CN108305826A - External electromagnetic field normal pressure open-type laser mass spectrograph - Google Patents

External electromagnetic field normal pressure open-type laser mass spectrograph Download PDF

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Publication number
CN108305826A
CN108305826A CN201810288496.5A CN201810288496A CN108305826A CN 108305826 A CN108305826 A CN 108305826A CN 201810288496 A CN201810288496 A CN 201810288496A CN 108305826 A CN108305826 A CN 108305826A
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CN
China
Prior art keywords
normal pressure
electromagnetic field
laser
pressure open
calutron
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CN201810288496.5A
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Chinese (zh)
Inventor
周云申
秦国双
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Innovo Laser Polytron Technologies Inc
Jiangsu Micro Nano Laser Application Technology Research Institute Co Ltd
INNO MACHINING Co Ltd
Original Assignee
Innovo Laser Polytron Technologies Inc
Jiangsu Micro Nano Laser Application Technology Research Institute Co Ltd
INNO MACHINING Co Ltd
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Application filed by Innovo Laser Polytron Technologies Inc, Jiangsu Micro Nano Laser Application Technology Research Institute Co Ltd, INNO MACHINING Co Ltd filed Critical Innovo Laser Polytron Technologies Inc
Priority to CN201810288496.5A priority Critical patent/CN108305826A/en
Publication of CN108305826A publication Critical patent/CN108305826A/en
Pending legal-status Critical Current

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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00Particle spectrometers or separator tubes
    • H01J49/02Details
    • H01J49/10Ion sources; Ion guns
    • H01J49/16Ion sources; Ion guns using surface ionisation, e.g. field-, thermionic- or photo-emission
    • H01J49/161Ion sources; Ion guns using surface ionisation, e.g. field-, thermionic- or photo-emission using photoionisation, e.g. by laser
    • H01J49/164Laser desorption/ionisation, e.g. matrix-assisted laser desorption/ionisation [MALDI]

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
  • Electron Tubes For Measurement (AREA)

Abstract

The invention discloses a kind of external electromagnetic field normal pressure open-type laser mass spectrographs, including mass analyzer, control unit, laser, beam delivery unit and the additional calutron being sequentially arranged, detected sample is positioned between additional calutron and mass analyzer, and the injection port of mass analyzer is towards additional calutron to collect sample ions.The mass spectrograph is using laser as the excitaton source for generating plasma, it can be operated under antivacuum atmospheric environment, application range is wider, additional calutron is for generating electromagnetic field to control the direction of motion of plasma intermediate ion and inhibit the diffusion of ion, to play extension plasma lifetime, it is enriched with ion concentration, the effect for improving ion motion speed and ion being guided to be moved to mass analyzer injection port, effectively increase signal-to-noise ratio and the sensitivity of normal pressure open-type laser mass spectral analysis, to improve mass spectrometric accuracy of detection, it is a kind of accurate detection device of portable and testing result.

Description

External electromagnetic field normal pressure open-type laser mass spectrograph
Technical field
The invention belongs to sample analysis instrument technical fields, are related to a kind of normal pressure open-type laser mass spectrograph, specifically It is related to a kind of external electromagnetic field enhancing normal pressure open type mass spectrograph using laser as ion source.
Background technology
Mass spectrograph is a kind of instrument for analyzing mass number according to the mass-to-charge ratio of ion, by measure mass-to-charge ratio and Chemical composition present in the abundance identification sample of gaseous ion contains amount and type, in the detection and analysis of Element and isotope On have irreplaceable role, with the continuous development of science and technology, mass spectrum is related research and the letter that practical work provides It ceases more and more, life science, food security, Homeland Security, clinic has been increasingly becoming using the method for spectrometer analysis sample Medicine detects and the primary analysis method of the popular domains such as space technology.Traditional mass spectrograph generally falls into typical " large-scale instrument Device ", average price is at million yuan or more.
Recently as the growth of mobile detection and the screening market demand, such as environment, customs, airport, station, mining industry, agriculture Fields, the portable normal pressure open type mass spectrographs such as field are got the attention, 2016《" major scientific instruments and equipment exploitation " weight 2016 annual project application guide of point special project (section of state hair money (2016) 38)》In explicitly point out research open type and ionize new skill Art, development of new electron spray, dielectric barrier discharge, laser/gas-assisted spray and Highgrade integration open type ion source, open Zhan Xin ionizes application process exploitation and database sharing, implements engineering and the industrialization development of new ion source, to meet original Position analysis real-time, single cell analysis, mass spectrum imaging analysis, ultra trace sample analysis demand, push China's mass ions The great-leap-forward development of technology and device.
Ion source is one of mass spectrometric core component, has been largely fixed mass spectrographic sensitivity, currently, conventional Ion source preparation method include electron impact ionization (EI), chemi-ionization (CI), fast atom bombardment (FAB), Matrix-assisted swash Light desorption ionization (MALDI), thermal ionization (TIMS) etc., the above method is required for operating in vacuum environment.In recent years, with electricity Spraying ionization (ESI), Direct Analysis in Real Time (DART), inductively coupled plasma (ICP), atmospheric pressure chemical ionization (APCI), The ionization sides such as atmospheric pressure photoionization (APPI), atmospheric pressure solid analysis probe ionization (ASAP), laser ablation electron spray (LAESI) The invention of method so that antivacuum mass-spectrometer measurement is possibly realized.But current antivacuum mass-spectrometer measurement is asked there is also following Topic:(1) it can not be operated under real atmospheric environment, need suitable atmosphere and temperature.Such as ICP, APCI, APPI, ASAP; (2) it is affected by the external environment very big.Such as ESI, DART, LAESI;(3) be all soft ionization method, can not successfully manage hard, Indissoluble, infusibility, difficult ionized sample;(4) it needs auxiliary device to crush sample, dissolve even atomization process.
Defect both is from the deficiency of ionization method itself existing for current antivacuum mass-spectrometer measurement.Either ESI is also It is the methods of DART, use is all electronics or ion injection method to make sample charge.Such soft ionization method is to easy Desorption, volatile, soluble material is very applicable, but just for hard, non-volatile, indissoluble, infusibility, the difficult sample ionized It is helpless.Especially current portable antivacuum mass spectroscopy device, usually need to be equipped with a series of mating sample preparations, sampling and Sample introduction facility.Also occurred some in recent years using laser as the mass spectrograph of ion source, can be crushed simultaneously under atmospheric environment Ionized material, since what is acquired in this method is the plasma generated after laser bombardment, the service life of plasma, point Cloth and density can all directly affect measurement effect.And the service life of plasma is very short, usually it is several it is delicate within, and with height Warm high pressure characteristics tell diffusion after generation to periphery free space so that the distribution of plasma and density are in one always A dynamic changing process, while open type atmospheric environment makes energetic plasma be exposed to air environment, easily in air The ingredients such as contained oxygen molecule, hydrone react, to directly affect plasma lifetime, stability and composition information, Cause testing result accuracy bad.
Invention content
For this purpose, the present invention exactly will solve above-mentioned technical problem, to propose that one kind improving plasma lifetime, stabilization Property, the external electromagnetic field normal pressure open-type laser mass spectrograph for inhibiting plasma diffusion, improving accuracy in detection.
In order to solve the above technical problems, the technical scheme is that:
The present invention provides a kind of external electromagnetic field normal pressure open-type laser mass spectrograph comprising the quality analysis being sequentially arranged Device, control unit, laser, beam delivery unit and additional calutron, detected sample be positioned over additional calutron with Between the mass analyzer, the injection port of the mass analyzer is inspired towards the additional calutron with collecting Sample ions.
Preferably, the calutron is made of at least one electrode.
Alternatively, preferably, the calutron is made of at least one magnet.
Alternatively, preferably, the calutron is made of at least one electrode and at least one magnet.
Preferably, the calutron is set to the peripheral position of detected sample.
The beam delivery unit includes in beam shaping, light beam conductor, condenser lens, laser direction regulating mechanism It is at least one.
Preferably, the beam delivery unit by be sequentially arranged along laser optical path beam shaping, light beam conductor, Condenser lens and laser direction adjust or sweep mechanism composition.
Preferably, the laser direction adjusts or sweep mechanism is laser galvanometer, multiple surface rotating mirror or polygon scanner.
Preferably, the electrode is positive electrode or negative electrode, the magnet is permanent magnet or electromagnet.
The above technical solution of the present invention has the following advantages over the prior art:
Normal pressure open-type laser mass spectrograph in external electromagnetic field of the present invention comprising the quality analysis being sequentially arranged Device, control unit, laser, beam shaping unit and additional calutron, detected sample be positioned over additional calutron with Between the mass analyzer, the injection port of the mass analyzer is towards the additional calutron to collect sample ions. The mass spectrograph can be operated, using model using laser as the excitaton source for generating plasma under antivacuum atmospheric environment It encloses more extensively, also, additional calutron is for generating electromagnetic field to control the direction of motion of plasma intermediate ion and inhibit The diffusion of ion extends plasma lifetime, enrichment ion concentration, improves ion motion speed and guides ion to play The effect moved to mass analyzer injection port effectively increases the signal-to-noise ratio of normal pressure open-type laser mass spectral analysis and sensitive Degree is a kind of accurate detection device of portable and testing result to improve mass spectrometric accuracy of detection.
Description of the drawings
In order to make the content of the present invention more clearly understood, it below according to specific embodiments of the present invention and combines Attached drawing, the present invention is described in further detail, wherein
Fig. 1 is the mass spectrometric structural schematic diagram of external electromagnetic field normal pressure open-type laser described in the embodiment of the present invention 1;
Fig. 2 is the mass spectrometric structural schematic diagram of external electromagnetic field normal pressure open-type laser described in the embodiment of the present invention 2;
Fig. 3 is the mass spectrometric structural schematic diagram of external electromagnetic field normal pressure open-type laser described in the embodiment of the present invention 3.
Reference numeral is expressed as in figure:1- mass analyzers;2- control units;3- lasers;4- beam delivery units;5- Additional calutron;51- magnets;52- electrodes;6- samples;7- plasmas.
Specific implementation mode
Embodiment 1
The present embodiment provides a kind of external electromagnetic field normal pressure open-type laser mass spectrographs, are passed through using Lorentz law outer Add magnetic field to control plasma ion motion direction and inhibit the diffusion of ion, to improve normal pressure open-type laser mass spectrum The signal-to-noise ratio of analysis and sensitivity.
As shown in Figure 1, the external electromagnetic field normal pressure open-type laser mass spectrograph includes the mass analyzer being sequentially arranged 1, control unit 2, laser 3, beam delivery unit 4 and additional calutron 5, sample to be detected are placed in additional calutron 5 insides.Wherein, the sample ions that the mass analyzer 1 is used to generate in ion source are divided by the size of mass-to-charge ratio (m/z) It opens, injection port collects the sample plasma of generation at additional calutron 5 towards the additional calutron 5, described Laser 3 comes out the plasma exciatiaon of sample for generating, and the laser 3 is set to the beam delivery unit 4 Side, beam delivery unit 4 are used for laser beam reshaping, focusing, conduction to sample surfaces, can be beam shaping, light Any one of beam conductor, condenser lens and laser direction regulating mechanism or several combinations, in the present embodiment, the light beam Transmission unit 4 is light beam conductor.The beam delivery unit 4 is set to 5 top of the additional calutron, the outer power-up Magnetic device 5 is for generating additional electromagnetic field (can be independent electric field or magnetic field, can also be compound electromagnetic field).
In the present embodiment, the additional calutron 5 includes the magnet 51 that a sectional view is arc, the magnet 51 Can be other shapes, such as rectangle.Specifically, the magnet 51 is set to the offside of the mass analyzer 1, and the magnet 51 can be permanent magnet or electromagnet, be set to around sample 6, be preferably disposed on 1 offside of mass analyzer, i.e. sample 6 It is placed between mass analyzer 1 and magnet 51, the magnetic fields that the plasma 7 inspired from sample 6 is generated in magnet 51 Lower to be moved towards mass analyzer 1, principle is as follows:
According to Coulomb's law:The size for the electrostatic force (F electrostatic force) that two charges interact with each other can be with following Equation is expressed:FElectrostatic force=ke(qq’/r2), wherein q and q ' they are net charges, and r is the distance between two charges, keIt is library Feudal order number;And Lorentz force law:Moving active force (i.e. Lorentz force) that the charged particle in electromagnetic field is experienced can To be expressed with lorentz equation:F=q (E+V × B), wherein F are Lorentz forces, and q is the quantity of electric charge of charged particle, and E is electric-field strength Degree, V is the speed of charged particle, and B is magnetic induction intensity.
Under electric field action, positive charge can accelerate towards the direction of electric field;Under magnetic fields, according to the right-hand rule, just Charge can be bent towards perpendicular to the direction of speed V and magnetic field B, and in the present embodiment, the ion inspired in sample powers up outside It is moved towards mass analyzer 1 under the action of magnetic device 5, to be enriched with.
In the present embodiment, the beam delivery unit includes that the beam shaping being sequentially arranged along laser optical path and light beam pass Device is led, the laser beam that laser 3 is sent out passes to device by light beam after beam shaping shaping and is transmitted to 6 surface of sample, will The plasma 7 of sample 6 ejects.
Embodiment 2
The present embodiment provides a kind of external electromagnetic field normal pressure open-type laser mass spectrographs, are passed through using Lorentz law outer Add magnetic field to control plasma ion motion direction and inhibit the diffusion of ion, to improve normal pressure open-type laser mass spectrum The signal-to-noise ratio of analysis and sensitivity.
As shown in Fig. 2, the external electromagnetic field normal pressure open-type laser mass spectrograph includes the mass analyzer being sequentially arranged 1, control unit 2, laser 3, beam delivery unit 4 and additional calutron 5, sample to be detected are placed in additional calutron 5 inside.Wherein, the sample ions that the mass analyzer 1 is used to generate in ion source are divided by the size of mass-to-charge ratio (m/z) It opens, injection port towards the additional calutron 5 to collect the ion generated in additional calutron 5, use by the laser 3 Sample plasma is ejected in generating, the laser 3 is set to the side of the beam delivery unit 4, and light beam passes Defeated unit 4 is used for laser beam focus, conduction to sample surfaces, and the beam delivery unit 4 is set to the additional electromagnetic installing 5 tops are set, the additional calutron 5 (can be independent electric field or magnetic field, can also be multiple for generating additional electromagnetic field The electromagnetic field of conjunction).
In the present embodiment, the additional calutron 5 includes a magnet 51 and the electricity for being set to 51 side of the magnet Pole 52, specifically, the electrode 52 are arranged perpendicular to the magnet 51, and it is set to the offside of the mass analyzer 1, i.e., The magnet 51 is set between the electrode 52 and the mass analyzer 1, wherein magnet 51 can be permanent magnet or electromagnetism Iron, the electrode 52 can be positive electrode or negative electrode, and sample 6 is also placed between electrode 63 and mass analyzer 51, electrode 52 It is set to 6 periphery of sample, the electromagnetism that the plasma 7 being inspired in sample 6 is generated in electrode 52 and magnet 51 with magnet 51 It is moved towards mass analyzer 1 under field action, principle is as follows:
According to Coulomb's law:The size for the electrostatic force (F electrostatic force) that two charges interact with each other can be with following Equation is expressed:FElectrostatic force=ke(qq’/r2), wherein q and q ' they are net charges, and r is the distance between two charges, keIt is library Feudal order number;And Lorentz force law:Moving active force (i.e. Lorentz force) that the charged particle in electromagnetic field is experienced can To be expressed with lorentz equation:F=q (E+V × B), wherein F are Lorentz forces, and q is the quantity of electric charge of charged particle, and E is electric-field strength Degree, V is the speed of charged particle, and B is magnetic induction intensity.
Under electric field action, positive charge can accelerate towards the direction of electric field;Under magnetic fields, according to the right-hand rule, just Charge can be bent towards perpendicular to the direction of speed V and magnetic field B, and in the present embodiment, the ion inspired in sample powers up outside It is moved towards mass analyzer 1 under the action of magnetic device 5, to be enriched with.
In the present embodiment, the beam delivery unit 4 is conducted by beam shaping, the light beam being sequentially arranged along laser optical path Device, condenser lens and laser direction adjust or sweep mechanism composition, wherein the laser direction adjusts or sweep mechanism is laser Galvanometer.
Embodiment 3
The present embodiment provides a kind of external electromagnetic field normal pressure open-type laser mass spectrograph, structure is basic with embodiment 1,2 It is identical, the difference is that, as shown in figure 3, the additional calutron 5 only includes an electrode 52, the electrode 52 is set to 1 offside of the mass analyzer, sample 6 are set between electrode 52 and quality generator 1, the plasma inspired from sample 6 Body 7 moves under the electromagnetic field effect that electrode 52 generates to mass analyzer 1.
In the present embodiment, the beam delivery unit 4 is conducted by beam shaping, the light beam being sequentially arranged along laser optical path Device, condenser lens and laser direction adjust or sweep mechanism composition, wherein the laser direction adjusts or sweep mechanism is laser Galvanometer or other similar devices, such as multiple surface rotating mirror or polygon scanner.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or It changes still within the protection scope of the invention.

Claims (9)

1. a kind of external electromagnetic field normal pressure open-type laser mass spectrograph, which is characterized in that including be sequentially arranged mass analyzer, Control unit, laser, beam delivery unit and additional calutron, detected sample be positioned over additional calutron with it is described Between mass analyzer, the injection port of the mass analyzer is towards the additional calutron to collect the sample being inspired Ion.
2. normal pressure open-type laser mass spectrograph in external electromagnetic field according to claim 1, which is characterized in that the outer power-up Magnetic device is made of at least one electrode.
3. normal pressure open-type laser mass spectrograph in external electromagnetic field according to claim 1, which is characterized in that the outer power-up Magnetic device is made of at least one magnet.
4. normal pressure open-type laser mass spectrograph in external electromagnetic field according to claim 1, which is characterized in that the outer power-up Magnetic device is made of at least one electrode and at least one magnet.
5. according to claim 2-4 any one of them external electromagnetics field normal pressure open-type laser mass spectrograph, which is characterized in that institute State the peripheral position that additional calutron is set to detected sample.
6. normal pressure open-type laser mass spectrograph in external electromagnetic field according to claim 5, which is characterized in that the light beam passes Defeated unit includes at least one of beam shaping, light beam conductor, condenser lens, laser direction regulating mechanism.
7. normal pressure open-type laser mass spectrograph in external electromagnetic field according to claim 6, which is characterized in that the light beam passes Defeated unit is adjusted or is swept by beam shaping, light beam conductor, condenser lens and the laser direction being sequentially arranged along laser optical path Retouch mechanism composition.
8. normal pressure open-type laser mass spectrograph in external electromagnetic field according to claim 7, which is characterized in that the laser side It is laser galvanometer, multiple surface rotating mirror or polygon scanner to adjusting or sweep mechanism.
9. normal pressure open-type laser mass spectrograph in external electromagnetic field according to claim 4, which is characterized in that the electrode is Positive electrode or negative electrode, the magnet are permanent magnet or electromagnet.
CN201810288496.5A 2018-04-03 2018-04-03 External electromagnetic field normal pressure open-type laser mass spectrograph Pending CN108305826A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111230299A (en) * 2020-03-12 2020-06-05 广东工业大学 Laser welding online detection device and method

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH039259A (en) * 1989-06-06 1991-01-17 Nippon Telegr & Teleph Corp <Ntt> Mass spectrometer by high-repetition laser stimulation
JPH11354072A (en) * 1998-06-09 1999-12-24 Hitachi Ltd Laser-ionized neutral particle mass spectrometer and analysis method therefor
CN203705342U (en) * 2014-01-15 2014-07-09 浙江师范大学 Alternating magnetic field intensifying laser inducing plasma light spectrum detection device
CN104241077A (en) * 2014-08-06 2014-12-24 四川大学 Normal pressure micro glow discharge desorption mass spectrum ion source based on magnetic field constraint and mass spectrometer
CN106248777A (en) * 2016-08-18 2016-12-21 东南大学 A kind of normal pressure open type sampling system

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH039259A (en) * 1989-06-06 1991-01-17 Nippon Telegr & Teleph Corp <Ntt> Mass spectrometer by high-repetition laser stimulation
JPH11354072A (en) * 1998-06-09 1999-12-24 Hitachi Ltd Laser-ionized neutral particle mass spectrometer and analysis method therefor
CN203705342U (en) * 2014-01-15 2014-07-09 浙江师范大学 Alternating magnetic field intensifying laser inducing plasma light spectrum detection device
CN104241077A (en) * 2014-08-06 2014-12-24 四川大学 Normal pressure micro glow discharge desorption mass spectrum ion source based on magnetic field constraint and mass spectrometer
CN106248777A (en) * 2016-08-18 2016-12-21 东南大学 A kind of normal pressure open type sampling system

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111230299A (en) * 2020-03-12 2020-06-05 广东工业大学 Laser welding online detection device and method

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