Method and system for detecting hydrogen isotope surface reactivity of metal foils

Abstract

This application relates to the field of materials science and proposes a method and system for detecting the surface reactivity of hydrogen isotopes on metal foil. The method includes: placing the metal foil in a sample chamber of a test chamber; evacuating the gas supply chamber and the permeation chamber separately, and heating the sample chamber; continuously introducing hydrogen isotope gas into the gas supply chamber while maintaining the gas pressure at a preset value, and maintaining a vacuum in the permeation chamber; detecting the gas in the gas supply chamber and the permeation chamber using Raman spectroscopy; detecting the gas flow rate in the permeation chamber; and determining the dissociation adsorption coefficient and recombination desorption coefficient of the hydrogen isotopes on the metal foil based on the acquired data. This method can effectively characterize the surface reactivity of hydrogen isotopes on metal foil, and is simple to operate, provides high data accuracy and excellent resolution, and can effectively evaluate and screen suitable metal materials for direct internal recovery loops in fusion reactors.

Description

Technical Field

[0001] This application relates to the field of materials, and more specifically, to a method and system for detecting the hydrogen isotope surface reactivity of metal foil. Background Technology

[0002] Metal foil pumps are key components in the direct internal recovery (DIR) loop of fusion reactors, and the adsorption / dissociation of hydrogen atoms on their surface, as well as the surface recombination and desorption rates, directly affect pump performance. However, there is a lack of dedicated experimental apparatus and methods for measuring hydrogen isotope surface reaction coefficients, with traditional research focusing more on diffusion and permeation behavior itself. For example, the published patent CN120741263B focuses on obtaining permeation-related parameters through dual-chamber pressure and temperature control and high-resolution mass spectrometry analysis on the permeation side. It primarily characterizes bulk diffusion / permeation parameters and is suitable for performance testing of gas leakage prevention materials in fusion reactors. However, permeation-related coefficients include separation factor, diffusion coefficient, permeation coefficient, and pressure index, which cannot individually characterize the surface reaction control process during hydrogen isotope transport in metal foil materials under vacuum or low-pressure conditions. Currently, there are no reported dedicated measurement methods for accurately measuring the surface recombination rate constants of gases such as deuterium and tritium on metal foil materials.

[0003] Therefore, how to decouple and quantify the hydrogen isotope surface reaction performance of metal surfaces under controllable conditions to guide material selection and surface engineering optimization has become an urgent technical problem to be solved. Summary of the Invention

[0004] This invention aims to address, to a certain extent, the technical problems existing in the prior art. To this end, this application proposes a method and system for detecting the surface reactivity of hydrogen isotopes on metal foil. The method proposed in this application can effectively characterize the dissociation and adsorption coefficients and recombination and desorption coefficients of hydrogen isotopes on metal foil, screening out suitable metal materials for direct internal recovery loops in fusion reactors, and providing a basis for the selection of functional materials for hydrogen isotope separation in fusion reactors and the optimization of surface engineering. The system proposed in this application can stably control the temperature or pressure in three chambers, thereby accurately acquiring unsteady transient response data while ensuring steady-state boundary conditions, further clarifying the evaluation of the surface reactivity of the metal foil. Furthermore, the device is easy to operate, with high data accuracy and excellent resolution.

[0005] This application was made by the inventor based on the following discoveries:

[0006] The current detection of hydrogen isotope permeation in metal foil still has the following defects: (1) The relevant parameters for hydrogen isotope permeation in metal foil are mainly the permeation / diffusion parameters of hydrogen isotopes in metal foil. They do not distinguish the complex reaction process of hydrogen isotopes in metal foil, including dissociation adsorption-permeation-composite desorption. For materials with extremely fast diffusion and slow surface reaction, the permeation may be limited by the surface reaction rate, making it impossible to effectively quantitatively evaluate them; (2) When measuring the permeation / diffusion parameters of metal foil, the "pressure rise method" is used. It only requires one vacuum treatment of the downstream permeation chamber, ignoring the reverse osmosis phenomenon that occurs during the slow accumulation of downstream permeation gas. This will affect the relevant permeation / diffusion parameters and surface reaction, and the accuracy of the obtained detection results will have a certain deviation; (3) Some detection devices / systems are cumbersome to operate and cannot detect the relevant parameters in the extraction device in real time. In addition, some devices are expensive to build or have complex material requirements.

[0007] The inventors have studied and designed to solve the above problems: (1) to clearly understand the surface reaction process of adsorption-permeation-composite desorption, and to accurately distinguish and quantify the dissociation adsorption coefficient and composite desorption coefficient of surface reaction performance by extracting the kinetic information controlled by the surface reaction, so as to effectively evaluate and screen out metal materials suitable for use in the direct internal recovery loop of fusion reactors; (2) to continuously evacuate the downstream permeation cavity during the measurement process to avoid reverse osmosis of the downstream permeation gas and improve the accurate quantification of the hydrogen isotope surface reaction performance of the metal foil; (3) to use a Raman spectrometer to collect the Raman scattering signal of the hydrogen isotope gas in the system in real time, so as to accurately identify the gas composition and its concentration, avoid the influence of non-real-time detection methods such as mass spectrometry on the stable pressure of the system, and Raman spectroscopy can meet the gas detection requirements in high temperature, high pressure or vacuum conditions, so that the detection system has a relatively lower construction cost and a wider range of applications.

[0008] Based on this, in a first aspect of this application, a method for detecting the surface reactivity of hydrogen isotopes on a metal foil is proposed. According to an embodiment of this application, the method includes: placing the metal foil in a sample receiving cavity of a test chamber, the sample receiving cavity dividing the inner cavity of the test chamber into a gas supply cavity and a permeation cavity; evacuating the gas supply cavity and the permeation cavity respectively, and heating the sample receiving cavity to a preset temperature value; continuously introducing hydrogen isotope gas into the gas supply cavity, the hydrogen isotope gas can enter the permeation cavity through the gas supply cavity, controlling the gas pressure in the gas supply cavity to maintain at a preset pressure value, and maintaining the permeation cavity in a vacuum state; during the introduction of hydrogen isotope gas, using Raman spectroscopy to detect the gas in the gas supply cavity and the permeation cavity respectively, and obtaining Raman spectral results; detecting the gas flow rate in the permeation cavity, and obtaining a gas flow rate result; and determining the dissociation adsorption coefficient and recombination desorption coefficient of the hydrogen isotopes on the metal foil based on the acquired data information, the data information including the Raman spectral results and the gas flow rate results.

[0009] According to the method of this application embodiment, a metal foil is placed between a gas supply chamber and a permeation chamber. Hydrogen isotope gas introduced through the gas supply chamber can enter the permeation chamber through the gas supply chamber. By using Raman spectroscopy to detect the gas in both chambers and simultaneously measuring the gas flow rate in the permeation chamber, it is beneficial to accurately distinguish and quantify the dissociation adsorption coefficient and recombination desorption coefficient of different hydrogen isotopes on the surface of the metal foil. In addition, by using a single-sided gas supply + continuous downstream vacuum pumping, the complex effects caused by upstream and downstream pressure difference changes in traditional permeation experiments are avoided. The obtained detection results can be used for lateral comparisons between different materials, making it suitable for the effective evaluation and screening of metal materials for the direct internal recovery loop of fusion reactors.

[0010] According to embodiments of this application, the method for detecting the hydrogen isotope surface reactivity of metal foil described above may also have at least one of the following additional technical features:

[0011] According to embodiments of this application, the hydrogen isotope gas includes at least one selected from hydrogen, deuterium, tritium, hydrogen deuteride, hydrogen tritide, and tritium deuteride. The detection method of this application can effectively detect and calculate the dissociation adsorption coefficient and recombination desorption coefficient of the above-mentioned gases during the surface reaction process of the metal foil, thus expanding the applicability of the above-mentioned detection method.

[0012] According to embodiments of this application, the preset pressure value is 0.1 Pa to 1000 Pa. In some embodiments, the preset pressure value is 0.1 Pa, 1 Pa, 10 Pa, 20 Pa, 50 Pa, 75 Pa, 100 Pa, 200 Pa, 300 Pa, 400 Pa, 500 Pa, 600 Pa, 700 Pa, 750 Pa, 800 Pa, 900 Pa, or 1000 Pa. Therefore, satisfying the above preset pressure values ​​ensures the dissociation and adsorption process of hydrogen isotope gas on the metal foil, thereby effectively calculating the dissociation and adsorption coefficients and recombination and desorption coefficients of hydrogen isotopes on the metal foil.

[0013] According to an embodiment of this application, the vacuum degree of the vacuum state is no greater than 10. -3 Pa. Therefore, the permeation chamber environment that meets the aforementioned vacuum level can ensure the recombination and desorption process of hydrogen isotope gas on the metal foil and avoid the reverse osmosis phenomenon that occurs during the slow accumulation of downstream permeation gas. This avoids the adverse effects of reverse osmosis on relevant permeation / diffusion parameters and surface reactions, thereby effectively calculating the dissociation adsorption coefficient and recombination desorption coefficient of hydrogen isotopes on the metal foil.

[0014] According to embodiments of this application, the thickness of the metal foil is 1 µm to 150 µm. Therefore, a metal foil with the aforementioned thickness allows for the effective calculation of the dissociation adsorption coefficient and recombination desorption coefficient of the hydrogen isotopes on the metal foil, and is suitable for the stringent requirements of metal foil pumps in fusion reactor direct internal recovery (DIR) loops.

[0015] According to an embodiment of this application, the preset temperature value is 50 ℃ to 500 ℃. Therefore, the calculated results of the dissociation adsorption coefficient and recombination desorption coefficient of the hydrogen isotopes of the metal foil obtained by satisfying the aforementioned preset temperature value are effective parameters for the surface reaction performance of the metal foil with hydrogen isotopes under different temperature conditions.

[0016] According to an embodiment of this application, the data information further includes: the preset temperature value, the thickness of the metal foil, and the partial pressure of the dissociated molecules of the hydrogen isotope gas in the gas supply chamber. The dissociation adsorption coefficient and recombination desorption coefficient of the hydrogen isotope of the metal foil are determined based on the following formula:

[0017]

[0018] Among them, K α,Q J represents the dissociation and adsorption coefficient of hydrogen isotopes in the metal foil under the preset temperature condition; Q This represents the stable gas flow rate of hydrogen isotopes entering the permeation chamber; P QThis indicates that the partial pressure of the dissociated molecules of the hydrogen isotope gas is calculated based on the preset pressure value and the Raman spectroscopy results; K r,Q b represents the hydrogen isotope recombination desorption coefficient of the metal foil under the preset temperature condition; b represents the exponential function 1-2e obtained by fitting the gas flow rate-time curve of the permeation chamber. -2Bt The time term coefficient B value; X M The thickness of the metal foil is indicated by ; Q represents a specific hydrogen isotope.

[0019] The inventors modeled and calculated the hydrogen isotope surface reaction performance of the metal foil by collecting real-time kinetic information and the above-mentioned relevant parameters, accurately distinguishing and quantifying the dissociation adsorption coefficient and recombination desorption coefficient of the surface reaction performance, so as to effectively evaluate and screen out metal materials suitable for application in the direct internal recovery loop of fusion reactors.

[0020] In a second aspect of this application, a system for implementing the method described in the first aspect embodiment is proposed. According to an embodiment of this application, the system includes: a testing unit having a sample receiving cavity for accommodating a metal foil sample and heating the metal foil sample, the sample receiving cavity dividing the inner cavity of the testing unit into a gas supply cavity and a permeation cavity; a vacuum pump connected to the gas supply cavity and the permeation cavity respectively; a ventilation device connected to the gas supply cavity for continuously introducing hydrogen isotope gas into the gas supply cavity, the hydrogen isotope gas entering the permeation cavity through the gas supply cavity; a data information acquisition unit including: a Raman spectrometer for detecting the gas in the gas supply cavity and the permeation cavity respectively; a gas flow detection device for detecting the gas flow rate in the permeation cavity; and an analysis unit for determining the dissociation adsorption coefficient and recombination desorption coefficient of the hydrogen isotope of the metal foil based on the data information obtained by the data information acquisition unit.

[0021] According to the method of this application embodiment, a metal foil is placed between a gas supply chamber and a permeation chamber. Hydrogen isotope gas introduced through the gas supply chamber can enter the permeation chamber through the gas supply chamber. By using Raman spectroscopy to detect the gas in both chambers and simultaneously measuring the gas flow rate in the permeation chamber, it is beneficial to accurately distinguish and quantify the dissociation adsorption coefficient and recombination desorption coefficient of different hydrogen isotopes on the surface reaction performance of the metal foil. The inventors of this application have discovered through research that the system for detecting the surface reaction performance of hydrogen isotopes on metal foil using the above method can effectively control the dissociation adsorption and recombination desorption processes of hydrogen isotopes on the metal foil and avoid the reverse osmosis phenomenon of downstream permeation gas from affecting the quantification of surface reaction performance parameters. Using a Raman spectrometer to accurately identify the composition and concentration of hydrogen isotope gas in the system in real time effectively avoids the influence of non-real-time detection methods on the surface reaction. Furthermore, the Raman spectrometer can meet the gas detection requirements under high temperature, high pressure, or vacuum conditions, making the detection system relatively cheaper to build and more widely applicable.

[0022] According to an embodiment of this application, the gas supply chamber includes a pressure sensor and a gas stabilizing valve to maintain the gas pressure within the gas supply chamber at a preset pressure value. Thus, the gas supply chamber, as described above, can provide a stable gas pressure value, ensuring the dissociation and adsorption process of hydrogen isotope gas on the metal foil, thereby effectively calculating the dissociation and adsorption coefficients and recombination and desorption coefficients of the hydrogen isotopes on the metal foil.

[0023] According to an embodiment of this application, the outer periphery of the metal foil sample is sealed to the sample receiving cavity via a sealing element. Thus, the metal foil sample satisfying the aforementioned sealing configuration can effectively ensure the surface reaction process of hydrogen isotope gas on the metal foil, preventing hydrogen isotopes from directly permeating / spreading from the circumferential surface of the metal foil into the permeation cavity, thereby improving the accuracy of the calculated dissociation adsorption coefficient and recombination desorption coefficient of the hydrogen isotopes on the metal foil.

[0024] According to an embodiment of this application, the sample receiving cavity includes a temperature sensor and a heater for maintaining the metal foil sample at a preset temperature value. Thus, a metal foil sample that is stable at the aforementioned preset temperature value can effectively assess and quantify the dissociation adsorption coefficient and recombination desorption coefficient of hydrogen isotopes in the metal foil under different temperature conditions, with the aim of evaluating and screening metal materials suitable for the temperature conditions of the direct internal recovery loop in a fusion reactor.

[0025] According to an embodiment of this application, the permeation chamber includes a pressure detector for maintaining a vacuum level within the permeation chamber not exceeding 10. -3Pa. Therefore, the permeation cavity that meets the aforementioned vacuum level can ensure the recombination and desorption process of hydrogen isotope gas on the metal foil and avoid reverse osmosis of the free permeation gas. This allows for the quantitative calculation of surface reaction performance parameters, thereby effectively determining the dissociation adsorption coefficient and recombination desorption coefficient of hydrogen isotopes on the metal foil.

[0026] According to an embodiment of this application, the gas flow detection device includes a mass flow meter. Therefore, the gas flow detection device, satisfying the aforementioned instrument settings, can effectively detect the hydrogen isotope gas flux generated during the recombination and desorption process within the permeation chamber in real time, thereby calculating the dissociation adsorption coefficient and recombination desorption coefficient of the hydrogen isotopes on the metal foil.

[0027] Therefore, this application has the following beneficial effects:

[0028] (1) The detection conditions are controllable and highly stable. The temperature of the metal foil, the pressure of the gas introduced and the gas permeated in the system are constant, ensuring that the surface of the metal foil is under uniform conditions without concentration gradient, which improves the accuracy of the calculated dissociation adsorption coefficient and recombination desorption coefficient, making them more consistent with the real simulation and having physical significance.

[0029] (2) No interference in measuring surface rate. With the design of single-sided gas supply and continuous downstream vacuum pumping, the limitation of the surface adsorption and recombination process on the transmission will be directly reflected in the characteristic differences of the pressure and gas flow rate over time curves, without being masked by the concentration gradient effect. The kinetic information controlled by the surface reaction can be accurately extracted, avoiding the complex effects caused by the change in upstream and downstream pressure difference in traditional permeation experiments.

[0030] (3) High sensitivity and resolution. The time-resolved pressure and gas flow rate measurement method can capture the kinetic process of hydrogen isotope reaction on the surface. The online Raman spectroscopy can distinguish the participation of different hydrogen isotopes (D2, T2 and mixed DT, etc.) in real time, monitor the pressure and concentration changes of different components, and realize the difference assessment of the surface reaction performance of each isotope.

[0031] (4) Complete data analysis model. An analytical model including surface adsorption-recombination kinetics was established. Using transient gas flow curves, the dissociation adsorption coefficient and recombination desorption coefficient of hydrogen isotopes on the surface of metal foil materials were solved by fitting time series data, which effectively improved the efficiency and reliability of the measurement. Attached Figure Description

[0032] The above and / or additional aspects and advantages of the present invention will become apparent and readily understood from the description of the embodiments taken in conjunction with the following drawings, in which:

[0033] Figure 1 This is a schematic diagram of a method for detecting the surface reactivity of hydrogen isotopes on metal foil;

[0034] Figure 2 This is a schematic diagram of the dissociation adsorption and recombination desorption process of hydrogen isotope gas on the surface of a metal foil.

[0035] Figure 3 This is a schematic diagram of the hydrogen isotope gas reaction process on the upstream and downstream sides of the detection system;

[0036] Figure 4 This is a schematic diagram of a method for detecting the surface reactivity of hydrogen isotopes on metal foil;

[0037] Figure 5 It is K a K r Comparison chart of numerical and model calculation results with measured data from the system mass flow meter.

[0038] Figure label:

[0039] Test unit 1000, sample receiving chamber 1100, gas supply chamber 1200, permeation chamber 1300.

[0040] Vacuum pumping device 2000,

[0041] Ventilation device 3000,

[0042] Data acquisition unit 4000, Raman spectrometer 4100, gas flow detection device 4200.

[0043] Analysis unit 5000. Detailed Implementation

[0044] The embodiments of the present invention are described in detail below. Those skilled in the art will understand that the following embodiments are for illustrative purposes only and should not be considered as limiting the scope of the invention. Where specific techniques or conditions are not specified in the embodiments, they are performed according to the techniques or conditions described in the literature in the art or according to the product instructions. Reagents or instruments used without specified manufacturers are all conventional products that can be obtained commercially. Model architectures or processing strategies used without specified details are all conventional products that can be obtained commercially or through online searches.

[0045] It should be noted that in the embodiments of this application, the terms "comprising" or "including" are open-ended expressions, that is, they include the content specified in this invention, but do not exclude other aspects.

[0046] In the embodiments of this application, the terms "optionally," "optionally," or "optionally" generally refer to events or conditions described subsequently that may but may not occur, and the description includes both cases in which the event or condition occurs and cases in which the event or condition does not occur.

[0047] In this application, the term "connection" should be interpreted broadly. For example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection or an indirect connection through an intermediate medium; it can be a connection within two components. Those skilled in the art can understand the specific meaning of the above terms in this invention based on the specific circumstances.

[0048] In this embodiment, the term "effective permeation area" refers to the area of ​​the sample that actually participates in gas permeation and allows gas to pass through after the sample is sealed and fixed on the periphery. Specifically, the effective permeation area of ​​the metal foil is the total area of ​​the metal foil.

[0049] In the embodiments of this application, the term "dissociation molecular partial pressure of hydrogen isotope gas" refers to the pressure generated by a certain hydrogen isotope molecular component in a mixed gas system.

[0050] In the embodiments of this application, the term "fusion reactor direct internal recovery loop" refers to a short-range, high-efficiency recovery system for the tritium fuel cycle of a fusion reactor. It refers to a closed-loop system that returns the plasma ash gas discharged from the tokamak vacuum chamber to the core fuel injection system directly after rapid purification and isotope separation, without going through the main process of an external tritium plant.

[0051] In this embodiment, the term "pressure rise method" refers to a classic method for measuring the gas permeation rate in a closed, constant-volume cavity. The sample is positioned on two sides as a high-pressure side and a sealed, initially low-pressure / vacuum side. Gas permeates into the sealed side under the influence of the pressure difference, causing the pressure within the cavity to gradually increase over time. By recording the pressure-time curve, the pressure rise rate is obtained. Combined with the cavity volume, temperature, and effective permeation area of ​​the sample, the steady-state permeation flux and related kinetic parameters of the gas are calculated.

[0052] In the embodiments of this application, the term "Raman scattering signal" refers to the scattered light signal that carries molecular vibration / rotation information generated by inelastic light scattering when a laser irradiates sample molecules.

[0053] In the embodiments of this application, the term "hydrogen isotope solubility K of metal foil" is used. s,Q "It refers to the rate constant of hydrogen isotope atoms per unit volume of metal when a specific hydrogen isotope atom Q (protium, deuterium, or tritium) dissolves into the interior of a metal foil lattice under certain temperature and pressure conditions and reaches a dissolution-precipitation equilibrium.

[0054] In this application, the term "Arrhenius equation" refers to an empirical equation describing the changes in chemical reaction rate constants and kinetic parameters such as diffusion, dissolution, and permeation with thermodynamic temperature. In hydrogen isotope and metallic material systems, this equation can quantitatively characterize the exponential dependence of parameters such as diffusion coefficient, solubility coefficient, and permeability coefficient on temperature, and is the core thermodynamic formula for calculating the hydrogen isotope transport characteristics of materials.

[0055] This application proposes a method and system for detecting the surface reactivity of hydrogen isotopes on metal foil, which will be described in detail below.

[0056] In one aspect of this application, a method for detecting the hydrogen isotope surface reactivity of a metal foil is proposed. (Reference) Figure 1 As shown, the method may include:

[0057] S100: The metal foil is placed in the sample receiving cavity of the test chamber, which divides the inner cavity of the test chamber into a gas supply cavity and a permeation cavity.

[0058] In this step, the thickness of the metal foil is 1 µm to 150 µm, and the effective penetration area of ​​the metal foil is 0.5 cm². 2 ~20cm 2 .

[0059] S200: Vacuum the gas supply chamber and the permeation chamber respectively, and heat the sample container chamber to the preset temperature value.

[0060] In this step, the vacuum level of the gas supply chamber and the permeation chamber shall not exceed 10. -3 Pa, the metal foil sample in the sample containing cavity needs to be heated and stably maintained at any preset temperature value between 50 ℃ and 500 ℃.

[0061] S300: Hydrogen isotope gas is continuously introduced into the gas supply chamber. The hydrogen isotope gas can enter the permeation chamber through the gas supply chamber, and the gas pressure in the gas supply chamber is controlled to be maintained at a preset pressure value, while the permeation chamber is maintained in a vacuum state.

[0062] In this step, the hydrogen isotope gas includes at least one of hydrogen, deuterium, tritium, hydrogen deuteride, hydrogen tritide, and tritium deuteride. The gas pressure in the supply chamber is stably maintained at any preset pressure value between 0.1 Pa and 1000 Pa. The permeation chamber is stably maintained at a pressure not exceeding 10 Pa. -3 Pa is a vacuum state.

[0063] S400: During the introduction of hydrogen isotope gas, Raman spectroscopy is used to detect the gas in the gas supply chamber and the permeation chamber respectively, and Raman spectroscopy results are obtained.

[0064] S500: Detects the gas flow rate in the permeation chamber and obtains the gas flow rate result.

[0065] S600: Based on the acquired data, determine the dissociation adsorption coefficient and recombination desorption coefficient of the hydrogen isotopes of the metal foil. The data includes the Raman spectroscopy results and gas flow rate results.

[0066] Specifically, based on the Raman spectroscopy results of the gas supply chamber, the proportion of different types of hydrogen isotopes in the gas supply chamber can be determined. Combined with the preset pressure value, the partial pressure of dissociation molecules corresponding to various types of hydrogen isotopes can be determined.

[0067] Based on the Raman spectroscopy results of the permeation cavity, the proportion of different types of hydrogen isotopes within the cavity can be determined. The gas flow rate within the cavity is measured using a mass flow meter; this flow rate represents the total gas flow rate of different types of hydrogen isotopes. Combined with the proportion of different types of hydrogen isotopes, the corresponding gas flow rates for each type of hydrogen isotope can be obtained.

[0068] In this step, the data information further includes: the preset temperature value of the metal foil, the thickness of the metal foil, the effective permeation area of ​​the metal foil, and the partial pressure of the dissociated molecules of hydrogen isotopes in the gas supply chamber.

[0069] Reference for the dissociation adsorption and recombination desorption process of hydrogen isotope gas on metal foil surface Figure 2 As shown. In the entire detection method, refer to... Figure 3 As shown (the upstream side represents the gas supply chamber, and the downstream side represents the permeation chamber), since the gas supply chamber is continuously at a preset pressure value, hydrogen isotope gas will undergo dissociation adsorption and recombination desorption processes on the surface of the metal foil near the gas supply chamber. However, since the permeation chamber is continuously in a vacuum state, only recombination desorption occurs on the surface of the metal foil near the permeation chamber.

[0070] The following key assumptions and equations are used to determine the calculation formulas for the dissociation adsorption coefficient and recombination desorption coefficient of hydrogen isotopes in metal foil under preset temperature conditions:

[0071] (1) Hydrogen isotope gas molecules undergo dissociation and adsorption on the surface of the metal foil near the gas supply chamber, and the dissociated hydrogen isotope atoms dissolve into the metal interior. The adsorption flux is directly proportional to the partial pressure of the dissociated molecules of the hydrogen isotope containing that type of atom in the gas phase of the gas supply chamber:

[0072]

[0073] Among them, I Q K represents the adsorption flux of hydrogen isotope gas molecules when they undergo dissociation and adsorption on the surface layer of the metal foil near the gas supply chamber. α,Q P represents the dissociation adsorption coefficient of hydrogen isotopes in a metal foil under a preset temperature condition. QThis represents the partial pressure of dissociated molecules of a hydrogen isotope gas containing one or two hydrogen isotopes, calculated based on a preset pressure value and gas composition detected by Raman spectroscopy. Q represents a specific hydrogen isotope in protium, deuterium, and tritium.

[0074] (2) Atoms dissolved in the metal recombine on the surface of the metal foil near the permeation chamber and desorb into the permeation chamber in molecular form. The desorption flux is proportional to the square of the concentration of dissolved atoms undergoing recombination / desorption:

[0075]

[0076] Among them, J Q(t) K represents the desorption flux of atoms dissolved in metal, which, at a certain moment, recombine on the surface of the metal foil near the permeation cavity and then desorb into the permeation cavity in molecular form. It is also the gas flow rate obtained by the gas flow detection device. r,Q C represents the recombination and desorption coefficient of hydrogen isotopes in a metal foil under a preset temperature condition. Q（t） This indicates the concentration of dissolved atoms in the metal foil material at a certain moment, and Q represents a specific hydrogen isotope in protium, deuterium, and tritium.

[0077] (3) The flux of each component entering the metal interior through the effective leakage area of ​​the metal foil will cause the concentration of that component in the effective leakage volume of the metal foil to increase over time. Therefore, the following model can be established:

[0078]

[0079] Among them, V M Let V represent the effective leakage volume of the metal foil, S represent the effective leakage area of ​​the metal foil, and t represent the reaction duration during detection. The effective leakage volume V of the metal foil is... M With the thickness X of the metal foil M The effective leakage area S of the metal foil has a calculation relationship: .

[0080] (4) As can be seen from (3), when the permeation reaction reaches equilibrium, the internal C of the metal foil Q The concentration no longer changes, therefore dC Q（t） / dt=0, at which point I can be obtained Q -2J Q =0, and combining the relational equation in (1), we can obtain:

[0081] K α,Q =2J Q / P Q

[0082] J Q This represents the stable gas flow rate of hydrogen isotopes entering the permeation chamber after the permeation reaction has reached equilibrium.

[0083] (5) Combining the relationships in (1), (2) and (3), we can obtain that C Q（t） A class of Riccati-type ordinary differential equations can be solved analytically by integration:

[0084]

[0085] The conversion yields:

[0086]

[0087] Once the osmosis reaction reaches equilibrium, this formula has a limit, as shown in the following formula:

[0088] K r,Q =b 2 X M 2 / 2K α,Q P Q

[0089] Where b is the experimentally measured desorption flux J Q(t) The coefficients of the time term of the exponential function obtained by curve fitting. J Q(t) The measured curve can be fitted into the following exponential function form:

[0090] J Q(t) =1-2e -2bt

[0091] Furthermore, for any time t, J is measured Q(t) K can be deduced from the data at that moment. r,Q And the results calculated for different t values ​​are consistent (within the experimental error range), K r,Q J can be taken from the experimental record process Q(t) The parameter values ​​calculated during the measurement time in the equilibrium period or the K values ​​calculated at each measurement time t. r,Q The average value.

[0092] It should be noted that the solubility K of hydrogen isotopes in metal foil is based on the known solubility of these isotopes. s,Q Its relationship with the dissociation adsorption coefficient K α,Q Composite desorption coefficient K r,Q The following computational relationships exist:

[0093]

[0094] The calculated K can be further verified through the calculation relationship of this formula. r,Q and K α,Q The accuracy.

[0095] In another aspect of this application, a system is proposed for implementing the method for detecting the hydrogen isotope surface reactivity of metal foil in the foregoing embodiments, with reference to... Figure 4 As shown, the system includes:

[0096] The test unit 1000 has a sample receiving cavity 1100 for accommodating metal foil samples. This cavity divides the inner cavity of the test unit 1000 into a gas supply cavity 1200 and a permeation cavity 1300. The sample receiving cavity 1100 is made of vacuum-resistant stainless steel or alloy material, and includes a flange with an O-ring seal and a stainless steel clamp for loading, unloading, or replacing the metal foil. It contains a temperature sensor and a heater, with a preferred temperature control accuracy within ±1°C, used to maintain the metal foil sample at a preset temperature. The outer periphery of the metal foil sample is sealed to the sample receiving cavity 1100 via a sealing element.

[0097] Vacuum pumping device 2000 is connected to gas supply chamber 1200 and permeation chamber 1300 respectively.

[0098] A ventilation device 3000 is connected to a gas supply chamber 1200 and is used to continuously supply hydrogen isotope gas into the gas supply chamber 1200. This hydrogen isotope gas can enter the permeation chamber 1300 through the gas supply chamber 1200. The gas supply chamber 1200 includes a pressure sensor and a gas stabilizing valve to maintain the gas pressure within the gas supply chamber 1200 at a preset pressure value. The permeation chamber 1300 includes a pressure detector, preferably with a range covering 10... -1 Pa to 10 3 A thin-film capacitive vacuum gauge with a pressure rating of Pa and an accuracy better than ±0.5% is used to maintain a vacuum level of no more than 10 Pa within the permeation chamber 1300. -3 Pa.

[0099] The data acquisition unit 4000 includes: a Raman spectrometer 4100 for detecting the gas in the gas supply chamber 1200 and the permeation chamber 1300; and a gas flow detection device 4200 for detecting the gas flow rate in the permeation chamber 1300. The Raman spectrometer comprises a laser, a spectrometer, and a fiber optic probe. The fiber optic probe is aligned with the gas supply chamber 1200 and the permeation chamber 1300 to collect the Raman scattering signal of the hydrogen isotope gas in real time. The gas flow detection device is preferably a mass flow meter with a range of 20 sccm and an accuracy of ±1% of the set value.

[0100] Analysis unit 5000 is used to determine the dissociation adsorption coefficient and recombination desorption coefficient of hydrogen isotopes in the metal foil based on the data information obtained by data acquisition unit 4000. This data information includes preset pressure value, preset temperature value, metal foil thickness, effective leakage area of ​​the metal foil, desorption flux, and partial pressure of dissociated hydrogen isotope molecules in gas supply chamber 1200.

[0101] It should be understood that the system embodiments and method embodiments can correspond to each other, and similar descriptions can be referred to the method embodiments. To avoid repetition, they will not be repeated here. Specifically, this system can execute the above-described method embodiments for detecting the surface reaction performance of hydrogen isotopes on metal foil individually or as a whole, and the aforementioned and other operations and / or functions of each unit in the device are respectively for implementing the corresponding processes in the above method, which will not be repeated here for the sake of brevity.

[0102] Example 1: Detection of the surface reactivity of metal foil with hydrogen isotopes

[0103] 1. A pure palladium (Pd) metal foil with a thickness of 82 μm and a diameter of 12 mm was selected as the sample to be tested. It was mounted on a stainless steel clamp in the sample receiving chamber of the testing unit. The clamp was equipped with a high-temperature resistant sealing gasket, and the flange was tightened to ensure a good seal around the foil. The upstream of the metal foil was the gas supply chamber, and the downstream was the permeation chamber. The heater and thermocouple feedback control were connected to raise the foil temperature to 250 ℃ and maintain it at that temperature.

[0104] 2. Turn on the vacuum device and use a vacuum pump to evacuate the system. After evacuation for 1 hour, the system pressure will drop to 5 × 10⁻⁶. -4 Pa. At this point, close the valves connecting to the atmosphere to ensure system isolation.

[0105] 3. Adjust the pressure regulating valve to set the upstream gas line pressure to 100 Pa. Through the pressure regulator, slowly open the inlet valve of the venting device leading to the gas supply chamber, allowing high-purity deuterium gas (D2) to enter the gas supply chamber. Simultaneously, continuously maintain the permeation chamber pressure at 5 × 10⁻⁶ Pa. -4 Pa is a vacuum state.

[0106] 4. The downstream mass flow meter begins to record the change in hydrogen composite gas flow rate over time, and continues to record the entire experiment for 250 seconds to obtain the gas flow rate curve of the permeation chamber, and records the stable gas flow rate value.

[0107] 5. Calculate the surface recombination and desorption coefficient K of the Pd film at 250 ℃ using the following formula. r and the deuterium dissociation adsorption coefficient K α .

[0108]

[0109] Among them, Kα J represents the dissociation adsorption coefficient of deuterium in a metal foil at 250 °C. Q P represents the steady-state gas flow rate of deuterium entering the permeation chamber. Q K represents the partial pressure of deuterium dissociation molecules in 100 Pa. r The desorption / resorption coefficient of deuterium in the metal foil at 250℃ is represented by b; 'b' represents the exponential function 1-2e obtained by fitting the gas flow rate-time curve of the permeation chamber. -2Bt The time term coefficient B value; X M This indicates the thickness of the metal foil; Q represents deuterium.

[0110] Example 2

[0111] The dissociation adsorption coefficient and recombination desorption coefficient were determined according to the method in Example 1, except that the temperature of the metal foil was replaced with 400 °C.

[0112] Example 3

[0113] 1. A pure palladium (Pd) metal foil with a thickness of 82 μm and a diameter of 12 mm was selected as the sample to be tested. It was mounted on a stainless steel clamp in the sample receiving cavity of the testing unit. The clamp was equipped with a high-temperature resistant sealing gasket, and the flange was tightened to ensure a good seal around the foil. The upstream of the metal foil was the gas supply chamber, and the downstream was the permeation chamber. The heater and thermocouple feedback control were connected to raise the foil temperature to 300 ℃ and maintain it at that temperature.

[0114] 2. Turn on the vacuum device and use a vacuum pump to evacuate the system. After evacuation for 1 hour, the system pressure will drop to 5 × 10⁻⁶. -4 Pa. At this point, close the valves connecting to the atmosphere to ensure system isolation.

[0115] 3. Adjust the pressure regulating valve to set the upstream gas line pressure to 100 Pa. Through the pressure regulator, slowly open the inlet valve of the venting device leading to the gas supply chamber, allowing high-purity deuterium gas (D2) to enter the gas supply chamber. Simultaneously, continuously maintain the permeation chamber pressure at 5 × 10⁻⁶ Pa. -4 Pa is a vacuum state.

[0116] 4. The downstream mass flow meter begins to record the change in the flow rate of the hydrogen composite gas over time, and continues to record the entire experiment for 250 seconds to obtain the gas flow rate curve of the permeation chamber.

[0117] Test Example 1

[0118] 1. The K values ​​measured in Example 1 at 250 °C were respectively... α and K r K as measured in Example 2 at 400 °C α and K rSubstituting into the Arrhenius equation, calculate the values ​​of lnA and Ea / R, and then, based on this equation, calculate K at 300 °C. α and K r .

[0119]

[0120] Where K represents K α or K r T represents the Kelvin thermodynamic temperature; in the same metallic material and hydrogen isotope system, the pre-exponential factor (frequency factor) A, activation energy Ea, and gas constant R in the Arrhenius equation are all constants.

[0121] 2. Calculate the K at 300 ℃ α K r Substituting into Riccati-type ordinary differential equations:

[0122]

[0123] based on The desorption gas flow rate curve J of the permeation chamber was derived by reverse calculation. Q（t） The theoretical gas flow rate data is recorded as follows. The mass flow meter data measured at 300℃ for different times in Example 3 are recorded as the measured gas flow rate data.

[0124] Test Examples 2-3

[0125] Following the method in Test Example 1, pure palladium (Pd) metal foil was replaced with He surface-irradiated Pd foil (Pd-He) or Ar surface-irradiated Pd foil (Pd-Ar) to obtain theoretical and measured gas flow data.

[0126] The results of test case 1 and test cases 2-3 are as follows Figure 5 As shown, compared with the measured gas flow rate data, the K values ​​at 300 °C for three groups of Pd foils were... α K r The desorption gas flow rate fitting curve data obtained by reverse calculation almost coincides with the measured data, effectively verifying the accuracy and efficiency of the method and system of this application for detecting the surface reaction performance of hydrogen isotopes on metal foils.

[0127] In the description of this specification, the references to terms such as "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the present 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.

[0128] 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 detecting the surface reactivity of hydrogen isotopes on metal foil, characterized in that, include: A metal foil is placed in the sample receiving cavity of the test chamber, and the sample receiving cavity divides the inner cavity of the test chamber into a gas supply cavity and a permeation cavity. The gas supply chamber and the permeation chamber are evacuated respectively, and the sample receiving chamber is heated to a preset temperature value. Hydrogen isotope gas is continuously introduced into the gas supply chamber. The hydrogen isotope gas can enter the permeation chamber through the gas supply chamber. The gas pressure in the gas supply chamber is controlled to be maintained at a preset pressure value, and the permeation chamber is maintained in a vacuum state. During the process of introducing hydrogen isotope gas, Raman spectroscopy was used to detect the gas in the gas supply chamber and the permeation chamber respectively, and Raman spectroscopy results were obtained. The gas flow rate within the permeation chamber is detected to obtain the gas flow rate result; Based on the acquired data, the dissociation adsorption coefficient and recombination desorption coefficient of the hydrogen isotopes of the metal foil are determined. The data includes the Raman spectroscopy results and the gas flow rate results.

2. The method according to claim 1, characterized in that, The hydrogen isotope gas includes at least one of hydrogen, deuterium, tritium, hydrogen deuteride, hydrogen tritide, and tritium deuteride.

3. The method according to claim 1, characterized in that, The preset pressure value is 0.1 Pa to 1000 Pa; The vacuum level in the vacuum state is no greater than 10. -3 Pa.

4. The method according to claim 1, characterized in that, The thickness of the metal foil is 1 µm to 150 µm; The preset temperature value is 50 ℃ to 500 ℃.

5. The method according to claim 1, characterized in that, The data information further includes: the preset temperature value, the thickness of the metal foil, and the partial pressure of the dissociated molecules of the hydrogen isotope gas in the gas supply chamber. The dissociation adsorption coefficient and recombination desorption coefficient of the hydrogen isotope of the metal foil are determined based on the following formula: Among them, K α,Q This represents the dissociation and adsorption coefficient of hydrogen isotopes in the metal foil under the preset temperature condition. J Q This represents the stable gas flow rate of hydrogen isotopes entering the permeation chamber; P Q This indicates that the partial pressure of the dissociated molecules of the hydrogen isotope gas is calculated based on the preset pressure value and the Raman spectroscopy results. K r,Q This represents the hydrogen isotope recombination desorption coefficient of the metal foil under the preset temperature condition; b represents the exponential function 1-2e obtained by fitting the gas flow rate-time curve of the permeation chamber. -2Bt The time term coefficient B value; X M This indicates the thickness of the metal foil; Q represents a specific hydrogen isotope.

6. A system for implementing the method according to any one of claims 1 to 5, characterized in that, include: The test unit has a sample receiving cavity, which can hold a metal foil sample and heat the metal foil sample. The sample receiving cavity divides the inner cavity of the test unit into a gas supply cavity and a permeation cavity. A vacuum pumping device, which is connected to the gas supply chamber and the permeation chamber respectively; A ventilation device is connected to the gas supply chamber and is used to continuously introduce hydrogen isotope gas into the gas supply chamber. The hydrogen isotope gas can enter the permeation chamber through the gas supply chamber. Data information acquisition unit, the data information acquisition unit includes: A Raman spectrometer, used to detect the gas in the gas supply chamber and the permeation chamber respectively; A gas flow detection device, wherein the gas flow detection device is used to detect the gas flow rate in the permeation chamber; An analysis unit is used to determine the dissociation adsorption coefficient and recombination desorption coefficient of the hydrogen isotopes of the metal foil based on the data information obtained by the data information acquisition unit.

7. The system according to claim 6, characterized in that, The air supply chamber contains a pressure sensor and an air stabilizing valve, which are used to maintain the air pressure in the air supply chamber at a preset pressure value.

8. The system according to claim 6, characterized in that, The outer periphery of the metal foil sample is sealed to the sample receiving cavity by a sealing element; The sample receiving cavity contains a temperature sensor and a heater for maintaining the metal foil sample at a preset temperature value.

9. The system according to claim 6, characterized in that, The permeation chamber contains a pressure detector to maintain a vacuum level within the permeation chamber not exceeding 10. -3 Pa.

10. The system according to claim 6, characterized in that, The gas flow detection device includes a mass flow meter.

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