CN110132943A - The method for improving laser induced breakdown spectroscopy repeatability based on mixed-gas environment - Google Patents

The method for improving laser induced breakdown spectroscopy repeatability based on mixed-gas environment Download PDF

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CN110132943A
CN110132943A CN201910467429.4A CN201910467429A CN110132943A CN 110132943 A CN110132943 A CN 110132943A CN 201910467429 A CN201910467429 A CN 201910467429A CN 110132943 A CN110132943 A CN 110132943A
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gas
mixed
sample
standard deviation
laser induced
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CN110132943B (en
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王哲
俞建龙
侯宗余
李天奇
李政
顾炜伦
刘家岑
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Tsinghua University
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/01—Arrangements or apparatus for facilitating the optical investigation
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/71—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited
    • G01N21/718—Laser microanalysis, i.e. with formation of sample plasma
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/01—Arrangements or apparatus for facilitating the optical investigation
    • G01N2021/0106—General arrangement of respective parts
    • G01N2021/0112—Apparatus in one mechanical, optical or electronic block
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2201/00—Features of devices classified in G01N21/00
    • G01N2201/12—Circuits of general importance; Signal processing
    • G01N2201/13—Standards, constitution

Abstract

Based on the method that mixed-gas environment improves laser induced breakdown spectroscopy repeatability, sample to be tested is placed in a cavity by this method first, and gas in cavity is evacuated to vacuum with aspiration pump；Then it is passed through mixed gas into vacuum chamber, when cavity internal pressure reaches an atmospheric pressure, records the composition ratio of mixed gas；Under the gaseous environment, the laser induced breakdown spectroscopy signal of sample to be tested is detected, and calculates the relative standard deviation of signal, the index as repeatability；The ratio for constantly changing mixed gas later is detected, and corresponding relative standard deviation is calculated；The relative standard deviation of spectral signal under more various mixed-gas environments obtains optimal mixed gas composition ratio, the gaseous environment as sample to be tested.The present invention can significantly reduce the relative standard deviation of spectral signal, improve the repeatability of laser induced breakdown spectroscopy, and then improve the measurement accuracy of LIBS.Have the characteristics that simple and practical, economical and practical.

Description

The method for improving laser induced breakdown spectroscopy repeatability based on mixed-gas environment
Technical field
The present invention relates to a kind of methods for improving laser induced breakdown spectroscopy repeatability based on mixed-gas environment, belong to original Sub- emission spectroscopy measurements technical field.
Background technique
Laser induced breakdown spectroscopy (abbreviation LIBS) technology is a kind of emerging element analysis technology.The work of the technology Principle is: using pulse laser ablation sample to be tested, forms laser induced plasma；Plasma resonance goes out specific frequency Photon generates characteristic spectrum；By analyzing characteristic spectrum, qualitative and quantitative analysis is carried out to the element composition of sample to be tested. LIBS technology has without sample pretreatment, that small to sample damage, analysis speed is fast, is able to achieve multielement measurement etc. is a variety of excellent Point, development potentiality are very big.
But the amount of the substance of ablation is seldom in LIBS technology detection process, the plasma decline of formation is rapid and real A series of fluctuation and interference can occur for the condition of testing, and the parameters such as total ion number density of plasma, temperature, electron density can be sent out Raw a series of fluctuation causes the repeatability of spectrum lower, and signal relative standard deviation (abbreviation RSD) numerical value is higher, usually super Cross 10%.This affects the detection accuracy of LIBS to a certain extent, and there are disadvantages when competing it with similar technique, limits The further development of the technology.
Laser induced plasma during generate, be expanded into dyingout, can and the environmental gas of surrounding generate The reciprocation of a series of complex, therefore the signal of environmental gas meeting plasma generates important influence.Different Rings The characteristics of border, the properties such as molecular weight, thermal coefficient, ionization energy are also different, reciprocation also changes correspondingly.LIBS at present System usually detects sample to be tested under atmospheric environment or pure inert gas environment (such as helium, neon, argon gas), Obtained spectral signal, relative standard deviation is higher, less reproducible.
Summary of the invention
The object of the present invention is to provide a kind of sides that laser induced breakdown spectroscopy repeatability is improved based on mixed-gas environment Method, the spectral signal relative standard deviation to solve to obtain under atmospheric environment or pure inert gas environment is higher, repeats Property poor problem, to improve laser induced breakdown spectroscopy repeatability, and then improve the measurement accuracy of LIBS.
The technical scheme is that
1. a kind of method for improving laser induced breakdown spectroscopy repeatability based on mixed-gas environment, it is characterised in that the party Method includes the following steps:
1) sample to be tested is placed in a cavity, seal cavity；
2) gas in aspiration pump suction chamber body is utilized；When the intracorporal pressure of chamber reaches vacuum state, stop pumping；
3) mixed gas is passed through into the vacuum cavity for exhaust gas；The mixed gas is by inert gas, air, nitrogen and two At least two compositions in carbonoxide；Record the composition ratio of these types of gas；During being passed through mixed gas, work as cavity When interior pressure reaches an atmospheric pressure, stops ventilation, be in sample to be tested under the mixed-gas environment；
4) under the mixed-gas environment, sample to be tested is detected using laser induced plasma spectroscopic system, is obtained To the laser induced breakdown spectroscopy signal of sample to be tested, and calculate the relative standard deviation RSD of signal1, as repeated finger Mark:
Wherein, σ I indicates the standard deviation of spectral signal under the mixed-gas environment,Indicate light under the mixed-gas environment The average value of spectrum signal；
5) composition ratio for constantly changing several gases in mixed gas, repeats step 2) -4), in new mixed gas ring Under border, sample to be tested is detected, corresponding spectral signal is obtained, calculates corresponding relative standard deviation RSDi；
6) under more various mixed-gas environments sample spectral signals relative standard deviation, find out minimum value；By this The corresponding composition ratio of minimum value detects sample using the gaseous environment as best proportion, lures to improve laser Lead the repeatability of breakdown spectral.
In above-mentioned technical proposal, the side of the composition ratio of several gases in continuous change mixed gas described in step 5) Method are as follows: it is changed by gradient, that is, chooses a positive integer n more than or equal to 5, withFor variable gradient, gradually change mixed Close the composition ratio of gas.
The present invention has the following advantages that and the technical effect of high-lighting: atmospheric environment or pure inert gas environment (such as Helium, neon, argon gas) under, laser induced breakdown spectroscopy signal it is less reproducible, the numerical value of relative standard deviation usually exists 10% or more；Also, when spectral signal is weaker, experiment condition fluctuation is larger, relative standard deviation can be more than even 20%；And Under the optimal mixed-gas environment of this method, the relative standard deviation of spectral line signal be can be effectively reduced to 10% hereinafter, aobvious Write the repeatability for improving spectrum；Also, the promotion effect of this method not only in spectrum a certain item or a few spectral lines it is effective, But it is generally effective to most of spectral line, i.e., this method has universality；Determine that the process of best proportion is not related to complexity substantially Experimental implementation and mathematical operation, it is simple and practical, convenient for grasp；After optimal ratio-dependent, only needed substantially using this method The nozzle of an air blowing is added in original LIBS system, required apparatus is very simple, whole system structure It is compact, it is economical and practical.
Detailed description of the invention
Fig. 1 is the flow diagram of the method for the present invention.
Fig. 2 is relative standard deviation (RSD) of the Ti 498.2nm spectral line under 22 kinds of gaseous environments.
Specific embodiment
The present invention is further illustrated with reference to the accompanying drawings and examples.
The method provided by the invention for improving laser induced breakdown spectroscopy repeatability based on mixed-gas environment is specific to wrap Include following steps:
1) sample to be tested is placed in a cavity, seal cavity；
2) gas in aspiration pump suction chamber body is utilized；When the intracorporal pressure of chamber reaches vacuum state, stop pumping；
3) mixed gas is passed through into the vacuum cavity for exhaust gas；The mixed gas is by inert gas, air, nitrogen and two At least two compositions in carbonoxide；Record the composition ratio of these types of gas；During being passed through mixed gas, work as cavity When interior pressure reaches an atmospheric pressure, stops ventilation, be in sample to be tested under the mixed-gas environment；
4) under the mixed-gas environment, sample to be tested is detected using laser induced plasma spectroscopic system, is obtained To the laser induced breakdown spectroscopy signal of sample to be tested, and calculate the relative standard deviation RSD of signal1, as repeated finger Mark:
Wherein, σ I indicates the standard deviation of spectral signal under the mixed-gas environment,Indicate light under the mixed-gas environment The average value of spectrum signal；
5) composition ratio for constantly changing several gases in mixed gas, repeats step 2) -4), in new mixed gas ring Under border, sample to be tested is detected, corresponding spectral signal is obtained, calculates corresponding relative standard deviation RSDi；Constantly change mixing The method of the composition ratio of several gases is preferred in gas are as follows: is changed by gradient, i.e., selection one just whole more than or equal to 5 Number n, withFor variable gradient, the composition ratio of mixed gas is gradually changed.
6) under more various mixed-gas environments sample spectral signals relative standard deviation, find out minimum value；By this The corresponding composition ratio of minimum value detects sample using the gaseous environment as best proportion, lures to improve laser Lead the repeatability of breakdown spectral.
Embodiment:
For LIBS to measure titanium alloy sample TC4-2 is detected, hit to induced with laser is improved based on mixed-gas environment The method for wearing spectrum repeatability is illustrated.
1) titanium alloy sample is placed in a cavity, seal cavity；The titanium alloy sample is using titanium as matrix, other elements Concentration is as shown in table 1；
Table 1.TC4-2 titanium alloy sample ingredient
2) aspiration pump, gas in suction chamber body are used；When cavity internal pressure reaches vacuum state, stop pumping；
3) the 1st kind of gas of number in table 2 is passed through into the vacuum cavity for exhaust gas, record helium in the gas, neon and The composition ratio of argon gas；During being passed through gas, when the intracorporal pressure of chamber reaches 101.3KPa (i.e. an atmospheric pressure), Stop ventilation；Sample to be tested is under the 1st kind of mixed-gas environment；
4) under the 1st kind of mixed-gas environment, the titanium alloy sample is carried out using laser induced plasma spectroscopic system Detection, obtains the laser induced breakdown spectroscopy signal of sample to be tested, and calculate the relative standard deviation RSD of signal1, as repetition The index of property；
5) n as shown in table 2, is taken to be equal to 5, withI.e. 20% be variable gradient, systematically change mixed gas in helium, The ratio of argon gas, neon repeats step 2) -4), 2-22 kind mixed gas in table 2 is each led into, and in every kind of new mixing Under gaseous environment, titanium alloy sample is detected, obtains corresponding spectral signal, and calculate corresponding relative standard deviation RSDi(note Meaning, the 1st kind, the 6th kind, the 21st kind and the 22nd kind gaseous environment is pure argon, pure neon, pure helium and air respectively, is not The mixed gas of helium, neon, argon gas, this is to carry out pair with the relative standard deviation result under other mixed-gas environments Than)；
The mixed-gas environment of 2.22 kinds of different components of table
(note: 1,6,21,22 be respectively pure argon, neon, helium and air)
6) compare under this 22 kinds of mixed-gas environments, the relative standard deviation of titanium alloy sample spectral signal finds out minimum Value；Here we by taking the atomic spectral line of Ti 498.2nm as an example, Fig. 2 show spectral line relative standard under 22 kinds of gaseous environments Deviation；It can be found that the relative standard deviation value under the 14th kind of mixed-gas environment is minimum, only 7.7%, hence it is evident that be lower than 10%；And the relative standard deviation under air, pure argon, pure neon, pure helium environment is respectively 14.3%, 11.9%, 16.9% and 11.7%, it is above 10%；That is, in the 14th kind of mixed-gas environment, laser induced breakdown spectroscopy Repeatability is significantly improved；So for the titanium alloy sample, helium in the 14th kind of mixed-gas environment, neon and argon gas Ratio (40% helium, 40% neon, 20% argon gas) is optimal composition ratio；Use the mixed gas ring of this ratio The relative standard deviation of the laser induced breakdown spectroscopy signal of titanium alloy sample can be effectively reduced in border, improves titanium alloy sample Laser induced breakdown spectroscopy repeatability, and then improve LIBS measurement accuracy.

Claims (2)

1. a kind of method for improving laser induced breakdown spectroscopy repeatability based on mixed-gas environment, it is characterised in that this method packet Include following steps:
1) sample to be tested is placed in a cavity, seal cavity；
2) gas in aspiration pump suction chamber body is utilized；When the intracorporal pressure of chamber reaches vacuum state, stop pumping；
3) mixed gas is passed through into the vacuum cavity for exhaust gas；The mixed gas is by inert gas, air, nitrogen and titanium dioxide At least two compositions in carbon；Record the composition ratio of several mixed gas；During being passed through mixed gas, when in cavity Pressure when reaching an atmospheric pressure, stop ventilation, be in sample to be tested under the mixed-gas environment；
4) under the mixed-gas environment, sample to be tested is detected using laser induced plasma spectroscopic system, obtain to The laser induced breakdown spectroscopy signal of sample, and calculate the relative standard deviation RSD of signal1, as repeated index:
Wherein, σ I indicates the standard deviation of spectral signal under the mixed-gas environment,Indicate that spectrum is believed under the mixed-gas environment Number average value；
5) composition ratio for constantly changing several gases in mixed gas, repeats step 2) -4), in new mixed-gas environment Under, sample to be tested is detected, corresponding spectral signal is obtained, calculates corresponding relative standard deviation RSDi；
6) under more various mixed-gas environments sample spectral signals relative standard deviation, find out minimum value；By this minimum It is worth corresponding composition ratio as best proportion, sample is detected using the gaseous environment, is hit to improve induced with laser Wear the repeatability of spectrum.
2. a kind of method that laser induced breakdown spectroscopy repeatability is improved based on mixed-gas environment as described in claim 1, It is characterized in that, in continuous change mixed gas described in step 5) several gas composition ratios method are as follows: by gradient into A positive integer n more than or equal to 5 is chosen in row variation, withFor variable gradient, the ratio of components of mixed gas is gradually changed Example.
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CN111610179A (en) * 2020-05-20 2020-09-01 北京科技大学 System and method for quickly detecting components LIBS of high-temperature sample in front of furnace
CN113310969A (en) * 2021-04-22 2021-08-27 清华大学 Method for improving repeatability of laser-induced breakdown spectroscopy based on time modulation

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CN111610179B (en) * 2020-05-20 2021-06-25 北京科技大学 System and method for quickly detecting components LIBS of high-temperature sample in front of furnace
CN113310969A (en) * 2021-04-22 2021-08-27 清华大学 Method for improving repeatability of laser-induced breakdown spectroscopy based on time modulation

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