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    • 专利摘要:
    The invention relates to a method for calibrating an electronic nose, said electronic nose comprising a plurality of optical sensors arranged on a surface and in contact with a gaseous medium of interest, said optical sensors being capable of delivering a signal representative of the local optical index of the gaseous medium when they are excited by photons, the method being characterized in that it comprises the following steps: a) emitting photons in the direction of the sensors; b) measuring the signal delivered by each of the sensors, this measurement providing as many responses as there are sensors; c) modifying the pressure and/or the temperature of the gaseous medium; d) repeating step b); and e) for each sensor, determining a corrective factor such that a signal variation between steps d) and b) corrected by said corrective factor is equal or substantially equal to a signal variation between these same steps for a reference, this reference being provided by a reference sensor or a combination of reference sensors. Such a method makes it possible to carry out a relative calibration between the various sensors.
    公开号:FR3063543A1
    申请号:FR1751751
    申请日:2017-03-03
    公开日:2018-09-07
    发明作者:Cyril HERRIER；Yanxia Hou-Broutin；Francois-Xavier Gallat；Thierry Livache；Tristan Rousselle
    申请人:Centre National de la Recherche Scientifique CNRS；Commissariat a lEnergie Atomique CEA；Universite Grenoble Alpes；Aryballe Technologies SCA；Commissariat a lEnergie Atomique et aux Energies Alternatives CEA；
    IPC主号:
    专利说明:

    Holder (s): COMMISSIONER OF ATOMIC ENERGY AND ALTERNATIVE ENERGY, NATIONAL CENTER FOR SCIENTIFIC RESEARCH, GRENOBLE ALPES UNIVERSITY, ARYBALLE TECHNOLOGIES.
    Extension request (s)
    Agent (s): GEVERS & ORES.
    METHOD FOR CALIBRATION OF AN ELECTRONIC NOSE.
    FR 3,063,543 - A1 (6 /) The invention relates to a method for calibrating one between the various sensors, electronic nose, said electronic nose comprising a plurality of optical sensors arranged on a surface and in contact with a gaseous medium d interest, said optical sensors being capable of delivering a signal representative of the local optical index of the gaseous medium when they are excited by photons, the method being characterized in that it comprises the following steps:
    a) emit photons towards the sensors;
    b) measuring the signal delivered by each of the sensors, this measurement providing as many responses as there are sensors;
    c) modify the pressure and / or the temperature of the gaseous medium;
    d) repeat step b); and
    e) for each sensor, determining a corrective factor such that a variation of the signal between steps d) and b) corrected by said corrective factor is equal or substantially equal to a variation of the signal between these same steps for a reference, this reference being provided by a reference sensor or a combination of reference sensors.
    Such a method makes it possible to carry out a relative calibration
    CALIBRATION PROCESS OF AN ELECTRONIC NOSE
    The invention relates to a method for calibrating an electronic nose.
    An electronic nose generally includes several sensors, aimed at recognizing the presence of a target compound, for example a chemical or biological analyte, in a gas sample.
    The sensors are generally not specific to a particular target compound. Also, in a given application, a comparison is generally made of the data supplied by the various sensors of the electronic nose, which provide a recognition imprint, to reference data, for example from prior learning for the target compound in question.
    A known technique for obtaining, in use, a recognition imprint is surface plasmon resonance imaging (better known by the acronym SPR for "Surface Plasmon Resonance"). This technique makes it possible to detect a local change in optical index (optical index - refractive index) which characterizes the interaction of the target compound with each sensor of the electronic nose.
    However, insofar as the chemical affinities of each sensor of the electronic nose vis-à-vis a given target compound are not known a priori and only the imprint of all the sensors is taken into account for the recognition of the target compound, it is necessary that each sensor responds in a reproducible manner with respect to each other and from one experiment to another. Similarly, it is necessary that different electronic noses, namely in particular from different manufacturing batches, can give reproducible responses.
    These same reproducibility difficulties are encountered with sensors designed to be specific to a particular target compound,
    Otherwise, it is not possible to obtain a reliable recognition imprint capable of being compared to the reference data.
    Indeed, although all the necessary care is taken in the manufacture of an electronic nose, the sensors present slight differences compared to their ideal design.
    There are already several techniques for calibrating an electronic nose.
    A first technique is proposed in the Permapure documentation of June 14, 2016, entitled "Gas Sensor Calibration" accessible on the site http://www.permapure.com/wp-content/uploads/2013/01/calibration.pdf, from book "Air Monitoring for Toxic exposure", Henry J. McDermott, 2 nd edition, 2004, John Wiley & Sons Inc., pp. 161-173 (D1).
    In this technique, the calibration is carried out by injecting a gas comprising a reference organic compound.
    A second technique consists in using a prediction model after injection of a reference organic compound at different concentrations. This is what is proposed by Tian & ai., "On-line calibration of semiconductor gas sensors based on, prediction model", J. of computers, vol. 8, p. 2204, September 2013 (D2).
    For these two techniques, the stimulus common to all of the sensors is therefore based on a reference organic compound. We are talking about chemical calibration.
    In addition and in practice, if one wishes to obtain a versatile electronic nose, then several reference organic compounds are provided.
    However, with these techniques, it can happen, depending on the concentration of the reference organic compound, or when switching from one reference organic compound to another, that there are distinct affinities of the various sensors of the electronic nose.
    This is then harmful for the quality of the calibration.
    Furthermore, this type of calibration is not very practical since it is sometimes necessary to have with you the various reference organic compounds.
    An objective of the invention is thus to propose a method for calibrating an electronic nose which does not have at least one of the aforementioned drawbacks.
    To achieve this objective, the invention proposes a method for calibrating an electronic nose, said electronic nose comprising a plurality of optical sensors arranged on a surface and in contact with a gaseous medium of interest, said optical sensors being capable of delivering a signal representative of the local optical index of the gaseous medium when they are excited by photons, the method being characterized in that it comprises the following steps:
    a) emit photons towards the sensors;
    b) measure the signal delivered by each of the sensors, this measurement providing as many responses as there are sensors;
    c) modify the pressure and / or the temperature of the gaseous medium;
    d) repeat step b); and
    e) for each sensor, determining a corrective factor such that a variation of the signal between steps d) and b) corrected by said corrective factor is equal or substantially equal to a variation of the signal between these same steps for a reference, this reference being provided by a reference sensor or a combination of reference sensors.
    The method according to the invention may include at least one of the following characteristics, taken alone or in combination:
    - Prior to step a), the pressure P o and / or the temperature T o of the gaseous medium is determined;
    - the measurement carried out in step b) or d), for example a reflectivity or transmittivity measurement, is carried out over a period of between 0.1s and 60mn, preferably between 1s and 10mn, then averaged;
    - before implementing step e), steps c) and d) are repeated N times, with N a natural integer greater than or equal to 1, so that the pressure and / or the temperature of the gaseous medium is different a pressure and / or a temperature of the gaseous medium for which a measurement has already been made;
    - during step c), the pressure of the gaseous medium and / or the temperature is modified to another known value;
    - in step c), the pressure of the gaseous medium is modified by a value between + 10mbar and + 2bar, preferably between + 50mbar and + 150mbar or by a value between -10mbar and -QOQmbar, preferably between -50mbar and -150mbar; and / or the temperature of the gaseous medium is modified by a value between + 1 ° C and + 100 ° C, preferably between + 5 ° C and + 15 ° C or between -1 ° C and -50 ° C, preferably between -5 ° C and -15 ° C;
    - just before step e), an additional step is implemented which consists in modifying the pressure and / or the temperature of the gaseous medium to the initial pressure (Po) and / or the initial temperature (To);
    the optical sensor is chosen from a piasmon effect sensor, for example on a flat surface, optical fiber or nanocavities or a sensor capable of operating by refractometry, for example a resonator sensor.
    To achieve this same objective, the invention also proposes a method for calibrating an electronic nose, said electronic nose comprising a plurality of optical sensors arranged on a surface and in contact with a gaseous medium of interest, said optical sensors being capable to deliver a signal representative of the local optical index of the gaseous medium when they are excited by photons, the method being characterized in that it comprises the following steps:
    A) determine the pressure Po and the temperature T o of the gaseous medium MG;
    B) emit photons towards the optical sensors;
    C) measure the signal delivered by each of the optical sensors, this measurement providing as many responses as there are optical sensors;
    D) modify the pressure and / or the temperature of the gaseous medium MG towards another or other known values;
    E) repeat step C); and
    F) for each sensor, calculate the evolution of the optical index of the gaseous medium using the measurements made in steps C) and E).
    This method according to the invention may include at least one of the following characteristics, taken alone or in combination;
    - before step A), the pressure and / or the temperature of the gaseous medium are adjusted to a predetermined value;
    - the measurement carried out in step C) or E), for example a reflectivity or transmittivity measurement, is carried out over a period of between 0.1s and 60mn, preferably between 1s and 10mn, then averaged;
    - before implementing step F), steps D) and E) are repeated N times, with N a natural integer greater than or equal to 1, so that the pressure or, as the case may be, the temperature of the medium gaseous is different from a pressure or according to the case of a temperature of the gaseous medium for which a measurement has already been made;
    - in step D) the pressure of the gaseous medium is modified by a value between + 10mbar and + 2bar, preferably between + 50mbar and + 150mbar or by a value between -10mbar and -900mbar, preferably between -50mbar and -150mbar; and / or the temperature of the gaseous medium is modified by a value between + 1 ° C and + 100 ° C, preferably between + 5 ° C and + 15 ° C, or between -1 ° C and -50 ° C , preferably between -5 ° C and -15 ° C;
    - Just before step F), an additional step is implemented consisting in modifying the pressure and / or the temperature of the gaseous medium at the initial pressure (P o ) and / or the initial temperature (To);
    the optical sensor is chosen from a plasmon effect sensor, for example on a flat surface, optical fiber or nanocavities, or a sensor capable of operating by refractometry, for example a resonator sensor.
    Other characteristics, objects and advantages of the invention will emerge on reading the description made with reference to the appended figures given by way of example, and in which;
    - Figure 1 shows a possible installation for implementing a method according to the invention, based on a reflectivity measurement and a pressure change of the gaseous medium associated with the electronic nose;
    - Figure 2 is a typical image generated by the above installation on which is visible the sensors of the electronic nose;
    - Figure 3 shows results of reflectivity measurement performed with the installation of Figures 1 and 2, with dry air as the gaseous medium;
    FIG. 4, which includes FIGS. 4 (a) to 4 (c), represents an application case capable of being carried out with the installation of FIGS. 1 and 2, with a gaseous medium comprising air ( dry) and ethanol, serving as an analyte;
    - Figure 5 shows a variant of the installation of Figures 1 and 2 to implement a method according to the invention, based on a reflectivity measurement and a temperature change of the gaseous medium associated with the electronic nose;
    - Figure 6 shows another variant of the installation of Figures 1 and 2 to implement a method according to the invention, based on a measurement in transmittivity and a change in pressure and temperature of the gaseous medium associated with the electronic nose .
    FIG. 1 represents an example of an experimental installation 100 making it possible to implement the method for calibrating an electronic nose according to the invention.
    This experimental installation 100 comprises a light source 10, for example an LED, capable of emitting a given wavelength, an electronic nose 20 and an optical probe 30, for example a CCD camera. A lens L1 and a polarizer P can be provided between the light source 10 and the electronic nose 20. A lens L2 can also be provided between the electronic nose 20 and the optical probe 30.
    It will be noted that the optical probe 30 is arranged on the same side of the metal layer 21 as the light source 20. This experimental installation 100 therefore makes it possible to carry out measurements in reflection.
    The electronic nose 20 comprises a metallic layer 21, in this case made of gold (Au), planar. The electronic nose 20 also comprises a plurality of sensors Ci, C N arranged on a first face F1 of said metal layer 21 so that said first face F1 of the metal layer 21 and said sensors are in contact with a gaseous medium, by nature dielectric. The electronic nose 20 also includes a support 22 for said metal layer 21. The support 22 is arranged against a second face F2 of the metal layer 21, said second face F2 being opposite to said first face F1. In general, the support 22 is chosen from a dielectric material, transparent at the wavelength that the light source 10 is intended to emit and having an optical index ns greater than the optical index n <s of the gaseous medium ( optical index = refraction index). In this case, it is a prism, made of glass. Another thin metal layer (not shown), for example made of Chrome (Cr), is provided between the second face F2 of the metal layer 21 and the support 22 to ensure the attachment of the metal layer 21 on the support 22.
    Such an installation 100 makes it possible to generate a plasmon resonance at the level of the first face of the metal layer 21 which is in contact with the gaseous medium. More precisely, if the angle of incidence between the direction of propagation of the light beam FL and the normal to the metal layer 21 is defined, the following relationship can be defined:
    or :
    ns is the refractive index of the support 22, is the permittivity of the metal forming the metal layer 21
    E g is the permittivity of the gaseous medium MG, and
    6 r is the angle of incidence of plasmon resonance.
    The relation (R1) implicitly involves the wavelength of the light beam FL emitted by the optical source 10. Indeed and for example, the optical index ne of the gaseous medium MG and therefore its permittivity ε 3 depend on the length d 'wave.
    Thus, for a given wavelength of the light beam FL, for a given metallic layer 21 (nature of the metallic material) and for a given gaseous medium MG, there is an angle of incidence Q R as defined above, which allows to get the plasmon resonance.
    This experimental installation 100 therefore takes up the characteristics of Kretschmann's configuration,
    The manufacture of such a Kretschmann configuration is known to those skilled in the art and is therefore not specified. However, reference may be made to the article by Guedon & al. titled “Characterization and Optimization of a Peal-Time, Parallel, Label-Free, Polypyrolle based DNA Sensorby Surface Plasmon Imaging”, Anal. Chem., 2000, vol. 72, pp. 6003-6009 for more information.
    In this case, the plasmon resonance makes it possible to induce a plasmon wave at the interface between the metal layer and the gaseous medium, the amplitude of which makes it possible to observe with good sensitivity local variations in optical properties, such as a variation of optical index or a variation of reflectivity. Also, in the case of plasmon resonance, the signal delivered by the sensors Ci, ..., Cn may in particular be representative of a variation in reflectivity.
    The applicant was able to perceive that it was possible, with the experimental installation 100, to carry out a calibration, in this case relative, of the sensors, by varying the pressure and / or the temperature of the gaseous medium MG.
    By relative calibration, it is necessary to understand a calibration of the sensors with respect to each other, and more precisely by choosing a sensor as a reference or a combination of sensors as a reference, the other sensors then being calibrated with respect to this reference sensor or this combination of sensors as reference. In this relative calibration, there is always a common stimulus, as this is necessary to ensure an identical response from all of the sensors. This common stimulus is in this case the pressure and / or the temperature of the gaseous medium MG. However, exact knowledge (value) of the common stimulus is not necessary to perform a relative calibration.
    On the other hand, this relative calibration does not make it possible to calibrate the electronic nose to ensure that in use (that is to say after calibration and to detect for example the presence of a particular target compound), the use of a device of the Kretschmann configuration type will provide absolute values of a variation of local optical index making it possible to characterize this particular target compound.
    However, chemical calibration can be carried out upstream, for example in the factory. This chemical calibration can in particular be carried out by a known technique, such as that described in document D1 or D2.
    In this case, the relative calibration carried out within the framework of the invention will certainly allow the electronic nose to be calibrated so that it is usable.
    The experimental installation 100 was more precisely designed to ensure a common pressure stimulus. To this end, the metal layer 21 and its sensors are housed in a chamber 40 comprising an inlet E and an outlet S. The outlet S is connected to a pump 50 making it possible to supply the chamber with a perfectly controlled gas flow. This means that the gas flow is controlled, namely known, to obtain a laminar gas flow in the chamber. There is indeed a link between the pressure and the speed of the gas flow. Typically, we can rely on Bernoulli's relation in the case of a Newtonian fluid.
    A first method according to the invention is a method for calibrating an electronic nose, said electronic nose 20 comprising a plurality of optical sensors arranged on a surface and in contact with a gaseous medium of interest, said optical sensors being able to deliver a signal representative of the local optical index of the gaseous medium when they are excited by photons, the method being characterized in that it comprises the following steps:
    a) emit photons towards the optical sensors;
    b) measure the signal delivered by each of the optical sensors, this measurement providing as many responses as there are optical sensors;
    c) modify the pressure and / or the temperature of the gaseous medium;
    d) repeat step b); and
    e) for each sensor, determining a corrective factor such that a variation of the signal between steps d) and b) corrected by said corrective factor is equal or substantially equal to a variation of the signal between these same steps for a reference, this reference being supplied by an optical reference sensor or a combination of optical reference sensors.
    This first calibration process makes it possible to implement a relative calibration.
    An example is presented below, in which this first method is implemented with the experimental installation 100,
    Figure 2 is a view of the metal layer 21 and its sensors Ci, .... C N.
    The metallic layer 21, produced in Gold, has a complex permittivity s m , at the wavelength of 632nm, which is expressed e m = ε Γ + / '* £, · = -11.6 + i * 1 , 5 (with i 2 = -1).
    In addition, the optical sensors are all trained by the technique proposed by Hou & a!., "Continuous evolution profiles for electronic-tongue-based analysis", Angewandte Chem. Int. Ed. 2012, vol. 51, pp. 10394-10398; with decanthiol for example The optical sensors obtained after functionalization of their surface then all have a round shape.
    Measurements can be made for all of the sensors. However, for the sole purpose of demonstration, it was chosen here to select only four of them. This can be easily done by providing a mask to cover the sensors for which one does not wish to obtain a response during the calibration.
    The gaseous medium MG is dry air.
    The pressure and temperature of the dry air in the chamber in which the experiment is carried out is such that the initial pressure is P o = 1.063 bar and the temperature T o is such that T o = 25 ° C.
    As a reminder, in order to obtain a relative calibration, it is not necessary to know these data T o , P o . This is however important for performing a chemical calibration.
    Furthermore, these values make it possible, by the relation R1, to calculate the theoretical angle of incidence making it possible to obtain the plasmon resonance.
    The wavelength λ of the light beam FL is such that λ =
    632nm.
    Under these conditions (T o , P o and λ), the relative static permittivity ε / εο of the gaseous medium is such that ε 9 / ε 0 = 1,00058986 where ε 0 is the permittivity of vacuum.
    Furthermore and as already indicated, the support 22 is a prism, correctly oriented, made of glass. Its optical index is r> s = 1.51.
    From these different values, it is then deduced that the angle of incidence 0 R as defined above which makes it possible to obtain the plasmon resonance, in accordance with the relation (R1), is Q R = 43 °.
    It should be noted that, as a variant, we can look for this angle experimentally.
    We can then obtain, at pressure Po, the reflectivity response of each of the four selected sensors. In this case, the acquisition of the variation in reflectivity for each of these sensors takes place over several minutes in order to obtain, for each sensor, a certain number of values which are then advantageously averaged in order to improve the accuracy of the measured,
    To implement the following step, a pressure jump, in this case positive, of 100mbar is made to set the pressure to a value P1 = 1.163 mbar. At the same time, the room temperature has not changed.
    In this example, it has been chosen to repeat steps b) and c) seven times in order to define eight pressure stages.
    The reflectivity measurement results are shown in FIG. 3 (signals delivered by the optical sensors C-i, Cn). This figure 3 provides the evolution of the change in reflectivity (%) over time and for each of the four selected sensors. The reflectivity (%) is defined by the ratio of the intensity of the light beam received by the optical probe to the intensity of the light beam emitted by the optical source.
    Insofar as, over time, several pressure stages of the gaseous medium are implemented, it can be observed that the reflectivity which is measured is also in the form of stages.
    These results demonstrate that it is entirely possible, with an apparatus operating by plasmon resonance, to measure the influence of the pressure of the gaseous medium, with the pressure of this gaseous medium as a common stimulus.
    These results also show the need to perform a calibration of the different sensors since there is a difference in the reflectivity response of each of the sensors when the pressure is no longer the reference pressure Po for which the experimental installation was initially prepared. Indeed, if the sensors provide different reflectivities under identical conditions (temperature and pressure of the gaseous medium, wavelength, in particular to define the permittivity of the gaseous medium) this means that each of the sensors does not see the same angle of resonance piasmon (cf. relation R1), or that they have a variable sensitivity linked to, for example, the nature of the compound forming the sensor, in other words that they are offset with respect to each other with respect to the plasmon resonance peak .
    This is why, once the results of FIG. 3 have been obtained, step e) is implemented.
    For this purpose, we have chosen in this case as a sensor, for which we consider that the variation in reflectivity is correct, for all of the pressure levels.
    For each of the other sensors, and at each pressure level, a corrective factor was then determined such that a difference in the signal between steps d) and b) (difference in reflectivity variation here) is equal or substantially equal to a variation of the reflectivity of the reference sensor.
    For example, in FIG. 3 at a pressure of 1.463 bar, the reference sensor, C1, indicates a variation in measured reflectivity of 0.54%, considered correct and the sensor C4 a variation in measured reflectivity of 0.42%. For the C4 sensor, the corrective factor is 54/42 to obtain a corrected reflectivity variation of the C4 sensor, equal to the reflectivity variation of the reference sensor, ie 0.54%.
    If a chemical calibration has been carried out beforehand (for example by a known method, in particular in the factory), it can then be ensured that its relative calibration carried out as proposed previously makes it possible to correctly calibrate the electronic nose because in this case, certain that the reference sensor provides correct values.
    In the example provided and leading to FIG. 3, the pressure jump is perfectly determined, which makes it possible to know the modified pressure after the implementation of step d).
    However, it should be noted that, in this relative calibration process, it is not important to know exactly the pressure jump made in step c), because the correction is not based on knowledge of this pressure jump. What matters is that the pressure range is consistent with the area of work of the electronic nose.
    In the context of the invention, it is possible to envisage implementing a second method for calibrating an electronic nose, also making it possible to perform relative calibration.
    More specifically, it is a method of calibrating an electronic nose, said electronic nose comprising a plurality of optical sensors arranged on a surface and in contact with a gaseous medium of interest, said optical sensors being capable of delivering a signal representative of the local optical index of the gaseous medium when they are excited by photons, ie method being characterized in that it comprises the following steps:
    A) determine the pressure P o and the temperature T o of the gaseous medium MG;
    B) emit photons towards the optical sensors;
    C) measure the signal delivered by each of the optical sensors, this measurement providing as many responses as there are optical sensors;
    D) modify the pressure and / or the temperature of the gaseous medium MG towards another or other known values;
    E) repeat step C); and
    F) for each sensor, calculate the evolution of the optical index of the gaseous medium using the measurements made in steps C) and E).
    Steps B), C) D) and E) of the second process are identical, respectively to steps a), b), c) and d) of the first process.
    However, in this second method, it is necessary to know the pressure P o and the temperature T o . This is the object of step A) which is not necessary in the first method according to the invention.
    Consequently, step D) of the second method differs from step c) of the first method, insofar as the value of the pressure, or of the temperature or of both the pressure and the temperature doi (Fri ) t be known.
    For example, if it is decided to vary only the pressure, as is possible with the experimental device 100 described above, the temperature can be kept constant (T o room temperature). Indeed, it is important, for this second method, to determine this value of the variation in pressure (in this example) in order to be able to implement step F).
    If we return to the concrete example described above, we obtain, after repeating steps C) and D) seven times, the curve of FIG. 3 comprising eight pressure levels.
    Step F) can be carried out as follows.
    We know that the optical index n G of a gaseous medium MG depends on the temperature T (in ° C), the pressure P (in Torr) and the wavelength λ (in pm) according to a relation of type:
    (¾ - 1) λ *
    720,775 'W + D * (0.817-0.033 * 7) * 10 ~ 6 1 + 0.003661 * 7 (R2) where:
    (n G - l) a is a quantity representative of the optical index n G of the gaseous medium MG, at a temperature of 15 ° C and a pressure of 1.013 bar (standard conditions), expressed in the form:
    (n G - 1) λ * 10 “ 8 = 8342.54 +
    406 147 130-Λ 2
    998 38.9 — A 2 (R3)
    For small pressure variations, namely between 1 bar and a few tens of bars, for example 50 bars, the quadratic term in pressure of the relation R2 contributes only very slightly in the evolution of the quantity For example, for i'air air at a temperature of about 25 ° C and for a pressure variation of 2 bars, the contribution of this quadratic term does not exceed 0.1%. Still for dry air at a temperature of around 25 ° C and for a pressure variation of 50 bars, the variation of this quadratic term does not exceed a few percent.
    This is why it can be considered, with the data in FIG. 3, corresponding to a total variation in pressure not exceeding 1 bar, that the quantity f - does not depend on the pressure. In other words, we oP 7 a can consider that the quantity (n G - l) rp evolves linearly with pressure.
    Furthermore, from FIG. 3, it can also be noted that the variation in reflectivity R which is measured changes linearly with the pressure since for each sensor and each pressure level, a constant value of this variation in reflectivity measured is obtained.
    Therefore, for each sensor, the quantity (n G - 1) TP changes linearly as a function of the variation in reflectivity. In other words, for each sensor C, where i denotes the index of the sensor with 1 <i <N (N a natural integer), we can construct a relation of the type:
    - ϊ) τ ο ρ, α / 3 (n G -l) To p * l 3P J ci * W ci
    l) r 0 p 0 , ci (R4) where:
    the quantity (^) comes from the linear regression carried out, for the sensor C;, from the measurement in reflectivity R, as a function of the pressure P (in the example provided, from the data in FIG. 3),
    - ~ p intervenes, for the sensor C ,, to normalize the variation in measured reflectivity,
    R ci is, for the sensor C, -, fa variation of measured reflectivity (from figure 3) ·
    In the example provided, the gaseous medium is dry air at T = T o = 25 ° C and the wavelength λ of the light beam FL is such that λ = 632nm.
    We deduce from it, thanks to the relations R2 and R3 and taking into account the linear approximation in the pressure range considered, that the quantity =
    2.64.10 -4 (with the units considered).
    Similarly, we also deduce by the relation that the quantity K - 1) ^, a = 0.000275545 (T o = 25 ° C and P o = 1.063 bar).
    We thus obtain a relation R4 giving, for each sensor Ο, the evolution of the local optical index as a function of the data from FIG. 3, namely (^) and R ci .
    As regards a calibration, each sensor therefore provides, according to the relationship R4, identical changes in this optical index loca! depending on the pressure of the gaseous medium.
    It is understood that more than a relative calibration, this second method also makes it possible to obtain an absolute calibration of the various sensors, insofar as it makes it possible to obtain the evolution of the optical index in accordance with the relation R4.
    In other words, by implementing this second caiibration method to achieve relative cafibration, an absolute calibration is also obtained.
    If there are slight differences, linked to measurement uncertainties, we can then choose one of these sensors as a reference and apply the relationship R4 obtained for this sensor to all the other sensors.
    For this second method, and unlike the first method, it is necessary to know the pressure jump with precision (step D)) to be able to correctly determine, for each sensor, the evolution of the local optical index (step F)).
    FIG. 4 represents a test carried out with the experimental installation 100 of FIG. 1, under the same conditions as above, with the exception of the number of sensors retained for the analysis (N = 14 sensors) and the nature of the medium gaseous MG. Indeed, here the gaseous medium is dry air charged with ethanol, at 200 ppm. Ethanol plays the role of an analyte.
    The objective of this test is to show a particular application case, with ethanol as an anafyte.
    Figure 4 includes Figures 4 (a) through 4 (c).
    FIG. 4 (a) represents, in the form of a histogram, your variation in measured reflectivity (raw data - to be compared with the data in FIG. 3).
    We can then deduce the corrective factors, based for example on the sensor C-t as a reference,
    Figure 4 (b) shows the corrective factors for each sensor.
    Finally, Figure 4 (c) shows the variation in corrected reflectivity for each sensor. This figure 4 (c) therefore corresponds to figure 4 (a) corrected by figure 4 (b).
    Advantageously, and taking into account the sensitivity of the experimental apparatus 100, it is possible advantageously to modify the pressure of the gaseous medium, at each pressure jump, by a value between + 10mbar and +2 bar, preferably between + 50mbar and + 150mbar or between -10mbar and 900mbar, preferably between -SOmbar and -150mbar.
    Furthermore, to perform precise measurements, it is advantageous to perform a reflectivity measurement (step b) or d) for the first method or step C) or E) for the second method) carried out over a period of between 0, 1s and 60mn, preferably between 1s and 10mn, then averaged. The duration of the measurement depends on the desired precision, but also on the characteristics of the device allowing the sampling.
    As was carried out in the example provided, steps c) and d) are advantageously repeated N times before the implementation of step e) or, as the case may be, steps D) and E are repeated N times before the implementation of step F), with N a natural integer greater than or equal to 1.
    Thus, at each repetition, the pressure of the gaseous medium is different from a pressure (or, as the case may be, the temperature or both the pressure and the temperature) for which a measurement has already been made. This allows for more than two measurements and thus increases the quality of the measurements.
    In any event, it is advantageous, at the end of the reflectivity measurement and before implementing step e) or, as the case may be, step F) to return the pressure to the initial value P o ( or as the case may be, the temperature T at the value TO or at the same time the temperature and the pressure), in order to eliminate any drifts of the measurement signals during the measurement. This is, moreover, what was done in the example provided here, where the last measurement is indeed carried out at the pressure P o = 1.063bar (cf. FIG. 3).
    It should be noted that the two methods described above can be the subject of variant embodiments.
    In particular, and as will be understood, it is entirely possible to carry out measurements in reflectivity (variation in reflectivity) based on an evolution of the temperature T of the gaseous medium MG, ie by maintaining the pressure Po at a value the pressure of this gaseous medium is constant either by also varying the pressure of the gaseous medium.
    This is shown in Figure 5.
    In comparison with FIG. 1, it is noted that the experimental installation 100 ′ includes a device 50 ’for regulating the temperature, in order to be able to change the temperature. In practice, this device can be in the form of an electric wire supplied by the sector to produce a Joule effect heating with which is associated a temperature regulation loop.
    To fix the ideas, it should be noted that a 10 ° C change in the temperature of the gaseous medium MG corresponds substantially to the effect obtained by a pressure change of 10Qmbar, We can rely on the relation R1 to this effect. Typically, we can therefore provide, for each measurement, a temperature change between + 1 ° C and + 100 ° C, preferably between + 5 ° C and + 15 ° C or between -1 ° C and -5Q ° C , preferably between -5 ° C and -15 ° C.
    Of course, the aforementioned regulating device may be replaced by a temperature and pressure regulating device, when it is desired to vary both the temperature and the pressure, this device being for example a combination of the means described previously to vary the temperature on the one hand and the pressure on the other.
    In addition, whether based (Figure 1) on a change in the pressure of the gaseous medium (at constant temperature) or (Figure 5) on a change in the temperature of the gaseous medium (at constant pressure or not), your processes according to the invention can be implemented with a measurement in transmittivity, instead of a measurement in reflectivity.
    In FIG. 6, a 100 ”experimental installation has thus been represented, making it possible to implement a change in pressure and / or temperature of the gaseous medium, with a measurement in transmittivity. For reasons of convenience, the pump 50 and / or, as the case may be, the temperature regulation device 50 ′ have not, however, been represented in this FIG. 6, the objective being simply to represent how the measurement can be carry out.
    More generally, a process in accordance with the invention can be implemented with an installation different from the installations 100, 100 ’, 100”, shown respectively in FIGS. 1, 5 and 6.
    Indeed, for all the installations described above, we base ourselves on the surface plasmon resonance (SPR) in the case of a flat surface (metal layer 21 placed on a flat support 22, in this case a prism).
    However, a person skilled in the art is well aware of other installations which allow measurements to be made based on plasmon resonance.
    We list below, without limitation, some possible techniques.
    A method according to the invention can be implemented using surface plasmon resonance on optical fiber, whether in reflection or in transmission. This technique is for example presented by Burgmeier & ai., “Plasmonic nanoshelled functionalized etch fiber Bragg gratings for highly sensitive refractive index measurements”, Optics Letters, vol. 40 (4), pp. 546-549 (2015). The device proposed in this document is used with a liquid medium, but could just as easily be used for a gaseous medium, therefore for an electronic nose.
    A method according to the invention can be implemented using surface plasmon resonance on beads, whether in reflection or in transmission. This technique is for example presented, in the case of a use in reflection by Frederix & al., "Biosensing based on light absorption on nanoscaled gold and silver nanoparticies", Anal. Chem. 2003, vol. 75, pp. 6894-6900, The dielectric medium considered is rather a liquid, but can be used for a gaseous medium and therefore an electronic nose.
    A method according to the invention can also be implemented using plasmon resonance based on nanocavities. For example, the article by Zhao Hua-Jîn, “High sensitivity refractive index gas sensing enhanced by surface plasmon resonance with nano-cavity anteanna array 2012, Chinese Physical Society and IOP Publishing Ltd, Chinese Physics B, vol. 21 (8), pp. clearly indicates that such nanocavities are sensitive to a change in local optical index. This can therefore be used to perform a calibration, for example for an electronic nose.
    Furthermore, the use of plasmon resonance is not the only conceivable technique for implementing the invention.
    Thus, we can consider a measurement technique based on refractometry, to measure a variation of the optical index. For this purpose, an optical sensor of the “optical resonator” type can be used. In this case, the resonator fulfills the function of the metal layer of a plasmon effect sensor.
    We can refer to the article by Luchansky & ai. "High-Q optical sensors for Chemical and biologicai analysis", Analytical chemistry, 2011, vo. 84 (2), pp. 793-821.
    We can also refer to the article by Kim & al, "Integrated photonic glucose biosensor using a verticaily coupled microring resonator in polymers", Optics Communications, 2008, vo. 281 (18), pp. 46444647 which uses this property to measure optical indices in liquid media.
    We can also refer to Passaro et al., "Ammonia Opticaf Sensing by Mîcroring Resonators", Sensors 2007, vol. 7, pp. 27412749 which measures local variations in optical index generated by the gaseous ammonia. In particular, we note that the diagram on page 7744 clearly shows that the measurement is made by changing the optical index. In this, it can therefore be sensitive to a variation in pressure or temperature.
    权利要求:
    Claims (15)
    [1" id="c-fr-0001]
    1. Method for calibrating an electronic nose, said electronic nose comprising a plurality of optical sensors arranged on a surface and in contact with a gaseous medium of interest, said optical sensors being capable of delivering a signal representative of the optical index local to the gaseous medium when they are excited by photons, the process being characterized in that it comprises the following stages:
    a) emit photons towards the sensors;
    b) measure the signal delivered by each of the sensors, this measurement providing as many responses as there are sensors;
    c) modify the pressure and / or the temperature of the gaseous medium;
    d) repeat step b); and
    e) for each sensor, determine a corrective factor te! that a variation of the signal between steps d) and b) corrected by said corrective factor is equal to or substantially equal to a variation of the signal between these same steps for a reference, this reference being provided by a reference sensor or a combination of reference sensors.
    [2" id="c-fr-0002]
    2. Method for calibrating an electronic nose according to claim 1, in which, prior to step a), the pressure P o and / or the temperature To of the gaseous medium are determined.
    [3" id="c-fr-0003]
    3. Method for calibrating an electronic nose according to one of the preceding claims, in which the measurement carried out in step b) or d), for example a measurement of reflectivity or transmittivity, is carried out over a period comprised between 0.1s and 60mn, preferably between 1s and 10mn, then averaged.
    [4" id="c-fr-0004]
    4. Method for calibrating an electronic nose according to one of the preceding claims, in which, before implementing step e), steps c) and d) are repeated N times, with N being a higher natural number or equal to 1, so that the pressure and / or the temperature of the gaseous medium is different from a pressure and / or a temperature of the gaseous medium for which a measurement has already been made.
    [5" id="c-fr-0005]
    5. Method for calibrating an electronic nose according to one of the preceding claims, in which, during step c), the pressure of the gaseous medium and / or the temperature is modified to another known value.
    [6" id="c-fr-0006]
    6. Method for calibrating an electronic nose according to the preceding claim, in which in step c):
    - The pressure of the gaseous medium is modified by a value between + 10mbar and + 2bar, preferably between + 50mbar and + 150mbar or by a value between -IQmbar and -900mbar, preferably between -50mbar and -150mbar; and or
    the temperature of the gaseous medium is modified by a value between + 1 ° C and + 100 ° C, preferably between + 5 ° C and + 15 ° C or between -1 ° C and -50 ° C, preferably between -5 ° C and -15 ° C.
    [7" id="c-fr-0007]
    7. Method for calibrating an electronic nose according to one of claims 5 or 6, in which, just before step e), an additional step is implemented consisting in modifying the pressure and / or the temperature of the medium gaseous at the initial pressure (P o ) and / or at the initial temperature (T Q ).
    [8" id="c-fr-0008]
    8. Method for calibrating an electronic nose according to one of the preceding claims, in which the optical sensor is chosen from a plasmon effect sensor, for example on a flat surface, optical fiber or nanocavities or a sensor capable of operating by refractometry , for example a resonator sensor.
    [9" id="c-fr-0009]
    9. Method for calibrating an electronic nose, said electronic nose comprising a plurality of optical sensors arranged on a surface and in contact with a gaseous medium of interest, said optical sensors being capable of delivering a signal representative of the optical index local to the gaseous medium when they are excited by photons, the process being characterized in that it comprises the following stages:
    A) determine the pressure P o and the temperature T o of the gaseous medium MG;
    B) emit photons towards the optical sensors;
    C) measure the signal delivered by each of the optical sensors, this measurement providing as many responses as there are optical sensors;
    D) modify the pressure and / or the temperature of the gaseous medium MG towards another or other known values;
    E) repeat step C); and
    F) for each sensor, calculate the evolution of the optical index of the gaseous medium using the measurements made in steps C) and E).
    [10" id="c-fr-0010]
    10, method for calibrating an electronic nose according to the preceding claim, in which, prior to step A), the pressure and / or the temperature of the gaseous medium are adjusted to a predetermined value.
    [11" id="c-fr-0011]
    11. Method for calibrating an electronic nose according to one of claims 9 or 10, in which the measurement carried out in step C) or E), for example a measurement of reflectivity or transmittivity, is carried out on a duration between 0.1s and 60mn, preferably between 1s and 10mn, then averaged,
    11. Method for calibrating an electronic nose according to one of claims 9 to 11, in which, before implementing step F), steps D) and E) are repeated N times, with N an integer natural greater than or equal to 1, so that the pressure or as the case may be, of the temperature of the gaseous medium is different from a pressure or according to the case of a temperature of the gaseous medium for which a measurement has already been made.
    [12" id="c-fr-0012]
    12. Method for calibrating an electronic nose according to one of claims 9 to 11, in which in step D):
    - the pressure of the gaseous medium is modified by a value between + 10mbar and + 2bar, preferably between + 50mbar and + 150mbar or by a value between -10mbar and -900mbar, preferably between -SOmbar and -150mbar; and or
    the temperature of the gaseous medium is modified by a value between + 1 ° C 5 and + 100 ° C, preferably between + 5 ° C and + 15 ° C, or between -1 ° C and -50 ° C, preferably between -5 ° C and -15 ° C.
    [13" id="c-fr-0013]
    13. Method for calibrating an electronic nose according to one of claims 9 to 12, in which, just before step F), an additional step consistantο is implemented consisting in modifying the pressure and / or the temperature of the gaseous medium at initial pressure (P o ) and / or ia initial temperature (T o ).
    [14" id="c-fr-0014]
    14. Method for calibrating an electronic nose according to one of claims 9 to 13, in which the optical sensor is chosen from an effect sensor
    [15" id="c-fr-0015]
    15 plasmon, for example on a flat surface, optical fiber or nanocavities, or a sensor capable of operating by refractometry, for example a resonator sensor.
    1/4
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    同族专利:
    公开号 | 公开日
    KR20200004785A|2020-01-14|
    EP3589946A1|2020-01-08|
    CA3055115A1|2018-09-07|
    AU2018226567A1|2019-10-10|
    FR3063543B1|2022-01-28|
    CN110520726A|2019-11-29|
    WO2018158458A1|2018-09-07|
    US20200088702A1|2020-03-19|
    JP2020509395A|2020-03-26|
    US10928369B2|2021-02-23|
    IL269109D0|2019-11-28|
    SG11201908116XA|2019-10-30|
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    2021-11-26| CD| Change of name or company name|Owner name: ARYBALLE, FR Effective date: 20211018 Owner name: UNIVERSITE GRENOBLE ALPES, FR Effective date: 20211018 Owner name: CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE, FR Effective date: 20211018 Owner name: COMMISSARIAT A L'ENERGIE ATOMIQUE ET AUX ENERG, FR Effective date: 20211018 |
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1751751|2017-03-03|
    FR1751751A|FR3063543B1|2017-03-03|2017-03-03|PROCEDURE FOR CALIBRATION OF AN ELECTRONIC NOSE.|FR1751751A| FR3063543B1|2017-03-03|2017-03-03|PROCEDURE FOR CALIBRATION OF AN ELECTRONIC NOSE.|
    US16/490,527| US10928369B2|2017-03-03|2018-03-02|Method of calibrating an electronic nose|
    AU2018226567A| AU2018226567A1|2017-03-03|2018-03-02|Method for calibrating an electronic nose|
    SG11201908116X| SG11201908116XA|2017-03-03|2018-03-02|Method for calibrating an electronic nose|
    CA3055115A| CA3055115A1|2017-03-03|2018-03-02|Method for calibrating an electronic nose|
    KR1020197027844A| KR20200004785A|2017-03-03|2018-03-02|How to Calibrate the Electronic Nose|
    PCT/EP2018/055233| WO2018158458A1|2017-03-03|2018-03-02|Method for calibrating an electronic nose|
    CN201880021091.3A| CN110520726A|2017-03-03|2018-03-02|Method for calibrating electronic nose|
    JP2019568817A| JP2020509395A|2017-03-03|2018-03-02|Electronic nose calibration method|
    EP18707921.5A| EP3589946A1|2017-03-03|2018-03-02|Method for calibrating an electronic nose|
    IL26910919A| IL269109D0|2017-03-03|2019-09-03|Method for calibrating an electronic nose|
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