CN114624319B - 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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CN114624319B
CN114624319B CN202210349512.3A CN202210349512A CN114624319B CN 114624319 B CN114624319 B CN 114624319B CN 202210349512 A CN202210349512 A CN 202210349512A CN 114624319 B CN114624319 B CN 114624319B
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gas
leak
mass spectrum
branch
valve
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CN114624319A (en
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陈长安
叶小球
吴吉良
李赣
朱吉鹏
杨蕊竹
***
饶咏初
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Institute of Materials of CAEP
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/44—Sample treatment involving radiation, e.g. heat
    • G—PHYSICS
    • 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
    • G—PHYSICS
    • 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
    • G—PHYSICS
    • 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
    • G01N2013/003—Diffusion; diffusivity between liquids

Abstract

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

Description

Method for quantitatively obtaining ppm-level hydrogen isotope content in material based on thermal analysis-quadrupole mass spectrometry measurement principle
Technical Field
The invention belongs to the technical field of measurement of hydrogen isotopes in materials, and particularly relates to a method for quantitatively acquiring the content of ppm-level hydrogen isotopes in materials based on a thermal analysis-quadrupole mass spectrometry measurement principle.
Background
With the increasing use of fossil energy sources such as petroleum and natural gas and the continuous reduction of reserves thereof, energy problems are receiving more and more attention. Among the many new energy sources, hydrogen energy and controlled nuclear fusion energy are solving the human energy problem. Both of these new energy systems are widely involved in the production, storage, transportation and use of hydrogen isotopes. However, as a relatively light gas element, hydrogen isotope (H, D, T) and helium isotope [ ] 3 He (He) 4 He) is extremely prone to diffusion and retention in the containment structure material in contact therewith. Hydrogen isotopes or helium isotopes that enter the material, even in the ppm range (parts per million), can carry the risk of hydrogen embrittlement failure of the material, leading to significant safety accidents and economic losses. Therefore, accurate measurement of the content of ppm-level hydrogen isotopes in a material is very important.
However, the conventional spectroscopic and chromatographic methods have difficulty in meeting the requirements of measurement and analysis of hydrogen isotopes or helium isotopes in ppm levels in materials. Although the hydrogen determination instrument based on the heat conduction or infrared principle can realize the measurement of the ppm-level hydrogen isotope or helium isotope in the material, the quantitative analysis of deuterium in the hydrogen isotope can not be performed; and the influence factors in the measuring process are more, especially the quality influence of the hydrogen-containing solid standard sample is great, and the accuracy of the measuring result is poor.
Disclosure of Invention
In view of the above, the invention provides a method for quantitatively acquiring the content of the ppm-level hydrogen isotope in the material based on the thermal analysis-quadrupole mass spectrometry measurement principle.
The invention provides a construction method of a linear relation curve of gas mass spectrum signals and leak rates, 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 into the upstream of the leak hole, detecting mass spectrum signals of the downstream gas 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 mass spectrum signals under different leak rate conditions to obtain a linear relation curve of the gas mass spectrum signals and the leak rate;
or comprises the following steps: introducing gas under the condition of constant pressure into the upstream of the leak hole, detecting mass spectrum signals of the downstream gas of the leak hole in different time intervals, integrating the mass spectrum signals with respect to time, wherein the number of the different time intervals is more than or equal to 3, and performing linear fitting on the time integral values of the mass spectrum signals under the condition of leak rate multiplied by time of the different time intervals to obtain a linear relation curve of the gas mass spectrum signals and the leak rate;
The second construction method comprises the following steps:
each leak hole is provided with a gas branch, the plurality of leak holes are at least 3 leak holes with leak rate, and the plurality of gas branches are connected in parallel;
introducing constant pressure gas into the upstream of each branch leak hole, detecting mass spectrum signals of the gas at the downstream of each branch leak hole, and performing linear fitting after obtaining mass spectrum signals under different leak rate conditions to obtain a linear relation curve of the gas mass spectrum signals and the leak rate.
The invention provides a method for measuring hydrogen isotopes or helium isotopes, which comprises the following steps:
carrying out vacuum continuous heating and thermal desorption on a sample to be detected, carrying out mass spectrum detection on released gas to obtain a signal-time relation curve of mass spectrum signals of hydrogen isotopes or helium isotopes released by the sample to be detected, and obtaining the release rate of the hydrogen isotopes or the helium isotopes at each time point according to the linear relation curve of the mass spectrum signals of the hydrogen isotopes or the helium isotopes and the leak rate, and obtaining the content of the hydrogen isotopes or the helium isotopes in the sample to be detected after time integration;
the linear relation curve of the hydrogen isotope or helium isotope mass spectrum signal and the leak rate is obtained according to the construction method of the technical scheme.
The invention provides a method for measuring characteristic parameters of diffusion and/or retention of hydrogen isotopes or helium isotopes in materials, which is characterized by comprising the following steps:
introducing hydrogen isotopes or helium isotopes at the upstream of the membrane material under different constant temperature conditions, penetrating the hydrogen isotopes or the helium isotopes through the membrane material, detecting mass spectrum signals of the hydrogen isotopes or the helium isotopes at the downstream of the material, obtaining a time-time relation curve of time variation of mass spectrum signals of the hydrogen isotopes or the helium isotopes penetrated by the membrane material under different constant temperature conditions, obtaining the leak rate of the hydrogen isotopes or the helium isotopes at each time point according to a linear relation curve of the mass spectrum signals and the leak rate of the hydrogen isotopes or the helium isotopes, and obtaining the penetration flux of the hydrogen isotopes or the helium isotopes of the membrane material under different constant temperature conditions after time integration; the linear relation curve of the hydrogen isotope or helium isotope mass spectrum signal and the leak rate is obtained according to the construction method of the technical scheme;
and calculating and obtaining characteristic parameters of diffusion and retention behaviors of the hydrogen isotope or helium isotope of the material under different temperature conditions according to the permeation flux of the hydrogen isotope or 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, comprising:
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 with a vacuum chamber H of a mass spectrum;
a gas supply/extraction part Q; the air supply/extraction component Q communicates with the first main conduit.
Preferably, 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; a first gas branch, a second gas branch and a third gas branch are arranged in parallel corresponding to the leak holes,
a seventh valve V7 and a third pressure sensor G6 are arranged on the first gas branch located at the 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 arranged on the first gas branch located at the downstream of the first leak hole D;
an eighth valve V8 and a fourth pressure sensor G7 are arranged on the second gas branch 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 positioned at the downstream of the second leakage hole E;
A ninth valve V9 and a fifth pressure sensor G8 are disposed on the third gas branch located 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 disposed on the third gas branch located downstream of the third leak hole F.
Preferably, a first valve V1 is disposed at an end of the first main pipe close to the air supply/extraction component 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 device further comprises a thermal desorption part B, wherein the thermal desorption part B replaces any one of the leak holes or further comprises a fourth gas branch connected in parallel, and an air outlet of the thermal desorption part B is communicated with an air inlet end of the fourth gas branch; when the air outlet of the thermal desorption part B is communicated with the air inlet end of the second air branch, the air outlet end of the fourth air branch is communicated with the second main pipeline; and the air inlet end of the fourth air branch is also communicated with the first main pipeline.
Preferably, a tenth valve V10 is disposed at one end, close to the fourth gas branch, of the pipe, where the gas inlet end of the fourth gas branch is connected to the first main pipe, and a fifteenth valve V15 is disposed at one end, where the fourth gas branch is connected to the second main pipe.
Preferably, the gas leakage 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 the penetration component C is arranged on the fifth gas branch; when the penetrating component is arranged on a fifth gas branch, the air inlet end of the fifth gas branch is communicated with the first main pipeline, and the air outlet end of the fifth gas branch is communicated with the second main pipeline; a sixth valve V6 is arranged in the fifth gas branch upstream of the permeable member C and an eleventh valve V11 is arranged in the fifth gas branch downstream of the permeable member C.
The invention provides a construction method of a linear relation curve of gas mass spectrum signals and leak rates, 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 into the upstream of the leak hole, detecting mass spectrum signals of the downstream gas 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 mass spectrum signals under different leak rate conditions to obtain a linear relation curve of the gas mass spectrum signals and the leak rate; or comprises the following steps: introducing gas under the condition of constant pressure into the upstream of the leak hole, detecting mass spectrum signals of the downstream gas of the leak hole in different time intervals, integrating the mass spectrum signals with respect to time, wherein the number of the different time intervals is more than or equal to 3, and performing linear fitting on the time integral values of the mass spectrum signals under the condition of leak rate multiplied by time of the different time intervals to obtain a linear relation curve of the gas mass spectrum signals and the leak rate; the second construction method comprises the following steps: each leak hole is provided with a gas branch, the plurality of leak holes are at least 3 leak holes with leak rate, and the plurality of gas branches are connected in parallel; introducing constant pressure gas into the upstream of each branch leak hole, detecting mass spectrum signals of the gas at the downstream of each branch leak hole, and performing linear fitting after obtaining mass spectrum signals under different leak rate conditions to obtain a linear relation curve of the gas mass spectrum signals and the leak rate. 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 leak holes with different leak rates to form the parallel gas branch, can realize the construction of the linear relation curve of the gas mass spectrum signal and the leak rate under the conditions of different gases and different gas pressures of the multiple branches, and improves the accuracy of the construction of the linear relation curve of the gas mass spectrum signal and the leak rate.
The invention provides a method for measuring hydrogen isotopes or helium isotopes, which comprises the following steps: carrying out vacuum continuous heating and thermal desorption on a sample to be detected, carrying out mass spectrum detection on released gas to obtain a signal-time relation curve of mass spectrum signals of hydrogen isotopes or helium isotopes released by the sample to be detected, and obtaining the release rate of the hydrogen isotopes or the helium isotopes at each time point according to the linear relation curve of the mass spectrum signals of the hydrogen isotopes or the helium isotopes and the leak rate, and obtaining the content of the hydrogen isotopes or the helium isotopes in the sample to be detected after time integration; the linear relation curve of the hydrogen isotope or helium isotope mass spectrum signal and the leak rate is obtained according to the construction method of the technical scheme. According to the measuring method provided by the invention, through the linear relation curve of the gas mass spectrum signal and the leak rate constructed by the technical scheme, the thermal desorption spectrum, namely the vacuum heating extraction and the mass spectrum measurement are combined, so that the accurate measurement of the ppm-level hydrogen isotope or helium isotope in different materials can be realized.
The invention provides a method for measuring characteristic parameters of diffusion and/or retention of hydrogen isotopes or helium isotopes in materials, which is characterized by comprising the following steps: introducing hydrogen isotopes or helium isotopes at the upstream of the membrane material under different constant temperature conditions, penetrating the hydrogen isotopes or the helium isotopes through the membrane material, detecting mass spectrum signals of the hydrogen isotopes or the helium isotopes at the downstream of the material, obtaining a time-time relation curve of time variation of mass spectrum signals of the hydrogen isotopes or the helium isotopes penetrated by the membrane sample under different constant temperature conditions, obtaining the leak rate of the hydrogen isotopes or the helium isotopes at each time point according to a linear relation curve of the mass spectrum signals and the leak rate of the hydrogen isotopes or the helium isotopes, and obtaining the penetration flux of the hydrogen isotopes or the helium isotopes of the membrane material under different constant temperature conditions after time integration; the linear relation curve of the hydrogen isotope or helium isotope mass spectrum signal and the leak rate is obtained according to the construction method of the technical scheme; and calculating and obtaining characteristic parameters of diffusion and retention behaviors of the hydrogen isotope or helium isotope of the material under different temperature conditions according to the permeation flux of the hydrogen isotope or 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. According to the measuring method provided by the invention, through the linear relation curve of the gas mass spectrum signal and the leak rate constructed by the technical scheme, the permeation line of the hydrogen isotope or helium isotope in the material is combined with mass spectrum measurement, so that the characteristic parameters of the diffusion and retention behaviors of the hydrogen isotope or helium isotope of the material under different temperature conditions can be accurately measured.
The invention provides a gas supply system for gas mass spectrometry detection, comprising: 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 with a vacuum chamber H of a mass spectrum; a gas supply/extraction part Q; the air supply/extraction component Q communicates with the first main conduit. When the gas supply system provided by the invention is combined with a mass spectrum detector, the advantages of high mass spectrum sensitivity and easiness in distinguishing hydrogen isotopes can be utilized to measure the ppm-level hydrogen isotopes in the material. The gas supply system for gas mass spectrum detection provided by the invention is a set of multifunctional system, not only can realize the functions such as the calibration of leak rate and mass spectrum ion flow signal calibration, but also can realize the measurement of the 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 in materials such as stainless steel, tungsten, zirconium-niobium alloy and the like.
Drawings
FIG. 1 is a schematic diagram of a test system according to an embodiment of the present invention;
Wherein, Q is a gas supply/extraction component, V1 is a first valve, V2 is a second valve, A is a standard gas storage container, V3 is a third valve, G1 is a first thin film 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 permeation 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, V15 is a fifteenth valve, B is a thermal desorption component, G4 is a second thin film capacitance gauge, G is a mass spectrum, G5 is a full-scale composite gauge, H is a sixteen-scale valve, V16 is a vacuum chamber I is a pump set;
FIG. 2 is a diagram of D in example 1 of the present invention 2 And He in example 2 and the leak rate under different pressure conditions and fitting the graph;
FIG. 3 is a diagram of D in example 1 of the present invention 2 And the measured data and fitted plots of mass spectrum signals at different leak rates for He in example 2;
FIG. 4 shows the sample to be tested D according to example 1 of the present invention 2 A graph of the variation of mass spectrum signals of the thermal desorption praseodymium over time;
FIG. 5 shows HD and D in the material for a membrane according to embodiment 4 of the invention 2 And calibration D 2 A graph of the mass spectrum signal of permeation versus temperature.
Detailed Description
The invention provides a construction method of a linear relation curve of gas mass spectrum signals and leak rates, 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 into the upstream of the leak hole, detecting mass spectrum signals of the downstream gas 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 mass spectrum signals under different leak rate conditions to obtain a linear relation curve of the gas mass spectrum signals and the leak rate;
or comprises the following steps: introducing gas under the condition of constant pressure into the upstream of the leak hole, detecting mass spectrum signals of the downstream gas of the leak hole in different time intervals, integrating the mass spectrum signals with respect to time, wherein the number of the different time intervals is more than or equal to 3, and performing linear fitting on the time integral values of the mass spectrum signals under the condition of leak rate multiplied by time of the different time intervals to obtain a linear relation curve of the gas mass spectrum signals and the leak rate;
The second construction method comprises the following steps:
each leak hole is provided with a gas branch, the plurality of leak holes are at least 3 leak holes with leak rate, and the plurality of gas branches are connected in parallel;
introducing constant pressure gas into the upstream of each branch leak hole, detecting mass spectrum signals of the gas at the downstream of each branch leak hole, and performing linear fitting after obtaining mass spectrum signals under different leak rate conditions to obtain a linear relation curve of the gas mass spectrum signals and the leak rate.
In the present invention, the leak hole is preferably a standard leak hole.
The invention has no special requirement on the source of the leak hole, and can be obtained by adopting a commercial product.
In the invention, when a linear relation curve of helium isotope gas mass spectrum signals and leak rates is established, since the leak rates of different leak holes of the helium isotopes are known, leak rate calibration is not needed.
In the present invention, when establishing the linear relationship of the hydrogen isotope gas mass spectrometry signal and the leak rate, the present invention preferably includes calibrating the leak rate of the hydrogen isotope before establishing the linear relationship of the hydrogen isotope gas mass spectrometry signal and the leak rate.
In the invention, the method for calibrating the hydrogen isotope leakage rate preferably comprises the following steps:
And introducing hydrogen isotope gas under different constant pressure conditions into 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 volumes of the pipeline and the vacuum chamber at the downstream of the leak hole are preferably calibrated by adopting a volume expansion method, and the method has no special requirement 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 the calibration of the leak rates of the plurality of leak holes under different hydrogen isotope gases and different constant air pressures.
The invention provides a method for measuring hydrogen isotopes or helium isotopes, which comprises the following steps:
carrying out vacuum continuous heating and thermal desorption on a sample to be detected, carrying out mass spectrum detection on released gas to obtain a signal-time relation curve of mass spectrum signals of hydrogen isotopes or helium isotopes released by the sample to be detected, and obtaining the release rate of the hydrogen isotopes or the helium isotopes at each time point according to the linear relation curve of the mass spectrum signals of the hydrogen isotopes or the helium isotopes and the leak rate, and obtaining the content of the hydrogen isotopes or the helium isotopes in the sample to be detected after time integration;
The linear relation curve of the hydrogen isotope or helium isotope mass spectrum signal and the leak rate is obtained according to the construction method of the technical scheme.
In the invention, the sample to be measured is preferably stainless steel, tungsten or zirconium-niobium alloy.
The present invention preferably performs pretreatment on a sample to be measured, and in the present invention, the pretreatment preferably includes: the washing and drying are sequentially carried out, and the specific implementation mode of the washing and drying is not particularly required.
The invention provides a method for measuring characteristic parameters of diffusion and/or retention of hydrogen isotopes or helium isotopes in materials, which is characterized by comprising the following steps:
introducing hydrogen isotopes or helium isotopes at the upstream of the membrane material under different constant temperature conditions, penetrating the hydrogen isotopes or the helium isotopes through the membrane material, detecting mass spectrum signals of the hydrogen isotopes or the helium isotopes at the downstream of the material, obtaining a time-time relation curve of time variation of mass spectrum signals of the hydrogen isotopes or the helium isotopes penetrated by the sample under different constant temperature conditions, obtaining the leak rate of the hydrogen isotopes or the helium isotopes at each time point according to a linear relation curve of the mass spectrum signals and the leak rate of the hydrogen isotopes or the helium isotopes, and obtaining the penetration flux of the hydrogen isotopes or the helium isotopes of the membrane material under different constant temperature conditions after time integration; the linear relation curve of the hydrogen isotope or helium isotope mass spectrum signal and the leak rate is obtained according to the construction method of the technical scheme;
And calculating and obtaining characteristic parameters of diffusion and retention behaviors of the hydrogen isotope or helium isotope of the material under different temperature conditions according to the permeation flux of the hydrogen isotope or 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 permeation test material is preferably a film sheet.
In the present invention, the membrane material is preferably in communication with the mass spectrometry vacuum-enhancing conduit after being in the permeation component by a vacuum-coupled radial seal (VCR seal).
In the invention, the method for calculating and obtaining the characteristic parameters of the diffusion and retention behaviors of the hydrogen isotope or helium isotope of the material under different temperature conditions by the permeation flux of the hydrogen isotope or helium isotope of the material under different temperature conditions preferably comprises the following steps: obtaining permeation fluxes of hydrogen isotopes or helium isotopes of the material under different temperature conditions, substituting the permeation fluxes into a permeation flux formula based on the Phak law to obtain characteristic parameters of diffusion and retention behaviors of the hydrogen isotopes or helium isotopes of the material under different temperature conditions, wherein the permeation flux formula generally has a form shown as a formula 1:
In the formula 1, J is the permeation flux (unit is mol.s -1 ) Phi is the permeability (unit: mol.m -1 ·s -1 ·Pa -n ) D is a diffusion coefficient (unit: m is m 2 ·s -1 ) S is solubility (unit: mol.m -3 ·Pa -n ) σ is the effective penetration area of the material (unit: m is m 2 ) D is the thickness of the material (unit: m), P in (unit: pa), P out The unit is Pa, the upstream side pressure and the downstream side pressure of the material respectively, and n is a pressure index (the value range is generally 1/2.ltoreq.n.ltoreq.1).
The invention provides a method for acquiring the characteristic parameters of hydrogen isotope diffusion and detention behavior in a material relatively objectively and reliably.
The invention provides a gas supply system for gas mass spectrometry detection, comprising:
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 with a vacuum chamber H of a mass spectrum;
a gas supply/extraction part Q; the air supply/extraction component Q communicates with the first main conduit.
The air supply system provided by the invention comprises an air supply/extraction component Q, and in the invention, the air supply/extraction component Q is communicated with the first main pipeline.
In the embodiment of the present invention, the air supply/exhaust part Q is composed of a vacuum pump and an air supply system.
In the present invention, the gas supply/extraction means Q is used for evacuating a gas supply system, supplying an isotope gas, preferably including a hydrogen isotope gas or a helium isotope gas, or an inert gas for leak detection and volume calibration of the gas supply system.
In the present invention, a first valve V1 is provided at an end of the first main pipe close to the air supply/exhaust part Q.
In the present invention, the first valve is preferably a high-pressure all-metal valve, the pressure resistance of the first valve V1 is not lower than 10MPa, and the first valve V1 is used for controlling the flow of gas.
In the invention, a first pipeline branch, a second pipeline branch, a third pipeline branch and a fourth pipeline branch are communicated with a first main pipeline positioned between the first valve V1 and the gas branch on the first main pipeline; 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 present 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 a flow passage.
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 to perform volume calibration on other parts of the system, and temporarily store 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 the first thin film capacitance gauge G1.
In the present 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 channel.
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 vacuum state change of the system.
In the invention, 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.
In the present invention, the fourth valve V4 is preferably a high-pressure all-metal valve, the pressure resistance of the fourth valve V4 is not lower than 10MPa, and the fourth valve V4 is used for controlling the flow of gas and the selection of a flow channel.
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 invention, 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.
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 lower than 10MPa, and the fifth valve V5 is used for controlling the flow of gas and the selection of a 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 air supply system provided by the invention comprises: the gas branch is provided with a gas branch path, one end of the gas branch path is communicated with a first main pipeline positioned at the upstream of the gas branch path, the other end of the gas branch path is communicated with a second main pipeline positioned at the downstream of the gas branch path, and the second main pipeline is used for communicating with a vacuum chamber H of a mass spectrum.
In the present invention, the inner diameter of the second main pipe is preferably not less than 16mm.
In the present invention, the second main pipe is preferably an internally 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 leak holes.
In the present invention, for the same isotope gas, the present invention preferably uses 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, to construct a relationship between the leak rate and the ion flow signal, and to construct a calibration curve.
In the invention, a seventh valve V7 and a third pressure sensor G6 are arranged on the first gas branch positioned at the 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 arranged on the first gas branch positioned at the 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 lower than 10MPa, and the seventh valve V7 is used to control the flow of gas and the selection of the flow passage.
In the invention, the range of the third pressure sensor G6 is preferably-0.1-5 bar, and the third pressure sensor G is used for monitoring the pressure change of the upstream side of the first leak hole D in real time; when the pressure change exceeds the initial pressure by 5%, the initial pressure needs to be maintained by the supplementary gas so as to ensure the stable leak rate of the leak hole.
In the present invention, the twelfth valve V12 is preferably an all-metal ultra-high vacuum angle valve for blocking the low vacuum and ultra-high vacuum parts so that the ultra-high 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 16mm.
In the present invention, the first gas branch located between the twelfth valve V12 and the second main pipe is preferably an internally polished stainless steel pipe.
In the present invention, the first gas branch between the twelfth valve V12 and the second main pipe is preferably provided with a heating belt, so that the baking and degassing can be performed at any time.
In the invention, an eighth valve V8 and a fourth pressure sensor G7 are arranged on the second gas branch positioned at the 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 arranged on the second gas branch positioned at the 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 lower than 10MPa, and the eighth valve V8 is used to control the flow of gas and the selection of the flow channel.
In the invention, the measuring range of the fourth pressure sensor G7 is preferably-0.1-5 bar, and the measuring range is used for monitoring the pressure change of the upstream side of the second leak hole D in real time; when the pressure change exceeds the initial pressure by 5%, the initial pressure needs to be maintained by the supplementary gas so as to ensure the stable leak rate of the leak hole.
In the present invention, the thirteenth valve V13 is preferably an all-metal ultra-high vacuum angle valve for blocking the low vacuum and ultra-high vacuum parts so that the ultra-high 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 16mm.
In the present invention, the second gas branch between the thirteenth valve V13 and the second main pipe is preferably an internally polished stainless steel pipe.
In the present invention, the second gas branch between the thirteenth valve V13 and the second main pipe is preferably provided with a heating belt, and the baking and degassing can be performed at any time.
In the present invention, a ninth valve V9 and a fifth pressure sensor G8 are disposed on the third gas branch located upstream of the third leak hole F, the fifth pressure sensor G8 is located close to the third leak hole F, and a fourteenth valve V14 is disposed on the third gas branch located 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 lower than 10MPa, and the ninth valve V9 is used for controlling the flow of gas and the selection of a flow passage.
In the invention, the range of the fifth pressure sensor G8 is preferably-0.1-5 bar, and the fifth pressure sensor G is used for monitoring the pressure change of the upstream side of the third leak hole D in real time; when the pressure change exceeds the initial pressure by 5%, the initial pressure needs to be maintained by the supplementary gas so as to ensure the stable leak rate of the leak hole.
In the present invention, the fourteenth valve V14 is preferably an all-metal ultra-high vacuum angle valve for isolating the low vacuum and ultra-high vacuum portions so that the ultra-high 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 16mm.
In the present invention, the third gas branch between the fourteenth valve V14 and the second main pipe is preferably an internally polished stainless steel pipe.
In the present invention, the third gas branch between the fourteenth valve V14 and the second main pipe is preferably provided with a heating belt, and the baking and degassing can be performed at any time.
The air supply system provided by the invention further comprises a thermal desorption part B, wherein the thermal desorption part B replaces any one of the leak holes or further comprises a fourth gas branch connected in parallel, and an air outlet of the thermal desorption part B is communicated with an air inlet end of the fourth gas branch; when the air outlet of the thermal desorption part B is communicated with the air inlet end of the second air branch, the air outlet end of the fourth air branch is communicated with the second main pipeline; and the air inlet end of the fourth air 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 16mm.
In the present invention, the fourth gas branch and the side pipe are preferably inner polished stainless steel pipes.
In the present invention, the fourth gas branch is preferably provided with a heating belt, so that the baking and degassing can be performed at any time.
In the invention, a tenth valve V10 is disposed at one end of the pipe, which is connected to the first main pipe, of the air inlet end of the fourth gas branch, and a fifteenth valve V15 is disposed at one end of the fourth gas branch, which is connected to the second main pipe.
In the present invention, the tenth valve V10 is preferably an all-metal ultra-high vacuum angle valve for blocking the low vacuum and ultra-high vacuum parts so that the ultra-high vacuum is more easily obtained and maintained.
In the present invention, the fifteenth valve V15 is preferably an all-metal ultra-high vacuum angle valve for isolating the low vacuum and ultra-high vacuum portions so that the ultra-high vacuum is more easily obtained and maintained.
In the present invention, the thermal desorption member B preferably includes a heating and temperature controlling device.
In the invention, the thermal desorption part B preferably adopts a CF flange with small gas release amount to weld a quartz tube, a sample is placed in the quartz tube, and the quartz tube is connected into the second gas branch through the CF flange by 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 tested is positioned in the thermal desorption part B; and heating the sample to enable the desorbed hydrogen isotope gas to pass through the mass spectrum G to obtain a corresponding ion flow signal.
The gas supply system provided by the invention preferably further comprises a permeation component C, wherein the permeation component C replaces any one of the leak holes or further comprises a fifth gas branch connected in parallel, and the permeation component C is arranged on the fifth gas branch; when the penetrating component is arranged on a fifth gas branch, the air inlet end of the fifth gas branch is communicated with the first main pipeline, and the air outlet end of the fifth gas branch is communicated with the second main pipeline; a sixth valve V6 is arranged in the fifth gas branch upstream of the permeable member C and an eleventh valve V11 is arranged in the fifth gas branch downstream of the permeable member C.
In the present invention, the penetrating member C preferably includes heating and temperature controlling means.
In the invention, a material membrane to be tested is preferably packaged in the permeable member C in a vacuum connection radial seal (VCR, vacuum Coupling Radius Seal) mode, a certain amount of hydrogen isotope gas is introduced into the upstream side of the permeable member C, a hydrogen isotope mass spectrometry signal of the downstream side of the permeable member C is measured, a leak is adopted for calibration, and characteristic data such as permeability, diffusion coefficient, solubility, respective corresponding activation energy and the like 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 the 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 pressure resistance of the sixth valve V6 is not lower than 10MPa, and the sixth valve V6 is used to control the flow of gas and the selection of the flow passage.
In the present invention, the eleventh valve V11 is preferably an all-metal ultra-high vacuum angle valve for blocking the low vacuum and ultra-high vacuum parts so that the ultra-high vacuum is more easily obtained and maintained.
In the present invention, the inner diameter of the fifth gas branch between said eleventh valve V11 and the second main pipe is preferably not less than 16mm.
In the present invention, the fifth gas branch located between the eleventh valve V11 and the second main pipe is preferably an internally polished stainless steel pipe.
In the present invention, the fifth gas branch between the eleventh valve V11 and the second main pipe is preferably provided with a heating belt, so that the baking and degassing can be performed at any time.
The second main pipeline of the gas supply system provided by the invention is used for communicating with the vacuum chamber H of the 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 spectrum is used to acquire ion flow signals of a gas flowing through the ultra-vacuum chamber H.
In the invention, the vacuum chamber H is provided with a second thin film capacitance gauge G4 and a full-range composite gauge G5, and the second thin film capacitance gauge G4 and the full-range composite gauge G5 are communicated with the vacuum chamber H.
In the present invention, the second thin film capacitance gauge G4 is used to monitor the vacuum state change of the vacuum chamber H.
In the present invention, the full-scale gauge G5 is used to measure the vacuum of the vacuum chamber H.
In the invention, the measurement range of the full-range composite gauge G5 is preferably 10 -8 Pa～1atm。
In the present invention, the inner diameter of the pipe through which the second thin film capacitance gauge G4 communicates with the vacuum chamber H is preferably not less than 16mm.
In the present invention, the pipe through which the second thin film capacitance gauge G4 communicates with the vacuum chamber H is preferably an internally polished stainless steel pipe.
In the present invention, the pipeline for connecting the second thin film capacitor gauge G4 and the vacuum chamber H is preferably provided with a heating belt, so that the baking and degassing can be performed at any time.
In the present invention, the inner diameter of the pipe communicating the full-range gauge G5 and the vacuum chamber H is preferably not less than 16mm.
In the invention, the pipeline for communicating the full-range composite gauge G5 with the vacuum chamber H is preferably an internally polished stainless steel pipe.
In the invention, the pipeline for communicating the full-range compound gauge G5 with the vacuum chamber H is preferably provided with a heating belt, so that baking and degassing can be carried out at any time.
In the invention, the vacuum chamber H is communicated 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 invention, a sixteenth valve V16 is arranged on a pipeline for communicating the vacuum pump group I with 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 separate the evacuation pump set I from the vacuum chamber H, and to control the evacuation of the vacuum chamber from the static vacuum hold.
In the present invention, the inner diameter of the pipe communicating the vacuum pump unit I and the vacuum chamber H is preferably not less than 16mm.
In the invention, the pipeline of the pipeline communicated with the vacuum pump set I and the vacuum chamber H is preferably an internal polished stainless steel pipe.
In the invention, the pipeline communicated with the vacuum pump group I and the vacuum chamber H is preferably provided with a heating belt, so that baking and degassing can be carried out at any time.
The method for calibrating the hydrogen isotope leakage rate by adopting the gas supply system shown in the figure 1 preferably comprises the following steps of
1) After the evacuation system of the valves V1-V5, V10, V15 and V16 is opened, closing the valves;
2) Opening V1, V2 and V4, and filling a standard gas storage container A with a known volume with a certain amount of inert gas, such as argon;
3) Closing the valve V2, and after evacuating the system through the Q end of the air supply/evacuation component, closing the valve V1;
4) Sequentially opening valves V2, V10 and V15, and sequentially calibrating the volumes of a pipeline and a vacuum mass spectrum chamber H by a volume expansion method;
5) After the volume calibration is completed, opening valves V1, V3-V5, V7, V12 and V16 to evacuate pipelines, a mass spectrum vacuum chamber H and upstream and downstream parts of a first leak hole D;
6) After the valve V16 is closed and hydrogen isotope gas with certain pressure is filled into the leak, the valve V1 is closed, the gas pressure passing through the mass spectrum chamber on the downstream side of the first leak D is collected in real time through the second thin film capacitance gauge G4 and the full-range composite gauge G5, and the leak rate of the first leak D under the environment temperature and the pressure is calculated according to the calibrated volume.
7) Repeating the steps 4) to 5) to obtain hydrogen isotope leak rate data of the second leak hole E and the third leak hole F under different pressures, and completing the leak rate calibration process of the leak hole.
The invention provides a multipoint calibration method for obtaining a calibration curve by calibrating a hydrogen isotope signal acquired by a mass spectrum by utilizing a leak orifice with known hydrogen isotope leak rate, 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 relation between the leak rate and the ion flow signal, and a calibration curve is established. In the invention, when a branch is adopted to establish a calibration curve, the invention preferably uses the integration of the actual gas quantity (leak rate multiplied by time) flowing into the vacuum mass spectrum chamber H through the leak holes in different time periods and the corresponding ion flow signals along with the time to construct a multipoint calibration method of the gas quantity and ion flow signal integration relation.
The method for establishing the linear relation curve of the mass spectrum signal and the leak rate of the hydrogen isotope or the helium isotope by utilizing the gas supply system shown in the figure 1 comprises the following steps:
1) Opening a valve V16, and keeping the vacuum mass spectrum cavity H in an ultrahigh vacuum state all the time through a vacuum pump group I; starting a quadrupole mass spectrum G, and stabilizing for a period of time to obtain a background hydrogen isotope signal;
2) Filling hydrogen isotope gas with 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 flow signal corresponding to the leak rate after the mass spectrum signal is stable, and closing the valve V12;
3) Repeating the step 2) to obtain mass spectrum ion flow signals corresponding to the second leakage hole E and the third leakage hole F with known hydrogen isotope leakage rate;
4) And establishing a linear relation curve of mass spectrum signals of the hydrogen isotope or helium isotope and the leak rate according to ion flow signals corresponding to different leak rates.
The invention adopts a vacuum heating extraction mass spectrometry method for measuring the content of ppm-level hydrogen isotopes or helium isotopes in a material to be measured. In the present invention, the thermal desorption spectrum method preferably adopts a thermal desorption component B shown in fig. 1 to heat a sample to be detected to enable desorbed hydrogen isotopes or helium isotopes to pass through a mass spectrum G to obtain corresponding ion flow signals, and adopts standard leak hole first leak hole D, second leak hole E and third leak hole F) to calibrate the ion flow signals, thereby realizing quantitative analysis.
In the invention, in order to reduce the influence of the hydrogen background of a sample tube in the sample heating process, a thermal desorption part B in the gas supply system adopts a CF flange with less gas discharge capacity to weld a quartz tube, a sample to be measured is placed in the quartz tube, and the quartz tube is connected into a system pipeline through the CF flange in a mode of adding a knife edge through a copper gasket; meanwhile, the scheme of heating the local position of the quartz tube where the sample is positioned by adopting the local heating modes such as electromagnetic induction heating and the like can further reduce the influence of hydrogen background caused by hydrogen release of the quartz tube in the heating process so as to improve the accuracy of a measurement result.
In the invention, the basic method for measuring the content of the ppm-level hydrogen isotope or helium isotope in the material to be measured by adopting the gas supply system shown in fig. 1 is as follows:
1) The valve V16 and the evacuation pump group (I) are always opened so as to ensure that the mass spectrum chamber is always in a high vacuum state;
2) Closing valves V10 and V15, and placing the cleaned and dried sample at the tail end of the quartz tube far away from the flange side;
3) Opening valves V1, V3 and V10, and vacuumizing the quartz tube to below 10Pa through the Q end of the air supply/exhaust component;
4) Closing the valve V10, opening the valve V15, and continuously pumping to high vacuum through the vacuum pump group I;
5) Opening a mass spectrum G, and collecting mass spectrum signals when the vacuum mass spectrum chamber is at room temperature;
6) Starting an induction heating device, heating a sample through a sample tube to release hydrogen isotope gas, and collecting a hydrogen isotope gas signal released by the sample through mass spectrometry;
7) And obtaining a standard curve through leak rate calibration mass spectrum signals, and calculating the release amount of hydrogen isotopes in the sample.
The present invention preferably further includes measuring a diffusion and retention behavior characteristic parameter of the hydrogen isotope or helium isotope in the material using the gas supply system shown in fig. 1. In the invention, the membrane material to be tested is preferably packaged in a permeation component C in FIG. 1 in a VCR sealing mode, a certain amount of hydrogen isotope or helium isotope gas is introduced into the upstream side of the membrane material, the mass spectrum signal of the hydrogen isotope on the downstream side of the membrane material is measured, the leak holes are used for calibration, and characteristic data such as the permeability, the diffusion coefficient, the solubility, the respective corresponding activation energy and the like of the hydrogen isotope in the material can be obtained through proper mathematical treatment. The gas supply system and the measuring method provided by the invention are relatively objective and reliable methods for acquiring the characteristic parameters of the diffusion and retention behaviors of the hydrogen isotopes in the material. As shown in fig. 1, the gas supply system provided by the invention ensures that the flow path of the gas at the downstream side of the leak hole is consistent with the flow path of the gas released by the sample in the permeation tool, thereby ensuring the reliability of test data. In the invention, the specific method for the hydrogen isotope permeation test in the material comprises the following steps:
1) Valve V16 and evacuation pump group I are always opened to ensure that the mass spectrum chamber is always in a high vacuum state;
2) The material membrane after cleaning and drying is connected into a permeation tool;
3) Opening valves V1, V3, V5, V6 and V11, and evacuating the upstream and downstream of the membrane in the permeation tool;
4) Opening a mass spectrum, introducing a certain amount of inert gas through a Q section of a gas supply/extraction component, and detecting whether an ion flow signal of the inert gas is obviously increased compared with a background through the mass spectrum, wherein if no obvious change exists, the sealing performance of the diaphragm is good;
5) After the inert gas at the upstream side of the diaphragm is pumped out, introducing hydrogen isotope gas with certain pressure, and collecting hydrogen isotope mass spectrum signals permeated from the downstream side of the diaphragm at different temperatures;
6) And obtaining the hydrogen isotope permeation characteristic parameter of the membrane material by calibrating the mass spectrum signal through the leak rate.
The measuring method and the air supply system have the following beneficial effects:
1. according to the invention, the parallel layout scheme of a plurality of leak holes, a thermal desorption tool and a permeation tool is adopted around the accurate measurement requirement of the ppm hydrogen isotope or helium isotope content in the hydrogen energy and nuclear energy materials, so that the flow path of the gas at the downstream side of the leak holes is ensured to be consistent with the flow path of the gas released by the sample in the thermal desorption tool or the permeation tool, and the calibration of the leak rates of the plurality of leak holes under different hydrogen isotope gases and different pressures are ensured.
2. The invention adopts a plurality of leak holes with different leak rates to construct the relation between the gas leak rate and the ion flow signal corresponding to the mass spectrum, and establishes a calibration curve. In particular, for the same leak rate, the invention provides a multi-point calibration method for constructing the integral relation between the gas quantity and the ion flow signal by adopting the integral of the actual gas quantity (leak rate multiplied by time) of the leak hole flowing into the mass spectrum chamber and the corresponding ion flow signal along with time in different time periods.
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 specifically comprises the following steps: 1) The thermal desorption tool adopts a CF flange with small gas release amount 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 mode of adding a knife edge through a copper gasket; 2) The scheme of heating the local position of the quartz tube where the sample is positioned by adopting local heating modes such as electromagnetic induction heating and the like is adopted, so that the hydrogen background influence caused by the self hydrogen release of the quartz tube in the heating process is further reduced, and the accuracy of a measurement result is improved.
4. The system designed by the invention is a set of multifunctional system, not only can realize the calibration of different leak rates and the signal calibration of mass spectrum ion flow, but also can realize the measurement of the diffusion and retention behavior characteristic parameters of hydrogen isotopes in materials, and particularly can realize the quantitative analysis of ppm-level hydrogen isotope gas released in the materials, thereby having important application in the fields of hydrogen energy and nuclear energy materials.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
First: pair D using a gas supply system as shown in FIG. 1 2 The leak rate calibration method comprises the following steps:
1) After the evacuation system of the valves V1-V5, V10, V15 and V16 is opened, closing the valves;
2) Opening V1, V2 and V4, and filling a standard gas storage container A with a known volume with a certain amount of inert gas, such as argon;
3) Closing the valve V2, and after evacuating the system through the Q end of the air supply/evacuation component, closing the valve V1;
4) Sequentially opening valves V2, V10 and V15, and sequentially calibrating the volumes of a pipeline and a vacuum mass spectrum chamber H by a volume expansion method;
5) After the volume calibration is completed, opening valves V1, V3-V5, V7, V12 and V16 to evacuate pipelines, a mass spectrum vacuum chamber H and upstream and downstream parts of a first leak hole D;
6) After the valve V16 is closed and hydrogen isotope gas with certain pressure is filled into the leak, the valve V1 is closed, the gas pressure passing through the mass spectrum chamber on the downstream side of the first leak D is collected in real time through the second thin film capacitance gauge G4 and the full-range composite gauge G5, and the leak rate of the first leak D under the environment temperature and the pressure is calculated according to the calibrated volume.
7) Repeating the steps 4) to 5) to obtain hydrogen isotope leak rate data of the second leak hole E and the third leak hole F under different pressures, and completing the leak rate calibration process of the leak hole, wherein the calibration curve is shown in figure 2.
Second,: d is built by adopting the air supply system shown in FIG. 1 2 The method of the linear relation curve of the mass spectrum signal and the leak rate is as follows:
1) Opening a valve V16, and keeping the vacuum mass spectrum cavity H in an ultrahigh vacuum state all the time through a vacuum pump group I; starting a quadrupole mass spectrum G, and stabilizing for a period of time to obtain a background hydrogen isotope signal;
2) Filling hydrogen isotope gas with 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 flow signal corresponding to the leak rate after the mass spectrum signal is stable, and closing the valve V12;
3) Repeating the step 2) to obtain mass spectrum ion flow signals corresponding to the second leakage hole E and the third leakage hole F with known hydrogen isotope leakage rate;
4) And establishing a linear relation curve of mass spectrum signals of hydrogen isotopes or helium isotopes and the leak rate according to ion flow signals corresponding to different leak rates, as shown in figure 3.
Third,: measuring ppm level D in the material under test using the gas supply system shown in FIG. 1 2 The basic method for the measurement of (a) is as follows:
1) The valve V16 and the evacuation pump group (I) are always opened so as to ensure that the mass spectrum chamber is always in a high vacuum state;
2) Closing valves V10 and V15, and placing the cleaned and dried sample at the tail end of the quartz tube far away from the flange side;
3) Opening valves V1, V3 and V10, and vacuumizing the quartz tube to below 10Pa through the Q end of the air supply/exhaust component;
4) Closing the valve V10, opening the valve V15, and continuously pumping to high vacuum through the vacuum pump group I;
5) Opening a mass spectrum G, and collecting mass spectrum signals when the vacuum mass spectrum chamber is at room temperature;
6) Starting an induction heating device, heating a sample through a sample tube to release hydrogen isotope gas, and collecting a signal of the hydrogen isotope gas released by the sample through mass spectrometry, as shown in fig. 4;
7) Obtaining a standard curve through leak rate calibration mass spectrum signals, and integrating and calculating the release amount of hydrogen isotopes in the sample to obtain a corresponding D 2 The content was 15.58ppm.
Example 2
First: the method for calibrating the He leakage rate by adopting the gas supply system shown in FIG. 1 comprises the following steps:
1) After the evacuation system of the valves V1-V5, V10, V15 and V16 is opened, closing the valves;
2) Opening V1, V2 and V4, and filling a standard gas storage container A with a known volume with a certain amount of inert gas, such as argon;
3) Closing the valve V2, and after evacuating the system through the Q end of the air supply/evacuation component, closing the valve V1;
4) Sequentially opening valves V2, V10 and V15, and sequentially calibrating the volumes of a pipeline and a vacuum mass spectrum chamber H by a volume expansion method;
5) After the volume calibration is completed, opening valves V1, V3-V5, V7, V12 and V16 to evacuate pipelines, a mass spectrum vacuum chamber H and upstream and downstream parts of a first leak hole D;
6) After the valve V16 is closed and hydrogen isotope gas with certain pressure is filled into the leak, the valve V1 is closed, the gas pressure passing through the mass spectrum chamber on the downstream side of the first leak D is collected in real time through the second thin film capacitance gauge G4 and the full-range composite gauge G5, and the leak rate of the first leak D under the environment temperature and the pressure is calculated according to the calibrated volume.
7) Repeating the steps 4) to 5) to obtain hydrogen isotope leak rate data of the second leak hole E and the third leak hole F under different pressures, and completing the leak rate calibration process of the leak hole, wherein a calibration curve is shown in figure 2;
second,: the method for constructing the linear relation curve of the mass spectrum signal and the leak rate of He by adopting the gas supply system shown in FIG. 1 comprises the following steps:
1) Opening a valve V16, and keeping the vacuum mass spectrum cavity H in an ultrahigh vacuum state all the time through a vacuum pump group I; starting a quadrupole mass spectrum G, and stabilizing for a period of time to obtain a background hydrogen isotope signal;
2) Filling hydrogen isotope gas with 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 flow signal corresponding to the leak rate after the mass spectrum signal is stable, and closing the valve V12;
3) Repeating the step 2) to obtain mass spectrum ion flow signals corresponding to the second leakage hole E and the third leakage hole F with known hydrogen isotope leakage rate;
4) And establishing a linear relation curve of mass spectrum signals of hydrogen isotopes or helium isotopes and the leak rate according to ion flow signals corresponding to different leak rates, as shown in figure 3.
Example 3
First: pair D using a gas supply system as shown in FIG. 1 2 The leak rate calibration method comprises the following steps:
1) After the evacuation system of the valves V1-V5, V10, V15 and V16 is opened, closing the valves;
2) Opening V1, V2 and V4, and filling a standard gas storage container A with a known volume with a certain amount of inert gas, such as argon;
3) Closing the valve V2, and after evacuating the system through the Q end of the air supply/evacuation component, closing the valve V1;
4) Sequentially opening valves V2, V10 and V15, and sequentially calibrating the volumes of a pipeline and a vacuum mass spectrum chamber H by a volume expansion method;
5) After the volume calibration is completed, opening valves V1, V3-V5, V7, V12 and V16 to evacuate pipelines, a mass spectrum vacuum chamber H and upstream and downstream parts of a first leak hole D;
6) After the valve V16 is closed and hydrogen isotope gas with certain pressure is filled into the leak, the valve V1 is closed, the gas pressure passing through the mass spectrum chamber on the downstream side of the first leak D is collected in real time through the second thin film capacitance gauge G4 and the full-range composite gauge G5, and the leak rate of the first leak D under the environment temperature and the pressure is calculated according to the calibrated volume.
7) Repeating the steps 4) to 5) to obtain hydrogen isotope leak rate data of the second leak hole E and the third leak hole F under different pressures, and completing the leak rate calibration process of the leak hole, wherein a calibration curve is shown in figure 2;
second,: d is built by adopting the air supply system shown in FIG. 1 2 The method of the linear relation curve of the mass spectrum signal and the leak rate is as follows:
1) Opening a valve V16, and keeping the vacuum mass spectrum cavity H in an ultrahigh vacuum state all the time through a vacuum pump group I; starting a quadrupole mass spectrum G, and stabilizing for a period of time to obtain a background hydrogen isotope signal;
2) Filling hydrogen isotope gas with 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 flow signal corresponding to the leak rate after the mass spectrum signal is stable, and closing the valve V12;
3) Repeating the step 2) to obtain mass spectrum ion flow signals corresponding to the second leakage hole E and the third leakage hole F with known hydrogen isotope leakage rate;
4) And establishing a linear relation curve of mass spectrum signals of hydrogen isotopes or helium isotopes and the leak rate according to ion flow signals corresponding to different leak rates, as shown in figure 3.
Third,: the specific method for measuring the diffusion and retention behavior characteristic parameters of the hydrogen isotope or helium isotope in the measurement material by adopting the gas supply system shown in fig. 1 comprises the following steps:
1) Valve V16 and evacuation pump group I are always opened to ensure that the mass spectrum chamber is always in a high vacuum state;
2) The membrane material after being cleaned and dried is connected into a permeation tool;
3) Opening valves V1, V3, V5, V6 and V11, and evacuating the upstream and downstream of the membrane in the permeation tool;
4) Opening a mass spectrum, introducing a certain amount of inert gas through a Q section of a gas supply/extraction component, and detecting whether an ion flow signal of the inert gas is obviously increased compared with a background through the mass spectrum, wherein if no obvious change exists, the sealing performance of the diaphragm is good;
5) After the inert gas at the upstream side of the membrane is pumped out, hydrogen isotope gas with certain pressure is introduced, and hydrogen isotope mass spectrometry signals permeated at the downstream side of the membrane under different temperature conditions (650 ℃, 700 ℃, 750 ℃, 800 ℃ and 850 ℃) are collected, as shown in figure 5;
6) And obtaining the hydrogen isotope permeation characteristic parameter of the membrane material by calibrating the mass spectrum signal through the leak rate.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (7)

1. A method for measuring a hydrogen isotope or helium isotope, comprising the steps of:
carrying out vacuum continuous heating and thermal desorption on a sample to be detected, carrying out mass spectrum detection on released gas to obtain a signal-time relation curve of mass spectrum signals of hydrogen isotopes or helium isotopes released by the sample to be detected, and obtaining the release rate of the hydrogen isotopes or the helium isotopes at each time point according to the linear relation curve of the mass spectrum signals of the hydrogen isotopes or the helium isotopes and the leak rate, and obtaining the content of the hydrogen isotopes or the helium isotopes in the sample to be detected after time integration;
the construction method of the linear relation curve of the hydrogen isotope or helium isotope mass spectrum signal and the leak rate comprises the following steps: a first construction method using one leak hole or a second construction method using a plurality of leak holes of different leak rates, the first construction method comprising the steps of: introducing gases under different constant pressure conditions into the upstream of the leak hole, detecting mass spectrum signals of the downstream gas 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 mass spectrum signals under different leak rate conditions to obtain a linear relation curve of the gas mass spectrum signals and the leak rate;
Or comprises the following steps: introducing gas under the condition of constant pressure into the upstream of the leak hole, detecting mass spectrum signals of the downstream gas of the leak hole in different time intervals, integrating the mass spectrum signals with respect to time, wherein the number of the different time intervals is more than or equal to 3, and performing linear fitting on the time integral values of the mass spectrum signals under the condition of leak rate multiplied by time of the different time intervals to obtain a linear relation curve of the gas mass spectrum signals and the leak rate;
the second construction method comprises the following steps:
each leak hole is provided with a gas branch, the plurality of leak holes are at least 3 leak holes with leak rate, and the plurality of gas branches are connected in parallel;
introducing constant pressure gas into the upstream of each branch leak hole, detecting mass spectrum signals of the gas at the downstream of each branch leak hole, and performing linear fitting after obtaining mass spectrum signals under different leak rate conditions to obtain a linear relation curve of the gas mass spectrum signals and the leak rate.
2. A method for measuring a characteristic parameter of diffusion and/or retention of a hydrogen isotope or helium isotope in a material, comprising the steps of:
introducing hydrogen isotopes or helium isotopes at the upstream of the membrane material under different constant temperature conditions, penetrating the hydrogen isotopes or the helium isotopes through the material, detecting mass spectrum signals of the hydrogen isotopes or the helium isotopes at the downstream of the material, obtaining a time-time relation curve of time variation of mass spectrum signals of the hydrogen isotopes or the helium isotopes penetrated by the membrane material under different constant temperature conditions, and obtaining the leak rate of the hydrogen isotopes or the helium isotopes at each time point according to the linear relation curve of the mass spectrum signals and the leak rate of the hydrogen isotopes or the helium isotopes, thereby obtaining the penetrating flux of the hydrogen isotopes or the helium isotopes passing through the unit area of the material under different constant temperature conditions; the construction method of the linear relation curve of the hydrogen isotope or helium isotope mass spectrum signal and the leak rate comprises the following steps: a first construction method using one leak hole or a second construction method using a plurality of leak holes of different leak rates, the first construction method comprising the steps of: introducing gases under different constant pressure conditions into the upstream of the leak hole, detecting mass spectrum signals of the downstream gas 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 mass spectrum signals under different leak rate conditions to obtain a linear relation curve of the gas mass spectrum signals and the leak rate;
Or comprises the following steps: introducing gas under the condition of constant pressure into the upstream of the leak hole, detecting mass spectrum signals of the downstream gas of the leak hole in different time intervals, integrating the mass spectrum signals with respect to time, wherein the number of the different time intervals is more than or equal to 3, and performing linear fitting on the time integral values of the mass spectrum signals under the condition of leak rate multiplied by time of the different time intervals to obtain a linear relation curve of the gas mass spectrum signals and the leak rate;
the second construction method comprises the following steps:
each leak hole is provided with a gas branch, the plurality of leak holes are at least 3 leak holes with leak rate, and the plurality of gas branches are connected in parallel;
introducing constant pressure gas into the upstream of each branch leak hole, detecting mass spectrum signals of the gas at the downstream of each branch leak hole, and performing linear fitting after obtaining mass spectrum signals under different leak rate conditions to obtain a linear relation curve of the gas mass spectrum signals and the leak rate;
and calculating and obtaining characteristic parameters of diffusion and retention behaviors of the hydrogen isotope or helium isotope of the material under different temperature conditions according to the permeation flux of the hydrogen isotope or 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.
3. A gas supply system for use in a method of measuring a hydrogen isotope or helium isotope as claimed in claim 1 or a method of measuring a characteristic parameter of diffusion and/or retention of a hydrogen isotope or helium isotope in a material as claimed in claim 2, comprising:
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 with a vacuum chamber (H) of mass spectrum; 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 leak holes,
a seventh valve (V7) and a third pressure sensor (G6) are arranged on the first gas branch which is positioned at the upstream of the first leak hole (D), the third pressure sensor (G6) is close to the first leak hole (D), and a twelfth valve (V12) is arranged on the first gas branch which is positioned at the downstream of the first leak hole (D);
an eighth valve (V8) and a fourth pressure sensor (G7) are arranged on the second gas branch which is positioned at the 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 arranged on the second gas branch which is positioned at the downstream of the second leak 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 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 at the downstream of the third leak hole (F)
A gas supply/extraction member (Q); the air supply/extraction component (Q) communicates with the first main conduit.
4. A gas supply system according to claim 3, characterized in that a first valve (V1) is arranged on the first main pipe at the end of the first main pipe that is located closer to the gas supply/extraction member (Q), and that a first pipe branch, a second pipe branch, a third pipe branch and a fourth pipe branch are connected to the first main pipe between the first valve (V1) and the gas 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).
5. A gas supply system according to claim 3, characterized in that the gas supply system further comprises a thermal desorption member (B) replacing any one of the leak holes;
or the gas supply system also comprises a thermal desorption part (B) and a fourth gas branch which is connected in parallel with the first gas branch, the second gas branch and the third gas branch, wherein a gas outlet of the thermal desorption part (B) is communicated with a gas inlet end of the fourth gas branch; when the air outlet of the thermal desorption part (B) is communicated with the air inlet end of the second air branch, the air outlet end of the fourth air branch is communicated with the second main pipeline; and the air inlet end of the fourth air branch is also communicated with the first main pipeline.
6. The gas supply system according to claim 5, characterized in that a tenth valve (V10) is arranged at the end of the pipe communicating with the first main pipe near the fourth gas branch, and a fifteenth valve (V15) is arranged at the end of the fourth gas branch communicating with the second main pipe.
7. A gas supply system according to claim 3, characterized in that the gas supply system further comprises a permeable member (C) replacing any one of the leak holes;
Or the gas supply system further comprises a permeation component (C) which is arranged on a fifth gas branch and is connected with the first gas branch, the second gas branch and the third gas branch in parallel; when the penetrating component is arranged on a fifth gas branch, the air inlet end of the fifth gas branch is communicated with the first main pipeline, and the air outlet end of the fifth gas branch is communicated with the second main pipeline; a sixth valve (V6) is arranged on the fifth gas branch upstream of the permeable member (C), and an eleventh valve (V11) is arranged on the fifth gas branch downstream of the permeable member (C).
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