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WO2010054420A1 - Détecteur pour la mesure de gaz basiques - Google Patents

Détecteur pour la mesure de gaz basiques Download PDF

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Publication number
WO2010054420A1
WO2010054420A1 PCT/AT2009/000436 AT2009000436W WO2010054420A1 WO 2010054420 A1 WO2010054420 A1 WO 2010054420A1 AT 2009000436 W AT2009000436 W AT 2009000436W WO 2010054420 A1 WO2010054420 A1 WO 2010054420A1
Authority
WO
WIPO (PCT)
Prior art keywords
sensor
substrate
materials
concentration
relative humidity
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.)
Ceased
Application number
PCT/AT2009/000436
Other languages
German (de)
English (en)
Inventor
Peter Pacher
Alexandra Lex
Egbert Zojer
Christian Slugovc
Gregor Trimmel
Emil J. W. List
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Forschungsholding TU Graz GmbH
Technische Universitaet Graz
Original Assignee
Forschungsholding TU Graz GmbH
Technische Universitaet Graz
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
Application filed by Forschungsholding TU Graz GmbH, Technische Universitaet Graz filed Critical Forschungsholding TU Graz GmbH
Publication of WO2010054420A1 publication Critical patent/WO2010054420A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
    • G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
    • G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
    • G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
    • G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
    • G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
    • G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
    • G01N27/126—Composition of the body, e.g. the composition of its sensitive layer comprising organic polymers
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/0004—Gaseous mixtures, e.g. polluted air
    • G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
    • G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector
    • G01N33/0036—General constructional details of gas analysers, e.g. portable test equipment concerning the detector specially adapted to detect a particular component
    • G01N33/0054—Ammonia
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Definitions

  • the subject invention relates to a sensor for the quantifiable measurement of basic gases with a substrate, electrical contacts and at least one sensor layer - namely a sensor layer, which consists of a mixture of at least two sensor materials, or at least two sensor layers, each consisting of a sensor material.
  • the printed expiration date is therefore often set to minimize risks, which may result in e.g. due to the elapsed expiration date alone, food may be prematurely discarded or disposed of, resulting in high costs.
  • US Pat. No. 5,653,941 proposes a "food spoilage detector" with which a specific volume of gas is removed from a packaging and analyzed outside the packaging. This is to get information about the quality of the packaged food.
  • the disadvantage of this invention is that for an assessment of the condition of packaged food, the packaging must be punctured, which is costly and often unacceptable.
  • EP 0699304 Bl, US 6,576,474 and US 6,593,142 describe sensors with color indicators which use the change of color to detect ammonia or volatile amines.
  • US 6,593,142 describes a "food spoilage sensor” consisting of a polymer-containing transition metal complex with Ni 2+ and in contact changes its color with biogenic amines. This color change should be visible through the package. But since heavy metal ions such as Ni 2+ are toxic, they must not get into food, which greatly limits the use of this sensor.
  • the measurement of a resistance, inductance or capacitance is also possible for detecting ammonia or volatile amines.
  • the readout value can not be read out directly at the sensor, but only at a connected readout system.
  • Such a readout system may be permanently connected to the sensor or it may only be brought into contact therewith for reading, such as checking a packaged foodstuff.
  • a further problem with sensors for basic gases is the humidity of the gas mixture to be measured (the indication of this moisture is hereinafter referred to as% relative humidity, in short% RH, at 25 ° C).
  • a sensor must function reliably for the widest possible range of relative humidities or partial pressures of water. For example, to monitor medication, a sensor must operate in very dry conditions, such as in the range of 0% RH to 15% RH. In the monitoring of packaged meat, however, higher and above all variable relative humidities can occur. Therefore, another important requirement of sensors is that they are able to detect basic gases even over as wide a range of variable humidity as possible.
  • Polyaniline PANI
  • PANI / PSS polyaniline / poly (styrenesulfonate)
  • PEDOT poly (3,4-ethylenedioxythiophene)
  • PDOT poly (3,4-ethylenedioxythiophene)
  • PDOT Poly (3,4-ethylenedioxythiophene)
  • transverse effect In practical application, the problem arises that it can not be distinguished whether the measurement signal results from the change in relative humidity or the presence of a basic gas, since both lead to a similar effect, namely the change in the electrical resistance , This effect is referred to below as transverse effect.
  • a sensor based on PANI describes the US 5,252,292. According to this patent, the sensor should also function in the presence of gases Bb, CO, NO, and O2; however, no measures and precautions are described to avoid or remedy the known critical influence of moisture (H2O). Also, the experimental findings in this patent show no indication of the versatility of the sensor.
  • the invention proposes for the detection of basic gases (such as ammonia and / or volatile amines, or amines with high vapor pressure, for example methylamine, ethylamine, propylamine, iso-propylamine, dimethylamine, diethylamine, trimethylamine, triethylamine, pyridine and / or volatile phosphines, or phosphines with high vapor pressure such as phosphine or trimethylphosphine) a sensor, in particular bifunctional sensor, from an organic sensor material with a sensor layer of PANI and / or PANI / PSS and / or PEDOT / PSS and a method for signal evaluation whereby basic gases (such as ammonia and / or volatile amines and / or volatile phosphines) can be advantageously measured even in the presence of atmospheric moisture.
  • basic gases such as ammonia and / or volatile amines and / or volatile phosphines
  • basic gases such as ammonia and / or volatile amines and / or volatile phosphines
  • the sensor materials of the sensor layer (s) consist of polymers whose respective electrical resistance changes differently when exposed to a change in the concentration of a basic gas and / or the relative humidity .
  • the various sensor materials can be arranged side by side on different regions of the substrate and, together with at least two of the contacts, form sensor elements with different sensitivity characteristics.
  • the invention relates to a sensor for the detection and determination of basic gases (such as ammonia and / or volatile amines and / or volatile phosphines) with simultaneous measurement of atmospheric moisture, using an organic sensor material.
  • the sensor is advantageously suitable for monitoring technical installations and for determining and evaluating the breakdown of protein in stored and / or packaged foods, such as, for example, meat, fish or other food and feed.
  • the invention also relates to a bifunctional sensor for the qualitative and quantitative measurement of the concentration of basic gases and moisture, which the detected concentrations by means of RF technology through gas-tight packaging, such as through to an external receivers. ger.
  • the measurement of the concentration of basic gases can also be used to monitor and / or check feed, food, hygiene products, body fluids, tissues, other biological materials, or medicines.
  • the sensor according to the invention can be produced in various ways. It can be particularly advantageous and inexpensive, e.g. be applied by an inkjet printer, an offset printing machine or similar device on substrates such as circuit boards, glass, silicon wafer, cardboard, paper, fabric or flexible films, semi-permeable membranes and also directly on or in product packaging.
  • the sensor materials involved can consist of different batches of the materials PEDOT / PSS or PANI / PSS.
  • the sensor materials may have a resistivity at 60% relative humidity and 25 ° C temperature, which is less than 1 ⁇ cm for at least one sensor material and more than 10 ⁇ cm for at least one other sensor material.
  • the sensor layers may in particular have a thickness between 1 nm and 500 nm.
  • the material of the substrate may preferably be selected from the group consisting of silicon wafer, glass, foil, solid polyethylene.
  • the material of the substrate may preferably be selected from the group consisting of: paper, cardboard, foil, flexible polyethylene, semipermeable membranes.
  • antennas and / or coils can be connected to the electrical contacts.
  • the electrical contacts can be formed as Interdigitalstruk- tures.
  • Another aspect of the invention relates to a packaging for a product, in particular for food, medicines, hygiene articles or animal feed, with a sensor according to the invention as described above.
  • at least the substrate of the sensor can be part of the packaging.
  • Another aspect of the invention relates to a method of making a sensor or package of the type described above in which the sensor's electrical contacts and / or the sensor materials of the sensor are applied by inkjet, offset, or other printing techniques.
  • a plurality of sensor elements can be generated, the sensor materials are applied in the form of different sensor elements for each different number of printed lines.
  • Another aspect of the invention relates to a use of a sensor according to the invention or a package according to the invention for determining the concentration of basic gases and the relative humidity with the steps: measuring the resistance of the sensor layers of the sensor, and determining the concentration of the basic gas and the relative humidity of the Resistance measurement and, if necessary, reading out the concentration values with a read-out device which uses RF technology to transmit these values.
  • the senor or packaging it may be brought into contact with a feed, food or hygiene product, body fluid, tissue or other biological material, or drug.
  • the sensor or packaging may be separated from a feed, food or hygiene product, body fluid, tissue or other biological material, or drug only by a semi-permeable gas membrane.
  • This semipermeable gas membrane can also serve as the substrate of the sensor.
  • FIG. 1 shows a cross section of a sensor according to a first embodiment of the invention.
  • FIG. 2 shows the sensor of FIG. 1 in a plan view
  • FIG. 3 shows a further embodiment, wherein for the realization of the bifunctional sensor according to the invention, the sensor layers are applied in the form of a plurality of webs;
  • FIG. 4 shows a third embodiment of the invention with a sensor layer, which consists of two different sensor materials with different resistivities;
  • FIG. 5 shows a block diagram for a sensor structure with measuring device
  • 6 and 7 show the measured resistances of the two sensor elements of a bifunctional sensor in the manner of the one shown in Figure 1 as a function of time.
  • FIG. 9 and 10 each show a time-dependent measurement of the two sensor elements of a sensor according to FIG. 1 for various compositions of the surrounding gas atmosphere;
  • Figures 11 and 12 show the time-dependent course of the ammonia concentration (% BG) and the humidity (% RH), respectively, calculated from the measurements shown in Figures 9 and 10;
  • 13 and 14 each show the measured course of the electrical resistance of two sensor elements of an embodiment of the sensor according to the invention with successive, brief exposure of the sensor to 0.7 ppm of ammonia and subsequent rinsing.
  • a first embodiment of the invention is shown in a schematic cross section.
  • the sensor 100 has two sensor elements 101 and 102 with dripped sensor layers 130, 131, which each consist of a sensor material on. 2 shows the arrangement of the sensor 100 in the plan view.
  • electrical contacts 120 are applied to a substrate 110 in a known manner for each sensor element 101, 102 and covered with the sensor materials of the sensor layers 130, 131 according to the invention.
  • the electrical contacts 120 with the two sensor layers 130, 131 form two sensor elements 101, 102 of the sensor 100 with different sensitivity characteristics.
  • the sensor layers 130, 131 has the task of covering the electrical contacts 120 in a conducting manner and at a change in the concentration of a basic gas - which contains, for example, ammonia and / or volatile amines and / or volatile phosphines - as well as simultaneous action or change in the relative humidity of the gas surrounding the sensor atmosphere 150 to address that of resistance and / or capacitance and or Ihdukt foundeds horren the change in the ammonia and / or amine content can be determined and the cross-sensitivity is corrected to moisture.
  • a basic gas - which contains, for example, ammonia and / or volatile amines and / or volatile phosphines - as well as simultaneous action or change in the relative humidity of the gas surrounding the sensor atmosphere 150 to address that of resistance and / or capacitance and or Ihdukt foundeds horren the change in the ammonia and / or amine content can be determined and the cross-sensitivity is corrected to moisture.
  • the substrate 110 may be a solid substrate such as silicon, silicon oxide, glass, a circuit board, a cardboard.
  • the electrical contacts in addition to the usual manufacturing methods, may also be specially applied by inkjet printing and offset printing in the form of conductive liquids (e.g., conductive silver).
  • a flexible material for example, a plastic film or a semipermeable film or membrane, cloth, or paper may be used. All usable substrate materials may also be parts of a package.
  • the sensor layers 130, 131 are both made of PEDOT / PSS with different resistivities.
  • the cross-sensitivity to moisture can be minimized or corrected, in particular in the case of a combination of PEDOT / PSS as sensor materials, if a first sensor material has a specific conductivity of less than 1 ⁇ cm (preferably less than 0.1 ⁇ cm) and a second sensor material has a specific conductivity of greater than 10 ⁇ cm , preferably greater than 100 ⁇ cm. This can be achieved, for example, by using the commercially available products Baytron PH 500 (with a specific resistance of approx.
  • both materials used as sensor materials show an increase in their electrical resistance. Surprisingly, however, it has been shown that the electrical resistances of both materials change differently on contact with moisture. Extensive tests have shown that the electrical resistance of the material with the originally lower resistivity increases with an increase in humidity, whereas it decreases with the originally higher resistivity material.
  • the present invention exploits this surprising property of determining basic gases at the same time as the relative humidity.
  • the sensor materials can be applied by drop-casting, spin-coating or a printing process such as ink-jet or offset printing.
  • the on-substrate electrical contacts 120 may be applied by conventional techniques or by methods such as inkjet and offset printing. Two or more electrical contacts are used per sensor element. These can be formed in a further exemplary embodiment as so-called interdigital structures (see FIGS. 3 and 4).
  • FIG. 3 shows a plan view of a further exemplary embodiment of the bifunctional sensor 300 according to the invention with two sensor elements 301, 302.
  • This sensor can be produced for example by inkjet printing or a similar method, and is characterized in that the sensor layers 330, 331 in the form of a or multiple lines, stripes or webs 333 are applied to the substrate 310.
  • the electrical contacts 320 may be implemented as hiterdigital Modellen or as branched contact paths.
  • This embodiment of the electrical contacts 320 and the sensor layers 330, 331 has the advantage that the resistance between the electrical contacts 320 can be advantageously adjusted by the number and / or width of the covering lines or tracks 333 of the sensor material.
  • the concentrations to be determined namely the percentages of the proportion of basic gases (% BG) and of the moisture content (% RH), can be calculated. This happens, for example, according to the equations:
  • the calibration functions Gl (Rl 7 RZ) and G2 (R1, R2) are determined by reference measurements which, for example, can be performed once for the sensor.
  • the bifunctional sensor 400 consists of only one sensor element with contacts 420 and a sensor layer 430, which, however, has two different sensor materials 440, 441 with different resistivities. These materials can be applied as lines in various numbers on the substrate 410 and contacts 420, for example by inkjet printing, whereby the individual resistances and the total resistance can be set advantageously.
  • the sensor materials of the sensor layer 430 are chosen such that they exhibit an opposite change in the resistance with varying humidity, whereas a same-direction change of the resistance in the presence of a basic gas.
  • the For example, two sensor materials are applied by inkjet or offset printing. The mixing ratio must be determined once to achieve the desired compensation in terms of water content.
  • Another aspect of the invention relates to the combination of the sensor elements according to the invention with an electronic circuit, which measures the resistances of the individual sensor layers. This resistance measurement is also linked to a concentration analyzer.
  • Fig. 5 shows a block diagram for a sensor assembly with measuring device, for example, for a sensor of Figures 1 and 2. Of course, this could also be another sensor according to the invention can be used.
  • the electrical contacts 120 of the two sensor elements 101 and 102 of the sensor 100 are led to a differential resistance measuring block 210.
  • This measurement block transmits the resistance values to a concentration analyzer 220 and the results are forwarded as concentrations via an output module 230.
  • Figures 6 and 7 show the measured resistances R of two sensor elements 101 and 102, respectively, of a bifunctional sensor 100 according to the invention as a function of time t (indicated in hours, e.g., 01:00 means one hour).
  • the two sensor elements 101 and 102 have been produced from the aforementioned materials Baytron PH 500 (FIG. 6) and Baytron P VP AI 4083 (FIG. 7).
  • the sensor 100 is in an ambient atmosphere (reference numeral 150 in FIG. 1) of pure, dry argon gas.
  • Multiple exposure of the sensor to 78 ppm of ammonia for 5 minutes in each case increases the electrical resistance of both sensor elements by leaps and bounds. After switching off the ammonia, the electrical resistance decreases again.
  • the sensor 100, or more precisely the sensor elements 101 and 102 show a good reversibility.
  • FIGS. 9 and 10 show measurements with a sensor having two sensor elements according to FIG. 1.
  • the course of the electrical resistance R 1 of a first sensor element based on the comparatively low-resistance sensor material Baytron PH 500 (in the figure: "PH500”) is shown in FIG 9 shows the course of the electrical resistance R2 of a second, comparatively high-impedance sensor element based on the sensor material Baytron P VP AI 4083 (in the figure briefly: "4083”) is shown in FIG.
  • Both figures show the measured course of the electrical resistance of the sensor elements as a function of time t (in hours). The time is divided into sections in Figs. 9 and 10 which correspond to successive phases 1-4 of the experiment.
  • the measured data show the result for phases 1 to 4 for various compositions of the surrounding gas atmosphere 150.
  • the sensor is surrounded by argon (with ⁇ 10% RH) in phase 3, which leads to a decrease of the electrical resistance in one sensor element (R1, FIG. 9), in the case of the further sensor element (R2, Fig. 10) to an increase.
  • ammonia concentration (% BG) and the relative humidity (% RH) can now be determined from the measured resistances R 1 of the first sensor element (101) and R 2 of the second sensor element (102):
  • the value of% BG (here as a size BG proportional to the ammonia concentration) is plotted, and here no cross-sensitivity to the variable relative humidity is to be seen. In contrast, in FIG. 12, the value% RH is plotted. Here is no. Detect influence of a variable ammonia concentration.
  • An expedient embodiment is characterized in that the angle between the vectors (a, b) and (d, e) is more than 10 °. This facilitates the evaluation in practice because it improves the discrimination between the basic gas and the relative humidity. This is achieved by the following two points:
  • the choice of the two sensor layers is such that the selected sensor materials show an opposite change in the resistance at varying humidity, however, a same-direction change in resistance in the presence of a basic gas. In the case described above, this means that e.g. a and d have different signs, while b and e have the same sign.
  • the adjustment of the angle is done by special choice of the distance d of the electrical contacts 120 and / or by choosing different cross sections A in the sensor materials. This changes according to the known formula the measured electrical resistance R with:
  • this calculation takes place in the concentration analyzer 220 (FIG. 5). This further passes on the determined values of% BG and% RH to an output module 230.
  • this output module is an RF transmission module so that the read-out of the values of% BG and% RH can take place without interruption. This makes it possible to integrate the entire sensor 100, 300, 400 in a package, so that it is visually hardly noticeable from the outside.
  • the advantage of the sensor according to the invention is that the sensor can be applied within a package, so that the already familiar from the consumer optics packaging must not be changed. Furthermore, the resulting sensor due to the good printability of the materials used is low and at the same time precisely produced. The simple adjustment of the total resistance by varying the number of printed lines is another significant advantage of the present invention.
  • Example 1 Preparation of an ammonia sensor on a silicon wafer
  • the substrate used is two pieces of silicon wafer (size 1 cm x 1 cm). Their surface is hydrophilized by plasma etching (30 seconds oxygen plasma) and purification in distilled water in an ultrasonic bath. Thereafter, a PEDOT / PSS Baytron PH 500 sensor layer is applied to the first substrate by spin-coating (first sensor material). On the second substrate, a sensor layer PEDOT / PSS Baytron P VP AI 4083 is applied (second sensor material). Thereafter, gold electrodes are vapor-deposited in vacuo (electrode spacing 25 ⁇ m, thickness of the gold layer 30 nm), which serve as electrical contacts (120).
  • Example 2 Preparation of an ammonia sensor on a polyethylene film
  • the substrate used is two sheets of polyethylene (PE) (size 1 cm x 1 cm).
  • the further preparation is carried out as in Example 1.
  • Example 3 Production of an ammonia sensor on a printed circuit board
  • the substrate selected is a copper-coated printed circuit board.
  • a photoresist By applying a photoresist, its exposure and development and subsequent etching in iron (III) chloride solution are obtained mutually insulated copper contacts, which serve as electrical contacts.
  • iron (III) chloride solution By simply dripping from a pipette, the sensor materials of the type described in Example 1 are applied.
  • Example 4 Production of an ammonia sensor by ink jet printing on a PE film
  • the substrate used is a PE film (size 5 cm x 5 cm). Its surface becomes hydrophilic by plasma etching (30 seconds oxygen plasma) and purification in distilled water in the ultrasonic bath.
  • interdigital structures serving as electrical contacts are printed using a multinozzle ink-jet printer (material is a silver ink). Via the contacts of the interdigital structure, a variable number of lines of the sensor materials PEDOT / PSS Baytron PH 500 or PVP AI 4083 are applied by means of the Singlenozzle inkjet printer. Both materials were diluted with water 2: 1 before printing. 16 sensors are placed on the substrate, 8 each with each sensor material.
  • Example 5 Manufacture of a sensor suitable for reading by means of RF technology
  • the sensor obtained in Example 4 is connected to a commercial circuit for contactless signal transmission.

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  • Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)

Abstract

L'invention concerne un détecteur (100) pour la mesure quantifiable de gaz basiques, qui comporte un substrat (110), des contacts électriques (120), ainsi qu'une couche de détection, qui est constituée d'un mélange d'au moins deux matériaux de détection, ou au moins deux couches de détection, qui sont chacune constituées d'un matériau de détection. Les matériaux de détection de la ou des couches de détection (130, 131) sont constitués de polymères, dont la résistance électrique respective se modifie différemment lorsqu'ils sont exposés à une modification de la concentration d'un gaz basique et/ou de l'humidité relative. Les différents matériaux de détection peuvent être placés les uns à côté des autres sur différentes zones du substrat, et forment chacun avec au moins deux des contacts (120) des éléments de détection (101, 102) à caractéristique de sensibilité différente.
PCT/AT2009/000436 2008-11-14 2009-11-13 Détecteur pour la mesure de gaz basiques Ceased WO2010054420A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ATA1775/2008 2008-11-14
AT0177508A AT507467B1 (de) 2008-11-14 2008-11-14 Bifunktionaler gassensor für basische gase

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WO2010054420A1 true WO2010054420A1 (fr) 2010-05-20

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EP2469272A1 (fr) * 2010-12-22 2012-06-27 Nederlandse Organisatie voor toegepast -natuurwetenschappelijk onderzoek TNO Capteur d'acide/base
CN113984850A (zh) * 2021-11-02 2022-01-28 西华大学 二维黑磷修饰聚苯胺的氨气传感器、制备方法及测试系统
US20240319129A1 (en) * 2023-03-22 2024-09-26 Peking University Methane sensor
US12326432B2 (en) 2020-05-06 2025-06-10 Blakbear Ltd Electrical sensing of gases in packaged products and monitoring freshness or condition of perishable products

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