CN103268851B - Thermal ionization time-of-flight mass spectrometer and thermal ionization flying time mass spectrum analysis method - Google Patents
Thermal ionization time-of-flight mass spectrometer and thermal ionization flying time mass spectrum analysis method Download PDFInfo
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Abstract
Thermal ionization time-of-flight mass spectrometer of the present invention and thermal ionization flying time mass spectrum analysis method, belong to analytical technique of mass spectrum field, this thermal ionization time-of-flight mass spectrometer forms primarily of ion source, ion transfer system and vertical reflection formula time of flight mass analyzer; Use this mass spectrometer, analytic sample is put on the filament band that is fixed in an ion source on specimen holder, sample ionization is made by increasing filament belt current, the transmission of the ion transfer set of lenses of ion beam in ion transfer system and modulation, arrive in vertical reflection formula time of flight mass analyzer, the ion of different quality arrives detector through the different flight time, qualitative, the quantitative or isotope analysis of Realization analysis sample.The present invention can fast, Measurement accuracy isotopic abundance monitor impurity element, be a kind of analytical technique of mass spectrum of innovation.
Description
Technical field
The invention belongs to mass spectral analysis field, the mass spectrometric analysis method being specifically related to a kind of mass spectrometer and utilizing this instrument to carry out.
Background technology
Mass spectrometry is by carrying out a kind of analytical method of composition analysis to the mensuration of the mass-to-charge ratio of test substance ion in sample.First analyzed sample wants ionization, then utilize different ions in the difference of the motor behavior in electric field or magnetic field, ion is separately obtained mass spectrum by mass-to-charge ratio (m/z), by mass spectrum and the relevant information of test substance in sample, this material qualitative, quantitative result in the sample to which can be obtained.Current mass spectrometry has been widely used in the every field such as chemistry, chemical industry, material, environment, geology, the energy, medicine, criminal investigation, life science, sports medical science.
Mass spectrometer kind is very many, and operation principle and range of application are also very different.From application point, mass spectrometer can be divided into organic mass spectrometer, inorganic mass spectrometer, special mass spectrometer (as isotope mass spectrometer) etc.But be no matter the mass spectrometer of which kind of type, its basic comprising is identical, all comprises ion source, mass analyzer, detector and vacuum system.Ion source is ion by ionization device sample ionization, and the ion of different mass-to-charge ratio separately, device can obtain the mass spectrogram of sample to mass analyzer after detecting after testing.Because organic sample, inorganic samples and isotope sample etc. have different shape, character and different analysis requirements, so ion source used, mass analyzer and detector are different.
Time-of-flight mass spectrometer (TOF-MS) utilizes kinetic energy identical and matter-He Bi is different ion moves in steady electric field, a kind of mass spectrometric analysis method that material composition or structure measure in the different principle of constant distance required time is to sample.TOF-MS has that sensitivity is good, resolution is high, analysis speed soon, ionization each time can obtain complete collection of illustrative plates, the quality testing upper limit only by advantages such as ion detector restrictions, becomes current the most promising mass spectrometer.At present, TOF-MS technology is applied to the numerous areas such as life science, analytical chemistry, Surface Science, atomic physics and process monitoring, one of analytical technique of mass spectrum most widely used since becoming the nineties in 20th century.
Owing to there is the problem of primary power dispersion, improve TOF-MS resolution is the target that researcher and apparatus manufacturer are made great efforts always.The progress of technical device is also main carries out around this target.Many ionization techniques for TOF-MS are developed.
Initial TOF-MS adopts the method for electronics bombardment to carry out ionization.The electron ionization sample molecule produced by electron gun, makes it dissociate into ion, enters movement area through accelerating to form ion beam.This method can be used for the analysis of gas, solid, liquid body sample.Its shortcoming is: 1) ionization times is longer, close with the flight time order of magnitude of general ion, easily causes large error; 2) ionization of electronics and input mode thereof determine the analysis that this ionization source is difficult to carry out macromolecular substances.Other technology of ion source coordinated with TOF-MS comprise: electric spray ion source (ESI), atmosphere pressure chemical ion source (APCI), pulse laser ion source and inductively coupled plasma (ICP) etc.Wherein pulsed laser technique is most widely used, comprise substance assistant laser desorpted (MALDI) conventional in laser desorption (LD), resonance laser ionization (RI), resonance reinforcement list/multi-photon ionization (RES/MPI) and biochemical analysis) etc., be applicable to the analysis of variety classes sample.Wherein, RES/MPI is good at complicated organic selectivity ionization.The advantage of MALDI is: 1) can obtain high sensitivity, several atoms in ionization district even can be detected; 2) can realize without fragment ion for heat-labile large biological molecule; 3) can analyze solid, liquid surface, control Ionized position or the degree of depth by the focal position adjusting laser beam, greatly shorten analysis time; 4) can combine from different Ionization mode.But its deficiency is pulse laser poor stability, and matrix effect is large.ICP also can be used as the Ionization mode of a kind of TOF-MS, and for multielement analysis, but operating cost is higher.Above-mentioned ion source is combined the mass-spectrometric technique formed with TOF-MS respectively have pluses and minuses, and play positive effect in respective field.
A kind of hot surface ionization type ion source (thermal ionization source, TI source) is also had to be succeeded in developing in 1918 by Dempster the earliest.This ionogenic basic functional principle be sample application on the atom on high-melting-point, high-work-function metal surface, then heating of metal, under the burning temperature of metal surface, in sample, part neutral particle is evaporated, and in evaporation process, loses (or obtaining) electronics and ionize.TI source has three advantages compared with other ion source: one, and ionizing efficiency is good, is usually greater than one of percentage or better; Its two, mainly single charge ion of generation, energy spread is little, and spectral line is simple, because test substance ionizes under the high temperature conditions, interfering ion is relatively less, and background ions is easily got rid of; 3rd, memory effect is low, to most metals element, when using the sample of Gamma Magnitude to analyze, memory impact can be considered, when sample size increasing or when measuring nonmetalloid, even if there is memory problems, also easily got rid of by cleaning ion source component.Therefore, thermal ionization source adapts to the isotope analysis requirement of high precision very much, but thermal ionization source, only for monofocal magnetic substance spectrum, forms thermal ionization mass spectrometry (tims) (TIMS) technology, for isotope analysis at present.But TIMS technical operation cost is high, sample analysis speed is slow, and requires higher to the separation purity of sample, needs Chemical Decomposition before sample determination.
In isotope measure, to can fast, Measurement accuracy isotopic abundance, the mass-spectrometric technique of simultaneously monitoring impurity element information has certain demand.
Summary of the invention
The present invention aim to provide one can fast, Measurement accuracy isotopic abundance, monitor the mass-spectrometric technique of impurity element information, therefore the present invention first object is to provide a kind of thermal ionization time-of-flight mass spectrometer simultaneously.
Thermal ionization time-of-flight mass spectrometer provided by the invention, main body comprises ion source, ion transfer system and vertical reflection formula time of flight mass analyzer, ion source is connected by a pneumatic operated valve with ion transfer system, the L-type cavity that ion transfer system and vertical reflection formula time of flight mass analyzer are integrated, respectively establishes an interface to be connected with external same molecular pump; Wherein: in described ion source, be equiped with specimen holder, analytic sample is ionized formation ion on this specimen holder; Be provided with ion transfer set of lenses in described ion transfer system, the entrance port of ion transfer set of lenses is connected with ion source by pneumatic operated valve, and exit portal is communicated with the lens of vertical reflection formula time of flight mass analyzer; Described vertical reflection formula time of flight mass analyzer comprise be connected with lens repulsion accelerating region, with the vertically disposed field-free flight district of repulsion accelerating region, the echo area be connected with bottom, field-free flight district and the detector that is connected with top, field-free flight district.
In thermal ionization time-of-flight mass spectrometer, described specimen holder comprises with the outer cover of slit, the lamp filament being placed in outer cover and the filament frame be fixed on lamp filament; Filament frame comprises fixed mount, two binding posts be arranged on fixed mount, the flat filament band be welded on two binding post legs, binding post is electrically connected with external power supply (the special power supply in thermal ionization source), and insulated by insulation cushion between fixed mount, filament band is towards the slit on outer cover.
Establish temperature observation hole facing on filament band position in the middle of described fixed mount, the location notch be connected with lamp filament is established at two ends.
Described filament frame is one or more, and multiple filament frame is arranged above and below and is fixed on lamp filament, and the binding post of each filament frame is electrically connected with the parallel connection of external thermal ionization source power supply.
In thermal ionization time-of-flight mass spectrometer, described ion transfer set of lenses comprises parallel to each other and axially keeps constant spacing to be contained in primary diaphragm set of lenses in tube lens seat, the second permeable membrane sheet mirror group, tertiary membrane sheet set of lenses and DC-shift four pole; Each diaphragm set of lenses is made up of three electrode wafer parallel interval, establishes insulating ceramics pad insulate and fix between electrode wafer, and each electrode wafer is electrically connected with external power supply parallel connection; The ion channel that rectangular opening forms ion transfer system is offered in each electrode wafer center.
Four parts, the upper and lower, left and right that described DC-shift four pole is divided into spacing by one section of stainless steel cylinder or block form four plate electrodes, and four plate electrodes are electrically connected with external power supply parallel connection.
Described tube lens seat is provided with shoulder hole end face, and the ceramic blanket of diaphragm set of lenses side is close to this shoulder hole end face and fixing, and diaphragm set of lenses is coaxial and insulate with tube lens seat; Primary diaphragm set of lenses is contained in the first lens mount, and secondary diaphragm set of lenses is contained in the second lens mount, and tertiary membrane sheet set of lenses is contained in the 3rd lens mount, and the first lens mount, the second lens mount and the 3rd lens mount are sequentially connected and fixed; 3rd lens mount end connects direct current quadrupole lens seat, and DC-shift four pole is fixed on direct current quadrupole lens seat inwall and utilizes insulating material to insulate.
In thermal ionization time-of-flight mass spectrometer, installing repeller plate in repulsion accelerating region top in described vertical reflection formula time of flight mass analyzer, the first grid electrode, the second grid electrode and the 3rd grid electrode are installed in bottom successively interval, in echo area, the 4th grid electrode, the 5th grid electrode and reflecting plate are established in interval, and the 6th aperture plate is established in top, field-free flight district and detector junction.
Another object of the present invention is to provide a kind of low cost, quick, practical thermal ionization flying time mass spectrum analysis method.
Thermal ionization flying time mass spectrum analysis method provided by the present invention, use aforementioned hot ionization time-of-flight mass spectrometer, analytic sample is put on the filament band of specimen holder, sample ionization is made by adjusting external thermal ionization source power supply increase filament belt current, by the voltage of each electrode wafer in external power supply adjustment ion transfer set of lenses and DC-shift four extremely in the voltage of four plate electrodes ion beam is transmitted and modulation, by the voltage parameter in external power supply adjustment vertical reflection formula time of flight mass analyzer, receive each stage ion by detector and transmit the mass spectral analysis carrying out sample.
This thermal ionization flying time mass spectrum analysis method, can be used for the qualitative, quantitatively or isotope analysis and impurity supervision and analysis of sample.
Adopt above scheme, thermal ionization time-of-flight mass spectrometer of the present invention adopts thermal ionization mode to realize material ionization, adopts the mass-to-charge ratio of flight time mass spectrum to sample ion to measure, thus realize the device that Mass Spectrometer Method is feature.The present invention is first by thermal ionization source and ionization time of flight coupling (TI-TOF-MS multiple techniques), the thermal ionization source that development is suitable for, installation method and ion transfer system, it is combined with time-of-flight mass spectrometer, forms a kind of new analytical test mass spectrometric apparatus---thermal ionization time-of-flight mass spectrometer (TI-TOF-MS).This instrument can be used for measuring isotopic ratio, the thermal ionization process of research element, and monitoring pre-treatment isolation technics, provides technical support for developing new thermal ionization mass spectrometry (tims) method of measurement.The present invention can fast, Measurement accuracy isotopic abundance, monitor impurity element information, be a kind of mass-spectrometric technique of innovation simultaneously.
Accompanying drawing explanation
Fig. 1 is TI-TOF-MS structural representation
Fig. 2 is specimen holder structure chart
Fig. 3 is filament frame structure chart
Fig. 4 is ion transfer and modulating device pie graph
Fig. 5 is inner ion transmission lens structure chart
Fig. 6 is DCQ profile
Fig. 7 is that TI-TOF-MS monitors impurity element information
Embodiment
The present invention aim to provide one can fast, Measurement accuracy isotopic abundance, monitor the mass-spectrometric technique of impurity element information simultaneously.
First, the present invention relates to a kind of thermal ionization time-of-flight mass spectrometer, it is that use thermal ionization mode realizes material ionization, the mass-to-charge ratio of flight time mass spectrum mode to sample ion measures, thus realize the device that Mass Spectrometer Method is feature.
This thermal ionization time-of-flight mass spectrometer, overall structure is illustrated see Fig. 1, forms primarily of ion source 1, ion transfer system 2 and vertical reflection formula time of flight mass analyzer 3.Wherein: in ion source 1, be equiped with specimen holder 4, ion source 1 is connected with ion transfer system 2 by a pneumatic operated valve 5.Pneumatic operated valve 5 cuts out when varying product, to maintain the vacuum degree of the ion transfer district in ion transfer system 2 and the analysis area in analyzer 3.The L-type that ion transfer system 2 and vertical reflection formula time of flight mass analyzer 3 are integrated designs, and has maintained vacuum degree since respectively establishing an interface 7 to be connected with same molecular pump.Ion transfer system 2 is a hollow and vacuum cavity, is equiped with ion transfer set of lenses 6 in its cavity, and transmission lens group 6 two ends are provided with entrance port 21 and exit portal 22; The ion that ion source 1 produces through this entrance port 21, after the extraction of ion transfer set of lenses 6, modulation deflection, enters time of flight mass analyzer 3 through exit portal 22.Vertical reflection formula time of flight mass analyzer 3 adopts existing matured product, and its entirety is hollow cavity form, and the order according to ion beam process comprises integer district, repulsion accelerating region, field-free flight district and echo area successively; Wherein, one end (exit end) that integer district and ion transfer system 2 set out loophole 22 is close to, wherein install lens 8, by regulating the voltage of lens 8, can reduce and transmit ion beam Rate Dispersion in the Y direction in transmission lens group 6, reduce the later time simultaneously, the rigging error between ion transfer system 2 and mass analyzer 3 can be made up to a certain extent, control optimized incidence and focusing that ion beam enters repulsion accelerating region, the exit slit 34 of scioptics 8 enters repulsion accelerating region, then enters detector 300 through field-free flight district and echo area.
After sample is finished changing, connect mechanical pump through ion source 1 and take out in advance, vacuum degree reaches 10
-2during mbar, open pneumatic operated valve 5, the vacuum degree of appliance requires can be reached soon, thus carry out apparatus measures.The sample ions that ion source produces, behind the extraction of ion transfer set of lenses 6, the focusing of modulating integer and lens 8, tune direction, enter the repulsion accelerating region of vertical reflection formula time of flight mass analyzer 3, through positive pulse repulsion and the accelerating voltage acceleration of repeller plate 31, obtain an initial kinetic energy in vertical incidence direction, enter field-free flight district.These ions obtaining identical energy possess different speed due to the difference of mass-to-charge ratio, through certain Flight Length in field-free flight district, after the reflection of echo area, detector 300 is arrived with the different flight time, difference according to the flight time of these ions can judge different ions quality, realizes the detection of ion.
Wherein: the structure of described specimen holder 4 as shown in Figure 2, comprise specimen holder outer cover 41 and slit above 411, fixing hole 412 and 413, lamp filament 42 and bayonet socket above 421, gim peg 422 and 423, and three filament frames---upper filament frame 43, middle filament frame 44, lower filament frame 45.Three filament frame apportions are screwed on lamp filament 42, to be then buckled in by stainless steel outer cover 41 on lamp filament 42 and to be fixedly connected with gim peg 422,423 by fixing hole 412,413; Whole specimen holder 4 is fixed on by bayonet socket 421 on a fixed mount in ion source 1 chamber.This specimen holder outer cover 41 has a rectangular slits 411, slit 411 just in time aims at the center of the entrance port 21 of ion transfer set of lenses 6, enters ion transfer system 2 to make the ion beam of the filament band ionization generation be installed on filament frame by this slit 411.
Fig. 3 is filament frame structure chart, comprises filament band 441, temperature observation hole 442, insulation cushion 443, fixed mount 444 and two binding posts 445.Filament material is generally high-purity rhenium, tantalum, tungsten, is welded on the leg of two binding posts 445 by the metal tape of above-mentioned material point, makes the filament band 441 in flat; Fixed mount 444 has two location notchs 446, by location notch 446 and screw, filament frame 44 is fixed on the lamp filament 42 of specimen holder, filament band 441 towards specimen holder outer cover 41 and above slit 411 direction.According to the difference wanting analytic sample character, sometimes single filament frame (as filament frame 44 in only retaining) structure is adopted, sometimes multi-filament frame (upper filament frame 43 is adopted, middle filament frame 44, lower filament frame 45) structure, when adopting multi-filament band structure, each filament frame, for being arranged above and below, is all fixed on the lamp filament 42 of specimen holder 4 by respective location notch 446; Two parallel wearing of binding post 445 are fixed on fixed mount 444, one end is connected with filament band (thermal ionization band) special power supply (external thermal ionization source power supply), the other end is welded with filament band 441, be filament band 441 galvanization by power supply, insulated by insulation cushion 443 between binding post 445 and fixed mount 444; In addition, be positioned at two binding post 445 interpositions at fixed mount 444 and install temperature observation hole 442, Minitype infrared temperature measurer can be established in addition after specimen holder 4, temperature measurer is by measuring the infrared ray through temperature observation hole 442, thus measure the actual temperature of filament band 441, so that Quality control ionization effect.
Before analytic sample, by the sample solution of separator well, adopt Autosampler point in the centre of filament band 441,1.5A electric current is passed in filament band 441, by sample solution evaporate to dryness, make sample light signal silk ribbon, the specimen holder 4 with this sample light signal silk ribbon is fixed in ion source 1.During analytic sample, by changing the size of current on filament band 441, control the effect of filament evaporation, ionized sample.The ion beam that the lower excited sample of energising produces, under the repulsion of the positive voltage that filament frame 44 loads, have towards the initial velocity of ion transfer set of lenses 6 (Z-direction shown in Fig. 4), by the slit 411 above specimen holder outer cover 41, enter ion transfer system 2.
Described ion transfer set of lenses 6, in the hollow being loaded on ion transfer system 2 and vacuum chamber, by regulating its diaphragm set of lenses 61,62,63 and DCQ (DC-shift four pole) 64 on current potential, between different diaphragm set of lenses, form different electric fields, realize ionic modulation, its electrode is formed as shown in Figure 4, and its bulk-breaking structure and installation diagram are as shown in Figure 5.Ion transfer set of lenses 6 comprises three lens cluster group and (is followed successively by primary diaphragm set of lenses 61, second permeable membrane sheet mirror group 62, tertiary membrane sheet set of lenses 63) and DCQ (DC-shift four pole) 64, its spatial relation is parallel to each other and axially keeps constant spacing.Diaphragm set of lenses is made up of (between each electrode wafer, the difference of spacing-visible requirement of experiment modulation effect adjusts) three ganoid electrode wafer intervals, electrode wafer is provided with 4 installing holes uniform relative to the center of circle, to be insulated location by the ceramic blanket with holes 65 of 4 thickness precisions between electrode wafer, ceramic blanket 65 is equal with electrode wafer aperture and put with one heart; Electrode wafer (diaphragm) offers rectangular opening 66 (the rectangular opening size on each diaphragm can be identical or different) in center, form the ion channel of ion transfer system; The ceramic blanket of diaphragm set of lenses side is close to the shoulder hole end face location of a tube lens seat, and utilize four insulated screw to fix through electrode wafer installing hole and ceramic pad holes, shoulder hole end face in tube lens seat is provided with axisymmetric four screwed holes for installing insulating screw, and final diaphragm set of lenses and tube lens seat keep coaxial and insulate.Concrete, primary diaphragm set of lenses 61 is contained in the shoulder hole end face in the first lens mount 611, and secondary diaphragm set of lenses 62 is contained in the shoulder hole end face in the second lens mount 621, and tertiary membrane sheet set of lenses 63 is contained in the shoulder hole end face in the 3rd lens mount 631.First lens mount 611, second lens mount 621 and the 3rd lens mount 631 are sequentially connected and fixed by screw rod; In an identical manner, the 3rd lens mount 631 end connects direct current quadrupole lens seat 641, and DC-shift four pole 64 (DCQ, directcurrent-quadrupole) is fixed on direct current quadrupole lens seat 641 inwall and utilizes insulating material to insulate.DC-shift four pole 64 is mature technology, and it is divided into discrete upper and lower, left and right 4 plate electrode by one section of stainless steel cylinder or block, and its cross section as shown in Figure 6; DCQ4 plate electrode, by 4 precision DC stabilizer independent regulation, realizes the control in ion flight direction, compensates Automatic manual transmission error.
Sample enters transmission system 2 after ionizing in ion source 1, and primary diaphragm set of lenses 61 pairs of ions have focussing force in the Y direction, makes the ion originally dispersed fly through less parallel in the rear Y-direction of set of lenses 61; Equally, ion flies through less parallel in the rear X-direction of the second set of lenses 62; 3rd set of lenses 63, for correcting the ion beam from secondary diaphragm set of lenses 62, enters DCQ64 with making its maximum; Ion beam is modulated into flat through DCQ, then enters vertical reflection formula time of flight mass analyzer 3 again after direction is adjusted in lens 8 focusing, through the repulsion of repulsion accelerating region, acceleration, obtains the initial kinetic energy in vertical incidence direction, enters field-free flight district; These ions obtaining identical energy possess different speed due to the difference of mass-to-charge ratio, through certain Flight Length in field-free flight district, after the reflection of echo area, arrive detector 300, realize the detection of different quality ion with the different flight time.
In the present invention, vertical reflection formula time of flight mass analyzer 3, adopt the mass analyzer structure in existing time-of-flight mass spectrometer (TOF-MS), it is formed as shown in Figure 1, its primary structure and operation principle are: lens 8 are close to the repulsion accelerating region of vertical reflection formula time of flight mass analyzer 3, the Z-direction end of repulsion accelerating region establishes Faraday cup 30, for monitoring the ion signal not pushed to field-free flight district by repulsion accelerating region; Repulsion accelerating region adopts two field to accelerate, top installing repeller plate (positive pulse) 31, the first grid electrode 32 (ground connection), the second grid electrode 33 (negative pulse) and the 3rd grid electrode 35 are installed in bottom successively interval, a Proportional Acceleration Field is formed between repeller plate 31 and the first grid electrode 32, the infiltration between electric field can be reduced, 3rd grid electrode 35 adds negative high voltage, namely can form second level accelerating field with the second grid electrode 33.After two fields acceleration of the second level accelerating field formed through first order accelerating field, the second grid electrode 33 and the 3rd grid electrode 35 that repeller plate 31 and the first grid electrode 32 are formed when the ion entering repulsion accelerating region, the incident direction entering this mass analyzer 3 at vertical ion obtains an initial kinetic energy, enters and ion transfer system 2 and the vertically disposed field-free flight district of repulsion accelerating region through the 3rd aperture plate 35;
Connection echo area, bottom, field-free flight district, in echo area, the 4th grid electrode 36 and the 5th grid electrode 37 are established in interval, and echo area is separated into two-stage by the 5th grid electrode 37, and form the uniform electric field of two-stage, its structure is similar to repulsion accelerating region; Top, field-free flight district connects a detector 300, and the 6th aperture plate 39 is established in junction; The ion of field-free flight district cavity is entered by the 3rd aperture plate 35, echo area is entered through the 4th aperture plate 36 (negative high voltage), after the reflection of the reflecting plate 38 (positive high voltage) of echo area lowermost end, pass field-free flight district by the 4th grid electrode 36 again, enter detector 300 from the 6th grid electrode 39.Regulate the voltage of each grid electrode can realize the resolution of different quality ion.
Wherein repulsion accelerating region adopts vertical introduction-type structure, by repeller plate 31, produce by ion source 1, the ion beam in Z (horizontal direction) direction incident after ion transfer system 2 is modulated, applies the pulse voltage that a vertical incidence direction is downward, makes it have the kinetic energy in a vertical incidence direction, through the acceleration of repulsion accelerating region 3 accelerating voltage, enter field-free flight district, through the reflection of Shuan Chang echo area after the flight of a segment length, finally detected by detector 300.
Detector 300 is the most frequently used microchannel plate (MCP) detector of current time-of-flight mass spectrometer, detection data are converted to real-time mass spectrogram by existing mass spectral analysis software and present on the display device by its external high-speed data acquisition card (ADC).
Thermal ionization time-of-flight mass spectrometer of the present invention is become by above design team.This mass spectrometer is used to carry out mass spectral analysis, analyze the sample solution after purifying, by its point on filament band 441 (when adopting three band structures, sample spot is on the filament band of lower filament frame 45, by increasing the electric current of lower filament band, sample evaporation is made to become gaseous state, add the filament belt current of big-and-middle filament frame 44, the sample vapor that the lower filament band of ionization is evaporated), sample ionization is made by increasing heater current, dispersion ion forms focused ion beam through the transmission of ion transfer set of lenses 6 with modulation, arrive mass analyzer 3 and carry out mass resolution, undertaken qualitative by detector 300 reception, quantitatively or isotope analysis.
The electrical quantity of thermal ionization time-of-flight mass spectrometer is a lot, as the heater current in ion source, repulsion voltage, various electrical quantitys in the voltage of the different voltages that three diaphragm set of lenses of ion transfer system apply, different voltages that DCQ tetra-electrodes apply, lens 8 and rectilinear time of flight mass analyzer, the adjustment of these electrical quantitys can be implemented by relevant control device, adjusts according to analyzing needs.
Below to adopt single rhenium band technology, TI-TOF-MS sounding lead isotopic abundance and monitoring impurity element is utilized to be described for example.
Detection example one
Test substance: the standard liquid of lead isotope standard substance Pb981 is testing sample, and isotopic abundance certificate reference value is: A (
204pb)=1.425%, A (
206pb)=24.145%, A (
207pb)=22.083%, A (
208pb)=52.348%.
Instrument: the above thermal ionization time-of-flight mass spectrometer (TI-TOF-MS);
Sample mode: lead isotope adopts single rhenium band (specimen holder only uses single filament frame 44, and intermediate lamp ribbon material is rhenium) method to measure, adopts phosphoric acid-silica gel method point sample.
Analytic process:
1) point sample: get appropriate amount of sample in quartz beaker, evaporate to dryness on electric hot plate, adds 5 ~ 6 microlitre phosphoric acid (mass concentration 1%) and dissolves in sample.A silica gel (about 2 ~ 3 microlitre) is put in the middle of rhenium band 441, power up and flow to 1 Amps, until closely dry, close current in time can seeing reflective silica gel granule.By 2 ~ 3 microliters of sample points on silica gel, power up and flow to 1 ampere, evaporate to dryness.Whole sample divides two to three points complete, 2 ~ 3 microlitres.After the complete evaporate to dryness of whole sample spot, slowly power up and flow to 2 ~ 3 amperes, until rhenium band heats up in dark red shape, maintain about 2 ~ 3 seconds, close current.
Illustrate: when detecting for actual sample, the sample (as galena) that some lead contents are large can lack point as one sees fit, namely adds 5 ~ 6 microlitre phosphoric acid and dissolves, and only gets part point to rhenium band.Some sample contains insoluble dregs, can get clear liquid point band after the abundant sample dissolution of phosphoric acid.
2) vary: be installed on by specimen holder 44 in ion source 1 chamber, start the mechanical pump that ion source chamber connects, in ion source, vacuum degree is less than 10
-2after mbar, closure molecule pump, opens pneumatic operated valve 5, vacuumizes through molecular pump, treats that in chamber, vacuum degree is less than 1 × 10
-6after mbar, can start to measure.
3) apparatus measures: open external thermal ionization source power supply, regulate the electric current of filament band on filament frame, (electric current of increase filament band can improve the evaporation efficiency of sample, but electric current is excessive to carry out combustion to sample, sample can consume very fast, and the easy disintegration of filament); The positive voltage size that filament band in adjustment on filament frame loads, and coordinate the electrical quantity regulating the voltage of each membrance electrode, the voltage of lens 8 in ion transfer set of lenses 6 and regulate rectilinear flight time mass spectrum mass analyzer 3, make to be sent to by detector 300 the mass spectra peak sensitivity that display device presents the highest, and resolution is better, obtain the Instrument working parameter combination of optimization with this, thus improve sensitivity and the resolution of instrument.
The TI-TOF-MS of embodiment one optimizes electrical quantity and is combined as: in ion source, filament belt current is 2.7A, the positive voltage 25.5V that filament band loads, and three diaphragm voltages of primary diaphragm set of lenses 61 are respectively 0V, 0V, 3V, three diaphragm voltages of secondary diaphragm set of lenses 62 are respectively 12.8V, 18V, 0V, three diaphragm voltages of tertiary membrane sheet set of lenses 63 are respectively 4.6V, 0V, four, the upper and lower, left and right voltage of 0V, direct current quadrupole rod DCQ is respectively 10.4V, 11.2V, 11.5V, 11.3V; The voltage of lens 8 is-14.0V and-14.5V, and the electrical quantity of rectilinear time of flight mass analyzer 3 is positive pulse is 431.6V, and negative pulse is-187.2V, B-Plate be 620.7V, Grid be-329.5V, ACCE is-2665V.
Measurement result: the abundance measurement value of 981Pb standard liquid is consistent with reference value, measures relative standard deviation
204pb is 5%,
206pb is 0.8%,
207pb is 1%,
208pb is 0.4%.This routine measurement result display, adopts single tape TI-TOF-MS can Quick Measuring lead isotope abundance, highly sensitive, accuracy good, can meet the analysis demand of plumbous spike aspect.
Detection example two
Detect sample: the standard liquid of lead isotope standard substance Pb981 is testing sample, and isotopic abundance certificate reference value is: A (
204pb)=1.425%, A (
206pb)=24.145%, A (
207pb)=22.083%, A (
208pb)=52.348%.
This routine object: measure Pb isotopic ratio, and monitor impurity element information.
The temperature of filament band affects the ionization effect of sample.When carrying out Lead Isotope Analysis, there is the temperature of the filament band of sample to monitor impurity element information by progressively elevated point.Concrete grammar is: the temperature of the sample belt in slowly raising on filament frame, makes lead atom ionize out from slow evaporation sample belt.In the process that sample belt heats up, element ionizes successively according to the complexity of ionization, and first the element that the first ionization energy is lower is ionized, as K, Na, Ca, Ba, Sr etc.When sample belt temperature continues to be increased to more than 2.2A, more stable plumbous signal can be obtained.By this method, other foreign ion in sample light signal silk ribbon can be monitored, be used for evaluating plumbous separating effect.
Specific experiment parameter is: in ion source, filament belt current is 2.65A, the positive voltage 25.4V that filament band loads, three diaphragm voltages of primary diaphragm set of lenses 61 are respectively 0V, 0V, 10.7V, three diaphragm voltages of secondary diaphragm set of lenses 62 are respectively 14.9V, 17.8V, 0.1V, three diaphragm voltages of tertiary membrane sheet set of lenses 63 are respectively 4.3V, 0V, 0V, direct current quadrupole rod DCQ's is upper, under, left, right four voltages are respectively 14.9V, 17.8V, 0.1V, the voltage of lens 8 is-14.2V and-14.4V, the electrical quantity of rectilinear time of flight mass analyzer is positive pulse is 432.0V, negative pulse is-187.6V, B-Plate is 621.0V, Grid is-328.9V, ACCE is-2670V.The impurity obtained and lead isotope flight time mass spectrum figure are as shown in Figure 7.
Measurement result: 981Pb standard liquid abundance measurement value is consistent with reference value, measures relative standard deviation
204pb is 5%,
206pb is 0.7%,
207pb is 0.8%,
208pb is 0.3%.The constituent contents such as Na, K, Rb in standard liquid are higher.
Visible by above detection example, utilize TI-TOF-MS technology of the present invention not only to can be used for isotope analysis, also can monitor impurity element information simultaneously.With existing arbitration isotope analysis technology " hot surface MALDI-MS " TIMS Technical comparing, Advantages found exists:
TI-TOF-MS has and entirely composes scan function, all ions that TI source produces can be detected simultaneously, the mass range of the ion simultaneously detected can comprise basic, normal, high mass number, and TIMS does not possess the ability that multielement detects simultaneously, because energy dispersion is low, at every turn only can the contiguous isotope of Detection job number; TI-TOF-MS analysis speed is faster than TIMS; The instrument cost of TI-TOF-MS is low, is about 20% of TIMS; In addition, TI-TOF-MS isotope analysis precision is 0.n%, though comparatively TIMS isotope analysis precision (0.n% ~ 0.0n%) is low, has the application of oneself, as this precision can meet the isotope analysis requirement in the fields such as plumbous spike, there is certain application potential.
Above-mentioned execution mode is only optimum embodiment of the present invention, but the present invention is not limited to above-described embodiment, in the ken that those of ordinary skill in the art possess, can also make a variety of changes under the prerequisite not departing from present inventive concept.
Claims (14)
1. a thermal ionization time-of-flight mass spectrometer, main body comprises ion source (1), ion transfer system (2) and vertical reflection formula time of flight mass analyzer (3), ion source is connected by a pneumatic operated valve (5) with ion transfer system, the L-type cavity that ion transfer system and vertical reflection formula time of flight mass analyzer are integrated, respectively establishes an interface to be connected with external same molecular pump; Wherein:
Be equiped with specimen holder (4) in described ion source, analytic sample is ionized formation ion on this specimen holder;
Ion transfer set of lenses (6) is provided with in described ion transfer system, the entrance port (21) of ion transfer set of lenses is connected with ion source by pneumatic operated valve, and exit portal (22) is communicated with the lens (8) of vertical reflection formula time of flight mass analyzer;
Described vertical reflection formula time of flight mass analyzer comprise be connected with lens repulsion accelerating region, with the vertically disposed field-free flight district of repulsion accelerating region, the echo area be connected with bottom, field-free flight district and the detector (300) that is connected with top, field-free flight district;
Described specimen holder comprises with the outer cover (41) of slit (411), the lamp filament (42) being placed in outer cover and the filament frame be fixed on lamp filament; Filament frame comprises fixed mount (444), two binding posts (445) be arranged on fixed mount, the flat filament band (441) be welded on two binding post legs, binding post is electrically connected with external power supply, and insulated by insulation cushion (443) between fixed mount, filament band is towards the slit on outer cover.
2. thermal ionization time-of-flight mass spectrometer according to claim 1, is characterized in that, establishes temperature observation hole (442) facing on filament band position in the middle of described fixed mount, the location notch (446) be connected with lamp filament is established at two ends.
3. thermal ionization time-of-flight mass spectrometer according to claim 2, it is characterized in that, described filament frame is one or more, and multiple filament frame is arranged above and below and is fixed on lamp filament, and the binding post of each filament frame is electrically connected with external power supply parallel connection.
4. thermal ionization time-of-flight mass spectrometer according to claim 1 or 2 or 3, is characterized in that,
Described ion transfer set of lenses comprises parallel to each other and axially keeps constant spacing to be contained in primary diaphragm set of lenses (61) in tube lens seat, the second permeable membrane sheet mirror group (62), tertiary membrane sheet set of lenses (63) and DC-shift four pole (64); Each diaphragm set of lenses is made up of three electrode wafer parallel interval, establishes insulating ceramics pad (65) insulate and fix between electrode wafer, and each electrode wafer is electrically connected with external power supply parallel connection; The ion channel that rectangular opening (66) forms ion transfer system is offered in each electrode wafer center.
5. thermal ionization time-of-flight mass spectrometer according to claim 4, it is characterized in that, four parts, the upper and lower, left and right that described DC-shift four pole is divided into spacing by one section of stainless steel cylinder or block form four plate electrodes, and four plate electrodes are electrically connected with external power supply parallel connection.
6. thermal ionization time-of-flight mass spectrometer according to claim 5, it is characterized in that, tube lens seat is provided with shoulder hole end face, and the ceramic blanket of diaphragm set of lenses side is close to this shoulder hole end face and fixing, and diaphragm set of lenses is coaxial and insulate with tube lens seat; Primary diaphragm set of lenses is contained in the first lens mount (611), secondary diaphragm set of lenses is contained in the second lens mount (621), tertiary membrane sheet set of lenses is contained in the 3rd lens mount (631), and the first lens mount, the second lens mount and the 3rd lens mount are sequentially connected and fixed; 3rd lens mount end connects direct current quadrupole lens seat (641), and DC-shift four pole is fixed on direct current quadrupole lens seat inwall and utilizes insulating material to insulate.
7. thermal ionization time-of-flight mass spectrometer according to claim 4, it is characterized in that, tube lens seat is provided with shoulder hole end face, and the ceramic blanket of diaphragm set of lenses side is close to this shoulder hole end face and fixing, and diaphragm set of lenses is coaxial and insulate with tube lens seat; Primary diaphragm set of lenses is contained in the first lens mount (611), secondary diaphragm set of lenses is contained in the second lens mount (621), tertiary membrane sheet set of lenses is contained in the 3rd lens mount (631), and the first lens mount, the second lens mount and the 3rd lens mount are sequentially connected and fixed; 3rd lens mount end connects direct current quadrupole lens seat (641), and DC-shift four pole is fixed on direct current quadrupole lens seat inwall and utilizes insulating material to insulate.
8., according to the arbitrary described thermal ionization time-of-flight mass spectrometer of claims 1 to 3, it is characterized in that,
Repulsion accelerating region top installing repeller plate (31) in described vertical reflection formula time of flight mass analyzer, the first grid electrode (32), the second grid electrode (33) and the 3rd grid electrode (35) are installed in bottom successively interval, in echo area, the 4th grid electrode (36), the 5th grid electrode (37) and reflecting plate (38) are established in interval, and the 6th aperture plate (39) is established in top, field-free flight district and detector junction.
9. thermal ionization time-of-flight mass spectrometer according to claim 4, is characterized in that,
Repulsion accelerating region top installing repeller plate (31) in described vertical reflection formula time of flight mass analyzer, the first grid electrode (32), the second grid electrode (33) and the 3rd grid electrode (35) are installed in bottom successively interval, in echo area, the 4th grid electrode (36), the 5th grid electrode (37) and reflecting plate (38) are established in interval, and the 6th aperture plate (39) is established in top, field-free flight district and detector junction.
10. thermal ionization time-of-flight mass spectrometer according to claim 5, is characterized in that,
Repulsion accelerating region top installing repeller plate (31) in described vertical reflection formula time of flight mass analyzer, the first grid electrode (32), the second grid electrode (33) and the 3rd grid electrode (35) are installed in bottom successively interval, in echo area, the 4th grid electrode (36), the 5th grid electrode (37) and reflecting plate (38) are established in interval, and the 6th aperture plate (39) is established in top, field-free flight district and detector junction.
11. thermal ionization time-of-flight mass spectrometers according to claim 6, is characterized in that,
Repulsion accelerating region top installing repeller plate (31) in described vertical reflection formula time of flight mass analyzer, the first grid electrode (32), the second grid electrode (33) and the 3rd grid electrode (35) are installed in bottom successively interval, in echo area, the 4th grid electrode (36), the 5th grid electrode (37) and reflecting plate (38) are established in interval, and the 6th aperture plate (39) is established in top, field-free flight district and detector junction.
12. thermal ionization time-of-flight mass spectrometers according to claim 7, is characterized in that,
Repulsion accelerating region top installing repeller plate (31) in described vertical reflection formula time of flight mass analyzer, the first grid electrode (32), the second grid electrode (33) and the 3rd grid electrode (35) are installed in bottom successively interval, in echo area, the 4th grid electrode (36), the 5th grid electrode (37) and reflecting plate (38) are established in interval, and the 6th aperture plate (39) is established in top, field-free flight district and detector junction.
13. 1 kinds of thermal ionization flying time mass spectrum analysis methods, use the arbitrary described mass spectrometer of claim 1 to 12, analytic sample is put on the filament band of specimen holder, sample ionization is made by adjusting external power supply increase filament belt current, by the voltage of each electrode wafer in external power supply adjustment ion transfer set of lenses and DC-shift four extremely in the voltage of four plate electrodes ion beam is transmitted and modulation, by the voltage parameter in external power supply adjustment vertical reflection formula time of flight mass analyzer, receive each stage ion by detector and transmit the mass spectral analysis carrying out sample.
14. according to thermal ionization flying time mass spectrum analysis method described in claim 13, qualitative, quantitatively or the monitoring of isotope analysis and impurity element for sample.
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