WO2007080398A1 - Capteur de gaz de differenciation - Google Patents

Capteur de gaz de differenciation Download PDF

Info

Publication number
WO2007080398A1
WO2007080398A1 PCT/GB2007/000060 GB2007000060W WO2007080398A1 WO 2007080398 A1 WO2007080398 A1 WO 2007080398A1 GB 2007000060 W GB2007000060 W GB 2007000060W WO 2007080398 A1 WO2007080398 A1 WO 2007080398A1
Authority
WO
WIPO (PCT)
Prior art keywords
gas sensor
emitted
filter
radiation
bands
Prior art date
Application number
PCT/GB2007/000060
Other languages
English (en)
Inventor
Michael J. Smith
Original Assignee
Gas Sensing Solutions Limited
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 GB0600381A external-priority patent/GB0600381D0/en
Priority claimed from GB0600382A external-priority patent/GB0600382D0/en
Application filed by Gas Sensing Solutions Limited filed Critical Gas Sensing Solutions Limited
Publication of WO2007080398A1 publication Critical patent/WO2007080398A1/fr

Links

Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
    • G01N21/3504—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing gases, e.g. multi-gas analysis
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/314—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry with comparison of measurements at specific and non-specific wavelengths
    • G01N21/3151—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry with comparison of measurements at specific and non-specific wavelengths using two sources of radiation of different wavelengths
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2201/00—Features of devices classified in G01N21/00
    • G01N2201/12—Circuits of general importance; Signal processing
    • G01N2201/121—Correction signals
    • G01N2201/1215—Correction signals for interfering gases

Definitions

  • the present invention relates to gas sensing, in particular gas sensors having a radiation source (emitter) and a radiation detector, such as non- dispersive infrared (NDIR) gas sensors.
  • a radiation source emitter
  • NDIR non- dispersive infrared
  • a low cost LED Light Emitting Diode
  • a LED does have relatively narrow emission bandwidth, the bandwidth is still broad enough to span the absorption bands of more than one gas. Thus sensing a change in the concentration of one gas may be confused by changes in another's concentration.
  • a gas sensor for differentiating gases in a gas mixture
  • the gas sensor comprising: a radiation source operable to emit radiation, the radiation having first and second emitted bands overlapping in frequency; a modulator configured to modulate the emitted radiation so as to provide each of the first and second emitted bands with a discrete modulation signal; a cavity for conveying the modulated emitted radiation through the gas mixture; a radiation detector operable to receive the modulated emitted radiation so as to provide a received detection signal; and a demodulator, configured to demodulate the discrete modulation signals from the received detection signal thereby providing a demodulated detection signal for each of the first and second emitted bands .
  • the gas sensor further comprises differentiation means configured to differentiate gases in the gas mixture.
  • differentiation means is configured to differentiate gases in the gas mixture using the demodulated detection signals of each of the first and second emitted bands.
  • the differentiation means is configured to differentiate gases by subtracting the demodulated detection signal of the first emitted band from the demodulated detection signal of the second emitted band.
  • the radiation source comprises at least one emitter.
  • the radiation source is configured such that the relative amount of radiation comprising each of the first and second emitted bands is unequal.
  • the radiation source comprises unequal emission areas for each of the first and second emitted bands .
  • the radiation source is configured to provide unequal emission power for each of the first and second emitted bands.
  • the unequal emission power is provided by varying the modulation duty cycle of at least one emitter.
  • the radiation source comprises at least one light emitting diode.
  • the radiation source further comprises at least one filter configured to trim the bandwidth of the at least one emitted band by filtering a portion of the emitted radiation.
  • the at least one filter comprises a band pass filter.
  • the at least one filter comprises a band stop filter .
  • the at least one filter comprises a low pass filter.
  • the at least one filter comprises a high pass filter.
  • the at least one filter is configured to filter the portion of the emitted radiation such that the bandwidth of at least one of the filtered emitted bands is narrower than the bandwidth of its corresponding emitted band.
  • the at least one filter is configured to filter the portion of the emitted radiation such that the bandwidth of at least one of the filtered emitted bands is no greater than 1.5 ⁇ m wide.
  • the at least one filter is configured to trim only one side of the bandwidth of the at least one emitted band.
  • the at least one filter is configured to trim both sides of the bandwidth of the at least one emitted band.
  • At least one emitter comprises the filter.
  • the at least one filter is formed by molecular beam epitaxial growth on at least one emitter.
  • the at least one filter comprises a coating on at least one emitter.
  • the coating comprises a conformal deposited coating.
  • the coating comprises a passivation coating.
  • the coating comprises epoxy resin.
  • the coating comprises cyanoacrylate .
  • the coating comprises glass.
  • the coating comprises acylic resin.
  • the coating comprises polyerethane resin.
  • the coating comprises silicone resin.
  • the coating comprises latex rubber.
  • the coating comprises a UV curable system.
  • the at least one filter further comprises a further material applied to the coating, wherein the further material is configured to enhance the band pass filter effect of the coating.
  • the at least one filter is configured to match the filtered radiation to the optical frequency cut off of the radiation detector.
  • the gas sensor further comprises: a reference radiation detector operable to receive the modulated emitted radiation so as to provide a received reference signal; and a reference demodulator, configured to demodulate the discrete modulation signals from the received reference signal thereby providing a demodulated reference signal for each of the first and second emitted bands.
  • a reference radiation detector operable to receive the modulated emitted radiation so as to provide a received reference signal
  • a reference demodulator configured to demodulate the discrete modulation signals from the received reference signal thereby providing a demodulated reference signal for each of the first and second emitted bands.
  • Figure 1 illustrates in schematic form a gas sensor in accordance with the preferred embodiment of the present invention
  • Figure 2 illustrates in schematic form the absorbance spectrum of three gases and the band widths of two LEDs and a photodiode configured for differentiating CO 2
  • Figure 3 illustrates in schematic form the absorbance spectrum of three gases and the band widths of two LEDs and a photodiode configured for differentiating CO
  • Figure 4 illustrates the absorption band of a filter shown superimposed on a graph of the unfiltered LED emission power.
  • the radiation source comprises two LED emitters 1,2.
  • the radiation source may have multiple LEDs with adjacent or overlapping emission frequency bands.
  • a single LED with multiple emission frequency bands may be used.
  • the bands 3, 4 are overlapping in frequency.
  • a modulator 5 modulates the emitted radiation so as to provide each emitted band with a discrete modulation signal.
  • the cavity 6 conveys the modulated emitted radiation through the gas mixture being sensed.
  • the gas mixture contains for example CO 2 , N 2 O and CO.
  • the photodiode radiation detector 7 receives the modulated emitted radiation and outputs a received detection signal.
  • two, three or more matched emitter/detector pairs may be used.
  • the demodulator 8 demodulates the discrete modulation signals from the received detection signal output from the photodiode. This provides the demodulated detection signal for each emitted band.
  • the processor 9 subtracts one demodulated detection signal from another in order to differentiate the absorption signals of different gases.
  • the modulation used in this embodiment is achieved by driving each LED with a different square wave.
  • the LED emitters are more efficient if driven with strong pulses and then allowed to rest for a period. Such modulation is used to reduce the overall power to the LED whilst maintaining the efficiency.
  • a LED may be driven with 200 to 250 mA, however this may only be maintained if the duty cycle is less than 25% as the LED would quickly overheat.
  • Another modulation requirement is to increase the signal to noise ratio and to make the gas sensor more compatible with standard devices that operate at frequencies well above 1 KHz.
  • Band pass filters 10, 11 may be applied to the surface of the LEDs.
  • a filter may alternatively be a band stop filter, a low pass filter or a high pass filter.
  • the filters are formed as part of the radiation source by molecular beam epitaxy during growth of the LEDs.
  • the structure of each filter is chosen so as to trim the emitted bandwidth by filtering only one side, or both sides, of the emitted bandwidth.
  • the filter enhances the gas sensor's output signal with respect to a specific gas and causes the overall sensor bandwidth and therefore sensitivity to only one gas to be enhanced.
  • the filter is applied as a coating to the surface of the LED, as a conformal / protection / passivation coating designed to protect the LED from environmental problems such as water ingress.
  • the coating is selected because it has an absorption band at a convenient location in the spectrum.
  • a further material may be added to a conventional coating material that enhances, moves or creates an optical filtering effect.
  • the further material may be applied to the processed and mounted chip sets to enhance their desired properties. In this way, single or multiple materials may be used for a combination of functions within the gas sensor application.
  • some conformal coating materials based on epoxies and similar materials naturally absorb radiation in the infrared spectrum at specific frequencies. Additionally, materials such as glass have precise optical cut offs around 4 ⁇ m and some cyanoacrylates have strong IR absorptions around 3.5 ⁇ m.
  • Other suitable coatings are acylic resins, polyerethane resins, silicone resins, latex rubber or a UV curable system. More than one of these coatings may be applied in combination to provide the filter.
  • the composition or mixture of the conformal / protection / passivation coating may be modified to tune the optical absorption to suit the optical requirements of the gas sensing application, with or without the need for conventional optical filter techniques being applied.
  • the use of a conformal / protection / passivation coating to assist optical bandwidth trimming provides a very low cost solution and alternative to conventional (expensive) optical filters.
  • the demodulated detection signal strength can be balanced or tailored to suit the gases being detected by the subtraction. This is achieved by making the relative amount of emitted radiation corresponding to each emitted band unequal. This may be done by varying the number of LED emission elements at an individual optical frequency or at discretely separated optical frequencies within one gas sensor assembly, thereby providing unequal emission areas for each emitted band.
  • Making the relative amount of emitted radiation corresponding to each emitted band unequal may also be achieved by varying the power supply to each emission element. Directly varying a continuous power supply provides unequal emission power for each emitted band instantaneously. Modulating the power supply, for example by changing the duty cycle of a pulsed power supply to each emitter, provides unequal emission power for each emitted band averaged over time.
  • a graph of absort>ance versus wavelength is shown, with indications of emitter bandwidths also shown.
  • the emission bandwidth of the first LED is shown as a rectangle 12.
  • the emission bandwidth of the second LED is also shown as a rectangle 13. These two emission bandwidths are overlapping but both within the detection bandwidth of the photodiode 14.
  • the absorption peaks are shown for the three gases CO 2 15, N 2 O 16 and CO 17.
  • the first LED emits at a bandwidth that spans the three absorption peaks. Therefore the demodulated detection signal for the first LED contains information about absorption by the three gases.
  • the demodulated detection, signal corresponding to the second LED contains information only relating to the two gases N 2 O and CO that have absorption peaks within the emission bandwidth of the second LED.
  • the processor subtracts the demodulated detection signal of the LED from that of the first LED. This provides a detection signal relating only to CO 2 therefore the gas sensor is able to differentiate between absorption signals of CO 2 relative to the other gases.
  • figure 3 shows the absorbance spectrum of three gases, however the LED emitters and photodiode are tuned to have different bands.
  • the bands are configured such that subtraction of the second LED's demodulated detection signal from that of the first provides the CO detection signal thereby differentiating the CO gas signal from that of the other gases.
  • the absorption band 18 of a band stop filter is shown superimposed on a graph of the unfiltered LED emission power 19.
  • the power curve actually shows a dip 20 due to absorption caused by the unintentional filtering effect of the glue used for mounting the LED.
  • the gas sensor may also include a reference diode as well as a detecting photodiode, to allow more accurate . differentiation between the two emitters and additionally assist in temperature compensation.
  • the reference photodiode receives the modulated emitted radiation so as to provide a received reference signal and a reference demodulator demodulates the discrete modulation signals from the received reference signal thereby providing a demodulated reference signal for each of the first and second emitted bands.
  • the reference demodulator demodulates the discrete modulation signals from the received reference signal output from the reference photodiode. This provides the demodulated reference signal for each emitted band.
  • a comparator or for example the processor, uses the demodulated detection signal and demodulated reference signal to perform temperature compensation.
  • the reference photodiode may be used in the same optical path as the detecting photodiode or may be located at another convenient point either having a shorter pathlength with the same optics or having a separate optical path entirely.

Abstract

La présente invention concerne un capteur de gaz à infrarouge non dispersif amélioré (NDIR) conçu pour différencier des gaz dans un mélange gazeux. Dans ce capteur de gaz, une source de rayonnement comprenant par exemple deux diodes électroluminescentes (LED) (1, 2) émet un rayonnement qui présente des premières bandes émises (3) et des secondes bandes émises (4) se chevauchant en fréquence. Un modulateur (5) est conçu pour moduler le rayonnement émis de manière à fournir à chacune des premières et secondes bandes émises un signal de modulation discret. Une fois que le rayonnement a traversé une chambre d'échantillon de gaz (6), un détecteur de rayonnement, par exemple une photodiode (7), reçoit le rayonnement. Des signaux de détection démodulés (8) pour chacune des premières et secondes bandes émises sont utilisés pour différencier,par soustraction, les gaz présents dans le mélange gazeux. Les bandes émises peuvent présenter une puissance différente résultant de différentes surfaces de diodes électroluminescentes ou de facteurs d'utilisation différents. Des filtres à croissance épitaxiale ou à dépôt épitaxial (10, 11) situés sur les diodes électroluminescentes ajustent la largeur de bande des bandes émises.
PCT/GB2007/000060 2006-01-10 2007-01-10 Capteur de gaz de differenciation WO2007080398A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB0600382.6 2006-01-10
GB0600381A GB0600381D0 (en) 2006-01-10 2006-01-10 Gas sensor with optical filter
GB0600381.8 2006-01-10
GB0600382A GB0600382D0 (en) 2006-01-10 2006-01-10 Differentiating gas sensor

Publications (1)

Publication Number Publication Date
WO2007080398A1 true WO2007080398A1 (fr) 2007-07-19

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB2007/000060 WO2007080398A1 (fr) 2006-01-10 2007-01-10 Capteur de gaz de differenciation

Country Status (1)

Country Link
WO (1) WO2007080398A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009019467A1 (fr) * 2007-08-06 2009-02-12 Gas Sensing Solutions Limited Compensation de température pour détection de gaz
GB2497296A (en) * 2011-12-05 2013-06-12 Gassecure As Gas sensor with adaptable light filter
WO2015045411A1 (fr) 2013-09-27 2015-04-02 旭化成エレクトロニクス株式会社 Capteur de gaz
WO2022015697A3 (fr) * 2020-07-13 2022-02-24 Analog Devices, Inc. Système et appareil de détection optique de gaz à compensation complète
US11747272B2 (en) 2019-06-10 2023-09-05 Analog Devices, Inc. Gas detection using differential path length measurement

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4500207A (en) * 1981-11-14 1985-02-19 Ferranti, Plc Non-dispersive optical determination of gas concentration
US4899053A (en) * 1987-10-21 1990-02-06 Criticare Systems, Inc. Solid state non-dispersive IR analyzer using electrical current-modulated microsources
US5957858A (en) * 1996-07-26 1999-09-28 Polestar Technologies, Inc. Systems and methods for monitoring relative concentrations of different isotopic forms of a chemical species
US6611333B1 (en) * 1999-03-26 2003-08-26 Japan Science And Technology Corporation Isopotomer absorption spectral analyzer and its method
DE10302165A1 (de) * 2003-01-22 2004-07-29 Robert Bosch Gmbh Infrarotquelle und Gassensor
US20040223342A1 (en) * 2001-12-31 2004-11-11 Klipstein Donald L. LED inspection lamp, cluster LED, and LED with stabilizing agents

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4500207A (en) * 1981-11-14 1985-02-19 Ferranti, Plc Non-dispersive optical determination of gas concentration
US4899053A (en) * 1987-10-21 1990-02-06 Criticare Systems, Inc. Solid state non-dispersive IR analyzer using electrical current-modulated microsources
US5957858A (en) * 1996-07-26 1999-09-28 Polestar Technologies, Inc. Systems and methods for monitoring relative concentrations of different isotopic forms of a chemical species
US6611333B1 (en) * 1999-03-26 2003-08-26 Japan Science And Technology Corporation Isopotomer absorption spectral analyzer and its method
US20040223342A1 (en) * 2001-12-31 2004-11-11 Klipstein Donald L. LED inspection lamp, cluster LED, and LED with stabilizing agents
DE10302165A1 (de) * 2003-01-22 2004-07-29 Robert Bosch Gmbh Infrarotquelle und Gassensor

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009019467A1 (fr) * 2007-08-06 2009-02-12 Gas Sensing Solutions Limited Compensation de température pour détection de gaz
GB2497296A (en) * 2011-12-05 2013-06-12 Gassecure As Gas sensor with adaptable light filter
GB2497296B (en) * 2011-12-05 2017-07-12 Gassecure As Gas sensors
WO2015045411A1 (fr) 2013-09-27 2015-04-02 旭化成エレクトロニクス株式会社 Capteur de gaz
US10082464B2 (en) 2013-09-27 2018-09-25 Asahi Kasei Microdevices Corporation Gas sensor
US10551314B2 (en) 2013-09-27 2020-02-04 Asahi Kasei Microdevices Corporation Gas sensor
US11747272B2 (en) 2019-06-10 2023-09-05 Analog Devices, Inc. Gas detection using differential path length measurement
WO2022015697A3 (fr) * 2020-07-13 2022-02-24 Analog Devices, Inc. Système et appareil de détection optique de gaz à compensation complète
US11821836B2 (en) 2020-07-13 2023-11-21 Analog Devices, Inc. Fully compensated optical gas sensing system and apparatus

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