EP0819315A1 - Procede et dispositif d'analyse de la composition chimique de particules - Google Patents
Procede et dispositif d'analyse de la composition chimique de particulesInfo
- Publication number
- EP0819315A1 EP0819315A1 EP96907788A EP96907788A EP0819315A1 EP 0819315 A1 EP0819315 A1 EP 0819315A1 EP 96907788 A EP96907788 A EP 96907788A EP 96907788 A EP96907788 A EP 96907788A EP 0819315 A1 EP0819315 A1 EP 0819315A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- particles
- detection
- ionization
- particle
- fragmentation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000002245 particle Substances 0.000 title claims abstract description 109
- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000004458 analytical method Methods 0.000 title claims abstract description 11
- 239000000126 substance Substances 0.000 title claims abstract description 10
- 239000000203 mixture Substances 0.000 title claims abstract description 6
- 238000001514 detection method Methods 0.000 claims abstract description 59
- 238000013467 fragmentation Methods 0.000 claims abstract description 30
- 238000006062 fragmentation reaction Methods 0.000 claims abstract description 30
- 239000012634 fragment Substances 0.000 claims abstract description 11
- 238000004949 mass spectrometry Methods 0.000 claims abstract description 3
- 238000000926 separation method Methods 0.000 claims abstract description 3
- 150000002500 ions Chemical class 0.000 claims description 26
- 230000009467 reduction Effects 0.000 claims description 4
- 230000000977 initiatory effect Effects 0.000 claims description 2
- 230000023077 detection of light stimulus Effects 0.000 claims 2
- 230000005672 electromagnetic field Effects 0.000 claims 2
- 239000007789 gas Substances 0.000 description 10
- 230000035939 shock Effects 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000031700 light absorption Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000000443 aerosol Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- VVNCNSJFMMFHPL-VKHMYHEASA-N D-penicillamine Chemical compound CC(C)(S)[C@@H](N)C(O)=O VVNCNSJFMMFHPL-VKHMYHEASA-N 0.000 description 1
- 235000013382 Morus laevigata Nutrition 0.000 description 1
- 244000278455 Morus laevigata Species 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000009089 cytolysis Effects 0.000 description 1
- 229940075911 depen Drugs 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001269 time-of-flight mass spectrometry Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/004—Combinations of spectrometers, tandem spectrometers, e.g. MS/MS, MSn
- H01J49/0045—Combinations of spectrometers, tandem spectrometers, e.g. MS/MS, MSn characterised by the fragmentation or other specific reaction
- H01J49/0059—Combinations of spectrometers, tandem spectrometers, e.g. MS/MS, MSn characterised by the fragmentation or other specific reaction by a photon beam, photo-dissociation
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N15/00—Investigating characteristics of particles; Investigating permeability, pore-volume or surface-area of porous materials
- G01N15/10—Investigating individual particles
- G01N15/14—Optical investigation techniques, e.g. flow cytometry
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/02—Details
- H01J49/10—Ion sources; Ion guns
- H01J49/16—Ion sources; Ion guns using surface ionisation, e.g. field-, thermionic- or photo-emission
- H01J49/161—Ion sources; Ion guns using surface ionisation, e.g. field-, thermionic- or photo-emission using photoionisation, e.g. by laser
- H01J49/162—Direct photo-ionisation, e.g. single photon or multi-photon ionisation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/26—Mass spectrometers or separator tubes
- H01J49/34—Dynamic spectrometers
- H01J49/40—Time-of-flight spectrometers
Definitions
- the present invention relates to a method for the analysis of the chemical composition of particles, which com ⁇ prises forming a particles-containing flow, detecting the presence of the individual particles, the subsequent fragmen- tation and ionization of particles and the identification of each fragment by means of mass spectroscopy, and relates to a device for the analysis of the chemical composition of par ⁇ ticles which comprises: bundling means for forming a parti ⁇ cles-containing flow, detecting means for detecting the pres- ence of the individual particles; fragmentation means and ionization means for the fragmentation and ionization of par ⁇ ticles; and a mass spectrometer for the identitification of each fragment, while the detecting means, the fragmentation means and the ionization means each comprise at least a laser generator.
- Such a method and device are used for the analysis of ambient air, for instance in a clean-room where products such as chips, are manufactured, which during the production process are particularly sensitive to dust particles floating around in the production room. Further, by means of such a device a quality control for products such as aerosol cans may be carried out. Such a method and device may also be applied for the detection of agents used in chemical or bio ⁇ logical warfare or of atmospheric pollution. Such a method and device is known from the article by Prather, Nordmeyer and Salt (1994) , in Anal. Chem. 66: 1403-1407, entitled "Real-time characterization of individual aerosol particles using time-of-flight mass spectrometry".
- the time interval between two successive detection signals is used to study the fragmenta ⁇ tion and ionization of particles.
- a device comprises an electronic timing circuit which measures the delay between two detection signals and activates the frag ⁇ mentation means and the ionization means on the subsequent arrival of a detected particle in a fragmentation and ioniza ⁇ tion area, which arrival is established by means of the measured time interval between the successive detection sig ⁇ nals.
- Such a method, and consequently the appertaining device is very sensitive to alignment faults.
- the laser fragmentation and ionization means may miss a particle if a beam followed by the particle travels such that said beam does not run exactly parallel to the axis of the formed particle-containing beam.
- Fig. 1 shows schematically the principle of the method and the device according to the present invention
- Fig. 2 shows a schematically perspective view of the configuration of an embodiment of a device according to the present invention
- Fig. 3 shows a cross-sectional view of a component of the device according to the present invention as shown in Fig. 2;
- Figs. 4 and 5 show embodiments of a nozzle which forms part of the bundling means shown in Figs. 1 and 2.
- the device shown in Fig. 1 comprises: bundling means formed by a particle flow generator 1; detection means formed by a detection laser 2 and detectors; fragmentation means formed by a fragmentation laser 3; ionization means formed by an ionization laser 4; a mass spectrometer 5; and an arithme ⁇ tic unit 7.
- the particle flow generator 1 creates a flow of par ⁇ ticles 8, which flow is propulsed under very low pressure, which is necessary to ensure the functioning of the mass spectrometer 5.
- the particles are formed by clusters of atoms and molecules, while the gas is removed from the bundled flow of particles 8 in the particle flow generator 1.
- the spectro ⁇ meter used is a ti e-of-flight mass spectrometer necessitat- ing the pressure of the bundled flow particles 8 to be lower than 10" Pa in order to ensure correct functioning of the spectrometer 5.
- the particles 8, formed by clusters of molecules and atoms, are detected in the area of action 13 due to the part- icles 8 scattering light coming from the detection laser 2, whereby detectors 10 are placed such that they only emit a detection signal if light coming from the detection laser 2 is scattered by a particle 8. Therefore the detection laser 2 need not be of high power so that the detection laser 2 may for instance be a 16 mW multimode HeNe laser.
- the fragmentation laser 3 fragmentates the particles into separate atoms and molecules after which the separate molecules and atoms are ionized with the aid of the ioniza ⁇ tion laser 4.
- the ions 9 formed in this manner are subsequently analyzed with the aid of the mass spectrometer 5, whereby the data gathered by the mass spectrometer 5, and pertaining to the identity of the ions, are processed by the arithmetic unit 7.
- the arithmetic unit 7 also functions as control cir- cuit for the fragmentation laser 3 and the ionization laser 4. In reaction to a detection signal coming from the det ⁇ ectors 10, the arithmetic unit 7 activates the fragmentation laser 3 and the ionization laser 4, so that the arithmetic unit 7 contains data relating to the moment in time at which the ions 9 are created.
- the mass spectrometer 5 an electric field is installed so that a previously known amount of kinetic energy is supplied to the ions 9.
- the thus accelerated ions 9 then travel over a precisely known distance to an ion-sensitive plate 6 in the mass spectrometer 5, where arrival of the ions is registered by the plate 6.
- the ions and thus the atoms and molecules can be identified from the linear rela- tion between the mass of the ions 9 and the velocity with which these ions 9 travel the distance between the place of their formation and the plate 6.
- the amplitude of the signal generated by the mass spectrometer 5 is a measure of the number of ions arriving at any one moment at the ion-sensitive plate 6. In this way it is not only possible to establish the presence of a type of molecule or atom in a particle 8, but also the amounts of the different atoms or molecules the particle 8 contained for fragmentation and ionization.
- Fig. 2 shows the configuration of an embodiment of a device according to the present invention comprising: a par ⁇ ticle flow generator 1 forming the bundling means; a detec ⁇ tion laser 2 appertaining to the detection means; a combina ⁇ tion laser forming the fragmentation means and the ionization means; detector appertaining to the detection means forming the photomultiplier tubes 10; a light absorption element 11 and electrode grids 12.
- the bundled flow of particles 8 created by the par ⁇ ticle flow generator 1 reaches the area of action 13 in which both the detection laser 2 and the combination laser 34 are focused, the particles 8 being propulsed by the particle flow generator 1 at a velocity of about between 200 and 300 m/s. This velocity is realized because the particles are sucked into the vacuum and due to the particle flow generator 1, which will be described in more detail below.
- the detection laser 2 sends a laser beam into the direction indicated by the arrow A.
- the laser beam coming from the detection laser 2 is influenced by the lens 21, the dichroitic mirror 23 and lens 24 such that the resulting focus corresponds with the size of the area of action 13.
- the size of the area of action 13 and thus the focus is 0,1 mm.
- the mirror 23 is of such a kind that it only reflects light having the same frequency as that generated by the detection laser 2.
- a particle 8 in the area of action 13 scatters light coming from the detection laser 2 into all directions, which scattered light is detected with the aid of photomultiplier tubes 10 in the directions indicated by arrows B.
- the photomultiplier 10 tubes are arranged at an angle of 90° and 45° in relation to the direction of the light coming from the detection laser 2 and falling onto the area of action 13. It is well known in the field of technology that an optimal amount of information relating to scattering can be obtained when detection takes place in the above-mentioned directions.
- the light absorption element 11 is arranged in the extension of the direction indicated by arrow A, so that light coming from the detection laser 2 in the direction indicated by arrow C, which is not scattered by a particle 8, is absorbed. This prevents that light wrongly reflected into the direction is deemed scattered light, causing a detection signal to be emitted by the photomultiplier tubes 10 as if a particle 8 were detected in the area of action 13.
- This embodiment of a device according to the present invention uses two photomultiplier tubes 10. Detection sig ⁇ nals coming from the photomultiplier tubes 10 are only then sent to the combination laser 34 as initiation signal for fragmentation and ionization of the particles 8 present in the area of action 13, if both photomultiplier tubes 10 sim- ultaneously emit such a detection signal. This avoids the combination laser 34 coming into action when there are no particles 8 present in the area of action 13, because this logical "AND" function compensates the adverse inherent prop ⁇ erty of photomultiplier tubes 10, which photomultiplier tubes 10 emit a detection pulse, even without incident light.
- photo ⁇ multiplier tubes 10 are chosen as detectors, although also a number of other detectors such as photodiodes, are known in the filed of technology. This was decided because photomulti- plier tubes have a very short reaction time (approx. 2 ns) , a very high amplification factor (approx. between 10 3 and 10 8 ) , and a very large active surface (up to maximally 97 cm 2 ) , and at the same time a superior signal-noise ratio.
- the photomultiplier tubes 10 are preferably pro ⁇ tected against high power laser pulses coming from the combi ⁇ nation laser 34 by means of filters (not shown) .
- a lens 26 is placed in front of the photomultiplier tube 10 detecting scattered light under an angle of 90°.
- a lens can also be placed in front of the photomultiplier tube 10 detec- ting scattered light under an angle of 45°, in order to increase the intensity of the scattered light detected by the photomultiplier tube 10, and thereby increasing the sensitiv ⁇ ity of the configuration.
- the combination laser 34 is activated, whereby this combination laser 34 is a pulsating Nd:YAG laser having an intensity of approx. 3->10 w W/m 2 , which suffices both to fragmentate part ⁇ icles 8 and to ionize fragments of particles 8 to ions 9. Because this Nd:YAG laser generates radiation of more than one frequency, this laser is able to provide fragmentation as well as ionization. In the shown embodiment of the device the flash lamps of the laser 34 pulsate at a fixed frequency of 10 Hz, and a Q-switch is controlled by the detection signals.
- the Q-switch When detection signals are simultaneously emitted by the photomultiplier tubes and the flash lamps of the laser are charged, the Q-switch is opened to let a short-time pulse of intensive rays through.
- the laser beam generated by the com ⁇ bination laser 34 is focused through the lens 22 and through the lens 24 to the area of action 13 in the direction indicated by the arrow D, while the mirror 23 forms practi ⁇ cally no impediment to the laser beam.
- the area of action 13 is formed by the joint focus ⁇ ing point of the laser beams coming from the detection laser 2 and the combination laser 34.
- the focusing point is formed such that it has a diameter of about 0.1 mm. With the aid of lenses the beam coming from the detection laser 2 can theor ⁇ etically be focused to a diameter of 16 ⁇ m, but the somewhat larger focusing point provides the laser beam coming from the detection laser 2 with an optimal chance of accurate aim. In addition, it is easier to align the focused laser beams coming from the detection laser 2 and the combination laser 34 than when the focusing point has a diameter of 16 ⁇ m.
- a particle 8 detected in the area of action 13 is, as a result of the high power of the combination laser 34, fragmentated and ionized, after which the thus formed ions 9 are sensitive to the electric fields provided with the aid of the electrode grids 12.
- the ions are accelerated in the direction of the plate 6 of the mass spectrometer 5.
- the travel direction of the particles 8 is perpendicular in rela ⁇ tion to the travel direction of the ions 9 formed from the particles 8, and as the moment in time at which the ions 9 were formed from the particles 8 is exactly known, reliable operation of the mass spectrometer 5 is ensured.
- the size of the particles 8 is important as well as the chemical compo ⁇ sition.
- the size of the particles 8 can be established based on the intensity of the light scattered by a particle 8, which intensity is measured by the photomultiplier tubes 10. There is a direct relation between this intensity of the scattered light and the size of the particle 8 scattering the light.
- this method of determining the size of a par- tide 8 is not in all cases completely reliable, because a particle 8 travelling partly through the focus of the laser beam coming from the detection laser 2 may scatter light hav ⁇ ing fractionally the intensity of the light that would be scattered by a particle 8 travelling completely through the focus of the laser beam coming from the detection laser 2. In this configuration in Fig.
- this problem is solved by plac ⁇ ing grid 25 before the detection laser 2, so that the laser beam coming from detection laser 2 creates an interference pattern (shown at the bottom of this Figure) in the area of action 13, whereby the distance between the maxima of the interference pattern is exactly known.
- the element used to create an interference pattern may be a grid 25 or, for instance a beam divider (not shown) .
- a separate ionization laser 4 may be provided in the configuration shown in Fig. 2 which could, for instance, be formed by a pulsating UV-laser. This pulsat ⁇ ing UV-laser increases ionization of the fragments of particle 8 consisting of molecules and atoms, which particle 8 was fragmentated with the aid of a laser beam formed by the combination laser 34 or with the aid of a laser beam formed by a separate fragmentation laser 3.
- Fig. 3 shows a particle flow generator 1, which par- tide flow generator 1 is attached air-tight to a housing 15.
- This housing 15 comprises a chamber 14 comprising an area of action 13, whereby the electrode grids 12 are arranged at either side of the area of action 13.
- the housing 15 is fur ⁇ ther provided with connecting tubes 16 to which in any case the mass spectrometer 5 is attached air-tight, while to another connecting tube 16 in the drawing at the rear the light absorption element 11 is airtight attached.
- the laser beams coming from the detection laser 2 and the combination laser 34 are directed (not shown) onto the area of action 13 through a transparent key element attached to a connecting tube 16. Further, each of the photomultiplier tubes 10 is attached air-tight to one of the connecting tubes 16.
- a chamber 14 is formed, of which the only link with the environment is the particle flow generator 1.
- the atmospheric pressure of an environment to be analyzed is usually 10 s Pa.
- Reliable application of a time-of- flight mass spectrometer requires that a particle flow is formed having a vacuum-approximating pressure of maximally 10"* Pa.
- the available present-day pressure-reducing means in this case the pumps 17, are able to effectuate per stage a pressure reduction with an approxi ⁇ mate factor of 1000, it follows, that three pressure-reducing stages are required in order to obtain a pressure in the chamber 14 of maximally 10"* Pa.
- the particle flow should have a very high streamflow-velocity. This shortens the time required for ana ⁇ lysis, which is particularly advantageous when measurements are carried out on samples of a low concentrations of par ⁇ ticles.
- the streamflow-velocity is directly depen ⁇ dent on the pumps 17 being used; to obtain a high streamflow- velocity large and costly pumps 17 are required, making an analysis device bulky and costly. Consequently, this consti- tutes a parameter to be considered when designing the device.
- the streamflow-velocity is determined by the size of the nozzle's 18 orifice, provided the ratio between the pressure before the nozzle 18 and the pressure after the nozzle 18 is greater than the critical threshold value: £" > - 0.5283
- the gas containing the particles reaches the velocity of sound at the exit of the nozzle 18, accelerating, after the nozzle 18, up to supersonic velocity in the travel direction of the gas. If the diameter of the orifice of the nozzle 18 is 0.3 mm, the streamflow-velocity will be approximately 0.9 1/min.
- the gas containing the particles If the gas containing the particles is sucked through a small nozzle orifice into the low-pressure chamber, the gas will rapidly expand with diverging flowlines. Because of their inertia, particles present in the gas do not follow the flowline and the particles continue their linear path. In this way the particles are separated from the gas and a par ⁇ ticle-containing beam is formed.
- the nozzle 18 discharges into a space between the nozzle 18 and a shear element 19, which space is connected with a first pump 17.
- the beam containing the particles 8 then passes a first shear element 19 which discharges into another space between this shear element 19 and a second shear element 19, which space is also connected with a separate pump 17. In this way, as described above, gas is drawn off from the beam containing the particles.
- the second shear element 19 discharges into the chamber 14 comprising the area of action 13, which chamber is also connected air-tight with yet another separate pump 17.
- shock waves may occur in the particle flow generator 1.
- These shock waves influence the flow of the gas and prevent optimal operation of the par- tide flow generator 1. Therefore the particle flow generator is designed such that the formation of shock waves is minima- lized.
- shock waves will not develop behind a shear ele ⁇ ment 19 if the distance between the nozzle 18 and this shear element 19 or the distance between a preceding shear element 19 and the shear element 19 is smaller than the distance at which the shock wave has a maximum diameter.
- a nozzle 18 having an orifice of 0.3 mm it has been calculated that with a shear element 19 at a distance of 4 mm there will be no adverse effect of a shock wave.
- the shear element 19 which is arranged first in the travel direction of the particles behind the nozzle 18, has an orifice of 0.4 mm to ensure an efficient particle trans ⁇ port and a reasonable load on the pump appertaining to the space behind this shear element.
- the next shear element having an orifice of 3 mm, is placed at a distance of 5 mm in the travel direction of the par ⁇ ticles 8 behind the preceding shear element.
- the design of the particle flow generator 1 is such that the conveyance efficiency of the particle flow generator is constant for en entire sample, irrespective of the size of the particles. Further, the step in which a sample is taken, is independent of the particle size. Experimentation has proven that the nozzle 18 shown in Fig. 4 yields the best conveyance efficiency when par ⁇ ticles of at least 2 ⁇ m have to be analyzed and the nozzle 18 shown in Fig. 5 is the best choice when particles of up to 2 ⁇ m have to be analyzed.
- the nozzle 18 shown in Fig. 4 may be made by drawing a glass tube in a capillary element, forming a gradually reducing, converging flow channel. This allows an unlimited diameter choice for the orifice 20 of the nozzle 18.
- the nozzle 18 shown in Fig. 5 may be made of metal by using the known methods of manufacture.
- the orifice 20 is formed with the aid of a spark discharge appar ⁇ atus, a method which is usually applied to make holes having a diameter of at least 0.1 mm.
- the use of specially designed spark electrodes make it possible, however, to make orifices having diameters of up to 20 ⁇ m.
- a nozzle 18 shown in Fig. 4 having an orifice of 0.3 mm or a nozzle 18 shown in Fig. 5 having an orifice of 0.2 mm may be used, taking into consideration the pump capacity of the pumps 17.
- the combination laser 34 used is a pulsating Nd:YAG-laser.
- a laser which may be put into operation at any moment, such as a nitrogen laser or an excination laser. In this way the analysis efficiency is raised by a factor of 2000.
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- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Engineering & Computer Science (AREA)
- Plasma & Fusion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
La présente invention concerne un procédé et un dispositif d'analyse de la composition chimique de particules. Ce procédé consiste à former un flux contenant des particules, à détecter la présence de particules séparées, à fragmenter et ioniser les particules et à identifier chaque fragment par une technique de spectroscopie de masse. Le dispositif de l'invention est constitué d'un moyen permettant la constitution d'un flux contenant des particules, d'un détecteur détectant les particules séparées, d'un fragmenteur et d'un ioniseur permettant de fragmenter et d'ioniser les particules et d'un spectromètre de masse permettant l'identification de chaque fragment, le détecteur, le fragmenteur et l'ioniseur comprenant chacun au moins un générateur laser. Le procédé se caractérise par la détection et la fragmentation des particules sans séparation spatiale, mais par l'ionisation des fragments, et le dispositif se caractérise par le fait que les faisceaux laser du détecteur, du fragmenteur et de l'ioniseur sont concentrés sur le même foyer.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NL1000011A NL1000011C2 (nl) | 1995-04-03 | 1995-04-03 | Werkwijze en inrichting voor het analyseren van de chemische samenstelling van deeltjes. |
NL1000011 | 1995-04-03 | ||
PCT/NL1996/000141 WO1996031900A1 (fr) | 1995-04-03 | 1996-04-02 | Procede et dispositif d'analyse de la composition chimique de particules |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0819315A1 true EP0819315A1 (fr) | 1998-01-21 |
Family
ID=19760794
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP96907788A Withdrawn EP0819315A1 (fr) | 1995-04-03 | 1996-04-02 | Procede et dispositif d'analyse de la composition chimique de particules |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0819315A1 (fr) |
AU (1) | AU5125896A (fr) |
NL (1) | NL1000011C2 (fr) |
WO (1) | WO1996031900A1 (fr) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19946110C1 (de) * | 1999-09-17 | 2001-02-01 | Apsys Advanced Particle System | Optisches Verfahren zur Charakterisierung von Partikeln in einem System, z.B. einem Reinraum, und Vorrichtung zur Durchführung des Verfahrens |
EP1193730A1 (fr) * | 2000-09-27 | 2002-04-03 | Eidgenössische Technische Hochschule Zürich | Dispositif d'analyse à ionisation à pression atmosphérique et méthode d'analyse d'échantillons associée |
NL1016887C2 (nl) * | 2000-12-15 | 2002-06-18 | Tno | Werkwijze en inrichting voor het detecteren en identificeren van bio-aÙrosoldeeltjes in de lucht. |
GB201111560D0 (en) | 2011-07-06 | 2011-08-24 | Micromass Ltd | Photo-dissociation of proteins and peptides in a mass spectrometer |
RU2765339C1 (ru) * | 2021-06-10 | 2022-01-28 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Волгоградский государственный технический университет" (ВолгГТУ) | Устройство для определения дисперсного состава и скорости оседания частиц пыли |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4383171A (en) * | 1980-11-17 | 1983-05-10 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Particle analyzing method and apparatus |
DE4036115C2 (de) * | 1990-11-13 | 1997-12-11 | Max Planck Gesellschaft | Verfahren und Einrichtung zur quantitativen nichtresonanten Photoionisation von Neutralteilchen und Verwendung einer solchen Einrichtung |
-
1995
- 1995-04-03 NL NL1000011A patent/NL1000011C2/xx not_active IP Right Cessation
-
1996
- 1996-04-02 EP EP96907788A patent/EP0819315A1/fr not_active Withdrawn
- 1996-04-02 AU AU51258/96A patent/AU5125896A/en not_active Abandoned
- 1996-04-02 WO PCT/NL1996/000141 patent/WO1996031900A1/fr not_active Application Discontinuation
Non-Patent Citations (1)
Title |
---|
See references of WO9631900A1 * |
Also Published As
Publication number | Publication date |
---|---|
AU5125896A (en) | 1996-10-23 |
WO1996031900A1 (fr) | 1996-10-10 |
NL1000011C2 (nl) | 1996-10-04 |
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