WO2010061536A1 - 窒素酸化物検出エレメント、窒素酸化物検出センサとこれを使用した窒素酸化物濃度測定装置および窒素酸化物濃度測定方法 - Google Patents
窒素酸化物検出エレメント、窒素酸化物検出センサとこれを使用した窒素酸化物濃度測定装置および窒素酸化物濃度測定方法 Download PDFInfo
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- WO2010061536A1 WO2010061536A1 PCT/JP2009/005891 JP2009005891W WO2010061536A1 WO 2010061536 A1 WO2010061536 A1 WO 2010061536A1 JP 2009005891 W JP2009005891 W JP 2009005891W WO 2010061536 A1 WO2010061536 A1 WO 2010061536A1
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- 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
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/22—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators
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- 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
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N2021/7769—Measurement method of reaction-produced change in sensor
- G01N2021/7773—Reflection
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- 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
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N2021/7769—Measurement method of reaction-produced change in sensor
- G01N2021/7783—Transmission, loss
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- 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
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/7703—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator using reagent-clad optical fibres or optical waveguides
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- 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
- G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
- G01N33/483—Physical analysis of biological material
- G01N33/497—Physical analysis of biological material of gaseous biological material, e.g. breath
Definitions
- the present invention relates to a nitrogen oxide detection sensor.
- NO nitric oxide
- NO gas analysis in exhaled breath is attracting attention as a marker of respiratory tract infections due to asthma and allergies that have been increasing in recent years. In addition, it is attracting attention as being able to diagnose non-invasive diseases without burdening patients.
- the NO gas concentration in exhaled breath is 2 ppb to 20 ppb in a normal person, but is known to increase about 3 times during airway inflammation such as asthma and allergy. Therefore, by measuring exhaled NO gas, it can be used for treatment guidelines for asthma such as determination of the degree of airway inflammation of a patient and determination of the dosage of an asthma therapeutic drug.
- Co ⁇ T (5-ST) P ⁇ cobalt tetrasulfothienylporphyrin supported on sol-gel silica is reacted with NO to produce Co ⁇ T (5-ST) P.
- ⁇ Is disclosed by spectroscopic measurement see, for example, Non-Patent Document 1).
- Co ⁇ T (5-ST) P ⁇ supported on the surface of sol-gel silica is heated to 200 ° C. and 17 ppm. NO gas detection is successful.
- Ga 2 O 3 is formed by oxidizing Ga on a GaAs field effect transistor, and hematoporphyrin IX, protoporphyrin IX, hemin, or cobalt is formed on this Ga 2 O 3.
- hematoporphyrin IX, protoporphyrin IX, hemin, or cobalt is formed on this Ga 2 O 3.
- a technique in which a monomolecular film of porphyrin II chloride is formed, a gate potential is applied in advance, and NO concentration is measured by a current change caused by reaction with NO see, for example, Patent Document 1).
- CoTPP cobalt tetraphenylporphyrin
- NO cobalt tetraphenylporphyrin
- NO tetraphenyl-21H, 23H-porphinecobalt
- a method of detecting by infrared spectroscopic measurement is known (see, for example, Non-Patent Document 2).
- a temperature controller formed of indium tin oxide is provided on the back side of the substrate for the purpose of improving reproducibility, and chromium (Cr 3+ ), vanadyl (VO), manganese ((Mn), cobalt (Co ),
- a gas sensor is prepared by forming a film containing a benzotriazaporphyrin containing a transition metal such as copper (Cu), and the sensor is preheated before gas exposure. In the case of non-pre-heat treatment, it takes 24 hours after gas exposure and the pre-heat treatment temperature is 190 ° C.
- tin (Sn4 + ), cobalt (Co 3+ , and Co 2+ ), chromium (Cr 3+ ), iron (Fe 3 + ), ruthenium (Ru 2+ ), zinc are used as the porphyrin central metal.
- a volatile gas detection method is disclosed in which a plurality of porphyrins (Zn 2+ ), silver (Ag 2+ ), and free base (2H + ) are arranged (see, for example, Patent Document 3).
- harmful substances such as halogen gas and hydrogen halide gas are detected using a polymer matrix using free base porphyrin containing no central metal or zinc tetraphenylporphyrin containing zinc (Zn) as the central metal.
- a method and an apparatus for detecting gas are disclosed (for example, see Patent Document 4).
- cobalt porphyrin a porphyrin having cobalt as a central metal
- the conventional method has a problem that it is not possible to accurately measure NO at a low concentration of ppb level in the atmosphere using a simple and small device.
- cobalt porphyrin is not affected by O 2 and CO, which are reaction inhibitory substances, in the atmosphere, and nitrogen oxide is highly sensitive and accurate.
- An object is to provide a nitrogen oxide detection element that can be measured.
- Patent Document 2 reactivity to NO gas is not disclosed, and even if a gas sensor is made using cobalt tetrabenzotriazaporphyrin, the optical absorption spectrum at an optical wavelength of 618 nm or 680 nm used for detection has little absorbance. , NO gas detection of 100 ppb or less is difficult.
- Patent Document 3 there is no detection example of NO which is nitrogen oxide.
- Patent Document 4 the pH dependence of porphyrin reactivity is used, and therefore acid gas and oxidizing gas can be detected.
- nitrogen oxide gas having a low concentration of 1 ppm or less.
- An object of the present invention is to provide a nitrogen oxide detection sensor that is excellent in reproducibility and can be measured a plurality of times.
- the nitrogen oxide detection element of the present invention is a detection film comprising a polymer in which a porphyrin having cobalt as a central metal or a derivative having a porphyrin skeleton having cobalt as a central metal is dispersed or a mixture on the surface of a substrate. Is formed.
- the nitrogen oxide detection element of the present invention is a carrier on which a detection film made of a polymer in which a porphyrin having cobalt as a central metal or a derivative having a porphyrin skeleton having cobalt as a central metal is dispersed or a mixture thereof is formed. Is supported on the surface of the substrate.
- the number of moles of a porphyrin having cobalt as a central metal or a derivative having a porphyrin skeleton having cobalt as a central metal relative to a unit weight of the polymer of the detection film is 1 ⁇ 10 ⁇ . 6 mol / g to 1 ⁇ 10 ⁇ 3 mol / g.
- the number of cobalt atoms per unit area of the detection film is 10 13 pieces / cm 2 to 10 16 pieces / cm 2 .
- the porphyrin having cobalt as a central metal is cobalt tetraphenylporphyrin.
- cobalt as a central metal of the porphyrin having cobalt as a central metal or a derivative having a porphyrin skeleton having cobalt as a central metal, or a mixture thereof is a divalent ion or a divalent ion and 3 It is a mixture of valence ions.
- the nitrogen oxide detection element of the present invention disperses a porphyrin having cobalt as a central metal or a derivative having a porphyrin skeleton having cobalt as a central metal alone or a mixture on the surface of a substrate that does not transmit detection light. It is characterized in that a sensing film made of the polymer is formed.
- the nitrogen oxide detection element of the present invention disperses a porphyrin having cobalt as a central metal or a derivative having a porphyrin skeleton having cobalt as a central metal alone or a mixture on the surface of a substrate through which detection light is transmitted. It is characterized in that a sensing film made of the polymer is formed.
- the substrate through which the detection light is transmitted is a glass substrate, a quartz substrate, a sapphire substrate, a gallium nitride substrate, a plastic substrate, paper, a resin, a woven fabric, or a non-woven fabric.
- the nitrogen oxide detection element of the present invention at least a part of the surface of the substrate serving as an optical waveguide through which detection light passes is porphyrin having cobalt as a central metal along the optical waveguide, or cobalt as a central metal.
- a sensing film made of a polymer in which a derivative having a porphyrin skeleton is dispersed alone or in a mixture is formed.
- a porphyrin having cobalt as a central metal or a derivative having a porphyrin skeleton having cobalt as a central metal alone or a mixture is dispersed on the surface of a substrate that does not transmit detection light.
- a measuring unit that detects light reflected through the detection film and calculates a nitrogen oxide concentration of the measurement gas in contact with the detection film based on a change in the detection light before and after contact with the measurement gas; Is provided.
- a porphyrin having cobalt as a central metal or a derivative having a porphyrin skeleton having cobalt as a central metal alone or a mixture is dispersed on the surface of a substrate through which detection light is transmitted.
- a measuring unit that detects and calculates a nitrogen oxide concentration of the measurement gas that has contacted the detection film based on a change in the detection light before and after contact with the measurement gas.
- At least a part of the surface of a substrate serving as an optical waveguide through which detection light passes is porphyrin having cobalt as a central metal along the optical waveguide, or cobalt is a central metal.
- the nitrogen oxide concentration measuring apparatus has a detection film made of a polymer in which a porphyrin having cobalt as a central metal or a derivative having a porphyrin skeleton having cobalt as a central metal alone or a mixture thereof is dispersed.
- a nitrogen oxide detection sensor in which a heater for bringing the temperature of the nitrogen oxide detection element close to a target temperature is integrally formed with the nitrogen oxide detection element formed on the surface of the non-transmitting substrate; Nitrogen oxidation of the measurement gas in contact with the detection film based on a change in the detection light before and after contact with the measurement gas by irradiating the substrate with detection light, detecting light reflected through the detection film And a measuring unit for calculating the concentration of the object.
- the nitrogen oxide concentration measuring apparatus has a detection film made of a polymer in which a porphyrin having cobalt as a central metal or a derivative having a porphyrin skeleton having cobalt as a central metal alone or a mixture thereof is dispersed.
- a nitrogen oxide detection sensor in which a heater for bringing the temperature of the nitrogen oxide detection element close to a target temperature is integrally formed with the nitrogen oxide detection element formed on the surface of the transmitting substrate; Nitrogen oxide concentration of the measurement gas in contact with the detection film based on a change in the detection light before and after contact with the measurement gas by irradiating the substrate with detection light, detecting light transmitted through the detection film And a measurement unit for calculating the value.
- the nitrogen oxide concentration measuring apparatus of the present invention is a porphyrin having cobalt as a central metal or a derivative having a porphyrin skeleton having cobalt as a central metal on at least a part of the surface of a substrate serving as an optical waveguide through which detection light passes.
- a heater for bringing the temperature of the nitrogen oxide detection element close to the target temperature is integrally formed with the nitrogen oxide detection element in which a detection film made of a polymer dispersed alone or in a mixture is formed along the optical waveguide.
- the nitrogen oxide detection sensor and the light of the nitrogen oxide detection element that has passed through the substrate are detected, and the measurement gas in contact with the detection film is detected based on a change in the detection light before and after contact with the measurement gas.
- a measurement unit for calculating the nitrogen oxide concentration is a porphyrin having cobalt as a central metal or a derivative having a porphyrin skeleton having cobalt as a central metal on at least a part of the surface of a substrate
- a porphyrin having cobalt as a central metal or a derivative having a porphyrin skeleton having cobalt as a central metal alone or a mixture is dispersed on the surface of a substrate that does not transmit detection light.
- a nitrogen oxide detection element in which a detection film made of a polymer is formed, irradiating detection light toward the base of the nitrogen oxide detection element, detecting light reflected through the detection film, Based on the change in the detection light before and after contact with the measurement gas, the nitrogen oxide concentration of the measurement gas in contact with the detection film is calculated, and the nitrogen oxide detection element is heat-treated when measuring the nitrogen oxide concentration It is characterized by doing.
- the heat treatment maintains the temperature of the nitrogen oxide detection sensor at a first temperature T1 lower than the limit temperature of the nitrogen oxide detection sensor before contacting the measurement gas.
- 2nd temperature: T2 is irradiated with detection light toward the nitrogen oxide detection sensor in the state of T2, and the light reflected through the detection film is detected as light output: V1
- the temperature of 2 The measurement gas is brought into contact with the nitrogen oxide detection sensor in the state of T2, and the light output toward the nitrogen oxide detection sensor and reflected through the detection film is output as light output: V2.
- the nitrogen oxide concentration of the measurement gas in contact with the nitrogen oxide detection sensor is calculated based on the light output: V1 and the light output: V2.
- the detection film is made of a polyethylene oxide (PEO) polymer in which CoTPP having cobalt as a central metal is dispersed, and the limit temperature in this case is 290 ° C.
- the first temperature: T1 is equal to or higher than the melting point of the polymer constituting the detection film.
- the second temperature T2 is equal to or higher than the glass transition point of the polymer constituting the detection film.
- the nitrogen oxide concentration measuring method of the present invention is such that the detection film made of a polymer in which a porphyrin having cobalt as a central metal or a derivative having a porphyrin skeleton having cobalt as a central metal alone or a mixture is dispersed is detected light.
- a nitrogen oxide detection element formed on the surface of a transmitting substrate the light passing through the detection film of the nitrogen oxide detection element is detected, and the change in the detection light before and after contacting the measurement gas And calculating the nitrogen oxide concentration of the measurement gas in contact with the detection film, and performing a heat treatment on the nitrogen oxide detection element when measuring the nitrogen oxide concentration.
- the heat treatment is performed.
- the nitrogen oxide detection sensor is irradiated with detection light and the light passing through the detection film is detected as light output: V1
- second The measurement gas is brought into contact with the nitrogen oxide detection sensor in the state of T2, and the detection light is irradiated toward the nitrogen oxide detection sensor, and the light passing through the detection film is detected as light output: V2.
- the nitrogen oxide concentration of the measurement gas in contact with the nitrogen oxide detection sensor is calculated based on the light output: V1 and the light output: V2.
- the detection film is made of a polyethylene oxide (PEO) polymer in which CoTPP having cobalt as a central metal is dispersed, and the limit temperature in this case is 290 ° C.
- the first temperature: T1 is equal to or higher than the melting point of the polymer constituting the detection film.
- the second temperature T2 is equal to or higher than the glass transition point of the polymer constituting the detection film.
- the method for measuring nitrogen oxide concentration according to the present invention is such that at least a part of the surface of a substrate serving as an optical waveguide through which detection light passes has a porphyrin having cobalt as a central metal or a derivative having a porphyrin skeleton having cobalt as a central metal Detecting light that has passed through the substrate of the nitrogen oxide detection element using a nitrogen oxide detection element in which a detection film made of a polymer dispersed alone or in a mixture is formed along the optical waveguide And calculating the nitrogen oxide concentration of the measurement gas in contact with the detection film based on the change in the detection light before and after contacting the measurement gas, and measuring the nitrogen oxide concentration of the nitrogen oxide detection element. A heat treatment is performed.
- the heat treatment is performed.
- second temperature: T2 is irradiated with detection light on the substrate, and the light passing through the substrate is detected as light output: V1
- the second temperature: T2 A measurement gas is brought into contact with the nitrogen oxide detection sensor and detection light is irradiated toward the substrate to detect light passing through the substrate as light output: V2, and the light output: V1 and the light output: V2. Based on the above, the nitrogen oxide concentration of the measurement gas in contact with the nitrogen oxide detection sensor is calculated.
- the detection film is made of a polyethylene oxide (PEO) polymer in which CoTPP having cobalt as a central metal is dispersed, and the limit temperature in this case is 290 ° C.
- the first temperature: T1 is equal to or higher than the melting point of the polymer constituting the detection film.
- the second temperature T2 is equal to or higher than the glass transition point of the polymer constituting the detection film.
- the optical wavelength of the detection light is an optical wavelength including a Sole band of the optical absorption band of the porphyrin.
- the nitrogen oxide sensor of the present invention even if it is a small device, by performing low temperature heating, the cobalt porphyrin is not affected by O 2 or CO which is a reaction inhibitor, and the nitrogen oxide Can be measured with high accuracy. In addition, measurement can be performed multiple times with good reproducibility.
- FIG. 1 shows a light reflection type nitrogen oxide measuring device using the nitrogen oxide detecting element 10A of the present invention.
- the nitrogen oxide detection element 10A includes a detection film 11 made of a polyethylene oxide (PEO) polymer in which CoTPP having cobalt as a central metal is dispersed, and an opaque substrate 12a such as an alumina substrate.
- the substrate 12a may be any material that reflects light, and is preferably a silicon substrate, a silicon carbide substrate, a gallium arsenide substrate, a ceramic substrate, a plastic substrate, a metal plate, or the like in addition to the alumina substrate. Any of these or a complex thereof can be employed.
- the nitrogen oxide detection element 10A is set in the measurement cell 13.
- a measurement gas 30 containing nitrogen oxides is introduced into the measurement cell 13 from the gas inlet 14, discharged from the gas exhaust port 15, and the detection film 11 is exposed to the measurement gas 30.
- the light projecting / receiving unit 18 faces the nitrogen oxide detecting element 10A. It is attached. More specifically, in the light projecting / receiving unit 18, the light from the light source 16 is irradiated perpendicularly to the detection film 11 of the nitrogen oxide detection element 10 ⁇ / b> A through the optical fiber 20, and the reflected light is projected and received by the projecting / receiving unit 18. And is detected by the light detection unit 17 through the optical fiber 21.
- the photodetection unit 17 includes an optical bandpass filter (not shown), a silicon photodiode (not shown), a photocurrent / voltage conversion circuit (not shown), and an amplifier circuit (not shown). It is converted into a light detection signal corresponding to the amount of reflected light and measured.
- the temperature controller 24 is provided in the measurement cell 13, and the temperature in the measurement cell 13 can be controlled by the temperature controller 24.
- the temperature controller 24 includes a heater and a thermocouple for temperature detection (not shown).
- the light source 16, the light detection unit 17, and the temperature controller 24 are connected to the measurement controller 19 via control lines 22, 23, and 25 in order to control respective operations.
- the nitrogen oxide detection element 10A is prepared as follows.
- the polymer preferably has a refractive index (hereinafter referred to as n) of 1.4 to 1.7 at an optical wavelength of 380 to 800 nm. This is because when n is 1.4 to 1.7, the amount of light absorption is small and almost transparent with respect to the optical wavelength used for nitrogen oxide detection, and the transmittance is 90% or more.
- an absorption change is caused by a reaction between a porphyrin having cobalt as a central metal, which will be described later, and a nitrogen oxide, and therefore changes in reflected light and transmitted light can be efficiently measured.
- the glass transition temperature (hereinafter referred to as Tg) of the polymer is preferably ⁇ 150 ° C. to 150 ° C.
- Tg gas permeability and nitrogen oxide gas responsiveness
- Fig. 2 shows the structure of CoTPP used as a NO detector.
- CoTPP is a porphyrin having cobalt as a central metal, and has four phenyl groups outside the porphine skeleton.
- NO binds to CoTPP having bivalent cobalt as a central metal
- electrons move from cobalt to NO, and cobalt is oxidized to trivalent.
- the absorption band having a central wavelength of 414 nm derived from CoTPP containing divalent cobalt (hereinafter referred to as Co (II) TPP) is attenuated as shown in FIG. 3, and CoTPP newly containing trivalent cobalt is added.
- the absorption band with a central wavelength of 435 nm derived from hereinafter referred to as Co (III) TPP) increases.
- the NO concentration can be determined from the amount of change in the CoTPP absorption band caused by NO exposure.
- the change in the absorption band can be confirmed by measuring the reflection spectrum of the detection film before and after exposure to NO.
- the NO concentration can be determined using CoTPP.
- CoTPP having divalent cobalt reactive with NO may be present in the detection film, and CoTPP in which divalent cobalt and trivalent cobalt are mixed may be used.
- an absorption band in which the absorption band of 414 nm derived from divalent CoTPP and the absorption band of 435 nm derived from trivalent CoTPP are superimposed in the absorption spectrum of FIG.
- the ratio of CoTPP having divalent cobalt to CoTPP having trivalent cobalt is determined by the concentration of CoTPP dispersed in the polymer of the detection film and the NO sensitivity of the system, and is not limited.
- the nitrogen oxide detecting element 10A produced by the above-described method reacts with O 2 and CO in the atmosphere, and Co (III) TPP having trivalent cobalt is a main component, and as it is, binding of NO The quantity cannot be measured accurately.
- NO is detected using Co (III) TPP having trivalent cobalt as a central metal, reaction efficiency with NO decreases because O 2 and CO which are reaction inhibitors are bound to cobalt. Because.
- a pretreatment for changing CoTPP to divalent is required immediately before measuring the nitrogen oxide gas.
- a pretreatment method light irradiation of the detection film 11, electromagnetic wave irradiation such as microwaves, or a combination of these means may be used. Considering the simplicity of nitrogen oxide detection and the miniaturization of the measuring device, heat treatment is preferable.
- FIG. 4 shows the change in absorbance of CoTPP at 414 nm and the change in absorbance at 435 nm when the nitrogen oxide detection element 10A is heated at 150 ° C.
- an inert gas such as N 2 gas or Ar gas, or air may be flowed. By flowing gas, desorbed gas molecules such as O 2 and CO can be effectively removed from the measurement cell.
- the absorbance of the peak of the absorption band with a central wavelength of 435 nm derived from Co (III) TPP decreases, and at the same time, the absorbance of the absorption band with a central wavelength of 414 nm derived from Co (II) TPP increases.
- the absorbance at both wavelengths is saturated, and a Co (II) TPP absorption band having a peak at the central wavelength of 414 nm shown in FIG. 3 is obtained.
- the nitrogen oxide detection element 10A of this embodiment can reduce CoTPP to divalent by a very short heat treatment and can be used for measurement of NO.
- the heating temperature is lowered to 50 ° C. in the heat treatment, the time for changing CoTPP to divalent becomes longer. However, if a predetermined time is required, the nitrogen oxide detection element 10A having the absorption band detection film 11 shown in FIG. Is obtained. On the other hand, at a heating temperature of 250 ° C., the absorbance decreases over the entire wavelength, probably due to deterioration of the CoTPP or PEO polymer.
- the setting of the heating temperature and the heating time is not specifically limited to the heating temperature and the heating time as long as the CoTPP and the PEO polymer are not deteriorated and can be quickly heated.
- the temperature range is preferably 50 ° C to 200 ° C.
- the effect of PEO contained in the detection film 11 can be considered.
- the mechanism will be described using a conceptual diagram of the detection film 11.
- FIG. 5 shows an enlarged conceptual diagram of a part of the detection film 11.
- 1 is PEO and 2 is CoTPP. Since PEO1 has a low glass transition temperature of ⁇ 53 ° C., the free space 3 that is not occupied by atoms (or molecules) is large at room temperature and is in a glass state, and some amorphous molecules are free vibrations. Therefore, the gas permeability is very good.
- the diffusion time due to gas diffusion which is a problem with normal solids, is negligible compared to the oxidation-reduction time of CoTPP.
- the reaction inhibitor adsorbed on CoTPP2 can be efficiently desorbed.
- PEO1 has an effect of preventing aggregation of CoTPP2.
- PEO1 When PEO1 is not included, most CoTPP2 aggregates with each other, and NO and the reaction efficiency are significantly reduced.
- the polymer is not limited to PEO, and may be any polymer that is transparent at the optical wavelength measured as described above, has a low glass transition temperature, and prevents CoTPP aggregation.
- the upper limit of Tg is preferably a polymer that does not affect the properties of CoTPP depending on the heat treatment temperature, and the upper limit of Tg is 150 ° C.
- polystyrene 1,4-bis(trimethacrylate)
- Tg ⁇ 53 ° C.
- Tm 68 ° C.
- These resins include copolymers for those that can be copolymerized, and those that can be modified with side chain substituents to improve the refractive index and heat resistance.
- the polymer may contain a plasticizer for the purpose of improving fluidity.
- a plasticizer for the purpose of improving fluidity.
- the reactivity between CoTPP and the test gas is determined by the relationship between the electronic state of CoTPP and the electronic state of the test gas. That is, the reactivity is determined by the magnitude of the redox potential difference determined by the electronic state of CoTPP and the test gas, and the CoTPP absorption band changes according to the redox reaction. Since the inventors have discovered that CoTPP has extremely low reactivity with other gases compared to NOx such as NO gas and NO 2 gas which are nitrogen oxide gas, oxidation of CoTPP and NOx The reduction potential difference is small compared to other gases, and it is assumed that the reactivity between CoTPP and NOx is high.
- the detection film of the present invention is divalent in at least 10 minutes.
- the inventor has confirmed that the state of CoTPP can be maintained. Therefore, it can be detected very effectively by exposing the nitrogen oxide gas to divalent CoTPP by pretreatment.
- the NO detection agent is not limited to CoTPP, and may be a porphyrin whose absorption band is changed by binding of cobalt to NO as a central metal, or a derivative having a porphyrin skeleton whose central metal is cobalt, or a mixture thereof. Any of them is acceptable.
- porphyrin derivatives having cobalt as a central metal include 2,3,7,8,12,13,17,18-octaethyl-21H, 23H-porphine cobalt, and 5,10,15,20-tetrakis.
- Co (p-OCH 3 ) TPP 4,8,12,18-tetraethyl-3,7,13,17-tetramethyl-21H , 23H-porphine cobalt, 5,10,15,20-tetrakis (4-sulfonatophenyl) -21H, 23H-porphine cobalt, or 5,10,15,20-tetrakis (4-hydroxyphenyl) ⁇ 21H, 23H-porphine cobalt (hereinafter, also using either CoTP (CoTP (OH) referred 4 P) It is possible to obtain the effect of the like.
- the production method of the nitrogen oxide detection element 10A will be described more specifically.
- a solution obtained by adding CoTPP and PEO to chloroform is stirred to prepare a CoTPP ⁇ PEO solution of CoTPP 1 ⁇ 10 ⁇ 4 mol / L, PEO 1% (wt / vol).
- the CoTPP ⁇ PEO solution is applied onto a 1 cm square alumina substrate 12a by a spin coating method and dried to produce the detection film 11.
- the film thickness of the detection film 11 was measured with a film thickness meter, it was about 0.5 ⁇ m.
- the nitrogen oxide detection element 10A is produced by the above method.
- the film thickness of the detection film 11 is set according to the reactivity of the detection film with the nitrogen oxide gas. If the CoTPP concentration is constant, the sensitivity improves as the film thickness increases, but the response to the nitrogen oxide gas is delayed. If the thickness of the detection film is thin, the detection film deteriorates with the number of uses. Therefore, in consideration of the detection limit of nitrogen oxide gas, responsiveness, and durability, 0.1 ⁇ m to 3 ⁇ m is preferable.
- the temperature controller 24 is used to perform heat treatment for changing CoTPP to divalent.
- the heat treatment conditions are, for example, a heating temperature of 150 ° C., nitrogen gas (flow rate 200 ml / min), and time 10 minutes.
- the temperature of the nitrogen oxide detecting element is set to 100 ° C. by the temperature controller 24, NO as the measurement gas is introduced into the measurement cell 13 through the gas inlet 14.
- NO is adsorbed to the CoTPP of the detection film 11
- electrons move from CoTPP cobalt to NO, and the CoTPP is oxidized.
- the absorption band at a wavelength of 414 nm decreases in the light reflection spectrum.
- the light reflectance increases, and at the same time, the absorption band at the wavelength of 435 nm increases, and as a result, the light reflectance at the wavelength of 435 nm decreases.
- an optical bandpass filter (not shown), a silicon photodiode (not shown), a photocurrent voltage conversion circuit (not shown), and an amplifier circuit (not shown) corresponding to the change in the absorption band. )
- the light detection signal corresponding to the nitrogen oxide concentration is converted and measured.
- FIG. 6 shows the time change of the optical signal output when NO gas (nitrogen base, concentration 1 ppm, flow rate 200 ml / min) and nitrogen gas (flow rate 200 ml / min) are alternately exposed to the light reflection measurement sensor 10A in a cycle of 2 minutes. Indicates.
- the optical signal output was measured by changing the NO gas concentration, which is the nitrogen oxide concentration, from 5 ppb to 10 ppm by the method described above.
- FIG. 7 shows the relationship between the NO concentration and the optical signal output measured by the nitrogen oxide detection element 10A of the present invention.
- FIG. 7 shows that the NO concentration can be measured in the range of NO concentration of 5 ppb to 10 ppm by using the nitrogen oxide detection element of the present invention.
- heat treatment is performed at a first predetermined temperature of 150 ° C., nitrogen gas (flow rate 200 ml / min), and 10 minutes, and CoTPP dispersed in the polymer is divalent cobalt as a central metal.
- operating the temperature controller 24 so that the inside of the measurement cell 13 continues to be the second predetermined temperature 70 ° C., then irradiating the detection film 11 with light having a center wavelength of 430 nm from the light source 16,
- the first optical signal output V (5 ppb) 01 of the initialized detection film is measured, and the measurement value is stored in the measurement controller 19.
- the NO gas concentration of 10 ppb, 50 ppb, 100 ppb, 500 ppb, and 1 ppm were measured for the NO gas concentration and the optical signal output, and the calibration curve of the NO gas concentration and the optical signal output was obtained and stored in the measurement controller 19. .
- the measurement controller 19 Based on the data obtained by measuring the known gas concentration, the measurement controller 19 obtains a change curve of the differential output ⁇ V corresponding to the gas concentration and determines this as a characteristic curve of the calibration curve.
- the test gas concentration is determined as follows.
- the NO gas concentration of the test gas can be obtained by the same method as that obtained from the calibration curve.
- heat treatment is performed at 150 ° C and nitrogen gas (flow rate 200 ml / min) for 10 minutes to initialize CoTPP dispersed in the polymer to CoTPP with divalent cobalt as the central metal. To do.
- the LED light (center wavelength 430 nm) 16 is irradiated, and the first optical signal output V (X) 01 of the initialized detection film is measured.
- the measurement value is stored in the measurement controller 19.
- the detection gas flow rate 200 ml / min
- the optical signal output after 10 seconds was obtained as a second optical signal V (X) 11.
- the difference output ⁇ V (X) 1 V (X) 11 ⁇ V (X) 01 at the time of measuring the test gas from the optical signal output.
- the gas concentration is read with reference to the previously stored characteristic curve of the calibration curve, or is substituted into an equation defining the characteristic curve of the calibration curve to calculate the NO gas concentration of the test gas. .
- the measurement method of the present invention first, heat treatment is performed at the time of measurement, the test gas is measured at a predetermined temperature, the obtained optical signal output, the NO gas concentration obtained in advance, and the calibration curve of the optical signal output. By comparing with the value of NO, the NO concentration can be measured over a wide range with high sensitivity.
- the heat treatment temperature, the treatment time, and the standard gas concentration used when preparing the calibration curve are not limited, and CoTPP dispersed in the polymer is divalent or mixed with divalent ions and trivalent ions.
- an opaque material that does not transmit light is used as the substrate 12a, but a light-transmitting material that transmits light is used as the substrate.
- a nitrogen oxide detection element 10A in which, for example, a metal film having a surface state in which light reflection is obtained with a film thickness that does not transmit light is formed on the translucent substrate, and a detection film 11 is formed on the metal film.
- the light reflection type nitrogen oxide measuring device can also be configured using In the case of a metal plate as long as it is in a surface state where light reflection can be obtained, a light reflection type nitrogen oxide measuring device is configured using a nitrogen oxide detection element 10A in which a detection film 11 is formed on the metal plate. Can do.
- FIG. 8 shows a light transmission type nitrogen oxide measuring device using the nitrogen oxide detecting element 10B of the present invention.
- the light-reflecting nitrogen oxide measuring device of (Embodiment 1) a surface state in which light reflection is obtained with a film thickness that does not transmit light on the substrate 12a that does not transmit light or a light-transmitting substrate.
- the nitrogen oxide detection element 10A having the detection film 11 formed thereon is used, but in this (Embodiment 2), the detection light passes through the detection film 11 and the substrate 12b. Is different.
- the substrate 12b is made of a material that transmits light well, and the other structure and manufacturing method are the same as those of the nitrogen oxide detection element 10A described above (Embodiment 1).
- the material of the substrate 12b is preferably a glass substrate, a quartz substrate, a sapphire substrate, a gallium nitride substrate, a plastic substrate, paper, a resin, a woven fabric, or a non-woven fabric.
- a nitrogen oxide detection element 10 ⁇ / b> B composed of the detection film 11 and a transparent, specifically transparent substrate 12 b is installed, and the measurement gas 30 is introduced into the measurement cell 13 from the gas inlet 14. Then, the detection film 11 is exposed to the measurement gas 30 and is discharged from the gas exhaust port 15.
- non-rigid paper, resin, woven fabric, or non-woven fabric nitrogen made of a substrate 12b made of paper, resin, woven fabric, or non-woven fabric is provided on a frame (not shown) having an opening in the light transmitting portion. It is preferable to support and use the oxide detection element 10B.
- the light emitted from the light source 16 is irradiated to the nitrogen oxide detection element 10B through the optical fiber 20 and the light projecting unit 26, and the light transmitted through the nitrogen oxide detection element 10B passes through the light receiving unit 27 and the optical fiber 21. It is sensed by the light detection unit 17.
- the light detection unit 17 includes an optical bandpass filter (not shown), a silicon photodiode (not shown), a photocurrent / voltage conversion circuit (not shown), and an amplifier circuit (not shown).
- a temperature controller 24 is provided in the measurement cell 13, and the temperature in the measurement cell 13 can be controlled by the temperature controller 24.
- the temperature controller 24 includes a heater and a thermocouple for temperature detection (not shown).
- the light source 16, the light detection unit 17, and the temperature controller 24 are connected to the measurement controller 19 via control lines 22, 23, and 25 in order to control respective operations.
- the procedure for detecting the nitrogen oxide gas is the same as that in the first embodiment.
- FIG. 9 shows an optical waveguide type nitrogen oxide measuring device using the nitrogen oxide detecting element 10C of the present invention.
- Nitrogen oxide detection element 10C has detection films 11 and 11 formed on both side surfaces of a plate-like substrate 12c that transmits light.
- the configuration other than the nitrogen oxide detection element 10C is the same as in (Embodiment 2).
- the refractive index n0 of the substrate 12c is 1.4 to 1.5, and the refractive index n1 of the detection films 11 and 11 is 1.5 to 1.8. If the diffused light is irradiated on the end face in the long direction of the nitrogen oxide detection element 10C under such conditions, most of the light enters the detection films 11 and 11 from the base 12c.
- the diffused light is applied to the end face of the nitrogen oxide detecting element 10C, but parallel light can also be used. In the case of this parallel light, the end surface of the nitrogen oxide detection element 10C is irradiated obliquely.
- the light that has entered the detection films 11 and 11 travels through the detection films 11 and 11 as shown in the schematic diagram of FIG. 10 and is reflected at the interface between the detection films 11 and 11 and the air. 12c and the detection films 11 and 11 are reflected.
- the light guided in the detection film in this manner propagates through the detection films 11 and 11 as indicated by J while being multi-reflected between the detection film and the air interface and between the detection film and the substrate interface, and is guided in the film. .
- the light transmittance can be greatly reduced, the sensitivity to NO can be increased, and the light can be amplified.
- the detection films 11 and 11 are formed on both side surfaces of the base 12c. However, the detection film 11 may be formed only on one side of the base 12c. In that case, the sensitivity to NO is approximately 50%.
- a solution obtained by adding CoTPP and PEO to chloroform is stirred to prepare a CoTPP ⁇ PEO solution of CoTPP 1 ⁇ 10 ⁇ 4 mol / L and PEO 1% (wt / vol).
- a glass plate (Eagle 2000 (manufactured by Corning) having a length of 125 mm, a width of 2.5 mm, and a thickness of 0.7 mm) is immersed in a CoTPP ⁇ PEO solution for 10 seconds. Thereafter, the substrate is pulled up at an appropriate speed and dried at room temperature. In this manner, the nitrogen oxide detection element 10C in which the detection films 11 and 11 are formed on the plate-like substrate 12c is manufactured.
- the detection film 11 When the detection film 11 is formed only on one side of the substrate 12c, only one side may be peeled after the production, or it may be covered with a masking tape at the time of application and immersed.
- light is repeatedly reflected between the detection film and the air, and can be guided in the film repeatedly to increase the sensitivity to NO gas.
- an incident angle effective for multiple reflection of the waveguide in the film can be set by using an optical prism.
- FIG. 11 shows an optical waveguide type nitrogen oxide measuring device using the nitrogen oxide detecting element 10D of the present invention.
- the nitrogen oxide detection element 10C a detection film was formed on both sides or one side of the plate-like base material 12c.
- the nitrogen oxide detection element 10D in this (Embodiment 4) is a round bar. The difference is that the detection film 11 is formed on the peripheral surface of the fiber base 12d.
- the configuration other than the nitrogen oxide detection element 10D is the same as (Embodiment 3).
- the diffused light guided to the end face of the base 12d is guided in the film as shown in FIG. Reflected at the air interface, the reflected light is also reflected at the interface between the substrate 12d and the detection film 11 and repeats multiple reflections.
- an absorption band that reacts to NO gas is amplified, and NO sensitivity is increased. can do.
- the NO sensitivity can be improved by efficiently amplifying the light.
- the nitrogen oxide detecting element 10D is manufactured as follows.
- a solution obtained by adding CoTPP and PEO to chloroform is stirred to prepare a CoTPP ⁇ PEO solution of CoTPP 1 ⁇ 10 ⁇ 4 mol / L, PEO 1% (wt / vol).
- a glass rod (a glass rod having a length of 150 mm and a diameter of 3 mm (TEWA 32 manufactured by IWAKI)) is immersed in a CoTPP ⁇ PEO solution for 10 seconds. Thereafter, the substrate is pulled up at an appropriate speed and dried at room temperature.
- a sensor device in which a detection film is formed on a round bar-shaped substrate is manufactured.
- polymer fibers such as polymethyl methacrylate (PMMA) fiber and polycarbonate (PC) fiber can also be used.
- the procedure for detecting nitrogen oxide gas using the optical waveguide type nitrogen oxide measuring device shown in FIG. 11 is the same as that in the third embodiment.
- the nitrogen oxide detection element 10D When the end face of the nitrogen oxide detection element 10D is irradiated with diffused light, the light can be repeatedly totally reflected between the substrate 12d and the detection film 11, and the number of reflections can be increased. Similar to the plate-like nitrogen oxide detection element 10A, the nitrogen oxide detection element 10D can greatly reduce the light transmittance, and can increase the sensitivity to NO. In the round bar-shaped nitrogen oxide detection element 10D, the optical component can be easily adjusted as compared with the plate-shaped nitrogen oxide detection element 10A.
- the diffused light is irradiated to the end face of the nitrogen oxide detecting element 10D, but parallel light can also be used.
- the end surface of the nitrogen oxide detection element 10D is irradiated obliquely.
- the temperature controller 24 for heat-treating the detection film is provided separately from the nitrogen oxide detection elements 10A, 10B, 10C, and 10D.
- a nitrogen oxide detection sensor 34A in which a heater 24a for heat-treating the detection film is integrally provided in the nitrogen oxide detection elements 10A, 10B, 10C, 10D. 34B, 34C, and 34D are used.
- FIG. 13 shows a light reflection type nitrogen oxide concentration measuring apparatus using the nitrogen oxide detection sensor 34A of the present invention.
- the nitrogen oxide sensor 34A is configured by integrally forming a heater 24a on the surface of the base 12a of the nitrogen oxide detection element 10A opposite to the surface on which the detection film 11 is formed. Energization of the heater 24a is controlled by a temperature controller 33 that brings the temperature of the nitrogen oxide detection element 10A close to the target temperature.
- the temperature controller 33 includes a temperature sensor 24b such as a thermocouple that detects the temperature of the heater 24a, and a controller 24c that controls energization of the heater 24a so that the temperature detected by the temperature sensor 24b approaches the target temperature.
- the heater 24a is installed on the surface of the base 12a opposite to the surface on which the detection film 11 is formed.
- the heater 24a is specifically a thin film heater, and the material thereof can be platinum (Pt), nichrome alloy (NiCr), tantalum nitride (TaN 2 ) or the like as is well known.
- a sheath heater embedded with NiCr wire may be brought into contact with the alumina substrate 12a.
- the nitrogen oxide detection sensor 34A is set in the measurement cell 13.
- a measurement gas 30 containing nitrogen oxides is introduced into the measurement cell 13 from the gas inlet 14, discharged from the gas exhaust port 15, and the detection film 11 is exposed to the measurement gas 30.
- the light reflection type nitrogen oxide concentration measuring device faces the nitrogen oxide detection sensor 34A and projects and receives the light projecting / receiving unit 18. Is attached. More specifically, in the light projecting / receiving unit 18, the light from the light source 16 is irradiated perpendicularly to the detection film 11 of the nitrogen oxide detection element 10 ⁇ / b> A through the optical fiber 20, and the reflected light is projected and received by the projecting / receiving unit 18. And is detected by the light detection unit 17 through the optical fiber 21.
- the photodetection unit 17 includes an optical bandpass filter (not shown), a silicon photodiode (not shown), a photocurrent / voltage conversion circuit (not shown), and an amplifier circuit (not shown). It is converted into a light detection signal corresponding to the amount of reflected light and measured.
- the light source 16, the light detection unit 17, and the controller 24c are connected to the measurement controller 19 via control lines 22, 23, and 25 in order to control their operations.
- the nitrogen oxide detection sensor 34A is created as follows.
- the polymer preferably has a refractive index (hereinafter referred to as n) of 1.4 to 1.7 at an optical wavelength of 380 to 800 nm. This is because when n is 1.4 to 1.7, the amount of light absorption is small and almost transparent with respect to the optical wavelength used for nitrogen oxide detection, and the transmittance is 90% or more.
- an absorption change is caused by a reaction between a porphyrin having cobalt as a central metal, which will be described later, and a nitrogen oxide, and therefore changes in reflected light and transmitted light can be efficiently measured.
- the glass transition temperature (hereinafter referred to as Tg) of the polymer is preferably ⁇ 150 ° C. to 150 ° C.
- Tg glass transition temperature
- the gas permeability and nitrogen oxide gas responsiveness can be improved by controlling the temperature of the nitrogen oxide detection sensor 34A.
- the heat treatment temperature (first temperature: T1) at initialization described later and the sensor temperature (second temperature: T2) at NO measurement described later are both In both cases, the melting point Tm of the polymer is exceeded, and the polymer is always in a molten state, and as a result, the sensitivity in detecting nitrogen oxides is reduced.
- the melting point Tm of the polymer is 250 ° C. or higher, and the heat treatment temperature (first temperature: T1) during initialization must be set to 250 ° C. or higher. is there.
- CoTPP has a limit temperature.
- the limit temperature is the temperature at which CoTPP decomposes
- the limit temperature is defined as the temperature at which an exothermic peak appears in weight loss in thermogravimetric analysis TG (THERMAL GRAVITY) measurement or differential thermal analysis DTA (DIFFERNTIAL THERMAL ANALYSIS). (Not shown).
- TG analysis was performed while flowing 200 ml of nitrogen gas per minute through the CoTPP used as the detection material this time, weight loss started at 293 ° C., and according to DTA analysis, an exothermic peak appeared at about 400 ° C. From the results of both, it can be seen that the decrease in weight of the detection material starting from 293 ° C. is oxidative decomposition.
- the first temperature T1 which is the sensor initialization processing temperature
- the CoTPP decomposition temperature of about 300 ° C. the sensor sensitivity gradually deteriorates with the processing time t1.
- the first temperature: T1 and the sensor temperature at the time of measurement are used. It is necessary to consider a certain second temperature: T2 according to the limit temperature of CoTPP, which is the material of the detection film, and the Tg and Tm of the polymer that holds the detection material, and T1 and T2 are preferably lower temperatures. I understood it.
- the absorption band of the central wavelength 414 nm of Co (II) TPP and the absorption band of 435 nm of Co (III) TPP in the nitrogen oxide detection element 10A shown in FIG. May shift.
- the superposition state of Co (II) TPP and Co (III) TPP is developed, there may be a shift within the range of the central optical wavelength depending on the existence ratio of the two band states.
- These optical absorption band of 414 nm and optical absorption band of 435 nm are both called a soret band or a B-band and have a large molar extinction coefficient.
- the NO concentration can be determined from the amount of change in the CoTPP absorption band caused by NO exposure.
- the change in the absorption band can be confirmed by measuring the reflection spectrum of the detection film before and after exposure to NO.
- the NO concentration can be determined using CoTPP.
- the nitrogen oxide detection element 10A produced by the above-described method usually reacts with O 2 or CO in the atmosphere, and the absorption band of Co (III) TPP having trivalent cobalt is the main component.
- the absorption band is superposed with the absorption band of divalent cobalt Co (III) TPP.
- the reflection spectrum absorption band of the untreated nitrogen oxide detection sensor 34A is shown in state 1 of FIG.
- Co (III) TPP is a main component and NO cannot be measured.
- CoTPP that can react with NO is only Co (II) TPP having divalent cobalt as a central metal.
- the following describes the temperature control method during initialization and NO gas measurement.
- FIG. 15 shows a timing chart of the pretreatment and measurement of the detection film 11 using the nitrogen oxide detection sensor 34A.
- the detection film 11 is irradiated with detection light from the light source 16 through the optical fiber 20 and the light projecting / receiving unit 18.
- the detection light remains irradiated until the measurement is completed.
- the light source 16 is desirably a light source including at least an optical wavelength of 400 nm to 450 nm. This is because the CoTPP-PEO film 11 of the detection film 11 has an absorption band having a large molar extinction coefficient called a soret band or a B-band in the optical wavelength region as described above.
- the CoTPP-PEO film of the detection film 11 is heated at a first temperature: T1 for a predetermined time t1, gas molecules such as O 2 and CO bonded to CoTPP are desorbed, and the state 1 in FIG. From the state 2, the cobalt of CoTPP is reduced to divalent Co (II) TPP as in the state 3.
- nitrogen gas (N 2 ) shows the change in absorbance of CoTPP at 414 nm and that at 435 nm when the heat treatment of the nitrogen oxide detection sensor 34A made of a CoTPP-PEO detection film is performed at a flow rate of 200 ml / min.
- the temperature of the CoTPP-PEO film is lowered to the preset second temperature: T2 by the temperature controller 33 while nitrogen (N2) gas is similarly supplied as the purge gas at 200 ml / min. Exposure to NO gas is maintained for a period of time t2.
- FIG. 16 shows an optical signal output (absorbance response) at a light wavelength of 414 nm and a light wavelength of 435 nm in the nitrogen oxide detection sensor 34A when intermittently exposed to NO gas (nitrogen base, concentration 1 ppm, flow rate 200 ml / min).
- the optical signal output (absorbance response) is shown in FIG.
- a multiphotometric detector MCPD-7000 manufactured by Otsuka Electronics Co., Ltd.
- nitrogen gas which is a base gas
- nitrogen gas is allowed to flow at a flow rate of 200 ml / min except during NO exposure. From FIG. 16, it was confirmed that the NiTP gas can be detected with high accuracy and high reproducibility by exposing the CoTPP-PEO film to NO gas after being stabilized at the second temperature: T2.
- the nitrogen oxide detection sensor 34A can increase the NO sensitivity by reducing CoTPP to divalent by a very short time low temperature heat treatment.
- the reproducibility of NO detection can be improved by a relatively low operating temperature. That is, it is possible to measure NO with high accuracy and high reproducibility at a low operating temperature by using a relatively low temperature heat treatment.
- the first pretreatment temperature T1 is set to 250 ° C. or higher, the absorbance decreases over the entire wavelength, probably because of degradation of the CoTPP or PEO polymer.
- the first temperature T1 as the pretreatment temperature of the CoTPP-PEO film is set to a temperature lower than the limit temperature 290 ° C. of the detection film 11 and higher than the melting point Tm of the polymer in which CoTPP is dispersed. It is possible to recover the film containing Co (II) TPP as a main component in a shorter time. Furthermore, it is preferable to set the temperature about 50 ° C. higher than the melting point of the polymer used for the detection film 11 in order to suppress deterioration.
- PEO1 Since PEO1 has a low glass transition temperature of ⁇ 53 ° C., it is in a glass state at room temperature (for example, 20 ° C.), and the amorphous molecules constituting the glass state vibrate freely. In the PEO1 film, there is a large free space 3 that is not occupied by atoms (or molecules). A part of CoTPP present dispersed in the PEO 1 is exposed to a free space forming a free volume of the polymer and repeats moving slowly into the polymer. CoTPP exposed on the surface of the polymer is usually fast in reactivity with gas (surface reaction).
- the NO reactivity is slower than in the case of surface reaction because the gas diffuses through the polymer (diffusion reaction). Accordingly, in order to shorten the CoTPP transfer period and improve the reaction rate, the divalent Co (II) TPP bonded to NO is increased and the Co (II) TPP is moved to the surface of the polymer as much as possible. Therefore, it is necessary to increase the collision probability between Co (II) TPP and NO gas. Therefore, the temperature of the detection film 11 may be heated at the first temperature T1 at which the polymer does not deteriorate to increase the Co (II) TPP concentration of the detection film.
- the bond between O 2 and CO gas and CoTPP is weaker than that of nitrogen oxide, and by setting the detection film temperature: T2, gas selectivity with O 2 and CO gas with NO gas is manifested. .
- the second temperature T2 which is the measurement temperature, may be set in consideration of whether the sensor sensitivity is given priority or the response speed is given priority.
- the second temperature T2 is at least a dispersion of the CoTPP detection material. It is preferable to set the temperature higher than the glass transition point Tg of the polymer as a body and not affected by the temperature around the measuring instrument.
- FIG. 17 shows the dependence of the second temperature, which is the sensor temperature, on the optical signal output and the response speed at the time of NO gas measurement of the nitrogen oxide detection sensor 34A of the CoTPP-PEO film: T2.
- the optical signal output (absorbance) in FIG. 17 was measured with a product name: multiphotometric detector (MCPD-7000 manufactured by Otsuka Electronics Co., Ltd.).
- T2 2nd temperature when measuring NO gas concentration: T2 was set to 60 ° C., 80 ° C., and 100 ° C.
- the heat treatment is performed at the initialization temperature (first temperature: T1).
- the NO gas concentration measurement is a nitrogen base gas, 1 ppm-NO, and a flow rate of 200 ml / min.
- the response speed is a response time required for 10% to 90% of the rectangular light signal output at the first NO gas exposure. From FIG.
- T2 is preferably 60 ° C., and in that case, the response time is delayed.
- the second temperature: T2 is preferably 100 ° C. In this case, it is understood that gas desorption is large and the optical signal output is slightly small.
- PEO1 in which CoTPP is dispersed and held also has an effect of preventing aggregation of CoTPP2.
- PEO1 is not included, most of CoTPP2 is likely to aggregate with each other, and the amount of CoTPP that can be held on the substrate is reduced, so that the NO gas sensitivity of the detection film cannot be increased.
- the polymer is not limited to PEO, and may be any polymer that is transparent or almost transparent at the optical wavelength measured as described above, has a low glass transition temperature, and prevents aggregation of CoTPP.
- the upper limit of Tg is preferably a polymer that does not affect the properties of CoTPP by heat treatment, and the upper limit of Tg is 150 ° C.
- Tg 100 ° C.
- the initialization temperature is preferably about 150 ° C. higher than the glass transition temperature: Tg.
- These resins are copolymers for those that can be copolymerized, and those that can be modified with side chain substituents to improve the refractive index and heat resistance, the modified substances are included, as well as the polymer flow.
- a plasticizer may be included for the purpose of improving the properties is as described above.
- the reactivity between CoTPP and the test gas is determined by the relationship between the electronic state of CoTPP and the electronic state of the test gas. That is, the reactivity is determined by the magnitude of the redox potential difference determined by the electronic state of CoTPP and the test gas, and the CoTPP absorption band changes according to the redox reaction. Since the inventors have discovered that CoTPP is less reactive with other gases than NOx such as NO gas and NO 2 gas, which are nitrogen oxide gases, redox of CoTPP and NOx The potential difference is small compared to other gases, and it is assumed that the reactivity between CoTPP and NOx is high.
- NOx such as NO gas and NO 2 gas, which are nitrogen oxide gases
- the detection film of the present invention is divalent in at least 10 minutes.
- the inventor has confirmed that the state of CoTPP can be maintained. Therefore, it can be detected very effectively by exposing it to nitrogen oxide gas after being initialized by pretreatment and reduced to divalent Co (II) TPP.
- the NO detecting material is not limited to CoTPP, and it may be a porphyrin having a cobalt as a central metal and an absorption band changing when NO is bonded, or a derivative having a porphyrin skeleton having cobalt as a central metal, or a mixture thereof. Any of these may be the same as in (Embodiment 1).
- the method for producing the nitrogen oxide detection element 10A is the same as in (Embodiment 1).
- the film thickness of the detection film 11 is set according to the reactivity of the detection film with the nitrogen oxide gas. If the CoTPP concentration is constant, the sensitivity improves as the film thickness increases. However, the gas diffusion time becomes longer and the response to nitrogen oxide gas becomes slower. If the thickness of the detection film is thin, the detection film deteriorates with the number of uses.
- heat treatment is performed to change CoTPP to divalent using the heater 24a.
- the first temperature T1
- the heat treatment is performed for a predetermined time at a temperature lower than 250 ° C. which is the limit temperature of CoTPP and the melting point of the polymer: Tm or more.
- Tm 68 ° C.
- T 1 is preferably 70 ° C. to 150 ° C.
- the alumina substrate (area 10 mm 2 , thickness 0.7 mm), measurement cell volume 500 mm 3 , purge gas 200 ml / min, t1 is 3 minutes or more. It is enough.
- the detection film 11 is set so that the second temperature: T2 is higher than the glass transition temperature: Tg of the polymer and higher than the ambient temperature.
- T2 80 ° C.
- t2 3 minutes after the detection film temperature is stabilized, NO as the measurement gas is introduced into the measurement cell 13 from the gas inlet 14.
- the stabilization time t2 may be set in consideration of the detection record and the gas flow rate.
- the specific set time is set as the time for the optical signal output of the sensor to stabilize.
- the absorption band at a wavelength of 414 nm decreases in the light reflection spectrum.
- the light reflectance increases, and at the same time, the absorption band at the wavelength of 435 nm increases, and as a result, the light reflectance at the wavelength of 435 nm decreases.
- an optical bandpass filter (not shown), a silicon photodiode (not shown), a photocurrent / voltage conversion circuit (not shown), and an amplification circuit corresponding to the change in the absorption band described above. (Not shown) was used to change the NO gas concentration from 5 ppb to 10 ppm and measure the light detection signal (voltage).
- the relationship between the difference between the optical signal output of the initialized detection film 11 and the optical signal output of the detection film 11 exposed to NO gas and the NO gas concentration was the same as in FIG. From this figure, it can be seen that by using the nitrogen oxide detection sensor 34A, the NO concentration can be measured in the range of NO concentration from 5 ppb to 10 ppm. 6 and 7 are different in numerical value on the vertical axis, but it was confirmed that the same sensor shows the same tendency.
- the NO gas concentration of 10 ppb, 50 ppb, 100 ppb, 500 ppb, and 1 ppm were measured for the NO gas concentration and the optical signal output, and the calibration curve of the NO gas concentration and the optical signal output was obtained and stored in the measurement controller 19. .
- the measurement controller 19 Based on the data obtained by measuring the known gas concentration, the measurement controller 19 obtains a change curve of the differential output ⁇ V corresponding to the gas concentration, and determines this as a characteristic curve of the calibration dose.
- the concentration of the test gas is determined in the following manner with reference to the characteristic curve of the dose stored in the measurement controller 19 in this way or the mathematical expression defining the characteristic curve of the dose.
- the detection gas (flow rate 200 ml / min) is caused to flow through the detection film 11 for 10 seconds, and the optical signal output after 10 seconds is output.
- An optical output V2 (X) was obtained.
- the difference output ⁇ V (X) V2 (X) ⁇ V1 when measuring the test gas from the optical signal output.
- the gas concentration is read out with reference to the characteristic curve of the calibration dose determined in advance and stored in the measurement controller 19, or the characteristic curve of the calibration dose is defined.
- the NO gas concentration of the test gas can be calculated by substituting it into the mathematical formula
- the heat treatment for initializing the detection film 11 is first performed at the time of measurement, and the NO film (the test gas) is reflected by the detection film 11 and returned before being exposed to the detection film 11.
- the reflected light is detected by the light detection unit 17, the light output V1 of the output of the light detection unit 17 at this time is measured, and then the detection film 11 is exposed to NO gas (test gas).
- the heat treatment temperature, the treatment time, and the standard gas concentration used at the time of creating the calibration curve are not limited, and CoTPP dispersed in the polymer is made bivalent, and the heat treatment temperature and treatment at the time of creating the calibration curve.
- the time and gas flow rate conditions By making the time and gas flow rate conditions the same, it is possible to measure from 5 ppb to 10 ppm of nitrogen oxide.
- an opaque material that does not transmit light is used as the substrate 12a.
- a light transmitting material that transmits light is used as the substrate.
- a nitrogen oxide detection sensor in which, for example, a metal film in a surface state in which light reflection is obtained with a film thickness that does not transmit light is formed on the translucent substrate, and a detection film 11 is formed on the metal film.
- the light reflection type nitrogen oxide concentration measuring apparatus can also be configured using 34A.
- a light reflection type nitrogen oxide concentration measuring device is configured using a nitrogen oxide detection sensor 34A in which a detection film 11 is formed on the metal plate. can do.
- the heater 24a can be a ceramic heater, a sheath heater, a thin film heater, or the like. In the case of a thin film heater, it is formed by a film forming technique, photolithography and etching, which are known methods. As the thin film material, any of nickel (Ni), chromium (Cr), tantalum (Ta), an alloy thereof, or any metal oxide or metal nitride can be used.
- the temperature sensor 24b is directly contacted with the heater 24a to indirectly detect the temperature of the detection film 11, but as shown in FIG. 18, the temperature sensor 24b is contacted with the substrate 12a to indirectly detect the temperature of the detection film 11.
- the temperature of the detection film 11 can be detected by directly contacting the detection film 11 like a temperature sensor 24b indicated by a broken line in FIG.
- the detection film 11 has been described as being continuously irradiated with detection light until the end of measurement. However, when the amount of light attenuation by the detection film 11 is large, the detection film 11 is irradiated toward the substrate 12a. In this case, when the light is continuously irradiated, the amount of heat input to the detection film 11 and the base 12a by the light increases, so that the base via the detection film 11 is increased. It is preferable to measure the optical signal outputs V1 and V2 by intermittently irradiating light toward 12a.
- FIG. 19 shows a nitrogen oxide detection sensor 34 using the nitrogen oxide detection element 10B of the present invention and a light transmission type nitrogen oxide concentration measuring apparatus using the same.
- a heater 24a is installed on the surface opposite to the surface on which the detection film 11 of the nitrogen oxide detection element 10B of (Embodiment 2) is formed.
- the heater 24a is a transparent or substantially transparent thin film heater through which detection light is transmitted.
- Other structures and manufacturing methods are the same as those of the nitrogen oxide detection sensor 34A of the above-described (Embodiment 5).
- the measurement gas 30 is introduced into the measurement cell 13 from the gas inlet 14, the detection film 11 is exposed to the measurement gas 30, and is discharged from the gas exhaust port 15.
- a temperature controller 33 that brings the temperature of the nitrogen oxide detection sensor 34B close to the target temperature includes a temperature sensor 24b such as a thermocouple, and a controller 24c that controls energization of the heater 24a so that the temperature detected by the temperature sensor 24b approaches the target temperature. It consists of
- the transparent or almost transparent thin film heater As a material for the transparent or almost transparent thin film heater, known indium oxide (In 2 O 3 ), tin oxide (SnO 2 ), ITO which is the composite film, or zinc oxide (ZnO) is used. It can. These films can be masked and formed by physical vapor deposition such as reactive sputtering or reactive ion plating. Moreover, a thin film heater can be formed by performing well-known photolithography after vapor deposition and etching an unnecessary part.
- a CoTPP / PEO solution is applied by a spin coating method to the back side of a glass substrate on which a transparent thin film heater produced by a known technique is formed, and dried to produce the detection film 11.
- CoTPP in the nitrogen oxide detection sensor 34B changes in the absorption spectrum when exposed to nitrogen oxide, by measuring the light transmittance of the detection film 11 before and after exposing the detection film 11 to the measurement gas 30, The nitrogen oxide concentration in the measurement gas can be calculated.
- the light emitted from the light source 16 is irradiated to the nitrogen oxide detection sensor 34B through the optical fiber 20 and the light projecting unit 26, and the light transmitted through the nitrogen oxide detection sensor 34B passes through the light receiving unit 27 and the optical fiber 21. It is sensed by the light detection unit 17.
- the light detection unit 17 includes an optical bandpass filter (not shown), a silicon photodiode (not shown), a photocurrent / voltage conversion circuit (not shown), and an amplifier circuit (not shown).
- the light emitted from the light projecting unit 26 is installed so that the light that hits the nitrogen oxide detection sensor 34B in the vertical direction and the light transmitted through the nitrogen oxide detection sensor 34B hits the light receiving unit 27.
- the light source 16, the light detection unit 17, and the temperature controller 33 are connected to the measurement controller 19 via control lines 22, 23, and 25 in order to control respective operations.
- the procedure for detecting the concentration of nitrogen oxide gas is the same as that in the fifth embodiment.
- the transmission type of (Embodiment 6) can reduce the optical path length by half compared to the reflection type of (Embodiment 5), so that the scattering loss can be reduced and the output can be increased.
- the temperature sensor 24b is directly contacted with the heater 24a to indirectly detect the temperature of the detection film 11, but as shown in FIG. 20, the temperature sensor 24b is contacted to the base body 12b to indirectly detect the temperature of the detection film 11.
- the temperature of the detection film 11 may be detected by directly contacting the detection film 11 like a temperature sensor 24b indicated by a broken line in FIG.
- the detection film 11 is continuously irradiated with detection light until the end of measurement. However, when the amount of light attenuation by the detection film 11 is large, the detection film 11 is directed toward the detection film 11. It is necessary to increase the power of the light to be irradiated. In this case, when the light is continuously irradiated, the amount of heat input to the detection film 11 and the base 12b by the light increases. It is preferable to measure the optical signal outputs V1 and V2 by intermittently irradiating light.
- FIG. 21 shows an optical waveguide type nitrogen oxide concentration measuring apparatus using the nitrogen oxide detection sensor 34C of the present invention.
- the nitrogen oxide detection sensor 34C is formed by forming detection films 11 and 11 on both side surfaces of a plate-like substrate 12c that transmits light.
- the configuration excluding the nitrogen oxide detection sensor 34C is almost the same as in (Embodiment 6).
- the temperature controller 33 that brings the temperature of the nitrogen oxide detection sensor 34C close to the target temperature is set so that the temperature sensor 24b such as a thermocouple that detects the temperature of the heaters 24a and 24a and the temperature sensor 24b approaches the target temperature.
- the controller 24c is configured to control energization to the heaters 24a and 24a.
- the heaters 24 a and 24 a are transparent or substantially transparent thin film heaters through which detection light is transmitted, and are installed between the base 12 c and the detection film 11.
- the temperature sensor 24 b detects the temperature of the detection film 11 by contacting the detection film 11.
- the heaters 24 a and 24 a and the controller 24 c are connected by a wiring 31, and the temperature sensor 24 b and the controller 24 c are connected by a wiring 32.
- the light source 16, the light detection unit 17, the controller 24 c and the measurement controller 19 are connected by control lines 22, 23 and 25.
- the refractive index n0 of the substrate 12c is 1.4 to 1.5, and the refractive index n1 of the detection films 11 and 11 is 1.5 to 1.8. Under such conditions, when the diffused light is irradiated on the end surface of the nitrogen oxide detection sensor 34C in the long direction, most of the light enters the detection films 11 and 11 from the base 12c.
- the diffused light is irradiated to the end face of the nitrogen oxide detection sensor 34C, but parallel light can also be used. In the case of this parallel light, the end surface of the nitrogen oxide detection sensor 34C is irradiated obliquely.
- the light that has entered the detection films 11 and 11 is a transparent or almost transparent thin film heater through which the heaters 24a and 24a transmit the detection light
- the light travels through the detection films 11 and 11 as in the schematic diagram shown in FIG.
- Most of the light reflected by the interfaces between the detection films 11 and 11 and the air is reflected by the base 12 c and the detection films 11 and 11.
- the light guided in such a detection film propagates in the detection films 11 and 11 as indicated by J while being reflected by the detection film and the air interface, and the detection film and the substrate interface, and is guided in the film.
- the light transmittance can be greatly reduced, the sensitivity to NO can be increased, and the light can be amplified.
- the detection films 11 and 11 are formed on both side surfaces of the base 12c. However, the detection film 11 may be formed only on one side of the base 12c. In that case, the sensitivity to NO is approximately 50%.
- a glass plate (length: 125 mm, width: 2.5 mm, thickness: 0.7 mm Eagle 2000 (manufactured by Corning)) as the substrate 12c is transparent or almost transparent as the heaters 24a, 24a.
- a transparent thin film heater is produced.
- the glass plate on which the thin film heater is formed is immersed in a CoTPP / PEO solution for 10 seconds. Thereafter, the substrate is pulled up at an appropriate speed and dried at room temperature. In this manner, the nitrogen oxide detection sensor 34C in which the detection films 11 and 11 are formed on the plate-like base 12c is manufactured.
- the detection film 11 When the detection film 11 is formed only on one side of the substrate 12c, only one side may be peeled after the production, or it may be covered with a masking tape at the time of application and immersed.
- the heater 24a since the heater 24a is transparent or almost transparent, the heater 24a may be on the detection film side or on the side where the detection film is not formed, and is not limited to the arrangement location.
- the procedure of introducing the measurement gas 30 into the measurement cell 13 and the measurement process are the same as those in the sixth embodiment.
- light is repeatedly reflected between the detection film and the air, and can be guided in the film repeatedly to increase the sensitivity to NO gas.
- an incident angle effective for multiple reflection of the waveguide in the film can be set by using an optical prism.
- the temperature sensor 24b is brought into contact with the detection film 11 to detect the temperature, and the controller 24c controls the detection film 11 to the first and second temperatures: T1 and T2, but the temperature sensor 24b is as shown in FIG.
- the temperature of the detection film 11 is indirectly detected by contacting the substrate 12c to control the temperature of the detection film 11, or the temperature sensor 24b is brought into contact with the heater 24a as shown by a broken line in FIG.
- the temperature of the detection film 11 can also be controlled by indirectly detecting the temperature.
- the base 12c is continuously irradiated with detection light until the measurement is completed.
- the base 12c is irradiated toward the base 12c. It is necessary to increase the power of light.
- the amount of heat input to the detection film 11 and the base 12c by the light increases, so that the light is intermittently directed toward the base 12c. It is preferable to measure the optical signal outputs V1 and V2 by irradiating light.
- FIG. 23 shows an optical waveguide type nitrogen oxide concentration measuring apparatus using the nitrogen oxide detection sensor 34D of the present invention.
- the detection film is formed on both sides or one side of the plate-like substrate 12c.
- the nitrogen oxide detection of this (Embodiment 8) The sensor 34D is different in that a detection film 11 is formed on the peripheral surface of a round rod-like fiber base 12d.
- the temperature controller 33 that brings the temperature of the nitrogen oxide detection sensor 34D close to the target temperature includes a temperature sensor 24b such as a thermocouple that detects the temperature of the heaters 24a and 24a, and a heater so that the detected temperature of the temperature sensor 24b approaches the target temperature.
- the controller 24c controls the energization to the 24a.
- the heater 24a is specifically a transparent or substantially transparent thin film heater, and is provided between the base 12d and the detection film 11.
- the temperature sensor 24b is in contact with the detection film 11 to detect the temperature of the detection film 11.
- the heater 24 a and the controller 24 c are connected by a wiring 31, and the temperature sensor 24 b and the controller 24 c are connected by a wiring 32.
- the light source 16, the light detection unit 17, the controller 24 c and the measurement controller 19 are connected by control lines 22, 23 and 25.
- the configuration other than the nitrogen oxide detection sensor 34D is the same as (Embodiment 7).
- This nitrogen oxide detection sensor 34D is guided to the end face of the base 12d because the entire surface of the base 12d is covered with the detection film 11 through a transparent or substantially transparent thin film heater through which the heater 24a transmits the detection light.
- the diffused light is guided in the film and reflected at the interface between the detection film and the air, and the reflected light is reflected at the interface between the substrate 12d and the detection film 11 to be multiplexed.
- an absorption band that reacts with NO gas is amplified, and NO sensitivity can be increased.
- NO sensitivity can be improved by efficiently amplifying the light.
- the nitrogen oxide detection sensor 34D is manufactured as follows.
- a transparent or nearly transparent thin film heater is manufactured as the heater 24a on a glass rod (150 mm long, 3 mm diameter glass rod (TEW32 manufactured by IWAKI)) as the substrate 12d.
- a glass rod 150 mm long, 3 mm diameter glass rod (TEW32 manufactured by IWAKI)
- a solution obtained by adding CoTPP and PEO to chloroform is stirred to prepare a CoTPP ⁇ PEO solution of CoTPP 1 ⁇ 10 ⁇ 4 mol / L and PEO 1% (wt / vol).
- the glass rod on which the heater 24a is formed is immersed in a CoTPP / PEO solution for 10 seconds. Thereafter, the substrate is pulled up at an appropriate speed and dried at room temperature.
- a sensor device in which the detection film 11 is formed on the round bar-shaped substrate 12d is manufactured.
- the substrate polymer fibers such as polymethyl methacrylate (PMMA) fiber and polycarbonate (PC) fiber can also be used.
- PMMA polymethyl methacrylate
- PC polycarbonate
- the nitrogen oxide detection sensor 34D When the end face of the nitrogen oxide detection sensor 34D is irradiated with diffused light, the light repeats total reflection between the substrate 12d and the detection film 11, and the number of reflections can be increased. Similarly to the plate-like nitrogen oxide detection sensor 34A, the nitrogen oxide detection sensor 34D can greatly reduce the light transmittance, and can increase the sensitivity to NO. In the round bar-shaped nitrogen oxide detection sensor 34D, the optical components can be adjusted more easily than the plate-shaped nitrogen oxide detection sensor 34A.
- the diffused light is applied to the end face of the nitrogen oxide detection sensor 34D, but parallel light can also be used.
- the end surface of the nitrogen oxide detection sensor 34D is irradiated obliquely.
- an incident angle effective for multiple reflection of waveguides in the film can be set by using an optical prism.
- the temperature sensor 24b directly contacts the base 12d and detects the temperature. However, the temperature sensor 24b contacts the base 12d as shown in FIG. 24 to indirectly detect the temperature of the detection film 11, or the like. It is also possible to control the temperature of the detection film 11 by detecting the temperature of the detection film 11 indirectly by contacting the heater 24a as in a temperature sensor 24b indicated by a broken line in FIG.
- the heater 24a is formed between the peripheral surface of the round rod-shaped fiber base 12d and the detection film 11.
- a sheath heater is used as shown in FIG.
- the detection film 11 can be set to the first and second temperatures T1 and T2.
- NiCr wire and Pt wire may be wound instead of the sheath heater.
- the temperature sensor 24b is attached so as to detect the temperature of the heater 24a, the temperature sensor 24b is provided so as to directly measure the temperature of the detection film 11, or the temperature of the detection film 11 is indirectly set.
- a temperature sensor 24b can be provided on the base 12d to measure.
- the base 12d is continuously irradiated with detection light until the end of measurement. However, if the amount of light attenuation by the detection film 11 is large, the base 12d is irradiated toward the base 12d. It is necessary to increase the power of light. In this case, when the light is continuously irradiated, the amount of heat input to the detection film 11 and the base 12d by the light increases, and therefore intermittently toward the base 12d. It is preferable to measure the optical signal outputs V1 and V2 by irradiating light.
- the detection film is formed directly on the substrate.
- the powder 29 as the carrier has porphyrin having cobalt as the central metal or cobalt as the central metal.
- the detection film 11 made of a polymer having a porphyrin skeleton derivative alone or a mixture dispersed therein is formed, and this powder 29 is formed on the surfaces of the substrates 12a, 12b, 12c and 12d to detect nitrogen oxides. Elements and nitrogen oxide sensors can also be constructed.
- the powder 29 becomes transparent with respect to the measurement optical wavelength, and nitrogen oxide can be detected.
- nanofibers may be used as the carrier.
- a solvent in which porphyrin and a polymer are dissolved is prepared, a support is disposed opposite to the spray nozzle, and an electric field is formed between the spray nozzle and the support.
- the solvent is instantly evaporated, and the nanofiber-like detection film 11 can be formed on the support (electric field spray method (ESD)).
- ESD electric field spray method
- a nonwoven fabric such as polycaprolactan, polybutylene succinate or polybutylene succinate adipate, which is made of cellulose, fluororesin or biodegradable plastic, is used.
- the solution in which the solution is dissolved is dipped, the solvent is dried and evaporated to form the detection film 11 on the nonwoven fabric, and this is formed on the surfaces of the substrates 12a, 12b, 12c, and 12d to form the nitrogen oxide detection element and the nitrogen oxide sensor.
- the solution having a PEO concentration of 1% (wt / vol) and a different CoTPP concentration (the number of CoTPP moles relative to the PEO weight (hereinafter referred to as CoTPP / PEO ratio) is 1 ⁇ 10 ⁇ 7 mol / g, 1 ⁇ 10 ⁇ 6 mol / g, 1 ⁇ 10 ⁇ 5 mol / g, 1 ⁇ 10 ⁇ 4 mol / g, 1 ⁇ 10 ⁇ 3 mol / g, 5 ⁇ 10 ⁇ 3 mol / g)
- CoTPP / PEO ratio the number of CoTPP moles relative to the PEO weight
- the spin coating was performed at the same rotation speed and rotation time for each detection film.
- the reactivity of the detection film produced by the above method with NO gas was evaluated. First, the light reflection spectrum before NO gas exposure was measured, and then NO gas (nitrogen base, 200 ml / min) 0.01 ppm, 0.1 ppm, 1 ppm, 10 ppm nitric oxide gas was exposed to each detection film. The change of the light reflection spectrum was measured.
- the number of moles of CoTPP with respect to the PEO weight of the detection film is preferably 1 ⁇ 10 ⁇ 6 mol / g to 1 ⁇ 10 ⁇ 3 mol / g.
- the film thicknesses of the detection films having different CoTPP loadings were actually measured, and the number of cobalt atoms per unit area was determined in consideration of the film density, and found to be 10 13 / cm 2 to 10 16 / cm 2 . Therefore, it was found that the number of cobalt atoms of CoTPP per unit area of the sensing film is preferably 10 13 pieces / cm 2 to 10 16 pieces / cm 2 .
- the change in absorbance and the NO concentration were approximately proportional to each other in the range of NO concentrations of 0.01 ppm, 0.1 ppm, 1 ppm, and 10 ppm.
- a detection film in which a single or mixture of derivatives having a porphyrin skeleton having cobalt as a central metal is dispersed in a polymer, Co (II Wavelength positions of the absorption bands of the absorption band and Co (III) of unchanged only about 5 nm, it was confirmed that can detect nitrogen oxides through a band pass filter.
- Example 4 This is an experimental example of NOx detection.
- FIG. 26 shows the measurement results of absorbance at that time.
- Experimental Example 4 shows an example of detecting nitrogen dioxide (NO 2 ) gas using the light reflection type nitrogen oxide measuring device of FIG.
- a light reflection type comprising a detection film with a CoTPP ⁇ PEO ratio of 1 ⁇ 10 ⁇ 5 mol / g
- NO 2 gas nitrogen base, concentration 10 ppm
- a flow rate of 200 ml / min was introduced into the measuring cell.
- NO gas introduction the absorption band with a wavelength of 414 nm decreases and the absorption band with a wavelength of 435 nm increases with the introduction of NO 2 gas.
- the reactivity of the sensing film absorption band with NO 2 gas is equivalent to the reactivity of NO gas, so that the sensing film 11 is effective as a NOx sensor and has an environmental NOx gas of about 50 ppb. It can be used for concentration measurement.
- the heater 24a is attached to the substrate.
- the temperature is controlled by the sensor 24b and the controller 24c.
- the temperature sensor 24b is not necessary. An example of this case is shown in FIG.
- FIG. 28 shows a surface opposite to the side on which the detection film 11 is formed in the substrate 12a of (Embodiment 5).
- the substrate 12a is provided with a first planar heater 24a1 having a PTC characteristic (Positive / Temperature / coefficient) and a second planar heater 24a2 having a PTC characteristic that increase in resistance and hardly flow of electricity when the temperature rises.
- the material and shape are set such that the temperature at which the first planar heater 24a1 is stabilized is the first temperature: T1, and the temperature at which the second planar heater 24a2 is stabilized is the second temperature: T2. Is designed.
- the controller 24c in this case is in a period for initializing the detection film 11.
- a voltage is applied to both ends of the first planar heater 24a1, the initialization of the detection film 11 is completed, and both ends of the second planar heater 24a2 are exposed during exposure of NO gas (test gas) to the detection film 11. Therefore, the temperature sensor 24b found in (Embodiment 5) is not required.
- Such a configuration that does not require the temperature sensor 24b using the heater having the PTC characteristic can be similarly implemented in the respective embodiments (Embodiment 6) to (Embodiment 9).
- the controller 24c has a control function to bring the temperature of the nitrogen oxide detection element close to the target temperature.
- the measurement controller 19 controls the energization of the heater 24a based on the detection signal of the temperature sensor 24b, It can also be configured to bring the temperature of the oxide sensing element closer to the target temperature.
- the nitrogen oxide detection element or sensor according to the present invention is useful for NOx detection for environmental measurement, medicine, pharmacy, bioresearch, drug development, chemical safety evaluation, and the like.
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Abstract
Description
図1は本発明の窒素酸化物検出エレメント10Aを用いた光反射型窒素酸化物測定装置を示す。
差分出力ΔV(5ppb)1=V(5ppb)11-V(5ppb)01
として保存する。
引続き第2の所定温度70℃にセンサ温度を設定した後、LED光(中心波長430nm)16を照射して、初期化された検知膜の第1の光信号出力V(X)01を測定し、計測コントローラ19に測定値を保存する。引続き被検ガス(流速200ml/分)で検知膜に10秒流し、前記10秒後の光信号出力を第2の光信号V(X)11を得た。計測コントローラ19で、上記光信号出力より被検ガス測定時の
差分出力ΔV(X)1=V(X)11-V(X)01
を計算し、前記予め保存していた検量線の特性カーブを参照してガス濃度を読み出したり、または検量線の特性カーブを規定する数式に代入して、被検ガスのNOガス濃度を計算できる。
図8は本発明の窒素酸化物検出エレメント10Bを用いた光透過型窒素酸化物測定装置を示す。
図9は本発明の窒素酸化物検出エレメント10Cを用いた光導波型窒素酸化物測定装置を示す。
図11は本発明の窒素酸化物検出エレメント10Dを用いた光導波型窒素酸化物測定装置を示す。
図13は本発明の窒素酸化物検出センサ34Aを用いた光反射型窒素酸化物濃度測定装置を示す。
差分出力ΔV(5ppb)1= V2(5ppb) - V1
として保存する。
差分出力ΔV(X) = V2(X) - V1
を計算する。次に、差分出力ΔV(X)をキーにして、予め決定して計測コントローラ19に保存されている前記検線量の特性カーブを参照してガス濃度を読み出したり、または検線量の特性カーブを規定する数式に代入して被検ガスのNOガス濃度を計算できる。
図19は本発明の窒素酸化物検出エレメント10Bを用いた窒素酸化物検出センサ34とこれを使用した光透過型窒素酸化物濃度測定装置を示す。
図21は本発明の窒素酸化物検出センサ34Cを用いた光導波型窒素酸化物濃度測定装置を示す。
図23は本発明の窒素酸化物検出センサ34Dを用いた光導波型窒素酸化物濃度測定装置を示す。
上記の各実施の形態においては、検知膜が基体に直接に形成されていたが、図27に示すように担体としての粉体29に、コバルトを中心金属とするポルフィリン、または、コバルトを中心金属とするポルフィリン骨格を有する誘導体の単独、または混合物を分散した高分子からなる前記検知膜11を形成し、この粉体29を基体12a,12b,12c,12dの表面に形成して窒素酸化物検出エレメントや窒素酸化物センサを構成することもできる。
上記の各実施の形態における検知膜11のCoTPP・PEO組成依存性について検討する。
CoTPP・PEO比5×10-3mol/gの場合、図3のような単独の中心波長414nmの吸光バンドは得られず、中心波長414nmの吸光バンドと中心波長435nmの吸光バンドが重なりあったバンドとなり、各濃度のNOガスとの反応は見られなかった。このように中心波長435nmの吸光バンドが残ることから、高濃度CoTPP領域では多数のCoTPPが凝集しており、凝集したCoTPPが分子を結合・解離できない状態となっているため、CoTPPにNOが配位結合できないと推察した。
CoTPP・PEO比1×10-3mol/gの場合、中心波長414nmの大きなバンドが見られるが、中心波長435nmのバンドもサブバンドとして確認できる。NOガスとの反応性を評価したところ、0.01ppm、0.1ppmに対しては、図7と同様に、吸光度の変化とNO濃度に比例関係が見られた。しかし、NOガス1ppm以上では、吸光度の変化量はほぼ一定の値となった。
CoTPP・PEO比1×10-5mol/g、および1×10-6mol/gの場合、中心波長414nmのバンドが確認される。NOガスとの反応性を評価したところ、1ppm、10ppmに対しては、吸光度の変化とNO濃度にほぼ比例関係が得られるが、NO低濃度領域では、明確な反応は見られなかった。
CoTPP・PEO比1×10-7mol/gの場合、中心波長414nmのバンドが見られたが、吸光度が小さい。NOガス濃度10ppmとの反応においては、図6に示すようなCoTPPと一酸化窒素との可逆的な反応が見られたが、1ppm以下の低濃度NOガスには、明確な反応は見られなかった。
コバルトを中心金属とするポルフィリン骨格を有する誘導体の混合物を分散した高分子からなる検知膜を形成した場合の実験結果について述べる。Co(p-OCH3)TPP・PEO比とCoTPP・PEO比の合計が1×10-6mol/g、1×10-5mol/g、1×10-4mol/g、1×10-3mol/gの混合物となるクロロホルム溶液を作製して、アルミナ基板2上にスピンコーティング法により塗布し、乾燥させて、検知膜を作製した。各センサの前処理として、第1の所定温度150℃10分間熱処理を行ったところ、中心波長414nmのCo(II)TPPの吸光バンドと併せて、中心波長419nmのCo(II)(p-OCH3)TPPの吸光バンドが重なった吸光バンドが得られた。各検知膜にNOガス(窒素ベース、200ml/分)0.01ppm、0.1ppm、1ppm、10ppmの一酸化窒素ガスを曝露して光反射スペクトルの変化を評価したところ、中心波長435nmのCo(III)TPPの吸光バンドと併せて、中心波長440nmのCo(III)(p-OCH3)TPPの(吸光バンドの重ね合わさった吸光バンドへと変化した。その結果、単独のCoTPPを分散したPEO高分子からなる検知膜を形成した場合と同様に、NO濃度0.01ppm、0.1ppm、1ppm、10ppmの範囲で吸光度の変化とNO濃度にほぼ比例関係が得られた。以上のことから、コバルトを中心金属とするポルフィリン骨格を有する誘導体の単独または混合物を高分子に分散した検知膜では、Co(II)の吸光バンドとCo(III)の吸光バンドの波長位置は5nm程度しか変わらず、バンドパスフィルタを介して窒素酸化物を検出できることを確認した。
これはNOx検出の実験例である。図26はそのときの吸光度の測定結果である。
Claims (26)
- 基体の表面に、コバルトを中心金属とするポルフィリン、または、コバルトを中心金属とするポルフィリン骨格を有する誘導体の単独、または混合物を分散した高分子からなる検知膜を形成した
窒素酸化物検出エレメント。 - コバルトを中心金属とするポルフィリン、または、コバルトを中心金属とするポルフィリン骨格を有する誘導体の単独、または混合物を分散した高分子からなる検知膜を形成した担体を、基体の表面に支持した
窒素酸化物検出エレメント。 - 前記検知膜の高分子の単位重量に対するコバルトを中心金属とするポルフィリン、または、コバルトを中心金属とするポルフィリン骨格を有する誘導体の単独、または混合物のモル数が、1×10-6mol/g~1×10-3mol/gである
請求項1または請求項2に記載の窒素酸化物検出エレメント。 - 前記検知膜の単位面積あたりのコバルト原子数が、1013個/cm2~1016個/cm2である
請求項1または請求項2に記載の窒素酸化物検出エレメント。 - 前記コバルトを中心金属とするポルフィリンが、コバルトテトラフェニルポルフィリンである
請求項1または請求項2に記載の窒素酸化物検出エレメント。 - 前記コバルトを中心金属とするポルフィリン、または、コバルトを中心金属とするポルフィリン骨格を有する誘導体の単独、または混合物の中心金属であるコバルトが、2価イオンまたは、2価イオンと3価イオンの混在である
請求項1または請求項2に記載の窒素酸化物検出エレメント。 - 検出光が透過しない基体の表面に、コバルトを中心金属とするポルフィリン、または、コバルトを中心金属とするポルフィリン骨格を有する誘導体の単独、または混合物を分散した高分子からなる検知膜を形成した
窒素酸化物検出エレメント。 - 検出光が透過する基体の表面に、コバルトを中心金属とするポルフィリン、または、コバルトを中心金属とするポルフィリン骨格を有する誘導体の単独、または混合物を分散した高分子からなる検知膜を形成した
窒素酸化物検出エレメント。 - 検出光が透過する前記基体が、ガラス基板、石英基板、サファイア基板、窒化ガリウム基板、プラスチック基板、紙、樹脂、織布、または不織布である
請求項8に記載の窒素酸化物検出エレメント。 - 検出光が通過する光導波路となる基体の表面の少なくとも一部が、前記光導波路に沿って、コバルトを中心金属とするポルフィリン、または、コバルトを中心金属とするポルフィリン骨格を有する誘導体の単独、または混合物を分散した高分子からなる検知膜が形成されている
窒素酸化物検出エレメント。 - 検出光が透過しない基体の表面に、コバルトを中心金属とするポルフィリン、または、コバルトを中心金属とするポルフィリン骨格を有する誘導体の単独、または混合物を分散した高分子からなる検知膜が形成されている窒素酸化物検出エレメントと、
前記窒素酸化物検出エレメントの温度を目標温度に近付ける温度コントローラと、
前記窒素酸化物検出エレメントの基体に向けて検出光を照射し、前記検知膜を介して反射した光を検出し、前記測定ガスに接触する前後の前記検出光の変化に基づいて前記検知膜に接触した測定ガスの窒素酸化物濃度を計算する測定部と
を設けた窒素酸化物濃度測定装置。 - 検出光が透過する基体の表面に、コバルトを中心金属とするポルフィリン、または、コバルトを中心金属とするポルフィリン骨格を有する誘導体の単独、または混合物を分散した高分子からなる検知膜が形成されている窒素酸化物検出エレメントと、
前記窒素酸化物検出エレメントの温度を目標温度に近付ける温度コントローラと、
前記窒素酸化物検出エレメントの前記検知膜を透過した光を検出し、前記測定ガスに接触する前後の前記検出光の変化に基づいて前記検知膜に接触した測定ガスの窒素酸化物濃度を計算する測定部と
を設けた窒素酸化物濃度測定装置。 - 検出光が通過する光導波路となる基体の表面の少なくとも一部が、前記光導波路に沿って、コバルトを中心金属とするポルフィリン、または、コバルトを中心金属とするポルフィリン骨格を有する誘導体の単独、または混合物を分散した高分子からなる検知膜が形成されている窒素酸化物検出エレメントと、
前記窒素酸化物検出エレメントの温度を目標温度に近付ける温度コントローラと、
前記窒素酸化物検出エレメントの前記基体を通過した光を検出し、前記測定ガスに接触する前後の前記検出光の変化に基づいて前記検知膜に接触した測定ガスの窒素酸化物濃度を計算する測定部と
を設けた窒素酸化物濃度測定装置。 - コバルトを中心金属とするポルフィリン、または、コバルトを中心金属とするポルフィリン骨格を有する誘導体の単独、または混合物を分散した高分子からなる検知膜が検出光が透過しない基体の表面に形成されている窒素酸化物検出エレメントとこの窒素酸化物検出エレメントの温度を目標温度に近付けるヒータが一体に形成された窒素酸化物検出センサと、
前記窒素酸化物検出センサの基体に向けて検出光を照射し、前記検知膜を介して反射した光を検出し、前記測定ガスに接触する前後の前記検出光の変化に基づいて前記検知膜に接触した測定ガスの窒素酸化物濃度を計算する測定部と
を設けた窒素酸化物濃度測定装置。 - コバルトを中心金属とするポルフィリン、または、コバルトを中心金属とするポルフィリン骨格を有する誘導体の単独、または混合物を分散した高分子からなる検知膜が検出光が透過する基体の表面に形成されている窒素酸化物検出エレメントにこの窒素酸化物検出エレメントの温度を目標温度に近付けるヒータが一体に形成された窒素酸化物検出センサと、
前記窒素酸化物検出センサの基体に向けて検出光を照射し、前記検知膜を透過した光を検出し、前記測定ガスに接触する前後の前記検出光の変化に基づいて前記検知膜に接触した測定ガスの窒素酸化物濃度を計算する測定部と
を設けた窒素酸化物濃度測定装置。 - 検出光が通過する光導波路となる基体の表面の少なくとも一部に、コバルトを中心金属とするポルフィリン、または、コバルトを中心金属とするポルフィリン骨格を有する誘導体の単独、または混合物を分散した高分子からなる検知膜が前記光導波路に沿って形成されている窒素酸化物検出エレメントにこの窒素酸化物検出エレメントの温度を目標温度に近付けるヒータが一体に形成された窒素酸化物検出センサと、
前記窒素酸化物検出エレメントの前記基体を通過した光を検出し、前記測定ガスに接触する前後の前記検出光の変化に基づいて前記検知膜に接触した測定ガスの窒素酸化物濃度を計算する測定部と
を設けた窒素酸化物濃度測定装置。 - 検出光が透過しない基体の表面に、コバルトを中心金属とするポルフィリン、または、コバルトを中心金属とするポルフィリン骨格を有する誘導体の単独、または混合物を分散した高分子からなる検知膜を形成した窒素酸化物検出エレメントを使用して、前記窒素酸化物検出エレメントの基体に向けて検出光を照射し、前記検知膜を介して反射した光を検出し、前記測定ガスに接触する前後の前記検出光の変化に基づいて前記検知膜に接触した測定ガスの窒素酸化物濃度を計算するとともに、
窒素酸化物濃度の測定に際して前記窒素酸化物検出エレメントの熱処理を実行する
窒素酸化物濃度測定方法。 - 前記熱処理が、
測定ガスを接触させる前に、前記窒素酸化物検出センサの温度をこの窒素酸化物検出センサの限界温度よりも低い第1の温度:T1に維持した後に前記第1の温度:T1より低い第2の温度:T2の状態で前記窒素酸化物検出センサに向けて検出光を照射して前記検知膜を介して反射した光を光出力:V1として検出し、
第2の温度:T2の状態の前記窒素酸化物検出センサに測定ガスを接触させるとともに前記窒素酸化物検出センサに向けて検出光を照射して前記検知膜を介して反射した光を光出力:V2として検出し、
前記光出力:V1と前記光出力:V2に基づいて前記窒素酸化物検出センサに接触した測定ガスの窒素酸化物濃度を計算する
請求項117に記載の窒素酸化物濃度の測定方法。 - コバルトを中心金属とするポルフィリン、または、コバルトを中心金属とするポルフィリン骨格を有する誘導体の単独、または混合物を分散した高分子からなる検知膜が検出光が透過する基体の表面に形成された窒素酸化物検出エレメントを使用して、前記窒素酸化物検出エレメントの前記検知膜を通過した光を検出し、前記測定ガスに接触する前後の前記検出光の変化に基づいて前記検知膜に接触した測定ガスの窒素酸化物濃度を計算するとともに、窒素酸化物濃度の測定に際して前記窒素酸化物検出エレメントの熱処理を実行する
窒素酸化物濃度測定方法。 - 前記熱処理が、
測定ガスを接触させる前に、前記前記窒素酸化物検出センサの温度をこの窒素酸化物検出センサの限界温度よりも低い第1の温度:T1に維持した後に前記第1の温度:T1より低い第2の温度:T2の状態で前記窒素酸化物検出センサに向けて検出光を照射して前記検知膜を通過した光を光出力:V1として検出し、
第2の温度:T2の状態の前記窒素酸化物検出センサに測定ガスを接触させるとともに前記窒素酸化物検出センサに向けて検出光を照射して前記検知膜を通過した光を光出力:V2として検出し、
前記光出力:V1と前記光出力:V2に基づいて前記窒素酸化物検出センサに接触した測定ガスの窒素酸化物濃度を計算する
請求項19に記載の窒素酸化物濃度の測定方法。 - 検出光が通過する光導波路となる基体の表面の少なくとも一部が、コバルトを中心金属とするポルフィリン、または、コバルトを中心金属とするポルフィリン骨格を有する誘導体の単独、または混合物を分散した高分子からなる検知膜が前記光導波路に沿って形成されている窒素酸化物検出エレメントを使用して、前記窒素酸化物検出エレメントの前記基体を通過した光を検出し、前記測定ガスに接触する前後の前記検出光の変化に基づいて前記検知膜に接触した測定ガスの窒素酸化物濃度を計算するとともに、
窒素酸化物濃度の測定に際して前記窒素酸化物検出エレメントの熱処理を実行する
窒素酸化物濃度測定方法。 - 前記熱処理が、
測定ガスを接触させる前に、前記前記窒素酸化物検出センサの温度をこの窒素酸化物検出センサの限界温度よりも低い第1の温度:T1に維持した後に前記第1の温度:T1より低い第2の温度:T2の状態で前記基体に検出光を照射して前記基体を通過した光を光出力:V1として検出し、
第2の温度:T2の状態の前記窒素酸化物検出センサに測定ガスを接触させるとともに前記基体に向けて検出光を照射して前記基体を通過した光を光出力:V2として検出し、前記光出力:V1と前記光出力:V2に基づいて前記窒素酸化物検出センサに接触した測定ガスの窒素酸化物濃度を計算する
請求項21に記載の窒素酸化物濃度の測定方法。 - 前記検知膜がコバルトを中心金属とするCoTPPを分散したポリエチレンオキシド(PEO)高分子からなり、この場合の前記限界温度が290℃である
請求項18,20,22の何れかに記載の窒素酸化物濃度の測定方法。 - 前記第1の温度:T1が前記検知膜を構成する高分子の融点以上である
請求項118,20,22の何れかに記載の窒素酸化物濃度の測定方法。 - 前記第2の温度:T2が前記検知膜を構成する高分子のガラス転移点以上である
請求項18,20,22の何れかに記載の窒素酸化物濃度の測定方法。 - 前記検知光の光学波長は、前記ポルフィリンの光学吸収帯のソーレ帯を含む光学波長である
請求項20~請求項22の何れかに記載の窒素酸化物濃度の測定方法。
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JP2014153348A (ja) * | 2013-02-04 | 2014-08-25 | Able Corp | 酸素濃度測定用センサーの製造方法 |
Also Published As
Publication number | Publication date |
---|---|
EP2360465A1 (en) | 2011-08-24 |
US20110228276A1 (en) | 2011-09-22 |
JP5339305B2 (ja) | 2013-11-13 |
EP2360465A4 (en) | 2014-12-17 |
CN102292631A (zh) | 2011-12-21 |
US8508738B2 (en) | 2013-08-13 |
JPWO2010061536A1 (ja) | 2012-04-19 |
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