mass m3 of the zirconium-based hydrogen sponge block after hydrogen absorption; and finally, calculating through a formula to obtain the hydrogen content in the zirconium / hafnium material sample. The determination method does not need to prepare a standard sample, the test process is simple and easy to implement, and the test result is accurate.

Description

Technical Field

[0001] This invention belongs to the field of zirconium and hafnium material analysis and testing technology. Specifically, this invention relates to a method and detection system for determining the hydrogen content in zirconium and hafnium materials. Background Technology

[0002] Zirconium alloys are widely used as cladding materials for nuclear reactors due to their excellent nuclear properties, corrosion resistance, and machinability. Zirconium is a highly chemically reactive metal with a strong affinity for various elements, including hydrogen and oxygen. Therefore, during reactor cooling with water, oxygen in the water reacts with the zirconium matrix, and the resulting hydrogen, as well as hydrogen present due to water chemistry control, is largely absorbed by the zirconium alloy. Since the solubility of hydrogen in zirconium alloys is less than 0.001% at room temperature and less than 0.03% at reactor operating temperatures, and in a nuclear reactor with a burnup of 55 GWd / tU, the hydrogen absorption in the fuel cladding tubes is around 600 µg / g. The hydride flakes formed during hydrogen absorption by the zirconium alloy can become fatigue sources in the fatigue failure process of the zirconium alloy.

[0003] In contrast to zirconium, hafnium has a larger thermal neutron trapping surface (10⁵b) and a high neutron absorption coefficient, and is often used in thermal neutron absorbing materials—control rods—in nuclear reactors. The chemical element content in hafnium control rods directly affects their efficiency in reactor control.

[0004] The hydrogen content in zirconium and hafnium materials directly affects product performance. To accurately determine the hydrogen content, a corresponding method for hydrogen content determination needs to be established. Existing methods, such as Chinese Patent (CN103713106A) on a method for determining the hydrogen content in nuclear-grade zirconium materials, GB / T 13747.21-2017 "Chemical Analysis Methods for Zirconium and Zirconium Alloys Part 21: Determination of Hydrogen Content by Inert Gas Fusion Infrared Absorption / Thermal Conductivity Method," and YS / T 1467.9-2021 "Chemical Analysis Methods for Hafnium Part 9: Determination of Hydrogen Content," all use a hydrogen analyzer to determine the hydrogen content in zirconium and hafnium materials. These methods are relative analytical methods, relying on standard samples and requiring matrix-matched standard samples to avoid matrix effects. Sample preparation is complex, and the testing process is cumbersome. Meanwhile, the above method is a single-point calibration, which requires the hydrogen content of the standard sample to be approximately the same as that of the actual sample. Therefore, different hydrogen content standard samples are needed for samples with different hydrogen contents in order to ensure the accuracy of the detection, which makes the detection process complicated, time-consuming and costly. Summary of the Invention

[0005] The present invention aims to at least partially solve one of the technical problems in the related art.

[0006] Therefore, this invention provides a method and detection system for determining the hydrogen content in zirconium and hafnium materials. This method does not require standard samples, and the sample preparation and testing process is simple and easy to implement, and can accurately determine the hydrogen content in zirconium and hafnium materials.

[0007] To achieve the above objectives, the first aspect of this invention provides a method for determining the hydrogen content in zirconium and hafnium materials, comprising the following steps: (1) Clean and dry the zirconium or hafnium material sample, and weigh it as m1; at the same time, obtain an unfilled zirconium-based hydrogen sponge block, weigh it, and record it as m2; (2) Place the treated zirconium material sample or hafnium material sample in a high-temperature container and place the unfilled zirconium-based hydrogen sponge in a low-temperature container. At the same time, open the solenoid valves at both ends of the transition pipe connecting the high-temperature container and the low-temperature container to perform a leak test. (3) After the leak test is passed, the entire system consisting of the high-temperature container, the low-temperature container and the transition pipeline is evacuated. (4) Close the solenoid valves at both ends of the transition pipeline, then heat the high-temperature container to a certain temperature for heat preservation, and monitor the pressure change in the high-temperature container through the pressure sensor inside the high-temperature container; at the same time, cool down the low-temperature container. (5) When the pressure inside the high-temperature container increases to a certain value and stabilizes, open the solenoid valves at both ends of the transition pipeline to connect the high-temperature container with the low-temperature container, and stop heating the high-temperature container. At the same time, monitor the pressure inside the high-temperature container and the low-temperature container through the pressure sensor inside the high-temperature container and the pressure sensor inside the low-temperature container respectively. When the pressure inside the high-temperature container is consistent with the pressure inside the low-temperature container and no longer changes, stop the test, weigh the mass of the zirconium-based hydrogen sponge block after hydrogen absorption, and record it as m3. (6) The hydrogen content in the zirconium material sample or the hafnium material sample can be calculated using the following formula: .

[0008] In some embodiments, in step (1), the degreasing and cleaning process is as follows: the zirconium material sample or the hafnium material sample is first soaked in an organic solvent, and then rinsed with water.

[0009] Furthermore, the organic solvent includes at least one of acetone and anhydrous ethanol; And / or, the soaking time is 10s to 120s.

[0010] In some embodiments, in step (3), when the pressure drop of the entire system consisting of the high-temperature container, the low-temperature container and the transition pipeline is ≤0.02MPa, it is determined that the leak detection is qualified.

[0011] In some embodiments, in step (3), the vacuum level during the vacuuming process is 1.0 × 10⁻⁶. -6 Pa ~ 1.0 × 10 -5 Pa.

[0012] In some embodiments, in step (4), when the sample is the zirconium material sample, the high-temperature container is heated to 600°C~700°C; when the sample is the hafnium material sample, the high-temperature container is heated to 680°C~770°C.

[0013] In some embodiments, the heat preservation treatment time in step (4) is 60 min to 150 min.

[0014] In some embodiments, in step (4), the temperature of the cryogenic container is reduced to -80°C to -60°C.

[0015] A second aspect of this invention also provides a detection system for the hydrogen content in zirconium and hafnium materials. The detection system is used to implement the determination method described in the first aspect and includes a weighing balance, a high-temperature container, a low-temperature container, a first pressure sensor, and a second pressure sensor. The high-temperature container and the low-temperature container are connected by a transition pipe, and a first solenoid valve and a second solenoid valve are respectively provided at both ends of the transition pipe. The first pressure sensor is located inside the high-temperature container, and the second pressure sensor is located inside the low-temperature container.

[0016] In some embodiments, the high-temperature container is a heating device with automatic temperature control, and the temperature of the high-temperature container is controlled between 600°C and 800°C. And / or, the cryogenic container is a cooling device with automatic temperature control, and the temperature of the cryogenic container is controlled between -80℃ and -60℃.

[0017] The advantages and beneficial effects of the embodiments of the present invention are as follows: This invention primarily addresses zirconium and hafnium materials widely used in China's nuclear energy industry, such as hafnium ingots, hafnium control rods, hafnium plates, zirconium ingots, zirconium tubes, zirconium wires, and zirconium rods. It provides a method for detecting the hydrogen content in these materials, solving the problem of potential result deviations and instability caused by using other standard samples due to the lack of hydrogen standard samples for zirconium and hafnium matrices. Furthermore, the method for determining the hydrogen content in zirconium and hafnium materials according to this invention provides stable and accurate test results, and the testing process is simpler and more convenient. Attached Figure Description

[0018] Figure 1 This is a schematic diagram of the structure of a system for detecting the hydrogen content in zirconium and hafnium materials according to an embodiment of the present invention.

[0019] Figure reference numerals: 1-Weighing balance, 2-High temperature container, 3-Low temperature container, 4-First pressure sensor, 5-Second pressure sensor, 6-First solenoid valve, 7-Second solenoid valve. Detailed Implementation

[0020] The embodiments of the present invention are described in detail below. These embodiments are exemplary and intended to explain the present invention, and should not be construed as limiting the present invention.

[0021] In this invention, when a value is described as a range, it should be understood that such disclosure includes disclosure of all possible subranges within that range, as well as specific numerical values ​​falling within that range, regardless of whether specific numerical values ​​or specific subranges are explicitly specified.

[0022] In this invention, the terms “comprising” and “including” and their various variations mean that other elements or wholes may be included but are not specifically described.

[0023] In this invention, the term "and / or" is merely a description of the relationship between related objects, indicating that there can be three relationships. For example, A and / or B can represent three situations: A exists alone, A and B exist simultaneously, and B exists alone.

[0024] The first aspect of this invention provides a method for determining the hydrogen content in zirconium and hafnium materials, comprising the following steps: (1) Clean and dry the zirconium or hafnium material sample, and weigh it as m1; at the same time, obtain an unfilled zirconium-based hydrogen sponge block, weigh it, and record it as m2; (2) Place the treated zirconium material sample or hafnium material sample in a high-temperature container and place the unfilled zirconium-based hydrogen sponge in a low-temperature container. At the same time, open the solenoid valves at both ends of the transition pipe connecting the high-temperature container and the low-temperature container to perform a leak test. (3) After the leak test is passed, the entire system consisting of the high-temperature container, the low-temperature container and the transition pipeline is evacuated. (4) Close the solenoid valves at both ends of the transition pipeline, then heat the high-temperature container to a certain temperature for heat preservation, and monitor the pressure change in the high-temperature container through the pressure sensor inside the high-temperature container; at the same time, cool down the low-temperature container. (5) When the pressure inside the high-temperature container increases to a certain value and stabilizes, open the solenoid valves at both ends of the transition pipeline to connect the high-temperature container with the low-temperature container, and stop heating the high-temperature container. At the same time, monitor the pressure inside the high-temperature container and the low-temperature container through the pressure sensor inside the high-temperature container and the pressure sensor inside the low-temperature container respectively. When the pressure inside the high-temperature container is consistent with the pressure inside the low-temperature container and no longer changes, stop the test, weigh the mass of the zirconium-based hydrogen sponge block after hydrogen absorption, and record it as m3. (6) The hydrogen content in the zirconium material sample or the hafnium material sample can be calculated using the following formula: .

[0025] In some embodiments, in step (1), the degreasing and cleaning process is as follows: the zirconium material sample or the hafnium material sample is first soaked in an organic solvent, and then rinsed with water.

[0026] Furthermore, the organic solvent includes at least one of acetone and anhydrous ethanol; And / or, the soaking time is 10s to 120s.

[0027] In some embodiments, in step (3), when the pressure drop of the entire system consisting of the high-temperature container, the low-temperature container and the transition pipeline is ≤0.02MPa, it is determined that the leak detection is qualified.

[0028] In some embodiments, in step (3), the vacuum level during the vacuuming process is 1.0 × 10⁻⁶. -6 Pa ~ 1.0 × 10 -5 Pa.

[0029] In some embodiments, in step (4), when the sample is the zirconium material sample, the high-temperature container is heated to 600°C~700°C; when the sample is the hafnium material sample, the high-temperature container is heated to 680°C~770°C.

[0030] In some embodiments, the heat preservation treatment time in step (4) is 60 min to 150 min.

[0031] In some embodiments, in step (4), the temperature of the cryogenic container is reduced to -80°C to -60°C.

[0032] like Figure 1As shown, a second aspect of the present invention also proposes a detection system for the hydrogen content in zirconium and hafnium materials. The detection system is used to implement the determination method described in the first aspect and includes a weighing balance 1, a high-temperature container 2, a low-temperature container 3, a first pressure sensor 4, and a second pressure sensor 5. The high-temperature container 2 and the low-temperature container 3 are connected by a transition pipe, and a first solenoid valve 6 and a second solenoid valve 7 are respectively provided at both ends of the transition pipe. The first pressure sensor 4 is located inside the high-temperature container 2, and the second pressure sensor 5 is located inside the low-temperature container 3.

[0033] In some embodiments, the high-temperature container 2 is a heating device with automatic temperature control, and the temperature of the high-temperature container 2 is controlled between 600°C and 800°C. And / or, the cryogenic container 3 is a cooling device with automatic temperature control, and the temperature of the cryogenic container 3 is controlled between -80℃ and -60℃.

[0034] The technical solution of the present invention will be further described in detail below with reference to specific embodiments. All raw materials used in the embodiments are conventional commercially available products, or can be prepared by known methods.

[0035] Example 1 This embodiment provides a method for determining the hydrogen content in zirconium materials, including the following steps: (1) Immerse the Zr-4 alloy rod sample in acetone for 30 seconds, then rinse with running water, dry with cold air, and weigh it as m1, which is 3g; at the same time, obtain an unfilled zirconium-based hydrogen sponge block and weigh it as m2, which is 5g. (2) Place the Zr-4 alloy rod sample processed in step (1) into a high-temperature container and place the unfilled zirconium-based hydrogen sponge into a low-temperature container. At the same time, open the solenoid valves at both ends of the transition pipe connecting the high-temperature container and the low-temperature container to perform a leak test. (3) After the leak test is passed, the entire system consisting of the high-temperature container, the low-temperature container, and the transition pipeline is evacuated until the vacuum level is 1.0 × 10⁻⁶. -6 Pa ~ 1.0 × 10 -5 Until the interval between Pa; (4) Close the solenoid valves at both ends of the transition pipeline, then heat the high-temperature container to 650°C and keep it at that temperature for 60 minutes. Monitor the pressure change inside the high-temperature container using the pressure sensor inside the high-temperature container. At the same time, cool the low-temperature container to -70°C. (5) When the pressure inside the high-temperature container increases to a certain value and stabilizes, open the solenoid valves at both ends of the transition pipeline to connect the high-temperature container with the low-temperature container, and stop heating the high-temperature container. At the same time, monitor the pressure inside the high-temperature container and the low-temperature container through the pressure sensor inside the high-temperature container and the pressure sensor inside the low-temperature container respectively. When the pressure inside the high-temperature container is consistent with the pressure inside the low-temperature container and no longer changes, stop the test and weigh the mass m3 of the zirconium-based hydrogen sponge block after hydrogen absorption as 5.00012g. (6) The hydrogen content in the Zr-4 alloy rod sample can be obtained by calculation and is denoted as H-1.

[0036] Example 2 This embodiment provides a method for determining the hydrogen content in zirconium materials, including the following steps: (1) Immerse the SZA-6 zirconium alloy tube sample in acetone for 30 seconds, then rinse with running water and dry with cold air. Weigh its mass m1 as 2g. At the same time, obtain an unfilled zirconium-based hydrogen sponge block and weigh its mass m2 as 5g. (2) Place the SZA-6 zirconium alloy tube sample processed in step (1) into a high-temperature container, and place the unfilled zirconium-based hydrogen sponge into a low-temperature container. At the same time, open the solenoid valves at both ends of the transition pipe connecting the high-temperature container and the low-temperature container to perform a leak test. (3) After the leak test is passed, the entire system consisting of the high-temperature container, the low-temperature container, and the transition pipeline is evacuated until the vacuum level is 1.0 × 10⁻⁶. -6 Pa ~ 1.0 × 10 -5 Until the interval between Pa; (4) Close the solenoid valves at both ends of the transition pipeline, then heat the high-temperature container to 700°C, keep it at that temperature for 100 minutes, and monitor the pressure change inside the high-temperature container through the pressure sensor inside the high-temperature container; at the same time, cool the low-temperature container to -75°C. (5) When the pressure inside the high-temperature container increases to a certain value and stabilizes, open the solenoid valves at both ends of the transition pipeline to connect the high-temperature container with the low-temperature container, and stop heating the high-temperature container. At the same time, monitor the pressure inside the high-temperature container and the low-temperature container through the pressure sensor inside the high-temperature container and the pressure sensor inside the low-temperature container respectively. When the pressure inside the high-temperature container is consistent with the pressure inside the low-temperature container and no longer changes, stop the test and weigh the mass m3 of the zirconium-based hydrogen sponge block after hydrogen absorption as 5.000074g. (6) The hydrogen content in the SZA-6 zirconium alloy tube sample can be obtained by calculation and is denoted as H-2.

[0037] Example 3 This embodiment provides a method for determining the hydrogen content in zirconium materials, including the following steps: (1) Immerse the 100-day steam corrosion sample of SZA-6 zirconium alloy pipe in acetone for 30 seconds, then rinse with running water and dry with cold air. Weigh the sample m1 as 2g. At the same time, obtain an unfilled zirconium-based hydrogen sponge block and weigh it m2 as 5g. (2) Place the 100-day vapor corrosion sample of SZA-6 zirconium alloy pipe after step (1) in a high-temperature container, and place the unfilled zirconium-based hydrogen sponge in a low-temperature container. At the same time, open the solenoid valves at both ends of the transition pipe connecting the high-temperature container and the low-temperature container to perform a leak test. (3) After the leak test is passed, the entire system consisting of the high-temperature container, the low-temperature container, and the transition pipeline is evacuated until the vacuum level is 1.0 × 10⁻⁶. -6 Pa ~ 1.0 × 10 -5 Until the interval between Pa; (4) Close the solenoid valves at both ends of the transition pipeline, then heat the high-temperature container to 600°C and keep it at that temperature for 120 minutes, and monitor the pressure change inside the high-temperature container through the pressure sensor inside the high-temperature container; at the same time, cool the low-temperature container to -65°C. (5) When the pressure inside the high-temperature container increases to a certain value and stabilizes, open the solenoid valves at both ends of the transition pipeline to connect the high-temperature container with the low-temperature container, and stop heating the high-temperature container. At the same time, monitor the pressure inside the high-temperature container and the low-temperature container through the pressure sensor inside the high-temperature container and the pressure sensor inside the low-temperature container respectively. When the pressure inside the high-temperature container is consistent with the pressure inside the low-temperature container and no longer changes, stop the test and weigh the mass m3 of the zirconium-based hydrogen sponge block after hydrogen absorption as 5.000508g. (6) The hydrogen content in the 100-day steam corrosion sample of the SZA-6 zirconium alloy pipe can be obtained by calculation and is denoted as H-3.

[0038] Example 4 This embodiment provides a method for determining the hydrogen content in hafnium materials, including the following steps: (1) Immerse the hafnium rod sample in acetone for 30 seconds, then rinse with running water and dry with cold air. Weigh its mass m1 as 3g. At the same time, obtain an unfilled zirconium-based hydrogen sponge block and weigh its mass m2 as 5g. (2) Place the hafnium rod sample processed in step (1) into a high-temperature container and place the unfilled zirconium-based hydrogen sponge into a low-temperature container. At the same time, open the solenoid valves at both ends of the transition pipe connecting the high-temperature container and the low-temperature container to perform a leak test. (3) After the leak test is passed, the entire system consisting of the high-temperature container, the low-temperature container, and the transition pipeline is evacuated until the vacuum level is 1.0 × 10⁻⁶. -6 Pa ~ 1.0 × 10 -5 Until the interval between Pa; (4) Close the solenoid valves at both ends of the transition pipeline, then heat the high-temperature container to 680°C and keep it at that temperature for 150 minutes, and monitor the pressure change inside the high-temperature container through the pressure sensor inside the high-temperature container; at the same time, cool the low-temperature container to -65°C. (5) When the pressure inside the high-temperature container increases to a certain value and stabilizes, open the solenoid valves at both ends of the transition pipeline to connect the high-temperature container with the low-temperature container, and stop heating the high-temperature container. At the same time, monitor the pressure inside the high-temperature container and the low-temperature container through the pressure sensor inside the high-temperature container and the pressure sensor inside the low-temperature container respectively. When the pressure inside the high-temperature container is consistent with the pressure inside the low-temperature container and no longer changes, stop the test and weigh the mass m3 of the zirconium-based hydrogen sponge block after hydrogen absorption as 5.000057g. (6) The hydrogen content in the hafnium rod sample can be obtained by calculation and is denoted as H-4.

[0039] Example 5 This embodiment provides a method for determining the hydrogen content in hafnium materials, including the following steps: (1) Immerse the hafnium plate sample in acetone for 30 seconds, then rinse with running water and dry with cold air. Weigh the sample and take its mass m1 as 4g. At the same time, obtain an unfilled zirconium-based hydrogen sponge block and weigh its mass m2 as 5g. (2) Place the hafnium plate sample processed in step (1) into a high-temperature container and place the unfilled zirconium-based hydrogen sponge into a low-temperature container. At the same time, open the solenoid valves at both ends of the transition pipe connecting the high-temperature container and the low-temperature container to perform a leak test. (3) After the leak test is passed, the entire system consisting of the high-temperature container, the low-temperature container, and the transition pipeline is evacuated until the vacuum level is 1.0 × 10⁻⁶. -6 Pa ~ 1.0 × 10 -5 Until the interval between Pa; (4) Close the solenoid valves at both ends of the transition pipeline, then heat the high-temperature container to 750°C, keep it at that temperature for 70 minutes, and monitor the pressure change inside the high-temperature container through the pressure sensor inside the high-temperature container; at the same time, cool the low-temperature container to -78°C. (5) When the pressure inside the high-temperature container increases to a certain value and stabilizes, open the solenoid valves at both ends of the transition pipeline to connect the high-temperature container with the low-temperature container, and stop heating the high-temperature container. At the same time, monitor the pressure inside the high-temperature container and the low-temperature container through the pressure sensor inside the high-temperature container and the pressure sensor inside the low-temperature container respectively. When the pressure inside the high-temperature container is consistent with the pressure inside the low-temperature container and no longer changes, stop the test and weigh the mass m3 of the zirconium-based hydrogen sponge block after hydrogen absorption as 5.000172g. (6) The hydrogen content in the hafnium plate sample can be obtained by calculation and is denoted as H-5.

[0040] The hydrogen content in each sample of Examples 1-5 above was calculated using the following formula, and the results are shown in Table 1:

[0041] Table 1. Test results of hydrogen content in samples

[0042] To verify the accuracy of the detection results of the determination method in the embodiments of the present invention, five samples from Examples 1, 2, 3, 4, and 5 were tested on a LECO H836 hydrogen analyzer (using a hydrogen standard sample in titanium). The results are shown in Table 2.

[0043] Table 2 Validation and Assessment Results of Examples

[0044] A comparison of Tables 1 and 2 shows that the hydrogen content values ​​detected by the method of this invention for each sample are basically consistent with the detection results of the hydrogen analyzer, indicating that the method of this invention is accurate and reliable.

[0045] In the description of this invention, it should be understood that the terms "center," "longitudinal," "lateral," "length," "width," "thickness," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," "clockwise," "counterclockwise," "axial," "radial," and "circumferential" indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. They are used only for the convenience of describing this invention and simplifying the description, and are not intended to indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on this invention.

[0046] Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one of that feature. In the description of this invention, "a plurality of" means at least two, such as two, three, etc., unless otherwise explicitly specified.

[0047] In this invention, unless otherwise explicitly specified and limited, the terms "installation," "connection," "linking," and "fixing," etc., should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral part; they can refer to a mechanical connection, an electrical connection, or a connection that allows communication between them; they can refer to a direct connection or an indirect connection through an intermediate medium; they can refer to the internal communication of two components or the interaction between two components, unless otherwise explicitly limited. Those skilled in the art can understand the specific meaning of the above terms in this invention according to the specific circumstances.

[0048] In this invention, the terms "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., refer to a specific feature, structure, material, or characteristic described in connection with that embodiment or example, which is included in at least one embodiment or example of the invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples. Moreover, without contradiction, those skilled in the art can combine and integrate the different embodiments or examples described in this specification, as well as the features of different embodiments or examples.

[0049] Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those skilled in the art can make changes, modifications, substitutions and variations to the above embodiments within the scope of the present invention.

Claims

1. A method for determining the hydrogen content in zirconium and hafnium materials, characterized in that, Includes the following steps: (1) Clean and dry the zirconium or hafnium material sample, and weigh it as m1; at the same time, obtain an unfilled zirconium-based hydrogen sponge block, weigh it, and record it as m2; (2) Place the treated zirconium material sample or hafnium material sample in a high-temperature container and place the unfilled zirconium-based hydrogen sponge in a low-temperature container. At the same time, open the solenoid valves at both ends of the transition pipe connecting the high-temperature container and the low-temperature container to perform a leak test. (3) After the leak test is passed, the entire system consisting of the high-temperature container, the low-temperature container and the transition pipeline is evacuated. (4) Close the solenoid valves at both ends of the transition pipeline, then heat the high-temperature container to a certain temperature for heat preservation, and monitor the pressure change in the high-temperature container through the pressure sensor inside the high-temperature container; at the same time, cool down the low-temperature container. (5) When the pressure inside the high-temperature container increases to a certain value and stabilizes, open the solenoid valves at both ends of the transition pipeline to connect the high-temperature container with the low-temperature container, and stop heating the high-temperature container. At the same time, monitor the pressure inside the high-temperature container and the low-temperature container through the pressure sensor inside the high-temperature container and the pressure sensor inside the low-temperature container respectively. When the pressure inside the high-temperature container is consistent with the pressure inside the low-temperature container and no longer changes, stop the test, weigh the mass of the zirconium-based hydrogen sponge block after hydrogen absorption, and record it as m3. (6) The hydrogen content in the zirconium material sample or the hafnium material sample can be calculated using the following formula: 。 2. The method for determining the hydrogen content in zirconium and hafnium materials according to claim 1, characterized in that, In step (1), the degreasing and cleaning process is as follows: the zirconium material sample or the hafnium material sample is first soaked in an organic solvent, and then rinsed with water.

3. The method for determining the hydrogen content in zirconium and hafnium materials according to claim 2, characterized in that, The organic solvent includes at least one of acetone and anhydrous ethanol; And / or, the soaking time is 10s to 120s.

4. The method for determining the hydrogen content in zirconium and hafnium materials according to claim 1, characterized in that, In step (3), when the pressure drop of the entire system consisting of the high-temperature container, the low-temperature container and the transition pipeline is ≤0.02MPa, it is determined that the leak detection is qualified.

5. The method for determining the hydrogen content in zirconium and hafnium materials according to claim 1, characterized in that, In step (3), the vacuum level during the vacuuming process is 1.0 × 10⁻⁶. -6 Pa ~ 1.0 × 10 -5 Pa.

6. The method for determining the hydrogen content in zirconium and hafnium materials according to claim 1, characterized in that, In step (4), when the sample is the zirconium material sample, the high-temperature container is heated to 600℃~700℃; when the sample is the hafnium material sample, the high-temperature container is heated to 680℃~770℃.

7. The method for determining the hydrogen content in zirconium and hafnium materials according to claim 1, characterized in that, In step (4), the heat preservation treatment time is 60 min to 150 min.

8. The method for determining the hydrogen content in zirconium and hafnium materials according to claim 1, characterized in that, In step (4), the temperature of the cryogenic container is reduced to -80℃ to -60℃.

9. A system for detecting the hydrogen content in zirconium and hafnium materials, characterized in that, The detection system is used to implement the measurement method according to any one of claims 1-8, and includes a weighing balance, a high-temperature container, a low-temperature container, a first pressure sensor and a second pressure sensor; the high-temperature container and the low-temperature container are connected by a transition pipe, and a first solenoid valve and a second solenoid valve are respectively provided at both ends of the transition pipe; the first pressure sensor is located inside the high-temperature container, and the second pressure sensor is located inside the low-temperature container.

10. The detection system for hydrogen content in zirconium and hafnium materials according to claim 9, characterized in that, The high-temperature container is a heating device with automatic temperature control, and the temperature of the high-temperature container is controlled between 600℃ and 800℃. And / or, the cryogenic container is a cooling device with automatic temperature control, and the temperature of the cryogenic container is controlled between -80℃ and -60℃.

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