EP0200645B1 - Sample introduction method and device for a mass spectrometer - Google Patents

Sample introduction method and device for a mass spectrometer Download PDF

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Publication number
EP0200645B1
EP0200645B1 EP19860400902 EP86400902A EP0200645B1 EP 0200645 B1 EP0200645 B1 EP 0200645B1 EP 19860400902 EP19860400902 EP 19860400902 EP 86400902 A EP86400902 A EP 86400902A EP 0200645 B1 EP0200645 B1 EP 0200645B1
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EP
European Patent Office
Prior art keywords
tube
gaseous
source
heating
microsample
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Expired
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EP19860400902
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German (de)
French (fr)
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EP0200645A1 (en
Inventor
Robert Boyer
Jean-Pierre Journoux
Claude Duval
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Orano Cycle SA
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Compagnie Generale des Matieres Nucleaires SA
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/02—Details
    • H01J49/04—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components
    • H01J49/0422—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components for gaseous samples
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/02—Details
    • H01J49/04—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components
    • H01J49/0468—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components with means for heating or cooling the sample
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/02—Details
    • H01J49/04—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components
    • H01J49/0495—Vacuum locks; Valves

Definitions

  • the invention relates to the field of analysis of samples by mass spectrometry and it relates more particularly to the methods and devices making it possible to introduce, into the spectrometer, a sample microdebit whose ions are subjected to analysis.
  • mass spectrometers use either a source of thermionic ions or a source of ions with electron bombardment of a gas flow.
  • the first solution has the advantage of making it possible to use samples of very low mass, frequently between 0.1 and 10 micrograms.
  • the sample is deposited, usually in liquid form, on a refractory metal tape. By evaporation of the liquid, a solid deposit is obtained.
  • the ribbon is placed in the ion source of the device, then brought to high temperature (2600 ° C for example) by Joule effect.
  • the sample then emits neutral molecules and ions. The latter, accelerated and focused in the form of a particle beam, are subjected to analysis.
  • a mass spectrometer using a thermionic source cannot be used to conduct chemical composition analyzes and can very easily be connected online to a separation or treatment line.
  • the usual method consists in introducing the sample from a sealed container through piping and micro-leakage valves allowing a well determined and very low gas flow to pass without altering the very low pressure which must prevail in the analyzer of the spectrometer.
  • the molecules of gas or vapor which pass at very low flow rate are subjected to the action of a beam of electrons of determined energy which ionizes the gas to give rise to ions subjected to analysis.
  • the intensity of ion currents obtained is usually of the order of 10 -9 A, that is to say, much higher than the thermal-spectrometer, which simplifies the measurement.
  • measurements made using a spectrometer using an ion source by electron bombardment are generally differential measurements, which guarantee high precision, typically 50 to 100 times higher than with a thermionization source.
  • document US-A-3 888 107 describes a thermal analysis cell using a reactive gas, the necessity of which stems from the requirements of the analysis method used.
  • the present invention aims to provide a supply method and device for a mass spectrometer, using the ionization technique of a very low flow rate, typically using an electron beam, but responding better than those previously known to the requirements of the practice, in particular in that they authorize the use of samples of very low mass.
  • the invention provides a method of introducing micro-samples in accordance with the characterizing part of claim 1 and a device making it possible to implement this method, in accordance with the characterizing part of claim 2.
  • this device keeps the device all the advantages of using an electron bombardment source it allows to work with relatively intense ion beams, which simplifies their measurement it avoids breaking the vacuum in the source to introduce the sample it is not necessary to have watertight containers to handle the samples and connect them to the device.
  • the proposed device has many advantages: the size of the samples to be analyzed is reduced to a few micrograms; It is not necessary to have sealed containers for handling the samples and introducing them into the device. The consumption of standards or reference products can be reduced to the order of magnitude of that of the samples, the preparation of which is simple and fast.
  • the device shown in Figures 1 and 2 can be viewed as comprising a reactor 10, the essential element of which is a micro-oven with adjustable temperature, a passage 12 sufficiently constricted for the flow to take place therein in the form of molecular flow, and a micro- sublimers 14.
  • the microsublimeter is connected, by means of a valve 16, to the ion source 18 of the spectrometer, which can be of any of the types making it possible to ionize a low flow of gas which penetrates him. Typically, this source will perform ionization by electron bombardment.
  • the reactor 10 the schematic diagram of which is shown in FIG. 1, comprises an enclosure, generally cylindrical, in the axis of which is placed the actual micro-oven 20 consisting of a metal tube capable of withstanding high temperatures, for example nickel , nichrome or "monel". Means are provided for heating the oven by the Joule effect.
  • these means are shown in the form of an electrical source 22 connected to one end of the tube of which the other is grounded.
  • Another solution consists in winding an electric heating resistor around the tube 20.
  • This tube can carry a temperature sensor 24 connected to a circuit 26 for regulating the temperature by modulating the electric power supplied by the source 22.
  • a sample holder 28 is provided to allow the introduction of a very small quantity of samples, in the form of a deposit on a needle or a thread.
  • the head of this sample holder will be provided to seal the microfour.
  • One end of the tube 20 forming a micro oven is connected, by a valve 30, to a vacuum source 32 (mechanical primary pump for example) and to a source 34 of reagent. of a nature such that it gives rise, with the sample, to a gaseous or volatile compound.
  • the sources 32 and 34 are each provided with a shut-off valve 36 and 38.
  • the valves 30 and 38 at least must be made of a material resistant to very corrosive gases, since it will frequently be necessary to use highly reactive chemical species, such as fluorine.
  • the valve 30 must also be strictly sealed.
  • the constricted passage 12 may have a fixed passage section.
  • a diaphragm or capillary conduit can also be adjustable and formed by a conventional type micro-leakage valve or a piezoelectric valve, the opening of which is caused by the deformation of a piezoelectric crystal under the action of an electric field.
  • the passage must prohibit any entry of ambient air and it must offer a passage section having a sufficiently small diameter (typically a few microns) so that the gas flow between the reactor 10 and the microsublimation tube maintained at low pressure or in molecular regime. We know that in this regime the free path of the gaseous molecules is greater than the transverse dimensions of the passage.
  • the microsublimator 14 will generally consist of a tube 40 of small diameter, one end of which is tightly connected to the passage 12 and the other end is connected, by means of the valve 16, to the ion source 18.
  • This tube is provided with cryogenic temperature cooling means.
  • cryogenic temperature cooling means These means are shown in Figure 1 in the form of an enclosure 42 provided with an inlet and an outlet for fluid at very low temperature.
  • adjustable heating means are associated with it. In the case of FIG. 1, these means consist of a heating resistor 44 wound around the tube 40 and supplied by an electric generator 46 of adjustable power.
  • a temperature probe can be placed on the tube 40 to regulate, via a circuit similar to circuit 26, the temperature of the tube to an adjustable value. This temperature can also be slaved to a reference value by the intensity of the ion beams received at the collectors of the mass spectrometer.
  • a signal is taken from the ion current amplifier. This is constantly compared with a reference representing the chosen temperature, this reference being able to be programmed itself using a computer. A voltage is therefore obtained which is converted into calibrated pulses giving quantities of energy supplying the heating systems of the tube 40.
  • a valve 46a in parallel with the valve 16, makes it possible to connect the outlet of the tube 40 to a vacuum pump.
  • An additional connector provided with a valve 47 may be provided to connect the ion source to a reference gas supply and / or to another device similar to that which has just been described.
  • the elements 10, 12 and 14 of FIG. 1 are grouped together to constitute a one-piece assembly in several assembled parts, for example by welding.
  • the reactor is delimited by two nozzles 48 and 50 and a cylindrical shell in the axis of which the tube 20 is placed, a few millimeters in internal diameter, forming the micro-oven.
  • the downstream end of this tube is grounded via the end piece 50.
  • the upstream end isolated from ground by a pin 52, is connected to the electrical heating source by means of a tab 54 which crosses the shell in a sealed manner.
  • the sample holder 28 comprises a head screwable into the end piece 48, the seal being ensured by a seal 58.
  • a locking screw 60 provided in the head makes it possible to retain a thread or a needle 62 for supporting the dry sample.
  • a channel 64 formed in the end piece 48 makes it possible to connect the tube 20 to a valve 30 for admitting the reagent (gaseous fluorinating agent in general) or to a vacuum pump.
  • a seat 66 intended to receive the micro-leakage valve (not shown) constituting the passage 12 towards the micro-sublimator 14.
  • the latter has a constitution very comparable to that of the reactor 10, if this n 'is that the ferrule is provided with inlet and outlet fittings 68 and 70 for cryogenic fluid.
  • the micro-sublimation tube 40 is connected, via an insulating pin 72, to the end piece 50 and its downstream end is welded to an end piece 74 provided with a seat intended for the valve 46a (not shown) .
  • this nozzle comprises a tubular extension 76 intended to be connected to the valve 16.
  • the device used is of the type shown in FIG. 2.
  • the sample must first be transferred to the sample holder 28.
  • the wire 62 which for example is 0.8 mm in diameter and 7 cm long, is deposited, using a micro-pipette , a few drops of uranyl nitrate containing a total of for example 10 micrograms of uranium to be analyzed.
  • Uranyl nitrate transforms into a deposit of U0 3 , then U 3 0 8 when the temperature exceeds 350 ° C.
  • the wire covered with the deposit is placed in the sample holder 28 and the latter fixed on the end piece 48.
  • the tube 20 is put under vacuum by pumping up to a pressure of the order of 0.133 Pa (10- 3 torr). Then we heat the tube 20, by current flow. up to a temperature of around 400 ° C to remove residual water vapor.
  • the temperature of the microsublimation tube 40 is then brought to that of the liquid nitrogen by circulation of this nitrogen around the tube 40, from the connector 68 to the connector 70 by the circulation of a heat transfer gas (helium for example) brought to the temperature. liquid nitrogen.
  • a heat transfer gas helium for example
  • valve 12 is closed.
  • the pumping valve 46a is open, and the tube 40 is very gradually heated by passing an electric current. The oxygen sublimes and it is evacuated by the vacuum pump, through the valve 46a.
  • the valve 46 is closed and the valve 16 is opened.
  • the heating is carried out with a temperature programming such that, as soon as the hexafluoride flow rate reaches a predetermined value (that is to say when the value is reached of the intensity of the ion beam in the spectrometer), the temperature is controlled, so that the flow rate, measured by means not shown, remains constant until the mass of trapped uranium hexafluoride is used up
  • a predetermined value that is to say when the value is reached of the intensity of the ion beam in the spectrometer
  • Another solution consists in using two devices of the kind shown in FIG. 2. One of them receives a wire carrying a deposit whose isotopic ratio is to be measured, the other a deposit of U 3 0 8 of known isotopic composition .
  • the invention is not however limited to these particular embodiments. It is applicable whenever a reaction giving a gaseous compound of the sample is available.
  • the method is applicable to the case of carbon, which can be fluorinated to give CF 4 , which is particularly interesting for the isotopic analysis C 12 / C l4 used in dating.

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Other Investigation Or Analysis Of Materials By Electrical Means (AREA)

Description

L'invention concerne le domaine de l'analyse d'échantillons par spectrométrie de masse et elle a plus particulièrement pour objet les procédés et dispositifs permettant d'introduire, dans le spectromètre, un Microdèbit d'échantillon dont les ions sont soumis à analyse.The invention relates to the field of analysis of samples by mass spectrometry and it relates more particularly to the methods and devices making it possible to introduce, into the spectrometer, a sample microdebit whose ions are subjected to analysis.

Elle trouve une application particulièrement importante dans le domaine de l'analyse isotopique, qui doit souvent être effectuée sur des échantillons de petite taille, par exemple parce que ces échantillons sont fortement radioactifs ou particulièrement précieux.It finds a particularly important application in the field of isotopic analysis, which often has to be carried out on small samples, for example because these samples are highly radioactive or particularly valuable.

A l'heure actuelle, les spectromètres de masse utilisent soit une source d'ions thermo-ionique, soit une source d'ions à bombardement électronique d'un flux gazeux.At present, mass spectrometers use either a source of thermionic ions or a source of ions with electron bombardment of a gas flow.

La première solution a l'avantagé de permettre d'utiliser des échantillons de masse très faible, fréquemment comprise entre 0.1 et 10 microgrammes. L'échantillon est déposé, habituellement sous forme liquide, sur un ruban en métal réfractaire. Par évaporation du liquide, on obtient un dépôt solide. Le ruban est placé dans la source d'ions de l'appareil, puis porté à haute température (2600°C par exemple) par effet Joule. L'échantillon émet alors des molécules neutres et des ions. Ces derniers, accélérés et focalisés sous forme d'un faisceau de particules, sont soumis à l'analyse.The first solution has the advantage of making it possible to use samples of very low mass, frequently between 0.1 and 10 micrograms. The sample is deposited, usually in liquid form, on a refractory metal tape. By evaporation of the liquid, a solid deposit is obtained. The ribbon is placed in the ion source of the device, then brought to high temperature (2600 ° C for example) by Joule effect. The sample then emits neutral molecules and ions. The latter, accelerated and focused in the form of a particle beam, are subjected to analysis.

Si cette technique a l'avantage de permettre l'utilisation de très faibles quantités d'échantillons, elle a en contrepartie de nombreux inconvénients. L'intensité des courants ioniques obtenue au collecteur du spectromètre est faible elle implique, dans la pratique, qu'il soit possible de mesurer des courants aussi faibles que 10-17 ampères, ce qui exige des multiplicateurs. L'émission d'ions par thermo-ionisation est mal connue, sa stabilité et son évolution dans le temps ne sont pas toujours parfaitement maitri- sées. Il est nécessaire de tenir compte d'effets de fractionnement isotopique ou de discrimination de masse par des corrections, établies généralement en étalonnant l'appareil avec des produits connus. On ne peut obtenir des mesures stables et reproductibles qu'en contrôlant avec précision la pureté de l'échantillon, son mode de préparation et de dépôt, la pureté du réfràctaire constituant le support, les dégazages, la vitesse de montée en température.If this technique has the advantage of allowing the use of very small quantities of samples, it has in return many disadvantages. The intensity of the ionic currents obtained at the spectrometer collector is low, it implies, in practice, that it is possible to measure currents as low as 10-17 amperes, which requires multipliers. The emission of ions by thermo-ionization is poorly understood, its stability and its evolution over time are not always perfectly controlled. It is necessary to take into account the effects of isotopic fractionation or mass discrimination by corrections, generally established by calibrating the apparatus with known products. Stable and reproducible measurements can only be obtained by precisely controlling the purity of the sample, its method of preparation and deposition, the purity of the refractory constituting the support, degassing, the rate of temperature rise.

Toutes ces limitations se traduisent par le fait qu'on ne peut espérer dépasser une précision de l'ordre du millième lorsque les rapports isotopiques dans l'échantillon sont de l'ordre de 1/200, ce qui est courant dans le domaine nucléaire.All these limitations translate into the fact that one cannot hope to exceed a precision of the order of a thousandth when the isotopic ratios in the sample are of the order of 1/200, which is common in the nuclear field.

Au surplus, un spectromètre de masse utilisant une source thermo-ionique n'est pas utilisable pour conduire des analyses de composition chimique et peut très difficilement être connecté en ligne sur une ligne de séparation ou de traitement.In addition, a mass spectrometer using a thermionic source cannot be used to conduct chemical composition analyzes and can very easily be connected online to a separation or treatment line.

Une partie des inconvénients énumérés ci- dessus des sources thermo-ioniques est écartée dans les sources à bombardement électronique, qui sont d'application beaucoup plus large puisqu'elles permettent des analyses chimiques aussi bien qu'isotopiques, mais impliquent que l'échantillon à analyser soit gazeux ou facilement vaporisable.Part of the disadvantages listed above of thermionic sources are eliminated in electron bombardment sources, which are of much wider application since they allow chemical as well as isotopic analyzes, but imply that the sample to analyze either gaseous or easily vaporizable.

Le procédé habituel consiste à introduire l'échantillon à partir d'un récipient étanche par des canalisations et des vannes à microfuite laissant passer un débit gazeux bien déterminé et très faible pour ne pas altérer la très basse pression qui doit régner dans l'analyseur du spectromètre. Les molécules de gaz ou de vapeur qui passent à très faible débit sont soumises à l'action d'un faisceau d'électrons d'énergie déterminée qui ionise le gaz pour donner naissance à des ions soumis à l'analyse.The usual method consists in introducing the sample from a sealed container through piping and micro-leakage valves allowing a well determined and very low gas flow to pass without altering the very low pressure which must prevail in the analyzer of the spectrometer. The molecules of gas or vapor which pass at very low flow rate are subjected to the action of a beam of electrons of determined energy which ionizes the gas to give rise to ions subjected to analysis.

L'intensité des courants ioniques obtenue est habituellement de l'ordre de 10-9 A, c'est-à-dire beaucoup plus élevée que dans les spectromètres à thermoionisation, ce qui simplifie la mesure.The intensity of ion currents obtained is usually of the order of 10 -9 A, that is to say, much higher than the thermal-spectrometer, which simplifies the measurement.

Comme il n'est pas nécessaire de "casser le vide" dans la source pour introduire l'échantillon, contrairement à ce qui se passe dans le cas d'une source thermo-ionique et que la durée avant stabilisation est plus courte, le temps nécessaire à l'obtention d'un résultat est globalement réduit dans un facteur de l'ordre de 4, ce qui rend l'appareil utilisable en ligne.As it is not necessary to "break the vacuum" in the source to introduce the sample, contrary to what happens in the case of a thermionic source and that the time before stabilization is shorter, the time necessary to obtain a result is generally reduced by a factor of the order of 4, which makes the device usable online.

En contrepartie des avantages mentionnés ci- dessus, les sources à bombardement électronique présentent des inconvénients qui les rendent difficilement utilisables dans certains cas.In return for the advantages mentioned above, electron bombardment sources have drawbacks which make them difficult to use in certain cases.

En particulier, il est nécessaire de disposer d'échantillons de taille plus importante que dans le premier cas et de les manipuler. On ne sait en effet pas concevoir des bouteilles à échantillons, des volumes de transfert et des vannes ayant des capacités internes inférieures à quelques centimètres cubes au total. De plus, l'interaction des molécules gazeuses avec les parois qui les contiennent fait apparaitre des phénomènes de mémoire qui influencent les résultats des mesures et obligent à tenir compte de facteurs correctifs, déterminés à partir d'étalons consommables.In particular, it is necessary to have larger samples than in the first case and to handle them. We do not know how to design sample bottles, transfer volumes and valves with internal capacities of less than a few cubic centimeters in total. In addition, the interaction of gaseous molecules with the walls which contain them reveals memory phenomena which influence the results of the measurements and make it necessary to take into account corrective factors, determined from consumable standards.

En d'autres termes, les mesures effectuées à l'aide d'un spectromètre utilisant une source d'ions par bombardement électronique sont en règle générale des mesures différentielles, qui garantissent une grande précision, typiquement 50 à 100 fois plus élevée qu'avec une source à thermo-ionisation.In other words, measurements made using a spectrometer using an ion source by electron bombardment are generally differential measurements, which guarantee high precision, typically 50 to 100 times higher than with a thermionization source.

On voit que chacune des solutions connues présente des inconvénients qui la rendent impropre à un certain nombre d applications. En particulier, les sources d'ions utilisant l'ionisation d'un débit moléculaire faible exigent des volumes importants d'échantillons, ce qui représente une contrainte grave ou même rédhibitoire dans certains cas.We see that each of the known solutions has drawbacks which make it unsuitable for a certain number of applications. In particular, ion sources using ionization at a low molecular rate require large volumes of samples, which represents a severe or even unacceptable constraint in certain cases.

On connait également (FR-A-1 132 049) un procédé d'introduction d'échantillons sous forme gazeuse dans la source d'ionisation d'un spectromètre de masse, suivant lequel on chauffe l'échantillon pour porter son écoulement à l'état gazeux vers la source. Cette solution exige des échantillons de volume important et ne permet pas de commander de façon précise l'alimentation de la source. Elle implique au surplus que l'échantillon à analyser soit facilement vaporisable.We also know (FR-A-1 132 049) a method of introducing samples in gaseous form into the ionization source of a spec mass trometer, according to which the sample is heated to bring its flow in the gaseous state towards the source. This solution requires large volume samples and does not allow precise control of the source supply. It also implies that the sample to be analyzed is easily vaporizable.

Il est également connu (EP-A-0 083 472) de prévoir un piège froid pour condenser un échantillon gazeux et le relàcher ultérieurement à travers une vanne (12). Ce piège n'a pour fonction que de stocker temporairement un volume gazeux déterminé d'échantillon et de permettre l'extraction des gaz non condensables. Il n'est pas prévu d'accumuler et de stocker des composés gazeux d'un micro-échantillon au fur et à mesure de leur formation.It is also known (EP-A-0 083 472) to provide a cold trap for condensing a gas sample and subsequently releasing it through a valve (12). The purpose of this trap is only to temporarily store a determined gaseous volume of sample and to allow the extraction of non-condensable gases. It is not intended to accumulate and store gaseous compounds from a micro-sample as they are formed.

Enfin, le document US-A-3 888 107 décrit une cellule d'analyse thermique utilisant un gaz réactif dont la nécessité découle des exigences de la méthode d'analyse utilisée.Finally, document US-A-3 888 107 describes a thermal analysis cell using a reactive gas, the necessity of which stems from the requirements of the analysis method used.

La présente invention vise à fournir un procédé et un dispositif d'alimentation pour spectromètre de masse, utilisant la technique de ionisation d'un très faible débit, typiquement à l'aide d'un faisceau d'électrons, mais répondant mieux que ceux antérieurement connus aux exigences de la pratique, notamment en ce qu'ils autorisent la mise en oeuvre d'échantillons de très faible masse.The present invention aims to provide a supply method and device for a mass spectrometer, using the ionization technique of a very low flow rate, typically using an electron beam, but responding better than those previously known to the requirements of the practice, in particular in that they authorize the use of samples of very low mass.

Dans ce but, l'invention propose un procédé d'introduction de micro-échantillons conforme à la partie caractérisante de la revendication 1 et un dispositif permettant de mettre en oeuvre ce procédé, conforme à la partie caractérisante de la revendication 2.To this end, the invention provides a method of introducing micro-samples in accordance with the characterizing part of claim 1 and a device making it possible to implement this method, in accordance with the characterizing part of claim 2.

On voit que ce dispositif conserve à l'appareil tous les avantages de l'utilisation d'une source à bombardement électronique il permet de travailler avec des faisceaux d'ions relativement intenses, ce qui simplifie leur mesure il évite de casser le vide dans la source pour introduire l'échantillon il n'est pas nécessaire de disposer de récipients étanches pour manipuler les échantillons et les relier au dispositif.We see that this device keeps the device all the advantages of using an electron bombardment source it allows to work with relatively intense ion beams, which simplifies their measurement it avoids breaking the vacuum in the source to introduce the sample it is not necessary to have watertight containers to handle the samples and connect them to the device.

Et, comparé au dispositif classique pour spectromètre à bombardement électronique, le dispositif proposé présente de nombreux avantages: la taille des échantillons à analyser est réduite à quelques microgrammes; il n'est pas nécessaire de disposer de récipients étanches pour manipuler les échantillons et les introduire dans le dispositif la consommation d'étalons ou produits de référence peut être réduite à l'ordre de grandeur de celle des échantillons, dont la préparation est simple et rapide.And, compared to the conventional device for electron bombardment spectrometer, the proposed device has many advantages: the size of the samples to be analyzed is reduced to a few micrograms; It is not necessary to have sealed containers for handling the samples and introducing them into the device. The consumption of standards or reference products can be reduced to the order of magnitude of that of the samples, the preparation of which is simple and fast.

Au surplus, on peut aisément placer plusieurs dispositifs à l'entrée de la source d'ions à bombardement électronique d'un spectromètre, ce qui autorise des comparaisons faciles d'echantillons entre eux ou avec un étalon. De plus, un dispositif permettant l'admission d'un gaz de référence contenu dans une bouteille étanche peut être prévu pour le comparer au gaz échantillon issu du tube de sublimation.In addition, several devices can easily be placed at the input of the electron bombardment ion source of a spectrometer, which allows easy comparisons of samples with one another or with a standard. In addition, a device allowing the admission of a reference gas contained in a sealed bottle can be provided to compare it with the sample gas from the sublimation tube.

L'invention sera mieux comprise à la lecture de la description qui suit d'un dispositif qui en constitue un mode particulier d'exécution donné à titre d'exemple non limitatif.The invention will be better understood on reading the following description of a device which constitutes a particular embodiment thereof given by way of non-limiting example.

La description se réfère aux dessins qui l'accompagnent, dans lesquels:

  • - la figure 1 est un schéma de principe du dispositif,
  • - la figure 2 montre un dispositif particulier suivant l'invention, en coupe suivant un plan passant par son axe.
The description refers to the accompanying drawings, in which:
  • FIG. 1 is a block diagram of the device,
  • - Figure 2 shows a particular device according to the invention, in section along a plane passing through its axis.

Le dispositif montré en Figures 1 et 2 peut être regardé comme comportant un réacteur 10 dont l'élément essentiel est un microfour à température réglable, un passage 12 suffisamment étranglé pour que l'écoulement y intervienne sous forme de débit moléculaire, et un micro-subli- meur 14. Le microsublimeur est relié, par l'intermédiaire d'une vanne 16, à la source d'ions 18 du spectromètre, qui peut être de l'un quelconque des types permettant d'ioniser un faible débit de gaz qui le pénètre. En règle générale, cette source effectuera l'ionisation par bombardement électronique.The device shown in Figures 1 and 2 can be viewed as comprising a reactor 10, the essential element of which is a micro-oven with adjustable temperature, a passage 12 sufficiently constricted for the flow to take place therein in the form of molecular flow, and a micro- sublimers 14. The microsublimeter is connected, by means of a valve 16, to the ion source 18 of the spectrometer, which can be of any of the types making it possible to ionize a low flow of gas which penetrates him. Typically, this source will perform ionization by electron bombardment.

Le réacteur 10 dont le schéma de principe est montré en figure 1 comporte une enceinte, généralement cylindrique, dans l'axe de laquelle est placé le microfour proprement dit 20 constitué par un tube en métal capable de supporter des hautes températures, par exemple en nickel, nichrome ou "monel". Des moyens sont prévus pour chauffer le four par effet Joule. Sur la figure 1, ces moyens sont représentés sous forme d'une source électrique 22 reliée à une extrémité du tube dont t'autre est à la masse. Une autre solution consiste à bobiner une résistance électrique chauffante autour du tube 20. Ce tube peut porter un capteur de température 24 relié à un circuit 26 de régulation de température par modulation de la puissance électrique fournie par la source 22.The reactor 10, the schematic diagram of which is shown in FIG. 1, comprises an enclosure, generally cylindrical, in the axis of which is placed the actual micro-oven 20 consisting of a metal tube capable of withstanding high temperatures, for example nickel , nichrome or "monel". Means are provided for heating the oven by the Joule effect. In Figure 1, these means are shown in the form of an electrical source 22 connected to one end of the tube of which the other is grounded. Another solution consists in winding an electric heating resistor around the tube 20. This tube can carry a temperature sensor 24 connected to a circuit 26 for regulating the temperature by modulating the electric power supplied by the source 22.

Un porte-échantillon 28 est prévu pour permettre d'introduire une quantité très faible d'échantillons, sous forme d'un dépôt sur une aiguille ou un fil. La tête de ce porte-échantillon sera prévue pour obturer de façon étanche le microfour.A sample holder 28 is provided to allow the introduction of a very small quantity of samples, in the form of a deposit on a needle or a thread. The head of this sample holder will be provided to seal the microfour.

Une des extrémités du tube 20 formant microfour est reliée, par une vanne 30, à une source de vide 32 (pompe primaire mécanique par exemple) et à une source 34 de réactif. de nature telle qu'il donne naissance avec l'échantillon à un composé gazeux ou volatil. Les sources 32 et 34 sont munies chacune d une vanne d'arrêt 36 et 38. En règle générale, les vannes 30 et 38 au moins doivent être en un matériau résistant aux gaz très corrosifs, étant donné qu'on sèra fréquemment amené à utiliser des espèces chimiques très réactives, telles que le fluor. La vanne 30 doit au surplus être rigoureusement étanche.One end of the tube 20 forming a micro oven is connected, by a valve 30, to a vacuum source 32 (mechanical primary pump for example) and to a source 34 of reagent. of a nature such that it gives rise, with the sample, to a gaseous or volatile compound. The sources 32 and 34 are each provided with a shut-off valve 36 and 38. As a general rule, the valves 30 and 38 at least must be made of a material resistant to very corrosive gases, since it will frequently be necessary to use highly reactive chemical species, such as fluorine. The valve 30 must also be strictly sealed.

Le passage étranglé 12 peut présenter une section de passage fixe. On peut dans ce cas utiliser un diaphragme ou un conduit capillaire. Elle peut également être ajustable et formée par une vanne à microfuite de type classique ou une vanne piézo-électrique, dont l'ouverture est provoquée par la déformation d'un cristal piézo-électrique sous l'action d'un champ électrique. Mais, dans tous les cas, le passage doit interdire toute entrée d'air ambiant et il doit offrir une section de passage ayant un diamètre suffisamment faible (typiquement quelques microns) pour que le débit gazeux entre le réacteur 10 et le tube de microsublimation maintenu à basse pression soit en régime moléculaire. On sait que dans ce régime le libre parcours des molécules gazeuses est supérieur aux dimensions transversales du passage.The constricted passage 12 may have a fixed passage section. We can in this case use a diaphragm or capillary conduit. It can also be adjustable and formed by a conventional type micro-leakage valve or a piezoelectric valve, the opening of which is caused by the deformation of a piezoelectric crystal under the action of an electric field. But, in all cases, the passage must prohibit any entry of ambient air and it must offer a passage section having a sufficiently small diameter (typically a few microns) so that the gas flow between the reactor 10 and the microsublimation tube maintained at low pressure or in molecular regime. We know that in this regime the free path of the gaseous molecules is greater than the transverse dimensions of the passage.

Le microsublimateur 14 sera généralement constitué par un tube 40 de faible diamètre, dont une extrémité est reliée de façon étanche au passage 12 et l'autre extrémité est reliée, par l'intermédiaire de la vanne 16, à la source d'ions 18. Ce tube est muni de moyens de refroidissement à température cryogénique. Ces moyens sont représentés sur la figure 1 sous forme d'une enceinte 42 munie d'une entrée et d'une sortie de fluide à très basse température. Une autre solution consiste à placer le tube dans le circuit d'un cryogénérateur. Pour permettre de régler la température du tube 40, des moyens de chauffage réglables lui sont associés. Dans le cas de la figure 1, ces moyens sont constitués par une résistance chauffante 44 bobinée autour du tube 40 et alimentée par un générateur électrique 46 de puissance réglable. Une sonde de température pourra être placée sur le tube 40 pour réguler, par l'intermédiaire d un circuit similaire au circuit 26, la température du tube à une valeur réglable. Cette température peut également être asservie à une valeur de référence par l'intensité des faisceaux d'ions reçus aux collecteurs du spectromètre de masse.The microsublimator 14 will generally consist of a tube 40 of small diameter, one end of which is tightly connected to the passage 12 and the other end is connected, by means of the valve 16, to the ion source 18. This tube is provided with cryogenic temperature cooling means. These means are shown in Figure 1 in the form of an enclosure 42 provided with an inlet and an outlet for fluid at very low temperature. Another solution is to place the tube in the circuit of a cryogenerator. To allow the temperature of the tube 40 to be adjusted, adjustable heating means are associated with it. In the case of FIG. 1, these means consist of a heating resistor 44 wound around the tube 40 and supplied by an electric generator 46 of adjustable power. A temperature probe can be placed on the tube 40 to regulate, via a circuit similar to circuit 26, the temperature of the tube to an adjustable value. This temperature can also be slaved to a reference value by the intensity of the ion beams received at the collectors of the mass spectrometer.

Pour ce faire, un signal est prélevé sur l'amplificateur de mesure du courant d'ions. Celui-ci est comparé en permanence à une référence représentant la température choisie, cette référence pouvant être elle-même programmée à l'aide d'un calculateur. On obtient donc une tension qui est convertie en impulsions calibrées donnant des quantités d'énergie alimentant les systèmes de chauffage du tube 40.To do this, a signal is taken from the ion current amplifier. This is constantly compared with a reference representing the chosen temperature, this reference being able to be programmed itself using a computer. A voltage is therefore obtained which is converted into calibrated pulses giving quantities of energy supplying the heating systems of the tube 40.

A chaque diminution du signal de mesure, une impulsion en quantité d'énergie correspondante est appliquée au chauffage régulant ainsi la quantité de produit introduit vers la source du spectromètre de masse. Dans la pratique, on sera amené à porter le tube à une température qui peut varier entre quelques ° K et quelques centaines de °K.Each time the measurement signal decreases, a corresponding energy quantity pulse is applied to the heating, thereby regulating the quantity of product introduced to the source of the mass spectrometer. In practice, it will be necessary to bring the tube to a temperature which can vary between a few ° K and a few hundred ° K.

Une vanne 46a, en paralléle avec la vanne 16, permet de relier la sortie du tube 40 à une pompe à vide.A valve 46a, in parallel with the valve 16, makes it possible to connect the outlet of the tube 40 to a vacuum pump.

Un raccord supplémentaire muni d'une vanne 47 (ou plusieurs) peut être prévu pour raccorder la source d'ions à une alimentation en gaz de référence et/ou à un autre dispositif similaire à celui qui vient d'être décrit.An additional connector provided with a valve 47 (or more) may be provided to connect the ion source to a reference gas supply and / or to another device similar to that which has just been described.

Dans le mode particulier de réalisation montré en figure 2, les éléments 10, 12 et 14 de la figure 1 sont regroupés pour constituer un ensemble monobloc en plusieurs pièces assemblées, par exemple par soudage.In the particular embodiment shown in FIG. 2, the elements 10, 12 and 14 of FIG. 1 are grouped together to constitute a one-piece assembly in several assembled parts, for example by welding.

Sur la figure 2, où les organes correspondant à ceux de la figure 1 sont désignés par le même numéro de référence, le réacteur est délimité par deux embouts 48 et 50 et une virole cylindrique dans l'axe de laquelle est placé le tube 20, de quelques millimètres de diamètre intérieur, formant le microfour. L'extrémité aval de ce tube est mise à la masse par l'intermédiaire de l'embout 50. L'extrémité amont, isolée de la masse par un pion 52, est reliée à la source électrique de chauffage par l'intermédiaire d'une patte 54 qui traverse la virole de façon étanche. Le porte-échantillon 28 comporte une tête vissable dans l'embout 48, l'étanchéité étant assurée par un joint 58. Une vis de blocage 60 prévue dans la tête permet de retenir un fil ou une aiguille 62 de support d'échantillon sec. Un canal 64 ménagé dans l'embout 48 permet de raccorder le tube 20 à une vanne 30 d'admission de réactif (agent fluorant gazeux en général) ou à une pompe à vide.In FIG. 2, where the members corresponding to those in FIG. 1 are designated by the same reference number, the reactor is delimited by two nozzles 48 and 50 and a cylindrical shell in the axis of which the tube 20 is placed, a few millimeters in internal diameter, forming the micro-oven. The downstream end of this tube is grounded via the end piece 50. The upstream end, isolated from ground by a pin 52, is connected to the electrical heating source by means of a tab 54 which crosses the shell in a sealed manner. The sample holder 28 comprises a head screwable into the end piece 48, the seal being ensured by a seal 58. A locking screw 60 provided in the head makes it possible to retain a thread or a needle 62 for supporting the dry sample. A channel 64 formed in the end piece 48 makes it possible to connect the tube 20 to a valve 30 for admitting the reagent (gaseous fluorinating agent in general) or to a vacuum pump.

Dans l'embout 50 est usiné un siège 66 destiné à recevoir la vanne à micro-fuite (non représentée) constituant le passage 12 vers le micro- sublimateur 14. Ce dernier a une constitution très comparable à celle du réacteur 10, si ce n'est que la virole est munie de raccords 68 et 70 d'entrée et de sortie de fluide cryogénique. Le tube 40 de micro-sublimation est relié, par l'intermédiaire d'un pion isolant 72, à l'embout 50 et son extrémité aval est soudée à un embout 74 pourvu d'un siège destiné à la vanne 46a (non représentée).In the nozzle 50 is machined a seat 66 intended to receive the micro-leakage valve (not shown) constituting the passage 12 towards the micro-sublimator 14. The latter has a constitution very comparable to that of the reactor 10, if this n 'is that the ferrule is provided with inlet and outlet fittings 68 and 70 for cryogenic fluid. The micro-sublimation tube 40 is connected, via an insulating pin 72, to the end piece 50 and its downstream end is welded to an end piece 74 provided with a seat intended for the valve 46a (not shown) .

Enfin, cet embout comprend un prolongement tubulaire 76 destiné à être raccordé à la vanne 16.Finally, this nozzle comprises a tubular extension 76 intended to be connected to the valve 16.

A titre de simple exemple de mise en oeuvre du procédé suivant l'invention, on décrira maintenant l'introduction d échantillons en vue de l'analyse isotopique de l'uranium.As a simple example of implementing the method according to the invention, the introduction of samples for the isotopic analysis of uranium will now be described.

Le dispositif utilisé est du genre montré en figure 2.The device used is of the type shown in FIG. 2.

L'échantillon doit d'abord être reporté sur le porte-échantillon 28. Sur le fil 62, qui a par exemple 0,8 mm de diamètre et 7 cm de long, on dépose, à l'aide d'une micro-pipette, quelques gouttes de nitrate d'uranyle contenant au total par exemple 10 microgrammes d'uranium à analyser.The sample must first be transferred to the sample holder 28. On the wire 62, which for example is 0.8 mm in diameter and 7 cm long, is deposited, using a micro-pipette , a few drops of uranyl nitrate containing a total of for example 10 micrograms of uranium to be analyzed.

Pour transformer ce dépôt en phase solide, on pose le fil entre deux contacts électriques et on fait circuler un courant de chauffage par effet Joule. Le nitrate d'uranyle se transforme en un dépôt de U03, puis U308 lorsque la température dépasse 350° C.To transform this deposit into a solid phase, the wire is laid between two electrical contacts and a heating current is circulated by the Joule effect. Uranyl nitrate transforms into a deposit of U0 3 , then U 3 0 8 when the temperature exceeds 350 ° C.

Le fil recouvert du dépôt est mis en place dans le porte-échantillon 28 et ce dernier fixé sur l'embout 48. Le tube 20 est mis sous vide par pompage jusqu'à une pression de l'ordre de 0,133 Pa (10-3 torr). Puis on chauffe le tube 20, par passage de courant. jusqu'à une température d'environ 400°C pour éliminer la vapeur d'eau résiduelle.The wire covered with the deposit is placed in the sample holder 28 and the latter fixed on the end piece 48. The tube 20 is put under vacuum by pumping up to a pressure of the order of 0.133 Pa (10- 3 torr). Then we heat the tube 20, by current flow. up to a temperature of around 400 ° C to remove residual water vapor.

On amène alors la température du tube de microsublimation 40 à celle de l'azote liquide par circulation de cet azote autour du tube 40, du raccord 68 au raccord 70 par la circulation d'un gaz caloporteur (hélium par exemple) amené à la température de l'azote liquide.The temperature of the microsublimation tube 40 is then brought to that of the liquid nitrogen by circulation of this nitrogen around the tube 40, from the connector 68 to the connector 70 by the circulation of a heat transfer gas (helium for example) brought to the temperature. liquid nitrogen.

On peut alors passer à la première phase de mise en oeuvre du procédé suivant l'invention, constituée par le piégeage de produits gazeux dans le micro-sublimateur 14.We can then proceed to the first phase of implementation of the method according to the invention, constituted by the trapping of gaseous products in the micro-sublimator 14.

Pour cela, on envoie un débit calibré de fluor très pur dans le tube 20, à travers les vannes 38 et 30. Les produits de la réaction (UF6 et 02) s'échappent à très faible débit à travers la vanne 12 et sont piégés dans le tube 40, en se répartissant suivant la température de solidification.For this, a calibrated flow of very pure fluorine is sent into the tube 20, through the valves 38 and 30. The products of the reaction (UF 6 and 0 2 ) escape at very low flow rate through the valve 12 and are trapped in the tube 40, distributing according to the solidification temperature.

Une fois le piégeage achevé, la vanne 12 est fermée. La vanne de pompage 46a est ouverte, et l'on chauffe très progressivement le tube 40 par passage d'un courant électrique. L'oxygène se sublime et il est évacué par la pompe à vide, à travers la vanne 46a.Once trapping is complete, the valve 12 is closed. The pumping valve 46a is open, and the tube 40 is very gradually heated by passing an electric current. The oxygen sublimes and it is evacuated by the vacuum pump, through the valve 46a.

Lorsque la température augmente au-delà du point de sublimation de l'oxygène et atteint le point de sublimation de l'hexafluorure, on peut passer à l'alimentation de la source d'ions.When the temperature increases beyond the sublimation point of oxygen and reaches the sublimation point of hexafluoride, we can switch to the supply of the ion source.

Pour cela, on ferme la vanne 46 et on ouvre la vanne 16. Le chauffage est réaliséavec une programmation en température telle que, dès que le débit d'hexafluorure atteint une valeur prédéterminée (c'est-à-dire lorsqu on atteint la valeur de consigne de l'intensité du faisceau d'ions dans le spectromètre), on asservit la température, de façon que le débit, mesuré par des moyens non représentés, reste constant jusqu'à épuisement de la masse d'hexafluorure d'uranium piégé.Dans la pratique, avec un débit de 1013 molécules par seconde, la durée d'épuisement est d'environ 30 minutes lorsqu'on a déposé 10 microgrammes d'uranium sur le fil 62To do this, the valve 46 is closed and the valve 16 is opened. The heating is carried out with a temperature programming such that, as soon as the hexafluoride flow rate reaches a predetermined value (that is to say when the value is reached of the intensity of the ion beam in the spectrometer), the temperature is controlled, so that the flow rate, measured by means not shown, remains constant until the mass of trapped uranium hexafluoride is used up In practice, with a flow rate of 1013 molecules per second, the depletion time is approximately 30 minutes when 10 micrograms of uranium have been deposited on wire 62

Toute cette durée est disponible pour effectuer les mesures de rapports isotopiques, qu'on peut ensuite comparer à celles d'un hexafluorure d'uranium étalon, admis au spectromètre à travers la vanne 47.All this time is available to make isotopic ratio measurements, which can then be compared to those of a standard uranium hexafluoride, admitted to the spectrometer through valve 47.

Une autre solution consiste à utiliser deux dispositifs du genre montré en figure 2. L'un d'eux reçoit un fil portant un dépôt dont le rapport isotopique est à mesurer, l'autre un dépôt d'U308 de composition isotopique connue.Another solution consists in using two devices of the kind shown in FIG. 2. One of them receives a wire carrying a deposit whose isotopic ratio is to be measured, the other a deposit of U 3 0 8 of known isotopic composition .

On voit que, quel que soit le mode de réalisation utilisé, on obtient tout à la fois la haute précision et la rapidité de mesure d'une source à gaz et la faible masse d'échantillon en jeu d'un spectromètre à thermo-ionisation.It can be seen that, whatever the embodiment used, both the high precision and the speed of measurement of a gas source and the small mass of sample in play of a thermionization spectrometer are obtained. .

Cette très faible masse autorise en particulier l'emploi d'un dispositif suivant l'invention pour l'analyse des combustibles irradiés contenant ces isotopes du plutonium, l'analyse étant alors conduite sur PuF6formé par fluoration de PU02' This very low mass allows in particular the use of a device according to the invention for the analysis of irradiated fuels containing these plutonium isotopes, the analysis then being carried out on PuF 6 formed by fluorination of P U 0 2 '

L'invention ne se limite cependant pas à ces modes particuliers de réalisation. Elle est applicable chaque fois qu'est disponible une réaction donnant un composé gazeux de l'échantillon. Par exemple, la méthode est applicable au cas du carbone, qui peut être fluoré pour donner CF4, ce qui est particulièrement intéressant pour l'analyse isotopique C12/Cl4 utilisée en datation.The invention is not however limited to these particular embodiments. It is applicable whenever a reaction giving a gaseous compound of the sample is available. For example, the method is applicable to the case of carbon, which can be fluorinated to give CF 4 , which is particularly interesting for the isotopic analysis C 12 / C l4 used in dating.

Claims (8)

  1. i. Method for introducing microsamples in gaseous form into the ionisation source of a mass spectrometer, wherein the sample is heated for causing it to flow in gaseous condition towards the source,
    characterized by the steps of:
    depositing the microsample on needle-like or wire-like holder (62)
    transforming the holder supported microsample into a gaseous compound by heating, it in an atmosphere of reactive gas in a space from which a molecular flow of the compound and of the reactive gas is organized towards a sublimation tube whose wall (40) is maintained at temperature low enough for trapping the gaseous compound and the reactant,
    selectively sublimating the gaseous compound by progressively heating the sublimation tube and,
    regulating the output flow rate of the gaseous compound by controlling the temperature of said wall and communicating the tube with the ionisation source.
  2. 2. Device for introducing microsamples into the ionisation source (18) of a mass spectrometer, comprising means (20, 22, 26) for heating the microsample and a calibrated restricted passage for a flow of the gaseous products resulting from heating,
    characterized in that it comprises a reactor (10) having means for receiving a needle-like sample holder (62) provided for receiving a deposit of the microsample, said means for connection with a vacuum source (32) and means (38, 30) for delivery of an adjustable flow rate of a reactant for transforming the microsample into said gaseous compounds which flow from the reactor and a sublimation tube (40) connected to the passage (12) and connected to the ion source (18) of the spectrometer through a valve (16) and means (46a) for connection with a vacuum source, said tube being located in an enclosure (42) for circulation of a cryogenic fluid and provided with heating means making it possible to meter the output flow rate towards the ion source.
  3. 3. Device according to claim 2,
    characterised in that the reactor comprises a tube (20) for receiving the microsample holder and provided with programmed the means for heating by Joule effect.
  4. 4. Device according to claim 2 or 3,
    characterized in that the restricted calibrated passage (12) has such dimensions that the flow is molecular therein.
  5. 5. Device according to claim 4,
    characterized in that the passage consists of a diaphragm formed with calibrated orifice, a capillary conduct or a microleak valve.
  6. 6. Device according to claim 2,
    characterized in that the reactor (10) and the sublimation tube (40) are provided with temperature probes (24) connected to circuits (26) for regulating the heating means (22).
  7. 7. Device according to claim 3,
    characterized in that the tube (20) of the reactor and the sublimation tube (40) are located coaxially and in alignment.
  8. 8. Device according to any one of,claims 2 - 7,
    characterized in that the cryogenic fluid consists of gaseous helium maintained at the temperature of liquid nitrogen.
EP19860400902 1985-04-24 1986-04-24 Sample introduction method and device for a mass spectrometer Expired EP0200645B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8506257A FR2581246B1 (en) 1985-04-24 1985-04-24 METHOD AND DEVICE FOR INTRODUCING SAMPLES FOR MASS SPECTROMETER
FR8506257 1985-04-24

Publications (2)

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EP0200645A1 EP0200645A1 (en) 1986-11-05
EP0200645B1 true EP0200645B1 (en) 1989-07-12

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EP (1) EP0200645B1 (en)
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DE (1) DE3664401D1 (en)
FR (1) FR2581246B1 (en)
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Publication number Priority date Publication date Assignee Title
FR2629270B2 (en) * 1988-03-25 1990-12-28 Cogema SAMPLE INTRODUCTION DEVICE FOR MASS SPECTROMETER

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1132049A (en) * 1954-05-26 1957-03-04 Thomson Houston Comp Francaise Device for introducing a sample into a mass spectrograph
US3888107A (en) * 1969-10-08 1975-06-10 Dow Chemical Co Differential thermal analysis cell assembly
EP0083472B1 (en) * 1981-11-30 1986-02-26 Vg Instruments Group Limited Automatic mass spectrometer inlet system

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EP0200645A1 (en) 1986-11-05
DE3664401D1 (en) 1989-08-17
FR2581246A1 (en) 1986-10-31
WO1986006545A1 (en) 1986-11-06
FR2581246B1 (en) 1987-07-10
CA1263765A (en) 1989-12-05

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