CN2874764Y - Single particle Gerosol online ionizing source - Google Patents

Single particle Gerosol online ionizing source Download PDF

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Publication number
CN2874764Y
CN2874764Y CN 200520120268 CN200520120268U CN2874764Y CN 2874764 Y CN2874764 Y CN 2874764Y CN 200520120268 CN200520120268 CN 200520120268 CN 200520120268 U CN200520120268 U CN 200520120268U CN 2874764 Y CN2874764 Y CN 2874764Y
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China
Prior art keywords
ionization
low pressure
laser
quadrupole
aerosol
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Expired - Lifetime
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CN 200520120268
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Chinese (zh)
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周振
傅忠
盛国英
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HEXIN AUTOMATION SYSTEM CO Ltd GUANGZHOU
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HEXIN AUTOMATION SYSTEM CO Ltd GUANGZHOU
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Abstract

The utility model provides a single-particle aerosol online ionization source, which is arranged outside the acceleration zone of a time-of-flight quality analyzer, and comprises an ionization laser and a low-voltage RF quadrupole. Laser beam emitted from the ionization laser is attached to the center of the internally tangent circle perpendicular to low-voltage RF quadrupole. A method utilizing the ionization source is mainly as follows: after aerodynamics calipers are used for single-particle aerosol, but before the aerosol enters the time-of-flight quality analyzer, the aerosol will be ionized into plasma with an ionization laser. The positive and negative ions that are created will be resent into the time-of-flight quality analyzer, with ion beams in very small image space in low-voltage RF quadrupole focus. The utility model can connect the ionization zone with the aerodynamics caliper zone. Aerosol ionization will be done at the same time of caliper completion, which can shorten floating distance of aerosol ultimately and considerably improve transmission efficiency. The focus effect of the low-voltage RF quadrupole can obviously improve resolution of the time-of-flight quality analyzer.

Description

Single-particle aerosol online ionization source
Technical field
The utility model relates to the aerosol particle line Measurement Technique, particularly a kind of single-particle aerosol online ionization source.
Background technology
Aerocolloidal size and chemical composition thereof cause significant impact to global climate, air quality, environmental health.Individual particle aerosol on-line monitoring time-of-flight mass spectrometer (Aerosol Time-of-flightMass Spectrometer, ATOFMS) be a kind of new technology that developed recently gets up, can real time on-line monitoring individual particle aerosol air kinetic diameter and air pollution composition thereof, be to judge that aerosol forms and the important means in source, its basic principle is to measure the aerosol diameter by the aerodynamics method, with aerosol ionization, the ion that ionization forms detects with mass spectrometer again.The method of concrete aerodynamic measurement aerosol particle diameter and time of flight mass analyzer detect the method for ion and consult document Mass Spectrometry of Aerosols, David T.Suess and Kimberly A.Prather, Chem.Rev.1999,99,3007-3035.Laser ionization source is adopted in the aerocolloidal online ionization of individual particle usually, and with the time of flight mass analyzer as the ion signal detector, in order to monitor a negative ions in the particle simultaneously, need two time of flight mass analyzers.
Because aerosol is the electric neutrality particle, and the transmission in a vacuum of electric neutrality particle can't be modulated with the electronic and ionic optical system, transmission range aerocolloidal detection efficiency far away more is just low more.In the existing device, aerocolloidal aerodynamics is calibrated distance and is generally 5~10 centimetres at present, and ion source also has other 10~20 centimetres from diameter measuring zone, and therefore aerocolloidal transmission range generally reaches 15~30 centimetres.This is because in existing device, ionization source (laser ionization source) is arranged in the time of flight mass analyzer, aerosol need enter in the time of flight mass analyzer and just can be ionized, so its transmission range is far away relatively, has produced the lower problem of aerosol detection efficiency thus.Simultaneously since in existing device laser ionization directly occur in the time of flight mass analyzer, the ion that ionization produces has bigger initial kinetic energy to be disperseed, and causes the mass resolution of time of flight mass analyzer on the low side, only about 500.
The utility model content
The purpose of this utility model is to overcome the shortcoming of prior art with not enough, provide a kind of rational in infrastructure, aerosol efficiency of transmission and ionization hit rate can be improved, and the single-particle aerosol online ionization source of the mass resolution of time of flight mass analyzer can be improved.
The purpose of this utility model is achieved through the following technical solutions: a kind of single-particle aerosol online ionization source, be arranged at outside the accelerating region of time of flight mass analyzer, comprise ionization laser, low pressure radiofrequency quadrupole, described ionization laser emitted laser bundle is incident to the incenter of low pressure radiofrequency quadrupole perpendicular to the low pressure radiofrequency quadrupole, will arrive the aerosol ionization of incenter position.
Described ionization laser emitted laser bundle is perpendicular to the low pressure radiofrequency quadrupole and in the axial center incident of low pressure radiofrequency quadrupole.
Described low pressure radiofrequency quadrupole is meant the quadrupole rod ion transfer device under certain air pressure.
Described low pressure radiofrequency quadrupole has the gap of four direction, is respectively the secondary ionization laser entrance port of calibrating laser entrance port, secondary scattered light exit portal and laser ionization system of aerocolloidal intake, laser diameter measurement system.
Described ionization laser is connected with the secondary photomultiplier of calibrating of laser diameter measurement system, and the trigger impulse of ionization laser is provided by secondary output signal of calibrating photomultiplier.
Every bar of described low pressure radiofrequency quadrupole mechanically is made up of more piece bar section, is provided with the gap between each pole section to guarantee electric insulation, and the gap between the adjacent two pole sections is less than 0.3mm.
Described low pressure radiofrequency quadrupole is provided with the axial DC electric field; The DC potential of the low pressure radiofrequency quadrupole position that described laser beam vertical incidence point is corresponding is set to 0V, increase respectively and reduce toward the opposite two ends DC potential of low pressure radiofrequency quadrupole direction, form the axial DC electric field to guarantee cation toward the negative voltage side migration, anion is toward the positive voltage terminal migration.
Each pole section of described low pressure radiofrequency quadrupole applies identical radio-frequency voltage with focused ion, and described radio-frequency voltage is in the same place by inductance, resistance and capacitive coupling with direct voltage.
Described low pressure radiofrequency quadrupole is positioned at a cavity, and the gas in the described cavity is generally the good gas of chemical stability, as: helium, nitrogen, argon gas etc.; The size that the air pressure of described gas is looked ion to be tested is arranged on the scope between 0.1Pa~100Pa.
The time of flight mass analyzer of this single-particle aerosol online ionization source is vertical introduction-type time of flight mass analyzer, and described vertical introduction-type time of flight mass analyzer is provided with two, detects negative ions respectively.In addition, if interested in the molecular structure of aerosol composition, can connect cascade mass spectrometer behind the low pressure radiofrequency quadrupole promptly can provide the tandem analysis.
This single-particle aerosol online ionization source and aerodynamics diameter measuring zone are connected as a single entity, and the secondary laser of calibrating is identical with the position of ionization laser action, promptly when finishing aerodynamics and calibrating, carry out ionization.It is same as the prior art that the aerosol air dynamics that the utility model relates to is calibrated technology.
In order to make all ions obtain detecting, negative ions can be sent into vertical introduction-type time of flight mass analyzer in low pressure radiofrequency quadrupole two ends tens microseconds of accumulation respectively again.The low pressure radiofrequency quadrupole principle of band axial field is identical with existing technology, and ion is also identical with prior art in the accumulation technology at quadrupole rod two ends.
The method of utilizing above-mentioned single-particle aerosol online ionization source to realize is: after utilizing aerodynamics to calibrate to the individual particle aerosol, before it enters the accelerating region of time of flight mass analyzer, utilize laser that it is ionized into plasma, the negative ions that is produced utilizes the low pressure radiofrequency quadrupole to be focused into the very little ion beam of phase space and sends in the time of flight mass analyzer again and detect.
Utilize the axial DC electric field of low pressure radiofrequency quadrupole setting to make the negative ions that produces after the ionization separately and respectively move (the past electronegative potential direction migration of cation wherein to the two ends of low pressure radiofrequency quadrupole, and anion is simultaneously toward the migration of high potential direction), detected by different time of flight mass analyzers respectively then.
The pulse that utilizes second photomultiplier of aerodynamics measurement diameter system to produce triggers the ionization laser immediately and sends laser pulse, utilizes this laser pulse that the individual particle aerosol is ionized into plasma; Owing to calibrate ionization take place when finishing immediately, can improve the ionization hit rate like this.
Action principle of the present utility model is: establish m i/ q, U Rf, ω, r 0Be respectively radio-frequency voltage, rf frequency, the quadrupole rod inscribed circle radius of ion mass-to-charge ratio, quadrupole rod, quadrupole rod is to leaving effective potential trough U of ion formation that inscribed circle centre distance is r Eff, its size is U eff = q m i U rf 2 r 0 4 ω 2 r 2 , Select suitable parameter, can be so that this effective potential trough reaches several even tens electron-volts.Therefore the utility model moves on to traditional aerosol ionized region the aerosol transmission range of low vacuum from the time of flight mass analyzer of high vacuum, and ionization is occurred in the center of low pressure radiofrequency quadrupole, utilize constraint and the aggtegation of the potential trough of low pressure radiofrequency quadrupole to ion, collect all ions that ionization obtains from aerosol, and be focused into the very little ion beam of phase space and deliver to again in the time of flight mass analyzer.Owing to have axial electric field, migration is separated negative ions to low pressure radiofrequency quadrupole two ends respectively, because grain diameter measurement and ionization take place in the same space position, improved the ionization hit rate, owing to detecting with mass of ion, aerocolloidal ionization separates fully again, ion source reduces to minimum to the influence of analyzer, has obviously improved the mass resolution of time of flight mass analyzer.
The relative prior art of the utility model has following advantage and effect: (1) the utility model is connected as a single entity ionized region and aerodynamics diameter measuring zone, aerodynamics is calibrated when finishing aerosol ionization, farthest dwindle aerocolloidal drift distance, obviously improved efficiency of transmission and ionization hit rate.(2) along with the increase of tested component molecules amount in the aerosol, structural analysis is more and more important, carry out structural analysis and need use the tandem mass spectrometry technology, and traditional individual particle aerosol on-line monitoring mass-spectrometric technique can not reach this purpose.Since the utility model technology earlier with ion collection in radiofrequency quadrupole, thereby can with the coupling of cascade mass spectrometry device, the ion that is produced can be detected by tandem mass spectrometry, for the structural analysis of molecular ion provides may.(3) utilize the utility model can make measurement of aerosol particle diameter and ionization take place in the same space position, and detect with mass of ion and to separate fully, utilize the low pressure radiofrequency quadrupole to reduce the phase space of ion beam in advance simultaneously, can improve the mass resolution of time of flight mass analyzer.
Description of drawings
Fig. 1 is the structural representation of the utility model device.
Fig. 2 is the dc offset voltage of low pressure radiofrequency quadrupole of device shown in Figure 1 and the coupling schematic diagram of radio-frequency voltage.
Fig. 3 is the schematic diagram and the pulse sequence figure of the utility model method.
Embodiment
Below in conjunction with embodiment and accompanying drawing the utility model is described in further detail, but execution mode of the present utility model is not limited thereto.
Embodiment
Fig. 1~Fig. 3 shows the concrete structure of the utility model device, as seen from Figure 1, this single-particle aerosol online ionization source vertical introduction-type time of flight mass analyzer 5,6 of comprising instrument vacuum cavity 1, aerosol injector 2, low pressure radiofrequency quadrupole 3 and quadrupole rod cavity 4, laser diameter measurement and laser ionization system and detecting positive and negative ion simultaneously; 7 is the aerosol of being introduced by aerosol injector 2; Low pressure radiofrequency quadrupole 3 is positioned at quadrupole rod cavity 4, and the gas in the described quadrupole rod cavity is generally purity and is higher than 99.99% the good gas of chemical stability, as: gas or other inert gases such as helium, nitrogen, argon gas; The size that the air pressure of described gas is looked ion to be tested is arranged on the scope between 0.1Pa~100Pa.
As shown in Figure 3, low pressure radiofrequency quadrupole 3 has the gap of four direction, and wherein two of horizontal direction gaps are respectively the intake of aerosol 7 and the intake of ionization laser beam 19; The gap of the upper and lower both direction of vertical direction is respectively the secondary entrance port of laser 17 and the measurement mouth of secondary scattered light 21 calibrated of laser diameter measurement system; The ionization laser beam 19 of ionization laser 18 emissions is perpendicular to low pressure radiofrequency quadrupole 3, and be incident to the incenter of low pressure radiofrequency quadrupole 3 in low pressure radiofrequency quadrupole 3 axial centers, ionization laser 18 is connected with the secondary photomultiplier 20 of calibrating, by its pulse-triggered that provides; The two ends of low pressure radiofrequency quadrupole 3 are connected with vertical introduction-type time of flight mass analyzer 5,6 respectively.
Every bar of described low pressure radiofrequency quadrupole 3 mechanically is made up of more piece bar section 8, and concrete structure is provided with the gap to guarantee electric insulation between each pole section 8 shown in Fig. 2 (a), and the gap between the adjacent two pole sections 8 is less than 0.3mm; Between adjacent two pole sections 8, resistance 9 and electric capacity 10 have been arranged in parallel; Each pole section 8 added radio-frequency voltage and dc offset voltage are coupled by resistance 9 and electric capacity 10, the direct current biasing negative voltage is added on the node 11, the direct current biasing positive voltage is added on the node 12, other respectively saves dc offset voltage and is formed by resistance 9 dividing potential drops, and radio-frequency voltage is added on the node 13, and pass to each pole section by electric capacity 10, thereby the added radio-frequency voltage of each pole section is identical.Fig. 2 (b) is depicted as low pressure radiofrequency quadrupole 3 direct current biasing Potential distribution vertically, center voltage is 0V, left end node 12 is provided with positive potential to attract anion, right-hand member node 11 is provided with negative potential to attract cation, increase respectively and reduce toward the opposite two ends DC potential of low pressure radiofrequency quadrupole direction, form the axial DC electric field, the potential difference Δ v at two ends can control the migration rate of ion.
Fig. 3 (a) calibrates and the ionization process schematic diagram for aerosol particle, and shown in Fig. 3 (a), the laser 14,16 of calibrating of laser diameter measurement and laser ionization system is in normally open and gives off laser beam 15,17.Aerosol 7 process laser beams 15,17 scattered beams of being introduced by aerosol injector 2 from atmosphere that produced 21,23 are respectively by photomultiplier 20,22 records, and produce two the at interval electric pulses 24,25 of t of certain hour are arranged, shown in Fig. 3 (b), aerocolloidal drift velocity v=l/t can be calculated according to the time interval t of two pulses and the space length l of two bundle laser 15,17, aerocolloidal aerodynamic diameter can be measured by the relation of proofreading and correct aerocolloidal drift velocity and particle diameter.The aerosol that photomultiplier 20 records arrives the trigger impulse 26 of pulse 25 as ionization laser 18, promptly when aerosol arrives low pressure radiofrequency quadrupole 3 incenter positions, applies ionization laser pulse 19, with aerosol ionization.Under the effect of ionization laser pulse 19, aerosol is ionized the generation plasma, cation wherein moves toward electronegative potential direction (node 11 ends among Fig. 2 (a)), and anion is detected by vertical introduction-type time of flight mass analyzer 5,6 respectively at last simultaneously toward high potential direction (node 12 ends among Fig. 2 (a)) migration.
Because in the utility model device, the generation of ion separates fully with the quality testing of ion, the ion that is produced can be delivered in any mass spectrometer and analyze.With the utility model device and the coupling of cascade mass spectrometry device, can carry out the structural analysis of aerosol component.
The foregoing description is the utility model preferred implementation; but execution mode of the present utility model is not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present utility model and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within the protection range of the present utility model.

Claims (7)

1, a kind of single-particle aerosol online ionization source, it is characterized in that: be arranged at outside the accelerating region of time of flight mass analyzer, comprise ionization laser, low pressure radiofrequency quadrupole, described ionization laser emitted laser bundle is incident to the incenter of low pressure radiofrequency quadrupole perpendicular to the low pressure radiofrequency quadrupole.
2, single-particle aerosol online ionization source according to claim 1 is characterized in that: described ionization laser emitted laser bundle is perpendicular to the low pressure radiofrequency quadrupole and in the axial center incident of low pressure radiofrequency quadrupole.
3, single-particle aerosol online ionization source according to claim 1 and 2, it is characterized in that: described low pressure radiofrequency quadrupole has the gap of four direction, wherein the horizontal direction gap is respectively the intake of aerocolloidal intake and ionization laser beam, and the gap of vertical direction is respectively the secondary intake of laser beam and the outlet of secondary scattering laser bundle calibrated of laser diameter measurement system.
4, single-particle aerosol online ionization source according to claim 1 and 2 is characterized in that: described ionization laser is connected with the secondary photomultiplier of calibrating of laser diameter measurement system, by its pulse-triggered that provides.
5, single-particle aerosol online ionization source according to claim 1 and 2, it is characterized in that: every bar of described low pressure radiofrequency quadrupole is made up of more piece bar section, be provided with clearance for insulation between each pole section, the clearance for insulation between the adjacent two pole sections is less than 0.3mm.
6, single-particle aerosol online ionization source according to claim 1 and 2 is characterized in that: described low pressure radiofrequency quadrupole is provided with the axial DC electric field; The DC potential of the low pressure radiofrequency quadrupole position that described laser beam vertical incidence point is corresponding is set to 0V, increases respectively and reduces toward the opposite two ends DC potential of low pressure radiofrequency quadrupole direction, forms the axial DC electric field; Each pole section of described low pressure radiofrequency quadrupole applies identical radio-frequency voltage, and described radio-frequency voltage is in the same place by resistance and capacitive coupling with direct voltage.
7, single-particle aerosol online ionization source according to claim 1 and 2 is characterized in that: described time of flight mass analyzer is vertical introduction-type time of flight mass analyzer or cascade mass spectrometry device.
CN 200520120268 2005-12-16 2005-12-16 Single particle Gerosol online ionizing source Expired - Lifetime CN2874764Y (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100454477C (en) * 2005-12-16 2009-01-21 广州禾信自动化系统有限公司 Single-particle aerosol online ionization source and realization method thereof
CN105403616A (en) * 2015-12-08 2016-03-16 南京信息工程大学 Detection method for gaseous sulfuric acid and sulfate and ion source used for detecting
CN109030297A (en) * 2018-08-22 2018-12-18 佛山融芯智感科技有限公司 A kind of high integration air particles detection components
WO2021142651A1 (en) * 2020-01-15 2021-07-22 Shanghai Polaris Biology Co., Ltd. Particle mass spectrometry

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100454477C (en) * 2005-12-16 2009-01-21 广州禾信自动化系统有限公司 Single-particle aerosol online ionization source and realization method thereof
CN105403616A (en) * 2015-12-08 2016-03-16 南京信息工程大学 Detection method for gaseous sulfuric acid and sulfate and ion source used for detecting
CN109030297A (en) * 2018-08-22 2018-12-18 佛山融芯智感科技有限公司 A kind of high integration air particles detection components
WO2021142651A1 (en) * 2020-01-15 2021-07-22 Shanghai Polaris Biology Co., Ltd. Particle mass spectrometry
CN115280132A (en) * 2020-01-15 2022-11-01 上海宸安生物科技有限公司 Particle mass spectrometry

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Effective date of abandoning: 20090121

C25 Abandonment of patent right or utility model to avoid double patenting