WO2023089114A1 - Dispositif de détection pour chromatographie en phase gazeuse - Google Patents

Dispositif de détection pour chromatographie en phase gazeuse Download PDF

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Publication number
WO2023089114A1
WO2023089114A1 PCT/EP2022/082442 EP2022082442W WO2023089114A1 WO 2023089114 A1 WO2023089114 A1 WO 2023089114A1 EP 2022082442 W EP2022082442 W EP 2022082442W WO 2023089114 A1 WO2023089114 A1 WO 2023089114A1
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WO
WIPO (PCT)
Prior art keywords
radiation source
radiation
detection device
measuring chamber
filter array
Prior art date
Application number
PCT/EP2022/082442
Other languages
German (de)
English (en)
Inventor
Thorsten Graunke
Wladimir Tschekalinskij
Sebastian HETTENKOFER
Stephan Junger
Jens-Uwe Garbas
Ruslan Rybalko
Original Assignee
Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e. V.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from DE102022111570.4A external-priority patent/DE102022111570A1/de
Application filed by Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e. V. filed Critical Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e. V.
Priority to EP22818722.5A priority Critical patent/EP4433819A1/fr
Publication of WO2023089114A1 publication Critical patent/WO2023089114A1/fr

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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/62—Detectors specially adapted therefor
    • G01N30/76—Acoustical detectors
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/60—Construction of the column
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/62—Detectors specially adapted therefor
    • G01N30/74—Optical detectors

Definitions

  • the present invention relates to a detection device for chromatography, in particular for gas chromatography, with at least one measuring chamber with an inlet and an outlet for a medium to be examined, a chromatographic separation device in front of the inlet into the measuring chamber and one or more detectors through which one or more Substances of a medium introduced into the measuring chamber can be detected.
  • Chromatography is a physical separation process in which mixtures of substances are separated into individual components or substances. Chromatography is often used to detect or quantify individual substances in a mixture of substances. In the case of mixtures of substances that are gaseous or can be converted into the gas phase without decomposition, the individual substances can be separated from one another using gas chromatography.
  • the substance mixtures are conducted with the aid of a carrier gas through a separation column (eg packed column or capillary column) into a measuring chamber in which the substances can be detected using suitable detectors.
  • the qualitative statement results from the retention times and the quantitative statement from the signal strength of the detector.
  • the individual substances in the substance mixture move at different speeds Velocities through the separating column (retention time), the velocities depending on the substances themselves and, among other things, the properties of the selected separating column.
  • the fastest-moving substance in the mixture leaves the separation column first is therefore the first to be eluted and can be detected in the measuring chamber.
  • the other substances in the substance mixture follow accordingly, depending on their speed. In this way, the individual substances can be detected in the measuring chamber at different, reproducible times and thus recorded as a component of the substance mixture.
  • EID Flame ionization detectors
  • ECD electron capture detectors
  • TCD thermal conductivity detectors
  • FPD flame photometric detectors
  • NPD nitrogen-phosphorus detectors
  • IMS ion mobility spectrometers
  • these detector systems are expensive, complex, have large chamber volumes or require a fuel gas (40% hydrogen, remainder helium) or have high power consumption cannot be integrated into semiconductor chips and also cannot be implemented as a highly integrated system.
  • the object of the present invention is to specify a detection device for chromatography, in particular for gas chromatography, which can be implemented inexpensively and in a miniaturized design, in particular at chip level.
  • the proposed detection device has at least one broadband radiation source that emits electromagnetic radiation of a spectral range, a measuring chamber with at least one inlet for a medium to be examined, a chromatographic separating device in front of the inlet into the measuring chamber and one or more detectors, by which a result of an interaction of the radiation of the broadband radiation source coupled into the measuring chamber with a medium introduced into the measuring chamber can be detected.
  • the one or more detectors include at least one pressure sensor, in particular a microphone, which is arranged in or on the measuring chamber. The medium can flow through the measuring chamber and then leave it again via at least one outlet or flow past the outside of the measuring chamber at the inlet, so that it enters the measuring chamber by diffusion via the inlet and also leaves it again via the inlet.
  • the measurement chamber and the broadband radiation source are designed and arranged in such a way that radiation from the broadband radiation source is coupled into the measurement chamber.
  • the measuring chamber can for example. have a suitable entry window for the electromagnetic radiation.
  • a broadband radiation source is to be understood as meaning a radiation source which emits electromagnetic radiation in a spectral range which has a width of at least 100 nm.
  • This radiation source is preferably a light source which emits in the visible and/or infrared and/or ultraviolet spectral range. Examples of thermal light sources that are preferably used are: radiant heaters, globars, MEMS heaters, NERNST pins, nickel-chrome fronds or LEDs.
  • Light sources are preferably used which emit in a spectral range which lies within the spectral range from 1.2 pm to 17 pm.
  • the medium to be examined which can exist in different aggregate states, is fed into the measuring chamber in liquid or gaseous form via the chromatographic separation device. Due to the function of the chromatographic separation device, different substances in the medium to be examined reach the measuring chamber at different times and can thus be detected separately from one another. The detection takes place by recording the result of the interaction of the respective substances with the electromagnetic radiation radiated in by the broadband radiation source.
  • One or more filters or membranes or else combinations thereof can also be connected upstream of the chromatographic separation device. The filters or membranes are selective for specific gases or dissolved gases.
  • Different measuring principles can be used for the detection, in particular in addition to the one or more pressure sensors or acoustic detectors in the measuring chamber, with which a photoacoustic interaction with the respective substance can be detected, also radiation detectors, in the case of light radiation optical detectors, with which absorption of the irradiated electromagnetic radiation by the respective substances can be detected.
  • the radiation detectors are preferably arranged outside the measurement chamber.
  • the measurement chamber must then be designed to be permeable not only on the entry side of the electromagnetic radiation, but also on a side opposite the entry side for the electromagnetic radiation.
  • the detection device has one or more pressure sensors, for example in the form of MEMS microphones, realizing the function of a photoacoustic gas sensor (PAS).
  • PAS photoacoustic gas sensor
  • Photoacoustic gas sensors make use of the fact that many gases or Constituents of a gas have a characteristic absorption spectrum with one or more absorption peaks.
  • Light absorption causes a change in pressure or acoustic wave in the measuring chamber, which is detected by the pressure sensor.
  • the change in pressure depends on the concentration and is converted into an electrical signal in the pressure sensor.
  • the proposed detection device preferably has a gas-chromatographic separating column as the separating device, ie in the preferred embodiment it is designed for gas chromatography.
  • the detection device can also have several of the measuring chambers and detectors, which are connected to a common separating device.
  • the individual measuring chambers are preferably stacked above the broadband radiation source and on both sides in the direction of radiation for the coupled or radiated electromagnetic radiation permeable.
  • an operation of the detection device can be implemented in which the individual detectors, in particular pressure sensors or Microphones that are activated in the different measuring chambers at different times that are slightly offset in time.
  • This increases the temporal resolution of the measurement of the medium to be examined, so that substances that arrive in the measurement chamber with only a small time difference can also be distinguished with the measurement, so that their lengths of stay in the measurement chamber overlap.
  • the detection device comprises a plurality of measurement chambers, separating devices and detectors, with the separating devices having different separating characteristics.
  • the separating performance and thus also the quality of the measurement can be increased by the simultaneous use of separating devices with different separating characteristics in connection with the corresponding measuring chambers.
  • the individual measuring chambers can be stacked over as in the previous embodiment arranged in the broadband radiation source and designed to be correspondingly radiation-transmissive.
  • the detection device in turn has a number of measuring chambers, separating devices and detectors.
  • the measuring chambers with the respective separating devices are connected to one another in such a way that the medium to be examined flows through all separating devices and measuring chambers one after the other. into this entrance .
  • a higher separating performance can also be achieved by this configuration.
  • the separating device(s), measuring chamber(s) and the detector(s) can be completely planar in the proposed detection device, e.g. are manufactured in semiconductor technology.
  • the structure of the detection device can then, for example. take place as a 3D stack (3D stack), in which several substrates, preferably the size of semiconductor chips, are stacked one on top of the other with integrated components of the detection device.
  • 3D stack 3D stack
  • detection devices can be realized in which several measuring chambers and possibly.
  • the 3D substrate stack then having more than three semiconductor substrates contains .
  • Such a miniaturization which could not previously be achieved with the available solutions, is only made possible by designing the detection device with a broadband light source and corresponding, in particular optical or acoustic, detectors.
  • an optical filter device is arranged between this broadband light source and the measuring chamber or chambers, through which the light coupled into the measuring chamber can be limited to a wavelength or a narrow spectral range and the wavelength or the spectral range can also be varied. Examples of such a filter device are given in DE 10 2021 108 745, which is directed to a multispectral light source. 7 described, the relevant disclosure content of which is included in the present patent application.
  • a multispectral light source can also be used in the proposed detection device. It has at least one broadband light source, a filter array and a switching device for controlling the passage of at least a portion of the light emitted by the broadband light source through the filter array.
  • the broadband light source emits light in a specific spectral range.
  • the spectral filters of the filter array have a correspondingly lower spectral width that is at least partially within the spectral range of the light source.
  • the switching device is designed as an optical switching device, with broadband light source, filter array and optical switching device are arranged so that light emitted by the broadband light source via the optical switching device, possibly also via other optical elements such.
  • the optical switching device has an array of micro-mirrors or micro-apertures and is designed and arranged in such a way that it can guide light emitted by the broadband light source in a targeted manner only through one or more arbitrarily definable spectral filters of the filter array to the measuring chamber(s) of the arrangement.
  • the optical switching device can be controlled accordingly for this purpose.
  • the broadband light source has either an array of light emitters that can be controlled separately via the switching device and is designed and arranged in such a way that by controlling the light emitters via the switching device, light emitted by the broadband light source is only selectively controlled by one or more arbitrarily specifiable spectral Filter of the filter array can be directed.
  • the broadband light source is formed by a single light emitter and the switching device has a mechanical XY adjustment device for this single emitter or the filter array, with which the single emitter under Different filters of the filter array can be positioned, so that the light emitted by the light source can only be directed through an arbitrarily predeterminable spectral filter of the filter array.
  • the light-emitting surface of the light emitters is preferably not larger than the lateral dimensions of the individual spectral filters of the filter array.
  • the individual spectral filters of the filter array have small lateral dimensions of ⁇ 10 mm ⁇ 10 mm, particularly preferably between 100 ⁇ m ⁇ 100 ⁇ m and 1000 ⁇ m ⁇ 1000 ⁇ m.
  • the filter array is preferably designed in such a way that the spectral filters are arranged in rows and columns in the filter array. In principle, however, a different arrangement is also possible, for example a concentric arrangement, a purely cellular arrangement or even any arrangement of the individual filters in the filter array.
  • the arrangement of the individual spectral filters of the filter array preferably correlates with the arrangement of the micro-mirrors or micro-apertures of the first alternative or with the arrangement of the individual light emitters of the array of light emitters of the second alternative, so that they are each arranged in the same way, e.g. according to rows and columns .
  • the number of units (micro-mirrors, micro-apertures, light emitters) present on the side of the optical switching device or the broadband light source preferably corresponds to the number of spectral filters in the filter array, so that each unit is assigned a spectral filter through which only that of the assigned unit outgoing light is directed .
  • each unit is then assigned a group of spectral filters arranged next to one another, for example two or four filters.
  • selecting the number of filters to be smaller than the number of these units, in which case several units arranged next to one another are assigned to each filter.
  • the configuration with a multispectral light source enables an adaptation or variation of the wavelength or spectral distribution of the optical radiation coupled into the measurement chamber(s) according to the number and characteristics of the different filters of the filter array. This allows the spectral distribution of the emitted light to be specifically adapted to the substances to be detected. Due to the structure chosen, the filter array and the broadband light source as well as the optical switching device can be made miniaturized.
  • Filters based on sub-wavelength structures or plasmonic filters are preferably used in the filter array. This means that a large number of filters can be implemented cost-effectively in the smallest of spaces. This enables, for example, the simulation of an absorption spectrum for almost any substance through a suitable combination of the individual optical channels or Filter, ie by simultaneously passing light through several of the spectral filters.
  • the filters can also be designed as interference filters.
  • Fig. 1 shows a first example of an embodiment of the proposed detection device
  • Fig. 2 shows a second example of an embodiment of the proposed detection device
  • Fig. 3 shows a third example of an embodiment of the proposed detection device
  • Fig. 4 shows a fourth example of an embodiment of the proposed detection device
  • Fig. 5 shows an example of an implementation of the proposed detection device as a substrate stack
  • Fig. 6 shows a fifth example of an embodiment of the proposed detection device
  • Fig. 7 shows a sixth example of an embodiment of the proposed detection device.
  • FIG. 1 shows a schematic structure of an example of the proposed detection device.
  • the detection device has a broadband light source 1 , a measurement chamber 2 , one or more Detectors 3, electronics 4 for reading the detectors 3, for signal processing and evaluation, and a gas chromatographic separation column 5.
  • the light emitted by the light source 1 is coupled into the measurement chamber 2 via an inlet window (not shown) in order to interact there with the medium 6 introduced via the separation column 5 .
  • a separation device working according to a different principle, for example based on one or more filters or membranes (eg fluoropolymers or thermoplastics) or combinations thereof, can in principle also be used, as described, for example, in Graunke, T.; Schmitt, K.; Raible, S.;
  • the medium 6 conducted via the separating column 5 into the measuring chamber 2 contains substances which elute into the measuring chamber 1 at different times (elution sequence). For this reason, as a rule, only one substance ever gets into the measuring chamber 2.
  • the measuring chamber 2 is permeable, at least on the side facing the light source 1, for the light emitted by the light source, e.g. B. IR light.
  • the light from the broadband light source 1 passes through the measuring chamber 2 and is absorbed by the eluting substances. Since a pre-separation takes place via the separating column 5, only the concentration of the substances that leave the separating column one after the other has to be measured.
  • At least one detector 3 is required for this, which is preferably arranged in the measuring chamber (eg as a MEMS microphone), but can also be placed outside.
  • the measuring chamber 2 represents a PAS cell with at least one pressure sensor (microphone).
  • no optical filters are preferably used in the proposed detection device, since only specific spectral ranges from the broadband spectrum of the light source are automatically absorbed by the respective substance. This creates an acoustic wave that correlates with the concentration of the substance in question.
  • the medium 6 to be examined is passed through the measuring chamber 2 during the measurement and leaves it via a suitable outlet, as indicated by the arrow (or arrows) in the present figures.
  • FIG. 2 shows another example of a possible configuration of the proposed detection device, in which several measuring chambers 2 with associated separation columns 5 (GC1 to GCx) are used.
  • the separation performance of the detector device is increased by using several separation columns 5 with different chromatographic and column-specific characteristics.
  • the separation efficiency of a column depends on the column dimensions (diameter, length and film thickness), the type of carrier gas, the flow rate or the mean linear velocity, as well as the substances to be separated and their retention behavior.
  • the medium 6 to be examined is passed through a number of columns 5 at the same time.
  • the columns are preferably in an oven or heated individually. They can also be unheated.
  • At the exit of each column 5 there is a measuring chamber 2 with its own detector, for example. a MEMS microphone (as PAS cell ) . All chambers 2 are penetrated by the broadband light source 1 . This is possible because the optical attenuation per chamber is very low.
  • FIG. 3A shows another exemplary embodiment with a number of measuring chambers 2 .
  • the measurement chambers 2 are stacked one on top of the other in the same way as in the previous embodiment above the broadband light source 1 and are designed to be correspondingly transparent for the incident radiation 7 .
  • the measuring chambers 2 are all connected to a common separation column 5 (GC1).
  • the detection preferably takes place via one or more pressure sensors, for example Microphones on or in each measuring cell 2, ie using PAS cells.
  • the microphones integrated in the measuring chambers 2 are controlled in such a way that they measure at different, consecutive times. This allows the temporal resolution of the entire measurement to be increased, since substances with a similar retention time and thus partial overlapping of their signal peaks S1, S2 can be better separated, as indicated in FIG. 3B.
  • the gas chromatographic column 5, the measuring chamber 2 and the one or more detectors 3 can be completely planar, e.g. in semiconductor technology, are manufactured, as is the case, for example. is shown in highly schematic form in FIG.
  • the gas chromatographic column 5 and the measuring chamber 2 can be located on the same or on different substrates. This also applies to the one or more detectors 3 .
  • the radiation source 1 can be separated be trained .
  • the construction of the detection device can then take place as a 3D stack (3D stack).
  • FIG. 5 shows, in a highly schematic form, an exemplary embodiment with a PAS cell, in which one or more pressure sensors 8, for example Microphones are used in the measuring chamber 2 .
  • the light source for example. in the form of a MEMS radiation source, and possibly. a heating device (also possible without a heating device)
  • the gas chromatographic column 5 in the second substrate 11 the gas chromatographic column 5 and in the third substrate 12 the measuring chamber 2 with one or more pressure sensors 8, e.g. MEMS microphones, and the electronics 4 formed.
  • the gas chromatographic column 5 with the measuring chamber 2 in one substrate and the detectors 3 with the electronics 4 in another substrate. All of the substrates are stacked one on top of the other, as indicated in FIG.
  • the wafer from which the chips are formed is made of silicon, since silicon is transparent to IR light from the IR radiation source that is preferably used. There are other materials such as Ge possible that are sufficiently transparent for the light of the radiation source used.
  • each measuring chamber 2 there is in each case at least one detector, in particular a pressure sensor or Microphone for realizing a PAS cell.
  • at least one of the separating columns 5 can also be exposed to radiation 7 from the light source 1 .
  • FIG. 7 shows a further exemplary embodiment of the proposed detection device.
  • a multispectral light source is used, which allows an exposure wavelength or a narrow spectral range for exposure to be set.
  • a suitable filter arrangement 9 in the form of a filter array is arranged in connection with an optical switching device made up of an array of micromirrors between the broadband light source 1 and the measuring chamber 2 .
  • the broadband light emitted by the light source 1 is directed by the micromirrors in a targeted manner via specific filters of the filter array 9 onto the measuring chamber 2 .
  • quasi-monochromatic light 13 can be generated and used to irradiate the measuring chamber 2 .
  • This monochromatic light 13 can be tuned through the spectral range of the broadband light source 1 by appropriate control of the micromirror array or . vary and thus adjust specifically to specific wavelengths.
  • the use of such a filter arrangement 13 makes it possible to identify substances from media 6 to be examined which elute almost simultaneously (similar retention time).
  • the signals of these substances are superimposed.
  • Different wavelengths can be continuously tuned through the filter arrangement 9 and the multispectral light source obtained thereby, preferably in the infrared spectral range.
  • several substances with a similar retention time can be selectively measured at the same time by the detector or detectors, in particular in an embodiment of the measuring chamber as a PAS cell.

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  • Physics & Mathematics (AREA)
  • Acoustics & Sound (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Investigating Or Analysing Materials By Optical Means (AREA)

Abstract

La présente invention concerne un dispositif de détection pour chromatographie, en particulier pour chromatographie en phase gazeuse. Le dispositif comprend : au moins une source de rayonnement à large bande (1) ; une chambre de mesure (2) qui présente une entrée pour un milieu (6) à examiner, et dans lequel le rayonnement (7) provenant de la source de rayonnement (1) est couplé ; un dispositif de séparation chromatographique (5) devant l'entrée dans la chambre de mesure (2) ; et un ou plusieurs détecteurs (3) au moyen desquels un résultat d'une interaction entre le rayonnement (7) couplé dans la chambre de mesure (2) et un milieu introduit dans la chambre de mesure (2) peut être détecté. Le dispositif de détection peut être mis en œuvre à peu de frais et entièrement miniaturisé, par exemple sous la forme d'une pile de substrats.
PCT/EP2022/082442 2021-11-19 2022-11-18 Dispositif de détection pour chromatographie en phase gazeuse WO2023089114A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP22818722.5A EP4433819A1 (fr) 2021-11-19 2022-11-18 Dispositif de détection pour chromatographie en phase gazeuse

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE102021130276 2021-11-19
DE102021130276.5 2021-11-19
DE102022111570.4 2022-05-10
DE102022111570.4A DE102022111570A1 (de) 2021-11-19 2022-05-10 Detektionseinrichtung für die Chromatographie, insbesondere für die Gaschromatographie

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Citations (6)

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Publication number Priority date Publication date Assignee Title
US5900533A (en) * 1995-08-03 1999-05-04 Trw Inc. System and method for isotope ratio analysis and gas detection by photoacoustics
US5913234A (en) * 1996-11-05 1999-06-15 Orbisphere Laboratories Neuchatel S.A. Spectroscopic method and apparatus
WO2020250086A1 (fr) * 2019-06-10 2020-12-17 Consiglio Nazionale Delle Ricerche Système d'analyse chimique au moyen d'une séparation par chromatographie en phase gazeuse et d'une spectroscopie photoacoustique de mélanges d'échantillons
US10883929B2 (en) * 2017-07-21 2021-01-05 Serguei Koulikov Optical absorption spectroscopy based gas analyzer systems and methods
CN212301293U (zh) * 2020-06-24 2021-01-05 大连世有电力科技有限公司 一种基于光声光谱原理检测微量气体的模块化实验室设备
DE102021108745A1 (de) 2021-03-05 2022-09-08 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung eingetragener Verein Anordnung zur multispektralen Lichtemission sowie damit ausgestatteter Multispektralsensor

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Publication number Priority date Publication date Assignee Title
US5900533A (en) * 1995-08-03 1999-05-04 Trw Inc. System and method for isotope ratio analysis and gas detection by photoacoustics
US5913234A (en) * 1996-11-05 1999-06-15 Orbisphere Laboratories Neuchatel S.A. Spectroscopic method and apparatus
US10883929B2 (en) * 2017-07-21 2021-01-05 Serguei Koulikov Optical absorption spectroscopy based gas analyzer systems and methods
WO2020250086A1 (fr) * 2019-06-10 2020-12-17 Consiglio Nazionale Delle Ricerche Système d'analyse chimique au moyen d'une séparation par chromatographie en phase gazeuse et d'une spectroscopie photoacoustique de mélanges d'échantillons
CN212301293U (zh) * 2020-06-24 2021-01-05 大连世有电力科技有限公司 一种基于光声光谱原理检测微量气体的模块化实验室设备
DE102021108745A1 (de) 2021-03-05 2022-09-08 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung eingetragener Verein Anordnung zur multispektralen Lichtemission sowie damit ausgestatteter Multispektralsensor

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Title
GRAUNKE, T.SCHMITT, K.RAIBLE, S.WÖLLENSTEIN, J.: "Towards Enhanced Gas Sensor Performance with Fluoropolymer Membranes", SENSORS, vol. 16, 2016, pages 1605, Retrieved from the Internet <URL:https://doi.org/10.3390/s16101605>
J. LEE ET AL.: "Development of Open-Tubular-Type Micro Gas Chromatography Column with Bump Structures", SENSORS, vol. 19, no. 17, 2019, pages 3706

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