CN114624319A - Method for quantitatively obtaining ppm-level hydrogen isotope content in material based on thermal analysis-quadrupole mass spectrometry measurement principle - Google Patents

Method for quantitatively obtaining ppm-level hydrogen isotope content in material based on thermal analysis-quadrupole mass spectrometry measurement principle Download PDF

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CN114624319A
CN114624319A CN202210349512.3A CN202210349512A CN114624319A CN 114624319 A CN114624319 A CN 114624319A CN 202210349512 A CN202210349512 A CN 202210349512A CN 114624319 A CN114624319 A CN 114624319A
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isotope
mass spectrum
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valve
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CN114624319B (en
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陈长安
叶小球
吴吉良
李赣
朱吉鹏
杨蕊竹
李强
饶咏初
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    • G01—MEASURING; TESTING
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    • G01N13/00—Investigating surface or boundary effects, e.g. wetting power; Investigating diffusion effects; Analysing materials by determining surface, boundary, or diffusion effects
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    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N13/00—Investigating surface or boundary effects, e.g. wetting power; Investigating diffusion effects; Analysing materials by determining surface, boundary, or diffusion effects
    • G01N13/04—Investigating osmotic effects
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    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N13/00—Investigating surface or boundary effects, e.g. wetting power; Investigating diffusion effects; Analysing materials by determining surface, boundary, or diffusion effects
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Abstract

The invention belongs to the technical field of hydrogen isotope measurement in materials, and particularly relates to a method for quantitatively obtaining the content of ppm hydrogen isotopes in materials based on a thermal desorption-quadrupole mass spectrometry measurement principle. The measuring method provided by the invention comprises the following steps: and obtaining the content of the hydrogen isotope or the helium isotope in the sample to be detected according to the linear relation curve of the mass spectrum signal of the hydrogen isotope or the helium isotope and the leak rate after obtaining the signal-time relation curve of the mass spectrum signal of the hydrogen isotope or the helium isotope released by the sample to be detected along with the change of time. The measuring method provided by the invention combines thermal desorption spectrum, namely vacuum heating extraction, and mass spectrometry through the constructed linear relation curve of the gas mass spectrum signal and the leakage rate, and can realize accurate measurement of ppm-level hydrogen isotopes or helium isotopes in different materials.

Description

Method for quantitatively acquiring content of ppm-level hydrogen isotopes in material based on thermal desorption-quadrupole mass spectrometry measurement principle
Technical Field
The invention belongs to the technical field of hydrogen isotope measurement in materials, and particularly relates to a method for quantitatively obtaining the content of ppm hydrogen isotopes in materials based on a thermal desorption-quadrupole mass spectrometry measurement principle.
Background
With the increasing use of fossil energy such as petroleum and natural gas and the continuous reduction of reserves thereof, the energy problem is receiving more and more extensive attention. Among the numerous new energy sources, hydrogen energy and controlled nuclear fusion energy are solutions to human energy problems. Both of these new energy systems are widely involved in the production, storage, transportation and use of hydrogen isotopes. However, as relatively light gas elements, hydrogen isotope (H, D, T) and helium isotope (b)3He and4he) readily diffuses and resides in the containment structure material with which it is in contact. Hydrogen isotopes or helium isotopes, even in the ppm range (parts per million), entering the material may bring about the risk of hydrogen embrittlement failure of the material, resulting in significant safety accidents and economic losses. Therefore, it is very important to accurately measure the content of hydrogen isotopes in the material in ppm level.
However, the conventional spectroscopic and chromatographic analysis methods have difficulty in meeting the measurement and analysis requirements of ppm-level hydrogen isotopes or helium isotopes in the materials. The hydrogen determination instrument based on the thermal conductivity or infrared principle can realize the measurement of ppm-level hydrogen isotopes or helium isotopes in the material, but cannot perform quantitative analysis on deuterium in the hydrogen isotopes; and the measuring process has more influence factors, particularly has great influence on the quality of the hydrogen-containing solid standard sample, and the accuracy of the measuring result is poor.
Disclosure of Invention
In view of the above, the invention provides a method for quantitatively obtaining the content of ppm-level hydrogen isotopes in a material based on a thermal desorption-quadrupole mass spectrometry measurement principle, and the method for constructing the linear relationship curve of the gas mass spectrometry signal and the leak rate can accurately construct the linear relationship curve of the gas mass spectrometry signal and the leak rate, so that the accurate measurement of ppm-level hydrogen isotopes or helium isotopes in different materials can be realized.
The invention provides a method for constructing a linear relation curve of a gas mass spectrum signal and a leak rate, which comprises a first construction method using one leak hole or a second construction method using a plurality of leak holes with different leak rates, wherein the first construction method comprises the following steps: introducing gases under different constant pressure conditions at the upstream of the leak hole, detecting mass spectrum signals of the gases at the downstream of the leak hole, wherein the number of the constant pressure conditions is more than or equal to 3, and performing linear fitting after obtaining the mass spectrum signals under different leak rates to obtain a linear relation curve of the gas mass spectrum signals and the leak rates;
or comprises the following steps: introducing gas under a constant pressure condition into the upstream of the leak hole, detecting mass spectrum signals of the gas at the downstream of the leak hole in different time intervals, integrating the mass spectrum signals with time, wherein the number of the different time intervals is more than or equal to 3, and performing linear fitting on the leak rate of the different time intervals multiplied by the time integral value of the mass spectrum signals under the time condition to obtain a linear relation curve of the gas mass spectrum signals and the leak rate;
the second construction method includes the steps of:
each leak hole is provided with a gas branch, the leak holes at least have 3 leak rates, and a plurality of gas branches are connected in parallel;
and introducing constant-pressure gas into the upstream of each branch road leakage hole, detecting mass spectrum signals of the gas at the downstream of each branch road leakage hole, performing linear fitting after mass spectrum signals under different leakage rates are obtained, and obtaining a linear relation curve of the gas mass spectrum signals and the leakage rates.
The invention provides a method for measuring a hydrogen isotope or a helium isotope, which comprises the following steps:
continuously heating the sample to be detected in vacuum to increase the temperature for thermal desorption, carrying out mass spectrum detection on the released gas to obtain a signal-time relation curve of the mass spectrum signal of the hydrogen isotope or the helium isotope released by the sample to be detected along with the change of time, obtaining the release rate of the hydrogen isotope or the helium isotope at each time point according to the linear relation curve of the mass spectrum signal of the hydrogen isotope or the helium isotope and the leak rate, and obtaining the content of the hydrogen isotope or the helium isotope in the sample to be detected after integrating the time;
the linear relation curve of the mass spectrum signal and the leakage rate of the hydrogen isotope or the helium isotope is obtained according to the construction method of the technical scheme.
The invention provides a method for measuring a characteristic parameter of diffusion and/or detention of a hydrogen isotope or a helium isotope in a material, which is characterized by comprising the following steps of:
introducing a hydrogen isotope or a helium isotope at the upstream of a membrane material under different constant temperature conditions, enabling the hydrogen isotope or the helium isotope to permeate through the membrane material, detecting mass spectrum signals of the downstream hydrogen isotope or the helium isotope of the material, obtaining a signal-time relation curve of the mass spectrum signals of the hydrogen isotope or the helium isotope permeating through the membrane material along with time change under different constant temperature conditions, obtaining the leakage rate of the hydrogen isotope or the helium isotope at each time point according to the linear relation curve of the mass spectrum signals and the leakage rates of the hydrogen isotope or the helium isotope, and obtaining the permeation flux of the hydrogen isotope or the helium isotope of the membrane material under different constant temperature conditions after integrating the time; the linear relation curve of the mass spectrum signal and the leakage rate of the hydrogen isotope or the helium isotope is obtained according to the construction method of the technical scheme;
and calculating the characteristic parameters of the diffusion and retention behaviors of the hydrogen isotope or the helium isotope of the material under different temperature conditions according to the permeation flux of the hydrogen isotope or the helium isotope of the material under different temperature conditions, wherein the characteristic parameters comprise permeability, diffusion coefficient, solubility, activation energy corresponding to the permeability, activation energy corresponding to the diffusion coefficient and activation energy corresponding to the solubility.
The invention provides a gas supply system for gas mass spectrometry detection, which comprises:
the leak hole is arranged on the gas branch, one end of the gas branch is communicated with a first main pipeline positioned at the upstream of the leak hole, the other end of the gas branch is communicated with a second main pipeline positioned at the downstream of the leak hole, and the second main pipeline is used for communicating a vacuum chamber H of the mass spectrum;
an air supply/exhaust part Q; the air supply/extraction part Q is communicated with the first main pipeline.
Preferably, the leakage holes are 3 leakage holes with different leakage rates, namely a first leakage hole D, a second leakage hole E and a third leakage hole F; a first gas branch, a second gas branch and a third gas branch are arranged in parallel corresponding to the leakage holes,
a seventh valve V7 and a third pressure sensor G6 are arranged on the first gas branch upstream of the first leakage hole D, the first pressure sensor G6 is close to the first leakage hole D, and a twelfth valve V12 is arranged on the first gas branch downstream of the first leakage hole D;
an eighth valve V8 and a fourth pressure sensor G7 are arranged on the second gas branch circuit positioned at the upstream of the second leakage hole E, the fourth pressure sensor G7 is close to the second leakage hole E, and a thirteenth valve V13 is arranged on the second gas branch circuit positioned at the downstream of the second leakage hole E;
a ninth valve V9 and a fifth pressure sensor G8 are arranged on the third gas branch upstream of the third leak hole F, the fifth pressure sensor G8 is close to the third leak hole F, and a fourteenth valve V14 is arranged on the third gas branch downstream of the third leak hole F.
Preferably, a first valve V1 is arranged at one end of the first main pipe close to the air supply/extraction part Q, and a first pipe branch, a second pipe branch, a third pipe branch and a fourth pipe branch are communicated with the first main pipe between the first valve V1 and the air branch; one end of the first pipeline branch is communicated with the first main pipeline through a second valve V2, and the other end of the first pipeline branch is communicated with a standard gas storage container A; one end of the second pipeline branch is communicated with the first main pipeline through a third valve V3, and the other end of the second pipeline branch is communicated with a first thin film capacitance gauge G1; one end of the third pipeline branch is communicated with the first main pipeline through a fourth valve V4, and the other end of the third pipeline branch is communicated with a first pressure sensor G2; one end of the fourth pipeline branch is communicated with the first main pipeline through a fifth valve V5, and the other end of the fourth pipeline branch is communicated with a second pressure sensor G3.
Preferably, the gas leakage detection device further comprises a thermal desorption component B, the thermal desorption component B replaces any one of the leakage holes or further comprises a fourth gas branch connected in parallel, and a gas outlet of the thermal desorption component B is communicated with a gas inlet end of the fourth gas branch; when the gas outlet of the thermal desorption component B is communicated with the gas inlet end of the second gas branch, the gas outlet end of the fourth gas branch is communicated with the second main pipeline; and the air inlet end of the fourth gas branch is also communicated with the first main pipeline.
Preferably, a tenth valve V10 is disposed at one end of a pipeline, which is close to the fourth gas branch, of the gas inlet end of the fourth gas branch and the pipeline, which is communicated with the first main pipeline, and a fifteenth valve V15 is disposed at one end of the fourth gas branch and the pipeline, which is communicated with the second main pipeline.
Preferably, the gas leakage detection device further comprises a penetration component C, wherein the penetration component C replaces any one of the leakage holes or further comprises a fifth gas branch connected in parallel, and is arranged on the fifth gas branch; when the penetration component is arranged on a fifth gas branch, the gas inlet end of the fifth gas branch is communicated with the first main pipeline, and the gas outlet end of the fifth gas branch is communicated with the second main pipeline; a sixth valve V6 is provided in the fifth gas branch upstream of the permeation component C, and an eleventh valve V11 is provided in the fifth gas branch downstream of the permeation component C.
The invention provides a method for constructing a linear relation curve of a gas mass spectrum signal and a leak rate, which comprises a first construction method using one leak hole or a second construction method using a plurality of leak holes with different leak rates, wherein the first construction method comprises the following steps: introducing gases under different constant pressure conditions at the upstream of the leak hole, detecting mass spectrum signals of the gases at the downstream of the leak hole, wherein the number of the constant pressure conditions is more than or equal to 3, and performing linear fitting after obtaining the mass spectrum signals under different leak rates to obtain a linear relation curve of the gas mass spectrum signals and the leak rates; or comprises the following steps: introducing gas under a constant pressure condition into the upstream of the leak hole, detecting mass spectrum signals of the gas at the downstream of the leak hole in different time intervals, integrating the mass spectrum signals with time, wherein the number of the different time intervals is more than or equal to 3, and performing linear fitting on the leak rate of the different time intervals multiplied by the time integral value of the mass spectrum signals under the time condition to obtain a linear relation curve of the gas mass spectrum signals and the leak rate; the second construction method includes the steps of: each leak hole is provided with a gas branch, the leak holes at least have 3 leak rates, and a plurality of gas branches are connected in parallel; and introducing constant-pressure gas into the upstream of each branch road leakage hole, detecting mass spectrum signals of the gas at the downstream of each branch road leakage hole, performing linear fitting after mass spectrum signals under different leakage rates are obtained, and obtaining a linear relation curve of the gas mass spectrum signals and the leakage rates. The construction method provided by the invention can simply, quickly and accurately construct the linear relation curve of the gas mass spectrum signal and the leak rate. The construction method provided by the invention adopts a plurality of leakage holes with different leakage rates to form the parallel gas branch, can realize the construction of the linear relation curve of the gas mass spectrum signal and the leakage rate under the conditions of a plurality of branches of different gases and different gas pressures, and improves the accuracy of the construction of the linear relation curve of the gas mass spectrum signal and the leakage rate.
The invention provides a method for measuring a hydrogen isotope or a helium isotope, which comprises the following steps: continuously heating the sample to be detected in vacuum to increase the temperature for thermal desorption, carrying out mass spectrum detection on the released gas to obtain a signal-time relation curve of the mass spectrum signal of the hydrogen isotope or the helium isotope released by the sample to be detected along with the change of time, obtaining the release rate of the hydrogen isotope or the helium isotope at each time point according to the linear relation curve of the mass spectrum signal of the hydrogen isotope or the helium isotope and the leak rate, and obtaining the content of the hydrogen isotope or the helium isotope in the sample to be detected after integrating the time; the linear relation curve of the mass spectrum signal and the leakage rate of the hydrogen isotope or the helium isotope is obtained according to the construction method of the technical scheme. According to the measurement method provided by the invention, the thermal desorption spectrum, namely vacuum heating extraction and mass spectrometry are combined through the linear relation curve of the gas mass spectrum signal and the leak rate constructed by the technical scheme, so that the accurate measurement of ppm-level hydrogen isotopes or helium isotopes in different materials can be realized.
The invention provides a method for measuring a characteristic parameter of diffusion and/or detention of a hydrogen isotope or a helium isotope in a material, which is characterized by comprising the following steps of: introducing a hydrogen isotope or a helium isotope at the upstream of a membrane material under different constant temperature conditions, enabling the hydrogen isotope or the helium isotope to permeate through the membrane material, detecting mass spectrum signals of the downstream hydrogen isotope or the helium isotope of the material, obtaining a signal-time relation curve of the mass spectrum signals of the hydrogen isotope or the helium isotope permeating through the membrane sample along with time change under different constant temperature conditions, obtaining the leakage rate of the hydrogen isotope or the helium isotope at each time point according to the linear relation curve of the mass spectrum signals and the leakage rates of the hydrogen isotope or the helium isotope, and obtaining the permeation flux of the hydrogen isotope or the helium isotope of the membrane material under different constant temperature conditions after integrating the time; the linear relation curve of the mass spectrum signal and the leakage rate of the hydrogen isotope or the helium isotope is obtained according to the construction method of the technical scheme; and calculating the characteristic parameters of the diffusion and retention behaviors of the hydrogen isotope or the helium isotope of the material under different temperature conditions according to the permeation flux of the hydrogen isotope or the helium isotope of the material under different temperature conditions, wherein the characteristic parameters comprise permeability, diffusion coefficient, solubility, activation energy corresponding to the permeability, activation energy corresponding to the diffusion coefficient and activation energy corresponding to the solubility. The measuring method provided by the invention combines permeation of the hydrogen isotope or the helium isotope in the material with mass spectrometry through the linear relation curve of the gas mass spectrum signal and the leak rate constructed by the technical scheme, and can realize accurate measurement of characteristic parameters of diffusion and retention behaviors of the hydrogen isotope or the helium isotope of the material under different temperature conditions.
The invention provides a gas supply system for gas mass spectrometry detection, which comprises: the leak hole is arranged on the gas branch, one end of the gas branch is communicated with a first main pipeline positioned at the upstream of the leak hole, the other end of the gas branch is communicated with a second main pipeline positioned at the downstream of the leak hole, and the second main pipeline is used for communicating a vacuum chamber H of the mass spectrum; an air supply/exhaust part Q; the air supply/extraction part Q is communicated with the first main pipeline. When the gas supply system provided by the invention is used together with a mass spectrum detector, the advantage that the hydrogen isotope is high in mass spectrum sensitivity and can be easily distinguished can be utilized to measure the ppm-level hydrogen isotope in the material. The gas supply system for gas mass spectrum detection provided by the invention can realize the functions such as leak hole leak rate calibration and mass spectrum ion current signal calibration, can also realize the measurement of characteristic parameters of hydrogen isotope diffusion and retention behavior in materials, and particularly can realize the quantitative measurement of ppm-level hydrogen isotope gas released from stainless steel, tungsten, zirconium-niobium alloy and other materials.
Drawings
FIG. 1 is a schematic diagram of a test system according to an embodiment of the present invention;
wherein Q is an air supply/extraction component, V1 is a first valve, V2 is a second valve, A is a standard air storage container, V3 is a third valve, G1 is a first membrane capacitance gauge, V4 is a fourth valve, G2 is a first pressure sensing gas, V5 is a fifth valve, G3 is a second pressure sensing gas, V6 is a sixth valve, C is a penetration component, V7 is a seventh valve, G6 is a third pressure sensing gas, D is a first leak, V8 is an eighth valve, G7 is a fourth pressure sensing gas, E is a second leak, V9 is a ninth valve, G8 is a fifth pressure sensing gas, F is a third leak, V10 is a tenth valve, V11 is an eleventh valve, V12 is a twelfth valve, V13 is a thirteenth valve, V14 is a fourteenth valve, V9358 is a fifteenth valve, G15 is a fifteenth valve, G4 is a compound thermal capacitance gauge, G3646 is a full-range desorption composite thermal gauge, h is a mass spectrum vacuum chamber, V16 is a sixteenth valve, and I is a vacuum pump set;
FIG. 2 shows a graph D in example 1 of the present invention2And He in example 2 and measurement data and fitted graphs of leak rate at different pressures;
FIG. 3 shows a graph D in example 1 of the present invention2And the measured data and the fitted curve chart of the mass spectrum signals under different He leak rates in example 2;
FIG. 4 shows a graph of D in a sample to be tested in example 1 of the present invention2A time-dependent change curve graph of mass spectrum signals of thermal desorption praseodymium;
FIG. 5 shows HD and D in the film material of example 4 of the present invention2And calibrating D2The mass spectrum signal of the permeation of (a) is plotted as a function of temperature.
Detailed Description
The invention provides a method for constructing a linear relation curve of a gas mass spectrum signal and a leak rate, which comprises a first construction method using one leak hole or a second construction method using a plurality of leak holes with different leak rates, wherein the first construction method comprises the following steps: introducing gases under different constant pressure conditions at the upstream of the leak hole, detecting mass spectrum signals of the gases at the downstream of the leak hole, wherein the number of the constant pressure conditions is more than or equal to 3, and performing linear fitting after obtaining the mass spectrum signals under different leak rates to obtain a linear relation curve of the gas mass spectrum signals and the leak rates;
or comprises the following steps: introducing gas under a constant pressure condition into the upstream of the leak hole, detecting mass spectrum signals of the gas at the downstream of the leak hole in different time intervals, integrating the mass spectrum signals with time, wherein the number of the different time intervals is more than or equal to 3, and performing linear fitting on the leak rate of the different time intervals multiplied by the time integral value of the mass spectrum signals under the time condition to obtain a linear relation curve of the gas mass spectrum signals and the leak rate;
the second construction method includes the steps of:
each leak hole is provided with a gas branch, the leak holes at least have 3 leak rates, and a plurality of gas branches are connected in parallel;
introducing constant-pressure gas into the upstream of each branch road leakage hole, detecting mass spectrum signals of the gas at the downstream of each branch road leakage hole, performing linear fitting after mass spectrum signals under different leakage rate conditions are obtained, and obtaining a linear relation curve of the gas mass spectrum signals and the leakage rate.
In the present invention, the leak is preferably a standard leak.
The invention has no special requirement on the source of the leak hole, and the product sold in the market can be adopted.
In the invention, when a linear relation curve of helium isotope gas mass spectrum signals and leak rates is established, leak rate calibration is not needed because the leak rates of different leak holes of the helium isotope are known.
In the present invention, when the linear relationship curve of the hydrogen isotope gas mass spectrum signal and the leak rate is established, the present invention preferably includes calibrating the leak rate of the hydrogen isotope before the linear relationship curve of the hydrogen isotope gas mass spectrum signal and the leak rate is established.
In the present invention, the method for calibrating the hydrogen isotope leakage rate preferably includes the following steps:
and introducing hydrogen isotope gas under different constant pressure conditions at the upstream of the leak hole, calibrating the leak rate of the hydrogen isotope gas under different constant pressure conditions by adopting a constant volume method, and establishing a leak rate calibration curve of the hydrogen isotope gas under different constant pressure conditions.
Before the hydrogen isotope gas leak rate is calibrated, the volume of the vacuum chamber and the pipeline downstream of the leak hole is preferably calibrated by adopting a volume expansion method, and the method has no special requirements on the specific implementation process of the volume expansion method.
The invention adopts a plurality of leak holes of the multi-branch parallel pipeline to establish a linear relation curve of gas mass spectrum signals and leak rates, and can realize the calibration and calibration of the leak rates of the plurality of leak holes under different hydrogen isotope gases and different constant gas pressures.
The invention provides a method for measuring a hydrogen isotope or a helium isotope, which comprises the following steps:
continuously heating the sample to be detected in vacuum to increase the temperature for thermal desorption, carrying out mass spectrum detection on the released gas to obtain a signal-time relation curve of the mass spectrum signal of the hydrogen isotope or the helium isotope released by the sample to be detected along with the change of time, obtaining the release rate of the hydrogen isotope or the helium isotope at each time point according to the linear relation curve of the mass spectrum signal of the hydrogen isotope or the helium isotope and the leak rate, and obtaining the content of the hydrogen isotope or the helium isotope in the sample to be detected after integrating the time;
the linear relation curve of the mass spectrum signal and the leakage rate of the hydrogen isotope or the helium isotope is obtained according to the construction method of the technical scheme.
In the present invention, the sample to be tested is preferably stainless steel, tungsten or zirconium-niobium alloy.
In the present invention, the sample to be tested is preferably subjected to a pretreatment, and in the present invention, the pretreatment preferably includes: the washing and drying are sequentially carried out, and the invention has no special requirements on the specific implementation modes of the washing and drying.
The invention provides a method for measuring a characteristic parameter of diffusion and/or detention of a hydrogen isotope or a helium isotope in a material, which is characterized by comprising the following steps of:
introducing a hydrogen isotope or a helium isotope into the upstream of a membrane material under different constant temperature conditions, wherein the hydrogen isotope or the helium isotope permeates through the membrane material, detecting mass spectrum signals of the downstream hydrogen isotope or the helium isotope of the material, obtaining a signal-time relation curve of the mass spectrum signals of the hydrogen isotope or the helium isotope permeated by the sample along with time change under different constant temperature conditions, obtaining the leakage rate of the hydrogen isotope or the helium isotope at each time point according to the linear relation curve of the mass spectrum signals and the leakage rates of the hydrogen isotope or the helium isotope, and obtaining the permeation flux of the hydrogen isotope or the helium isotope of the membrane material under different constant temperature conditions after time integration; the linear relation curve of the mass spectrum signal and the leakage rate of the hydrogen isotope or the helium isotope is obtained according to the construction method of the technical scheme;
and calculating the characteristic parameters of the diffusion and retention behaviors of the hydrogen isotope or the helium isotope of the material under different temperature conditions according to the permeation flux of the hydrogen isotope or the helium isotope of the material under different temperature conditions, wherein the characteristic parameters comprise permeability, diffusion coefficient, solubility, activation energy corresponding to the permeability, activation energy corresponding to the diffusion coefficient and activation energy corresponding to the solubility.
In the present invention, the shape of the material for permeation test is preferably a membrane shape.
In the present invention, the membrane material is preferably piped to the mass spectrometer vacuum after being in the permeable member through a vacuum connection radial seal (VCR seal).
In the present invention, the method of obtaining the characteristic parameters of the diffusion and retention behavior of the hydrogen isotope or the helium isotope of the material under different temperature conditions by calculating the permeation flux of the hydrogen isotope or the helium isotope of the material under different temperature conditions is preferably: obtaining the permeation flux of the hydrogen isotope or the helium isotope of the material under different temperature conditions, and substituting the obtained permeation flux into a permeation flux formula based on Fick's law to obtain characteristic parameters of diffusion and retention behaviors of the hydrogen isotope or the helium isotope of the material under different temperature conditions, wherein the permeation flux formula generally has a form shown in formula 1:
Figure BDA0003578963370000091
in the formula 1, J represents a permeation flux (unit: mol. multidot.s)-1) Phi is the permeability (unit: mol. m-1·s-1·Pa-n) And D is the diffusion coefficient (unit: m is2·s-1) And S is solubility (unit: mol. m-3·Pa-n) σ is the effective penetration area of the material (unit: m is2) And d is the thickness of the material (unit: m), Pin(unit: Pa), Pout(Pa) is the pressure of the upstream and downstream sides of the material, and n is the pressure index (the value range is generally 1/2 ≦ n ≦ 1).
The invention provides a method for obtaining characteristic parameters of diffusion and retention behaviors of hydrogen isotopes in a material, which is relatively objective and reliable.
The invention provides a gas supply system for gas mass spectrometry detection, which comprises:
the leak hole is arranged on the gas branch, one end of the gas branch is communicated with a first main pipeline positioned at the upstream of the leak hole, the other end of the gas branch is communicated with a second main pipeline positioned at the downstream of the leak hole, and the second main pipeline is used for communicating a vacuum chamber H of the mass spectrum;
an air supply/exhaust part Q; the air supply/extraction part Q is communicated with the first main pipeline.
The gas supply system provided by the invention comprises a gas supply/extraction part Q, and the gas supply/extraction part Q is communicated with the first main pipeline.
In the embodiment of the present invention, the gas supply/exhaust part Q is composed of a vacuum pump and a gas supply system.
In the present invention, the gas supply/exhaust component Q is used for evacuating a gas supply system, providing an isotope gas, or an inert gas for leak detection and volume calibration of the gas supply system, and the isotope gas preferably includes a hydrogen isotope gas or a helium isotope gas.
In the present invention, a first valve V1 is provided at an end of the first main duct close to the air supply/extraction part Q.
In the present invention, the first valve is preferably a high-pressure all-metal valve, the first valve V1 has a pressure resistance of not less than 10MPa, and the first valve V1 is used to control the flow of gas.
In the invention, a first main pipeline positioned between the first valve V1 and the gas branch on the first main pipeline is communicated with a first pipeline branch, a second pipeline branch, a third pipeline branch and a fourth pipeline branch; one end of the first pipeline branch is communicated with the first main pipeline through a second valve V2, and the other end of the first pipeline branch is communicated with the standard gas storage container A.
In the invention, the second valve V2 is preferably a high-pressure all-metal valve, the pressure resistance of the second valve V2 is not lower than 10MPa, and the second valve V2 is used for controlling the flow of gas and the selection of flow channels.
In the present invention, the volume of the standard gas container a is known, and the standard gas container a is used as a standard volume for volume calibration of other parts of the system, and for temporary storage of the reaction gas.
In the invention, one end of the second pipeline branch is communicated with the first main pipeline through a third valve V3, and the other end of the second pipeline branch is communicated with a first thin film capacitance gauge G1.
In the invention, the third valve V3 is preferably a high-pressure all-metal valve, the pressure resistance of the third valve V3 is not lower than 10MPa, and the third valve V3 is used for controlling the flow of gas and the selection of a flow passage.
In the invention, the first thin film capacitance gauge G1 is connected to a computer through a data line and is used for measuring and monitoring the change of the vacuum state of the system.
In the present invention, one end of the third pipe branch is communicated with the first main pipe through a fourth valve V4, and the other end of the third pipe branch is communicated with a first pressure sensor G2.
In the present invention, the fourth valve V4 is preferably a high-pressure all-metal valve, the fourth valve V4 has a pressure resistance of not less than 10MPa, and the fourth valve V4 is used to control the flow of gas and the selection of flow channels.
In the present invention, the first pressure sensor G2 is connected to a computer through a data line for measuring and monitoring the gas pressure value of the system.
In the present invention, one end of the fourth pipe branch is communicated with the first main pipe through a fifth valve (V5), and the other end of the fourth pipe branch is communicated with a second pressure sensor G3.
In the present invention, the fifth valve V5 is preferably a high pressure all metal valve, the pressure resistance of the fifth valve V5 is not less than 10MPa, and the fifth valve V5 is used to control the flow of gas and the selection of flow passage.
In the present invention, the second pressure sensor G3 is connected to a computer through a data line for measuring and monitoring the gas pressure value of the system.
The gas supply system provided by the present invention includes: the leak hole, the leak hole sets up on the gas branch road, the one end of gas branch road with be located the first trunk line intercommunication of leak hole upper reaches, the other end of gas branch road with be located the second trunk line intercommunication of leak hole lower reaches, the second trunk line is used for communicating the vacuum chamber H of mass spectrum.
In the present invention, the inner diameter of the second main pipe is preferably not less than 16 mm.
In the present invention, the second main pipe is preferably an inner polished stainless steel pipe.
In the invention, the second main pipeline is preferably provided with a heating belt, so that baking and degassing can be carried out at any time.
In the invention, the leak holes are 3 leak holes with different leak rates, namely a first leak hole D, a second leak hole E and a third leak hole F; and a first gas branch, a second gas branch and a third gas branch are arranged in parallel corresponding to the leakage hole.
In the invention, for the same isotope gas, a plurality of leak holes with different leak rates, such as a first leak hole D, a second leak hole E and a third leak hole F, are preferably adopted to construct the relationship between the leak rate and the ion flow signal so as to establish a calibration curve.
In the present invention, a seventh valve V7 and a third pressure sensor G6 are provided in the first gas branch upstream of the first leak hole D, the first pressure sensor G6 is close to the first leak hole D, and a twelfth valve V12 is provided in the first gas branch downstream of the first leak hole D.
In the present invention, the seventh valve V7 is preferably a high-pressure all-metal valve, the pressure resistance of the seventh valve V7 is not less than 10MPa, and the seventh valve V7 is used to control the flow of gas and the selection of flow passage.
In the invention, the range of the third pressure sensor G6 is preferably-0.1-5 bar, and the third pressure sensor G6 is used for monitoring the pressure change of the upstream side of the first leakage hole D in real time; when the pressure change exceeds 5% of the initial pressure, the gas needs to be supplemented to maintain the initial pressure so as to ensure that the leak rate of the leak hole is stable.
In the present invention, the twelfth valve V12 is preferably an all-metal ultrahigh vacuum angle valve for blocking the low vacuum and ultrahigh vacuum portions, so that ultrahigh vacuum is more easily obtained and maintained.
In the present invention, the inner diameter of the first gas branch between the twelfth valve V12 and the second main pipe is preferably not less than 16 mm.
In the present invention, the first gas branch between the twelfth valve V12 and the second main pipe is preferably an inner polished stainless steel pipe.
In the present invention, the first gas branch between the twelfth valve V12 and the second main pipe is preferably equipped with a heating belt, so that the baking degassing can be performed at any time.
In the present invention, an eighth valve V8 and a fourth pressure sensor G7 are provided on the second gas branch upstream of the second leak hole E, the fourth pressure sensor G7 is close to the second leak hole E, and a thirteenth valve V13 is provided on the second gas branch downstream of the second leak hole E.
In the present invention, the eighth valve V8 is preferably a high-pressure all-metal valve, the pressure resistance of the eighth valve V8 is not less than 10MPa, and the eighth valve V8 is used to control the flow of gas and the selection of flow channel.
In the invention, the range of the fourth pressure sensor G7 is preferably-0.1-5 bar, and the fourth pressure sensor G7 is used for monitoring the pressure change of the upstream side of the second leakage hole D in real time; when the pressure change exceeds 5% of the initial pressure, the gas needs to be supplemented to maintain the initial pressure so as to ensure that the leak rate of the leak hole is stable.
In the present invention, the thirteenth valve V13 is preferably an all-metal ultrahigh vacuum angle valve for blocking the low vacuum and ultrahigh vacuum portions, so that ultrahigh vacuum is more easily obtained and maintained.
In the present invention, the inner diameter of the second gas branch between the thirteenth valve V13 and the second main pipe is preferably not less than 16 mm.
In the present invention, the second gas branch between the thirteenth valve V13 and the second main pipe is preferably an inner polished stainless steel pipe.
In the present invention, the second gas branch between the thirteenth valve V13 and the second main pipe is preferably equipped with a heating belt, which can be used for roasting and degassing at any time.
In the present invention, a ninth valve V9 and a fifth pressure sensor G8 are provided in the third gas branch upstream of the third leak hole F, the fifth pressure sensor G8 is close to the third leak hole F, and a fourteenth valve V14 is provided in the third gas branch downstream of the third leak hole F.
In the present invention, the ninth valve V9 is preferably a high pressure all metal valve, the pressure resistance of the ninth valve V9 is not less than 10MPa, and the ninth valve V9 is used to control the flow of gas and the selection of flow passage.
In the invention, the range of the fifth pressure sensor G8 is preferably-0.1-5 bar, and the fifth pressure sensor G8 is used for monitoring the pressure change of the upstream side of the third leakage hole D in real time; when the pressure change exceeds 5% of the initial pressure, the gas needs to be supplemented to maintain the initial pressure so as to ensure that the leak rate of the leak hole is stable.
In the present invention, the fourteenth valve V14 is preferably an all-metal ultrahigh vacuum angle valve for blocking the low vacuum and ultrahigh vacuum portions, so that ultrahigh vacuum is more easily obtained and maintained.
In the present invention, the inner diameter of the third gas branch between the fourteenth valve V14 and the second main pipe is preferably not less than 16 mm.
In the present invention, the third gas branch between the fourteenth valve V14 and the second main pipe is preferably an inner polished stainless steel pipe.
In the present invention, the third gas branch between the fourteenth valve V14 and the second main pipe is preferably equipped with a heating belt, so that the baking degassing can be performed at any time.
The gas supply system provided by the invention also comprises a thermal desorption part B, wherein the thermal desorption part B replaces any one of the leak holes or also comprises a fourth gas branch connected in parallel, and a gas outlet of the thermal desorption part B is communicated with a gas inlet end of the fourth gas branch; when the gas outlet of the thermal desorption component B is communicated with the gas inlet end of the second gas branch, the gas outlet end of the fourth gas branch is communicated with the second main pipeline; and the air inlet end of the fourth gas branch is also communicated with the first main pipeline.
In the present invention, the inner diameters of the fourth gas branch and the side pipe are preferably not less than 16 mm.
In the present invention, the fourth gas branch and the side pipe are preferably internally polished stainless steel pipes.
In the present invention, the fourth gas branch is preferably provided with a heating belt, so that the baking degassing can be performed at any time.
In the invention, a tenth valve V10 is arranged at one end, close to the fourth gas branch, of a pipeline, of which the gas inlet end of the fourth gas branch is communicated with the first main pipeline, and a fifteenth valve V15 is arranged at one end, communicated with the second main pipeline, of the fourth gas branch.
In the present invention, the tenth valve V10 is preferably an all-metal ultrahigh vacuum angle valve for blocking low vacuum and ultrahigh vacuum portions, so that ultrahigh vacuum is more easily obtained and maintained.
In the present invention, the fifteenth valve V15 is preferably an all-metal ultrahigh vacuum angle valve for blocking the low vacuum and ultrahigh vacuum portions, so that ultrahigh vacuum is more easily obtained and maintained.
In the present invention, the thermal desorption unit B preferably comprises a heating and temperature control device.
In the invention, the thermal desorption part B preferably adopts a CF flange with small outgassing amount to weld a quartz tube, the sample is placed in the quartz tube, and the quartz tube is connected into the second gas branch by the CF flange through a copper gasket and a knife edge.
The invention preferably adopts a local heating mode of electromagnetic induction heating to heat the local position of the quartz tube where the sample to be detected in the thermal desorption part B is located; and heating the sample to ensure that the desorbed hydrogen isotope gas passes through the mass spectrum G to obtain a corresponding ion current signal.
The gas supply system provided by the invention preferably further comprises a penetration component C, wherein the penetration component C replaces any one of the leakage holes or further comprises a fifth gas branch connected in parallel, and the penetration component C is arranged on the fifth gas branch; when the penetration component is arranged on a fifth gas branch, the gas inlet end of the fifth gas branch is communicated with the first main pipeline, and the gas outlet end of the fifth gas branch is communicated with the second main pipeline; a sixth valve V6 is provided in the fifth gas branch upstream of the permeation component C, and an eleventh valve V11 is provided in the fifth gas branch downstream of the permeation component C.
In the present invention, the penetrating component C preferably contains a heating and temperature control device.
In the invention, preferably, a material membrane to be tested is packaged in the penetration component C in a Vacuum Coupling radial Seal (VCR) mode, a certain amount of hydrogen isotope gas is introduced to the upstream side of the penetration component C, a hydrogen isotope mass spectrum signal at the downstream side of the penetration component C is measured and calibrated by using a leak hole, and characteristic data such as permeability, diffusion coefficient, solubility and corresponding activation energy of the hydrogen isotope in the material can be obtained through proper mathematical treatment; the method is a relatively objective and reliable method for obtaining characteristic parameters of diffusion and retention behaviors of hydrogen isotopes in the material.
In the present invention, the sixth valve V6 is preferably a high pressure all metal valve, the sixth valve V6 has a pressure resistance of not less than 10MPa, and the sixth valve V6 is used to control the flow of gas and the selection of flow passage.
In the present invention, the eleventh valve V11 is preferably an all-metal ultrahigh vacuum angle valve for blocking the low vacuum and ultrahigh vacuum portions, so that ultrahigh vacuum is more easily obtained and maintained.
In the present invention, the inner diameter of the fifth gas branch between the eleventh valve V11 and the second main pipe is preferably not less than 16 mm.
In the present invention, the fifth gas branch between the eleventh valve V11 and the second main pipe is preferably an inner polished stainless steel pipe.
In the present invention, the fifth gas branch between the eleventh valve V11 and the second main pipe is preferably equipped with a heating belt, so that the baking degassing can be performed at any time.
The second main pipeline of the gas supply system is used for communicating a vacuum chamber H of a mass spectrum.
In the present invention, the vacuum chamber H is provided with a mass spectrometry probe G.
In the present invention, the mass spectrum is preferably a quadrupole mass spectrum.
In the present invention, the mass spectrometer is used to collect ion current signals of the gas flowing through the ultra-vacuum chamber H.
In the present invention, the vacuum chamber H is provided with a second thin film capacitance gauge G4 and a full-scale composite gauge G5, and the second thin film capacitance gauge G4 and the full-scale composite gauge G5 are communicated with the vacuum chamber H.
In the present invention, the second film capacitance gauge G4 is used to monitor the vacuum state change of the vacuum chamber H.
In the present invention, the full-scale compound gauge G5 is used to measure the vacuum of the vacuum chamber H.
In the invention, the measuring range of the full-range compound gauge G5 is preferably 10-8Pa～1atm。
In the present invention, the inner diameter of the pipe connecting the second film gauge G4 and the vacuum chamber H is preferably not less than 16 mm.
In the present invention, the pipe connecting the second film gauge G4 and the vacuum chamber H is preferably an inner polished stainless steel pipe.
In the present invention, the pipe connecting the second film gauge G4 and the vacuum chamber H is preferably provided with a heating belt, and can be baked and degassed as needed.
In the present invention, the inner diameter of the pipe connecting the full-scale compound gauge G5 and the vacuum chamber H is preferably not less than 16 mm.
In the present invention, the pipe through which the full-scale compound gauge G5 communicates with the vacuum chamber H is preferably an inner-polished stainless steel pipe.
In the present invention, the pipe connecting the full-scale combination gauge G5 and the vacuum chamber H is preferably provided with a heating belt, and can be baked and degassed as needed.
In the present invention, the vacuum chamber H communicates with a vacuum pump group I.
In the present invention, the vacuum pump set I is used to control vacuum chamber evacuation and static vacuum maintenance.
In the present invention, a sixteenth valve V16 is disposed on a pipeline connecting the vacuum pump set I and the vacuum chamber H.
In the present invention, the sixteenth valve V16 is preferably an ultra-high vacuum gate valve.
In the present invention, the sixteenth valve V16 is used to isolate evacuation pump set I from vacuum chamber H, controlling vacuum chamber evacuation and static vacuum hold.
In the present invention, the inner diameter of the pipe through which the vacuum pump group I and the vacuum chamber H communicate is preferably not less than 16 mm.
In the present invention, the piping of the piping through which the vacuum pump group I and the vacuum chamber H communicate is preferably an internally polished stainless steel pipe.
In the invention, the pipeline for communicating the vacuum pump set I and the vacuum chamber H is preferably provided with a heating belt, so that the baking and degassing can be carried out at any time.
The method for calibrating the leakage rate of the hydrogen isotope by using the gas supply system shown in FIG. 1 preferably comprises the following steps
1) Opening valves V1-V5, V10, V15 and V16, evacuating the system, and then closing the valves;
2) opening V1, V2 and V4, and filling a certain amount of inert gas such as argon into a standard gas container A with a known volume;
3) the valve V2 is closed, and after the air supply/exhaust part Q end evacuates the system, the valve V1 is closed;
4) sequentially opening valves V2, V10 and V15, and sequentially calibrating the volumes of the pipeline and the vacuum mass spectrum chamber H by a volume expansion method;
5) after the volume calibration is finished, opening valves V1, V3-V5, V7, V12 and V16 to evacuate the pipeline, the mass spectrum vacuum chamber H and the upstream and downstream parts of the first leak hole D;
6) and (3) closing the valve V16, filling hydrogen isotope gas with certain pressure into the leak hole, closing the valve V1, acquiring the gas pressure entering the mass spectrum chamber through the downstream side of the first leak hole D in real time through the second thin film capacitance gauge G4 and the full-range composite gauge G5, and calculating the leak rate of the first leak hole D under the environment temperature and the pressure according to the calibrated volume.
7) And repeating the steps 4) -5) to obtain hydrogen isotope leakage rate data of the second leak hole E and the third leak hole F under different pressures, and completing the leakage rate calibration process of the leak holes.
The invention relates to a multipoint calibration method for calibrating a hydrogen isotope signal acquired by mass spectrometry by using a leak hole with known hydrogen isotope leak rate to obtain a calibration curve, which comprises the following steps: for the same hydrogen isotope or helium isotope gas, a plurality of leak holes (a first leak hole D, a second leak hole E and a third leak hole F) with different leak rates are adopted to construct the relationship between the leak rate and an ion flow signal, and a calibration curve is established. In the invention, when a calibration curve is established by adopting one branch, the invention preferably uses the actual gas quantity (leak rate multiplied by time) flowing into the vacuum mass spectrum cavity H from the leak hole in different time periods and the integral of the corresponding ion current signal along with time to construct the multipoint calibration method of the gas quantity and ion current signal integral relation.
The method for establishing the linear relation curve between the mass spectrum signal and the leak rate of the hydrogen isotope or the helium isotope by using the gas supply system shown in FIG. 1 comprises the following steps:
1) opening a valve V16, and maintaining the ultrahigh vacuum state of the vacuum mass spectrum chamber H through a vacuum pump group I; starting a quadrupole mass spectrum G, and obtaining a background hydrogen isotope signal after stabilizing for a period of time;
2) filling hydrogen isotope gas with a certain pressure into the first leak hole D (the corresponding leak rate under the pressure is known), closing the valve V7, opening the valve V12, obtaining a hydrogen isotope ion flow signal corresponding to the leak rate after the mass spectrum signal is stable, and closing the valve V12;
3) repeating the step 2), and obtaining mass spectrum ion current signals corresponding to the second leak hole E and the third leak hole F with known hydrogen isotope leak rates;
4) and establishing a linear relation curve of the mass spectrum signal and the leak rate of the hydrogen isotope or the helium isotope according to the ion current signals corresponding to different leak rates.
The invention adopts a vacuum heating extraction mass spectrometry method for measuring the content of ppm hydrogen isotope or helium isotope in a material to be measured. In the present invention, the thermal desorption spectroscopy method is preferably implemented by heating a sample to be detected by using a thermal desorption part B shown in fig. 1 to obtain a corresponding ion current signal through a mass spectrum G, and calibrating the ion current signal by using a standard first leak D, a second leak E, and a third leak F), thereby implementing quantitative analysis.
In the invention, in order to reduce the influence of the hydrogen background of the sample tube in the sample heating process, a thermal desorption part B in the gas supply system adopts a CF flange with small gas release amount to weld a quartz tube, a sample to be detected is placed in the quartz tube, and the quartz tube is connected into a system pipeline through the CF flange in a copper gasket cutting edge mode; meanwhile, the scheme that the local position of the quartz tube where the sample is located is heated by adopting local heating modes such as electromagnetic induction heating and the like is adopted, so that the influence of hydrogen background caused by hydrogen discharge of the quartz tube in the heating process can be further reduced, and the accuracy of the measurement result is improved.
In the present invention, the basic method for measuring the content of ppm hydrogen isotope or helium isotope in the material to be measured by using the gas supply system shown in fig. 1 is as follows:
1) the valve V16 and the evacuation pump set (I) are always opened to ensure that the mass spectrum chamber is always in a high vacuum state;
2) closing the valves V10 and V15, and placing the cleaned and dried sample at the end of the quartz tube, far from the flange side;
3) opening valves V1, V3 and V10, and vacuumizing the quartz tube to below 10Pa through the end Q of the gas supply/exhaust part;
4) closing the valve V10, opening the valve V15, and continuously pumping high vacuum through the vacuum pump set I;
5) opening the mass spectrum G, and collecting mass spectrum signals of the vacuum primitive cavity at room temperature;
6) starting an induction heating device, heating a sample through a sample tube to release hydrogen isotope gas in the sample, and collecting a hydrogen isotope gas signal released by the sample through mass spectrometry;
7) and (4) obtaining a standard curve through leak rate calibration mass spectrum signals, and calculating the hydrogen isotope release amount in the sample.
The present invention preferably further comprises measuring the diffusion and retention behavior characteristic parameters of the hydrogen isotope or helium isotope in the material using the gas supply system shown in fig. 1. In the invention, preferably, the membrane material to be tested is packaged in a penetrating component C in a graph 1 in a VCR sealing mode, a certain amount of hydrogen isotope or helium isotope gas is introduced to the upstream side of the membrane material, a hydrogen isotope mass spectrum signal at the downstream side of the membrane material is measured and calibrated by using a leak hole, and characteristic data such as the permeability, the diffusion coefficient, the solubility and the corresponding activation energy of the hydrogen isotope in the material can be obtained by proper mathematical processing. The gas supply system and the measurement method provided by the invention are relatively objective and reliable methods for obtaining characteristic parameters of diffusion and retention behaviors of hydrogen isotopes in materials. As shown in fig. 1, the gas supply system provided by the present invention ensures that the gas flow path on the downstream side of the leak hole is consistent with the gas flow path released by the sample in the permeation tool, thereby ensuring the reliability of the test data. In the invention, the specific method for testing the hydrogen isotope permeability in the material comprises the following steps:
1) the valve V16 and the evacuation pump set I are always opened to ensure that the mass spectrum chamber is always in a high vacuum state;
2) connecting the cleaned and dried material membrane into a permeation tool;
3) opening valves V1, V3, V5, V6 and V11, and evacuating the upstream and downstream sides of the membrane in the permeation tool;
4) opening a mass spectrum, introducing a certain amount of inert gas through a Q section of the gas supply/extraction part, and detecting whether the ion current signal of the inert gas is obviously increased compared with the background through the mass spectrum, wherein if the ion current signal is not obviously changed, the sealing performance of the diaphragm is intact;
5) after the inert gas on the upstream side of the diaphragm is pumped out, introducing hydrogen isotope gas with certain pressure, and collecting hydrogen isotope mass spectrum signals permeating from the downstream side of the diaphragm at different temperatures;
6) and calibrating mass spectrum signals through leak rate to obtain hydrogen isotope permeation characteristic parameters of the membrane material.
The measuring method and the gas supply system have the following beneficial effects:
1. according to the invention, the requirement of accurate measurement of the content of ppm hydrogen isotope or helium isotope in hydrogen energy and nuclear energy materials is met, and the parallel layout scheme of the multiple leak holes, the thermal desorption tool and the permeation tool is adopted, so that the flow path of gas at the downstream side of the leak holes is consistent with the flow path of gas released by a sample in the thermal desorption tool or the permeation tool, and the calibration and calibration of the leak rate of the multiple leak holes under different hydrogen isotope gases and different gas pressures can be realized.
2. The invention adopts a plurality of leak holes with different leak rates to construct the relationship between the gas leak rate and the ion current signal corresponding to the mass spectrum, and establishes a calibration curve. Particularly, for the situation of the same leak rate, the invention provides a multipoint calibration method for constructing the integral relation of the gas volume and the ion flow signal by adopting the actual gas volume (leak rate multiplied by time) of the leak hole flowing into the mass spectrum cavity in different time periods and the integral of the corresponding ion flow signal along with time.
3. The invention adopts a series of measures to reduce the influence of the hydrogen background of the sample tube in the sample heating process, and the method specifically comprises the following steps: 1) the thermal desorption tool adopts a CF flange with less air release to weld a quartz tube, a sample is placed in the quartz tube, and the quartz tube is connected into a system pipeline through the CF flange in a copper gasket knife edge mode; 2) the scheme that the local position of the quartz tube where the sample is located is heated by adopting local heating modes such as electromagnetic induction heating and the like is adopted, so that the influence of hydrogen background caused by hydrogen discharge of the quartz tube in the heating process is further reduced, and the accuracy of the measuring result is improved.
4. The system designed by the invention is a set of multifunctional system, can realize the calibration of different leak rates and the calibration of mass spectrum ion flow signals, can also realize the measurement of characteristic parameters of diffusion and retention behaviors of hydrogen isotopes in the material, and particularly can realize the quantitative analysis of ppm-level hydrogen isotope gas released in the material, thereby having important application in the field of hydrogen energy and nuclear energy materials.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the disclosed embodiments are merely exemplary of the invention, and are not intended to be exhaustive or exhaustive. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Firstly, the method comprises the following steps: by means of the pair D of air supply systems shown in FIG. 12The calibration method of the leakage rate comprises the following steps:
1) opening valves V1-V5, V10, V15 and V16, evacuating the system, and then closing the valves;
2) opening V1, V2 and V4, and filling a certain amount of inert gas such as argon into a standard gas container A with a known volume;
3) the valve V2 is closed, and after the system is pumped out through the end Q of the air supply/exhaust part, the valve V1 is closed;
4) sequentially opening valves V2, V10 and V15, and sequentially calibrating the volumes of the pipeline and the vacuum mass spectrum chamber H by a volume expansion method;
5) after the volume calibration is finished, opening valves V1, V3-V5, V7, V12 and V16 to evacuate the pipeline, the mass spectrum vacuum chamber H and the upstream and downstream parts of the first leak hole D;
6) and (3) closing the valve V16, filling hydrogen isotope gas with certain pressure into the leak hole, closing the valve V1, acquiring the gas pressure entering the mass spectrum chamber through the downstream side of the first leak hole D in real time through the second thin film capacitance gauge G4 and the full-range composite gauge G5, and calculating the leak rate of the first leak hole D under the environment temperature and the pressure according to the calibrated volume.
7) And repeating the steps 4) to 5) to obtain hydrogen isotope leakage rate data of the second leakage hole E and the third leakage hole F under different pressures, and completing the leakage rate calibration process of the leakage holes, wherein the calibration curve is shown in fig. 2.
Secondly, the method comprises the following steps: the gas supply system D shown in FIG. 1 is adopted2The method for the linear relation curve of the mass spectrum signal and the leakage rate comprises the following steps:
1) opening a valve V16, and maintaining the ultrahigh vacuum state of the vacuum mass spectrum chamber H through a vacuum pump group I; starting a quadrupole mass spectrum G, and obtaining a background hydrogen isotope signal after stabilizing for a period of time;
2) filling hydrogen isotope gas with a certain pressure (the corresponding leak rate under the pressure is known) into the first leak hole D, closing the valve V7, opening the valve V12, obtaining a hydrogen isotope ion current signal corresponding to the leak rate after the mass spectrum signal is stable, and closing the valve V12;
3) repeating the step 2), and obtaining mass spectrum ion current signals corresponding to the second leak hole E and the third leak hole F with known hydrogen isotope leak rates;
4) according to the ion current signals corresponding to different leak rates, a linear relation curve of the mass spectrum signal and the leak rate of the hydrogen isotope or the helium isotope is established, as shown in fig. 3.
Thirdly, the method comprises the following steps: the gas supply system shown in FIG. 1 is adopted to measure the ppm level D in the material to be measured2The basic method of the assay of (1) is:
1) the valve V16 and the evacuation pump set (I) are always opened to ensure that the mass spectrum chamber is always in a high vacuum state;
2) closing the valves V10 and V15, and placing the cleaned and dried sample at the end of the quartz tube, far from the flange side;
3) opening valves V1, V3 and V10, and vacuumizing the quartz tube to below 10Pa through the end Q of the gas supply/exhaust part;
4) the valve V10 is closed, the valve V15 is opened, and high vacuum is continuously pumped through the vacuum pump group I;
5) opening the mass spectrum G, and collecting mass spectrum signals of the vacuum primitive chamber at room temperature;
6) starting the induction heating device, heating the sample through the sample tube to release hydrogen isotope gas in the sample tube, and acquiring a hydrogen isotope gas signal released by the sample through mass spectrometry, as shown in fig. 4;
7) obtaining a standard curve by calibrating a mass spectrum signal through leak rate, and calculating the release amount of hydrogen isotopes in the sample through integration to obtain corresponding D2The content was 15.58 ppm.
Example 2
Firstly, the method comprises the following steps: the method for calibrating the He leakage rate by adopting the gas supply system shown in FIG. 1 comprises the following steps:
1) after valves V1-V5, V10, V15 and V16 are opened to evacuate the system, the valves are closed;
2) opening V1, V2 and V4, and filling a certain amount of inert gas such as argon into a standard gas container A with a known volume;
3) the valve V2 is closed, and after the system is pumped out through the end Q of the air supply/exhaust part, the valve V1 is closed;
4) sequentially opening valves V2, V10 and V15, and sequentially calibrating the volumes of the pipeline and the vacuum mass spectrum chamber H by a volume expansion method;
5) after the volume calibration is finished, opening valves V1, V3-V5, V7, V12 and V16 to evacuate the pipeline, the mass spectrum vacuum chamber H and the upstream and downstream parts of the first leak hole D;
6) and (3) closing the valve V16, filling hydrogen isotope gas with certain pressure into the leak hole, closing the valve V1, acquiring the gas pressure entering the mass spectrum chamber through the downstream side of the first leak hole D in real time through the second thin film capacitance gauge G4 and the full-range composite gauge G5, and calculating the leak rate of the first leak hole D under the environment temperature and the pressure according to the calibrated volume.
7) Repeating the steps 4) to 5) to obtain hydrogen isotope leakage rate data of the second leakage hole E and the third leakage hole F under different pressures, and completing a leakage rate calibration process of the leakage holes, wherein a calibration curve is shown in fig. 2;
secondly, the method comprises the following steps: the method for establishing the linear relation curve of the mass spectrum signal and the leak rate of the He by adopting the gas supply system shown in the figure 1 comprises the following steps:
1) opening a valve V16, and maintaining the ultrahigh vacuum state of the vacuum mass spectrum chamber H through a vacuum pump group I; starting a quadrupole mass spectrum G, and obtaining a background hydrogen isotope signal after stabilizing for a period of time;
2) filling hydrogen isotope gas with a certain pressure into the first leak hole D (the corresponding leak rate under the pressure is known), closing the valve V7, opening the valve V12, obtaining a hydrogen isotope ion flow signal corresponding to the leak rate after the mass spectrum signal is stable, and closing the valve V12;
3) repeating the step 2), and obtaining mass spectrum ion current signals corresponding to the second leak hole E and the third leak hole F with known hydrogen isotope leak rates;
4) according to the ion current signals corresponding to different leak rates, a linear relation curve of the mass spectrum signal and the leak rate of the hydrogen isotope or the helium isotope is established, as shown in fig. 3.
Example 3
Firstly, the method comprises the following steps: by means of the pair D of air supply systems shown in FIG. 12The calibration method of the leakage rate comprises the following steps:
1) opening valves V1-V5, V10, V15 and V16, evacuating the system, and then closing the valves;
2) opening V1, V2 and V4, and filling a certain amount of inert gas such as argon into a standard gas container A with a known volume;
3) the valve V2 is closed, and after the system is pumped out through the end Q of the air supply/exhaust part, the valve V1 is closed;
4) sequentially opening valves V2, V10 and V15, and sequentially calibrating the volumes of the pipeline and the vacuum mass spectrum chamber H by a volume expansion method;
5) after the volume calibration is finished, opening valves V1, V3-V5, V7, V12 and V16 to evacuate the pipeline, the mass spectrum vacuum chamber H and the upstream and downstream parts of the first leak hole D;
6) and (3) closing the valve V16, filling hydrogen isotope gas with certain pressure into the leak hole, closing the valve V1, acquiring the gas pressure entering the mass spectrum chamber through the downstream side of the first leak hole D in real time through the second thin film capacitance gauge G4 and the full-range composite gauge G5, and calculating the leak rate of the first leak hole D under the environment temperature and the pressure according to the calibrated volume.
7) Repeating the steps 4) to 5) to obtain hydrogen isotope leakage rate data of the second leakage hole E and the third leakage hole F under different pressures, and completing a leakage rate calibration process of the leakage holes, wherein a calibration curve is shown in fig. 2;
secondly, the method comprises the following steps: the gas supply system D shown in FIG. 1 is adopted2The method for the linear relation curve of the mass spectrum signal and the leakage rate comprises the following steps:
1) opening a valve V16, and maintaining the ultrahigh vacuum state of the vacuum mass spectrum chamber H through a vacuum pump group I; starting a quadrupole mass spectrum G, and obtaining a background hydrogen isotope signal after stabilizing for a period of time;
2) filling hydrogen isotope gas with a certain pressure (the corresponding leak rate under the pressure is known) into the first leak hole D, closing the valve V7, opening the valve V12, obtaining a hydrogen isotope ion current signal corresponding to the leak rate after the mass spectrum signal is stable, and closing the valve V12;
3) repeating the step 2), and obtaining mass spectrum ion current signals corresponding to the second leak hole E and the third leak hole F with known hydrogen isotope leak rates;
4) according to the ion current signals corresponding to different leak rates, a linear relation curve of the mass spectrum signal and the leak rate of the hydrogen isotope or the helium isotope is established, as shown in fig. 3.
Thirdly, the method comprises the following steps: the specific method for measuring the characteristic parameters of the diffusion and detention behaviors of the hydrogen isotope or the helium isotope in the measurement material by adopting the gas supply system shown in FIG. 1 comprises the following steps:
1) the valve V16 and the evacuation pump set I are always opened to ensure that the mass spectrum chamber is always in a high vacuum state;
2) connecting the cleaned and dried membrane material into a permeation tool;
3) opening valves V1, V3, V5, V6 and V11, and evacuating the upstream and downstream sides of the membrane in the permeation tool;
4) opening a mass spectrum, introducing a certain amount of inert gas through a Q section of the gas supply/extraction part, and detecting whether the ion current signal of the inert gas is obviously increased compared with the background through the mass spectrum, wherein if the ion current signal is not obviously changed, the sealing performance of the diaphragm is intact;
5) after the inert gas on the upstream side of the diaphragm is pumped out, hydrogen isotope gas with certain pressure is introduced, and hydrogen isotope mass spectrum signals permeating from the downstream side of the diaphragm under different temperature conditions (650 ℃, 700 ℃, 750 ℃, 800 ℃ and 850 ℃) are collected, as shown in FIG. 5;
6) and calibrating mass spectrum signals through leak rate to obtain hydrogen isotope permeation characteristic parameters of the membrane material.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (9)

1. A method for constructing a linear relationship curve between a gas mass spectrum signal and a leak rate, which is characterized by comprising a first construction method using one leak orifice or a second construction method using a plurality of leak orifices with different leak rates, wherein the first construction method comprises the following steps: introducing gases under different constant pressure conditions at the upstream of the leak hole, detecting mass spectrum signals of the gases at the downstream of the leak hole, wherein the number of the constant pressure conditions is more than or equal to 3, and performing linear fitting after obtaining the mass spectrum signals under different leak rates to obtain a linear relation curve of the gas mass spectrum signals and the leak rates;
or comprises the following steps: introducing gas under a constant pressure condition into the upstream of the leak hole, detecting mass spectrum signals of the gas at the downstream of the leak hole in different time intervals, integrating the mass spectrum signals with time, wherein the number of the different time intervals is more than or equal to 3, and performing linear fitting on the leak rate of the different time intervals multiplied by the time integral value of the mass spectrum signals under the time condition to obtain a linear relation curve of the gas mass spectrum signals and the leak rate;
the second construction method includes the steps of:
each leak hole is provided with a gas branch, the leak holes at least have 3 leak rates, and a plurality of gas branches are connected in parallel;
and introducing constant-pressure gas into the upstream of each branch road leakage hole, detecting mass spectrum signals of the gas at the downstream of each branch road leakage hole, performing linear fitting after mass spectrum signals under different leakage rates are obtained, and obtaining a linear relation curve of the gas mass spectrum signals and the leakage rates.
2. A method for measuring a hydrogen isotope or a helium isotope, comprising the steps of:
continuously heating the sample to be detected in vacuum to increase the temperature for thermal desorption, carrying out mass spectrum detection on the released gas to obtain a signal-time relation curve of the mass spectrum signal of the hydrogen isotope or the helium isotope released by the sample to be detected along with the change of time, obtaining the release rate of the hydrogen isotope or the helium isotope at each time point according to the linear relation curve of the mass spectrum signal of the hydrogen isotope or the helium isotope and the leak rate, and obtaining the content of the hydrogen isotope or the helium isotope in the sample to be detected after integrating the time;
the linear relation curve of the mass spectrum signal and the leak rate of the hydrogen isotope or the helium isotope is obtained according to the construction method of claim 1.
3. A method for measuring a characteristic parameter of diffusion and/or retention of a hydrogen isotope or a helium isotope in a material, comprising the steps of:
introducing a hydrogen isotope or a helium isotope at the upstream of the membrane material under different constant temperature conditions, enabling the hydrogen isotope or the helium isotope to permeate through the material, detecting mass spectrum signals of the downstream hydrogen isotope or the helium isotope of the material, obtaining a signal-time relation curve of the mass spectrum signals of the hydrogen isotope or the helium isotope permeating through the membrane material along with time change under different constant temperature conditions, and obtaining the leakage rate of the hydrogen isotope or the helium isotope at each time point according to the linear relation curve of the mass spectrum signals and the leakage rates of the hydrogen isotope or the helium isotope, so that the permeation flux of the hydrogen isotope or the helium isotope passing through the unit area of the material under different constant temperature conditions can be obtained; the linear relation curve of the mass spectrum signal and the leakage rate of the hydrogen isotope or the helium isotope is obtained according to the construction method of claim 1;
and calculating the characteristic parameters of the diffusion and retention behaviors of the hydrogen isotope or the helium isotope of the material under different temperature conditions according to the permeation flux of the hydrogen isotope or the helium isotope of the material under different temperature conditions, wherein the characteristic parameters comprise permeability, diffusion coefficient, solubility, activation energy corresponding to the permeability, activation energy corresponding to the diffusion coefficient and activation energy corresponding to the solubility.
4. A gas supply system for mass spectrometry detection of a gas, comprising:
the leak hole is arranged on the gas branch, one end of the gas branch is communicated with a first main pipeline positioned at the upstream of the leak hole, the other end of the gas branch is communicated with a second main pipeline positioned at the downstream of the leak hole, and the second main pipeline is used for communicating a vacuum chamber (H) of the mass spectrum;
a gas supply/exhaust part (Q); the air supply/extraction part (Q) is communicated with the first main pipeline.
5. The air supply system according to claim 4, wherein the orifices are 3 orifices with different leakage rates, namely a first orifice (D), a second orifice (E) and a third orifice (F); a first gas branch, a second gas branch and a third gas branch are arranged in parallel corresponding to the leakage holes,
a seventh valve (V7) and a third pressure sensor (G6) are arranged on the first gas branch circuit which is positioned at the upstream of the first leakage hole (D), the first pressure sensor (G6) is close to the first leakage hole (D), and a twelfth valve (V12) is arranged on the first gas branch circuit which is positioned at the downstream of the first leakage hole (D);
an eighth valve (V8) and a fourth pressure sensor (G7) are arranged on the second gas branch circuit which is positioned at the upstream of the second leakage hole (E), the fourth pressure sensor (G7) is close to the second leakage hole (E), and a thirteenth valve (V13) is arranged on the second gas branch circuit which is positioned at the downstream of the second leakage hole (E);
a ninth valve (V9) and a fifth pressure sensor (G8) are arranged on the third gas branch at the upstream of the third leakage hole (F), the fifth pressure sensor (G8) is close to the third leakage hole (F), and a fourteenth valve (V14) is arranged on the third gas branch at the downstream of the third leakage hole (F).
6. Air supply system according to claim 4 or 5, characterised in that a first valve (V1) is provided on the first main pipe at the end that comes into abutment against said air supply/extraction unit (Q), said first main pipe communicating, on the first main pipe between said first valve (V1) and said gas branch, a first, second, third and fourth pipe branch; one end of the first pipeline branch is communicated with the first main pipeline through a second valve (V2), and the other end of the first pipeline branch is communicated with a standard gas storage container (A); one end of the second pipeline branch is communicated with the first main pipeline through a third valve (V3), and the other end of the second pipeline branch is communicated with a first thin film capacitance gauge (G1); one end of the third pipeline branch is communicated with the first main pipeline through a fourth valve (V4), and the other end of the third pipeline branch is communicated with a first pressure sensor (G2); one end of the fourth pipeline branch is communicated with the first main pipeline through a fifth valve (V5), and the other end of the fourth pipeline branch is communicated with a second pressure sensor (G3).
7. The gas supply system according to claim 4, further comprising a thermal desorption part (B) replacing any one of the leak holes or further comprising a fourth gas branch connected in parallel, wherein the gas outlet of the thermal desorption part (B) is communicated with the gas inlet end of the fourth gas branch; when the gas outlet of the thermal desorption component (B) is communicated with the gas inlet end of the second gas branch, the gas outlet end of the fourth gas branch is communicated with the second main pipeline; and the air inlet end of the fourth gas branch is also communicated with the first main pipeline.
8. The air supply system according to claim 7, wherein a tenth valve (V10) is provided at an end of a pipe where an air inlet end of the fourth gas branch communicates with the first main pipe, the end being close to the fourth gas branch, and a fifteenth valve (V15) is provided at an end of the fourth gas branch communicating with the second main pipe.
9. The gas supply system according to claim 4, further comprising a permeable member (C) replacing any one of the leak holes or further comprising a fifth gas branch connected in parallel, the permeable member (C) being arranged on the fifth gas branch; when the penetration component is arranged on a fifth gas branch, the gas inlet end of the fifth gas branch is communicated with the first main pipeline, and the gas outlet end of the fifth gas branch is communicated with the second main pipeline; a sixth valve (V6) is provided in the fifth gas branch upstream of the permeation element (C), and an eleventh valve (V11) is provided in the fifth gas branch downstream of the permeation element (C).
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