WO2009154216A1 - Capteur d’hydrogène à fibre optique réparti, capteur d’hydrogène à fibre optique réparti pour observation multipoint, film sensible à l’hydrogène, et procédé de fabrication de ceux-ci - Google Patents

Capteur d’hydrogène à fibre optique réparti, capteur d’hydrogène à fibre optique réparti pour observation multipoint, film sensible à l’hydrogène, et procédé de fabrication de ceux-ci Download PDF

Info

Publication number
WO2009154216A1
WO2009154216A1 PCT/JP2009/061002 JP2009061002W WO2009154216A1 WO 2009154216 A1 WO2009154216 A1 WO 2009154216A1 JP 2009061002 W JP2009061002 W JP 2009061002W WO 2009154216 A1 WO2009154216 A1 WO 2009154216A1
Authority
WO
WIPO (PCT)
Prior art keywords
hydrogen
optical fiber
sensor
fiber
film
Prior art date
Application number
PCT/JP2009/061002
Other languages
English (en)
Japanese (ja)
Inventor
慎司 岡崎
Original Assignee
国立大学法人横浜国立大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 国立大学法人横浜国立大学 filed Critical 国立大学法人横浜国立大学
Priority to JP2010517938A priority Critical patent/JP5540248B2/ja
Publication of WO2009154216A1 publication Critical patent/WO2009154216A1/fr

Links

Images

Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75—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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/652—Chromium, molybdenum or tungsten
    • B01J23/6527—Tungsten
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/0004—Gaseous mixtures, e.g. polluted air
    • G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
    • G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector
    • G01N33/0036—General constructional details of gas analysers, e.g. portable test equipment concerning the detector specially adapted to detect a particular component
    • G01N33/005—H2

Definitions

  • the present invention relates to a distributed optical fiber hydrogen sensor capable of detecting hydrogen leakage and specifying the position thereof, a distributed optical fiber hydrogen sensor for multipoint observation, a hydrogen sensitive film applied to these, and a method of manufacturing the same. They detect hydrogen leaks, for example, in hydrogen supply lines such as fuel cells, hydrogen storage tanks, fuel supply systems such as rockets and space transports that use liquid hydrogen fuel, and test facilities for evaluating them. In addition, the present invention can be applied to specify a leaked portion.
  • This application claims priority based on Japanese Patent Application No. 2008-162364 filed in Japan on June 20, 2008, the contents of which are incorporated herein by reference.
  • Patent Document 1 discloses a sensor mainly composed of tungsten oxide (WO 3 ) that operates at a low temperature.
  • Patent Document 2 The inventors have studied hydrogen detection technology using an optical detection sensor that captures changes in the optical characteristics of a hydrogen-sensitive film that reacts quickly with hydrogen at room temperature, and previously described a method for producing a film for a gas sensor.
  • Patent application for example, see Patent Document 2.
  • the invention in the previous patent application aims to provide a method for producing a film for a gas sensor, which has sufficient sensitivity at a low temperature of 0 ° C. or less, and which is safe and has high reliability and device lifetime.
  • This method for producing a film for a gas sensor is a method for producing a film for a gas sensor comprising an element having a film composed of a mixed layer of a catalytic metal and a solid compound semiconductor, and optical means, and comprises a sol-gel solution of a solid compound semiconductor
  • a sol-gel solution in which a catalytic metal compound such as chloroplatinic acid or palladium chloride is uniformly dispersed at a molecular level is applied to a substrate and baked to form a film, and then in dry air at 30 to 100 ° C. Heat treatment for a predetermined time.
  • the catalytic metal has a function of dissociating and adsorbing hydrogen or a hydrogen-containing compound gas.
  • the solid compound semiconductor has a function of being reduced by hydrogen atoms generated by dissociative adsorption in the catalyst metal and returning to a state before being reduced when the hydrogen atoms are no longer present.
  • the optical means has a function of detecting a change in light absorption (evanescent wave) of the solid compound semiconductor due to reduction.
  • the film for a gas sensor obtained by this manufacturing method has practical sensitivity even at a low temperature of 0 ° C. or less, and does not require heating to the sensing element, and is safe, highly reliable, and element Has a long life.
  • FIG. 15A and 15B are schematic diagrams illustrating the operation principle of the evanescent absorption gas sensor disclosed in Patent Document 2.
  • FIG. Normally, light propagates in the fiber while being totally reflected in the core. At this time, the light component that slightly leaks to the interface between the core and the clad is called an evanescent wave.
  • a distributed optical fiber hydrogen sensor in which a platinum oxide-catalyzed tungsten oxide (Pt / WO 3 ) film is provided as a cladding on the outer peripheral surface of an optical fiber core, as shown in FIG. Since the evanescent absorption coefficient is close to 0, there is no absorption of the evanescent wave, and the light propagates while being totally reflected in the core as in an ordinary optical fiber. Accordingly, the traveling light is efficiently transmitted, and a sufficient amount of light reaches the rear light receiving element.
  • Pt / WO 3 platinum oxide-catalyzed tungsten oxide
  • the Pt / WO 3 film reacts with hydrogen to form tungsten bronze (H x WO 3 ), so that the evanescent absorption coefficient increases and the amount of propagating light is increased. Is greatly attenuated.
  • hydrogen atoms generated in platinum (Pt), which is a catalytic metal reduce tungsten oxide (WO 3 ), which is a solid compound semiconductor, and light absorption increases.
  • the amount of light transmitted is reduced.
  • Gas detection is performed by detecting a decrease in the amount of light transmitted through the optical fiber with a light receiving element.
  • a multipoint hydrogen gas sensor formed by forming the above-described Pt / WO 3 film (hydrogen-sensitive film) at a predetermined interval on a plurality of positions on an optical fiber is installed in a measurement region.
  • OTDR Optical Time Domain Reflectometry
  • the position of measurement points A, B, and C is specified by the time difference of reflected light, and the change in the amount of light received due to light absorption of the film is measured, thereby detecting the position of the hydrogen leak point Suggests that it will be possible.
  • the propagation loss of light increases due to the connection loss of the sensor and the disturbance of the waveguide structure caused by the Pt / WO 3 film, so the number and length of the sensor elements are limited, and practical application is difficult.
  • FBG Bragg grating
  • the Bragg wavelength ⁇ B in Expression (1) is shifted by a change in the refractive index n eff or the grating period ⁇ . That is, when a strain or a temperature change is applied to the portion where the grating is provided, n eff and ⁇ are changed, and the Bragg wavelength is shifted.
  • a broadband light source such as LED, SLD, and ASE (light power and cost increase in order) is used as the light source.
  • This FBG sensor is used for monitoring ships, buildings, or large-scale equipment as the value and position of heat generation / deformation can be specified.
  • an FBG sensor is used for structural monitoring, a single-ended method for observing reflected light is often used.
  • the present inventors have an explosion-proof structure, and can detect not only hydrogen leakage by making the detection part of the sensor long or linear, but also obtain positional information regarding the hydrogen leakage point.
  • a hydrogen sensor a distributed optical fiber hydrogen sensor in which an FBG portion is arranged on a long optical fiber at a predetermined interval, and a hydrogen sensitive film having a film thickness of 1 ⁇ m or more is provided on the outer peripheral surface of the clad of the FBG portion. (For example, refer to Patent Document 3).
  • a Pt having a refractive index of about 1.9 as a hydrogen-sensitive film (cladding) is formed on the outer peripheral surface of a core of a quartz core fiber having a refractive index of about 1.5. / WO 3 film is provided. Since the refractive index of the core is lower than the refractive index of the cladding, there is a problem that it is difficult to make the length longer because light cannot be completely confined in the core, the optical loss is large, and the amount of propagation light is attenuated. It was.
  • the present invention is suitable for specifying a hydrogen leak location, and is capable of realizing a long hydrogen sensor, a distributed optical fiber hydrogen sensor for multipoint observation, and these An object of the present invention is to provide a hydrogen-sensitive membrane applied to the above and a manufacturing method thereof.
  • a first aspect of the present invention includes an optical fiber, a hydrogen-sensitive film including a platinum catalyst provided on an outer peripheral surface of the optical fiber, and a carrier made of tungsten oxide supporting the optical catalyst, the refractive index n 1, if the refractive index of the hydrogen sensitive film was n 2, provides a distributed optical fiber hydrogen sensor that satisfies the relationship of n 1> n 2.
  • the optical fiber is preferably a bismuth oxide fiber.
  • an optical fiber a platinum catalyst provided on the outer peripheral surface of the optical fiber, and provided at a predetermined interval along the longitudinal direction of the optical fiber, and an oxidation supporting the same.
  • a plurality of sensor parts made of a hydrogen sensitive film including a carrier made of tungsten, where n 1 > n when the refractive index of the optical fiber is n 1 and the refractive index of the hydrogen sensitive film is n 2.
  • a distributed optical fiber hydrogen sensor for multipoint observation satisfying the relationship 2 is provided.
  • a hydrogen-sensitive membrane having a membrane comprising a platinum catalyst and a carrier made of tungsten oxide supporting the platinum catalyst, wherein the membrane is colored dark blue when a reduction reaction with hydrogen proceeds.
  • a fourth aspect of the present invention is a method for producing a hydrogen-sensitive film comprising a platinum catalyst and a carrier made of tungsten oxide supporting the platinum catalyst, wherein a tungstic acid precursor and a platinum compound are mixed, A step A for preparing a sol-gel solution of tungstic acid; a step B for applying the sol-gel solution to the surface of the substrate; and drying the substrate coated with the sol-gel solution, A process for forming a coating film on the surface of the substrate and a process D for irradiating the coating film on the substrate with ultraviolet rays in an atmosphere containing a reducing gas are provided.
  • a fifth aspect of the present invention provides a method for manufacturing a hydrogen sensor including the fourth aspect.
  • a light hydrogen transmission loss is very low, and a long hydrogen sensor can be realized. Therefore, in the past, hydrogen sensors using evanescent wave absorption in hydrogen sensitive membranes had sensor lengths on the order of centimeters, whereas distributed optical fiber hydrogen sensors with sensor lengths on the order of several meters to hundreds of meters were used. Can be realized. In addition, by utilizing evanescent wave absorption in the hydrogen sensitive film, it is possible to accurately identify the location of hydrogen leakage.
  • FIG. 1 is a schematic cross-sectional view showing an embodiment of the distributed optical fiber hydrogen sensor of the present invention.
  • the distributed optical fiber hydrogen sensor 10 is schematically composed of an optical fiber 11 and a hydrogen sensitive film 12 provided on the outer peripheral surface 11 a of the optical fiber 11.
  • n 1 is the refractive index of the optical fiber 11
  • n 2 is the refractive index of the hydrogen sensitive film 12.
  • a bismuth oxide-based fiber made of glass containing a predetermined amount of bismuth oxide (Bi 2 O 3 ) and other components and including only a core is used.
  • the outer diameter of this bismuth oxide fiber is 125 ⁇ m and the refractive index is about 2.02.
  • the hydrogen sensitive film (Pt / WO 3 film) 12 is a thin film comprising a platinum (Pt) catalyst and a carrier made of tungsten oxide (WO 3 ) supporting the platinum catalyst, and on the outer peripheral surface 11 a of the optical fiber 11.
  • the thickness is uniform.
  • the refractive index of the Pt / WO 3 film 12 is about 1.95.
  • the thickness of the Pt / WO 3 film 12 is preferably 10 nm or more and 1 ⁇ m or less, more preferably 50 nm or more and 200 nm or less.
  • the thickness of the Pt / WO 3 film 12 is less than 10 nm, even if the distributed optical fiber hydrogen sensor 10 is exposed to hydrogen, sufficient hydrogen response behavior cannot be obtained.
  • the thickness of the Pt / WO 3 film 12 exceeds 1 ⁇ m, there is no difference in hydrogen response behavior as compared with the case where the thickness is thinner than that, and the material cost increases, which is not practical.
  • This distributed optical fiber hydrogen sensor 10 utilizes evanescent wave absorption, and the Pt / WO 3 film 12 covering the outer peripheral surface 11a of the optical fiber 11 functions as a hydrogen sensitive film that reacts with hydrogen. This is the sensor that was used. That is, when the Pt / WO 3 film 12 reacts with hydrogen, its optical absorption coefficient changes, so the amount (light quantity) of light propagating through the optical fiber 11 that changes with the change of the absorption coefficient is measured. Thus, hydrogen detection can be performed.
  • the distributed optical fiber hydrogen sensor 10 will be described using the following chemical reaction formulas (1) and (2).
  • the Pt / WO 3 film 12 is light yellow green in a state where tungsten oxide does not react with hydrogen. However, as tungsten oxide reacts with hydrogen and the reduction reaction proceeds (tungsten). As the bronze is formed, it gradually becomes colored (colored). Conversely, the Pt / WO 3 film 12 is gradually colored (colored) as the tungsten bronze reacts with oxygen and the oxidation reaction proceeds (as tungsten oxide is generated). To do.
  • a sol-gel method or an electron beam method (EB method) can be used.
  • sodium tungstate dihydrate Na 2 WO 4 .H 2 O
  • a solvent to prepare a sodium tungstate solution having a predetermined concentration (step A).
  • Water or the like is used as the solvent.
  • the concentration of the sodium tungstate solution is preferably 0.1 mol / liter or more and 1.0 mol / liter or less, more preferably 0.4 mol / liter or more and 0.5 mol / liter or less, particularly preferably 0. .5 mol / liter.
  • this sodium tungstate solution is brought into contact with the H-type ion exchange resin by using a pump to prepare a tungstic acid solution.
  • the concentration of the obtained tungstic acid solution is equal to the concentration of the sodium tungstate solution.
  • the flow rate of the sodium tungstate solution is preferably 0.5 ml / min or more and 5 ml / min or less, more preferably 3 ml / min or more and 5 ml. / Min or less, particularly preferably 4 ml / min.
  • a predetermined amount of hexachloroplatinic (VI) acid hexahydrate H 2 PtCl 6 .H 2 O
  • ethanol for example, 99.5% ethanol
  • ethanol is considered to have an effect of delaying the condensation reaction in the sol-gel method, and by adding this, the film quality and uniformity of the film formed can be improved.
  • alcohols such as methanol and 2-propanol can also be used.
  • the mixing ratio (volume ratio) of the tungstic acid solution, hexachloroplatinic acid (VI) hexahydrate and ethanol is preferably in the range of 13/3/8 to 13/5/8, particularly preferably 13 / 4/8.
  • the concentration of hexachloroplatinic (VI) acid hexahydrate is preferably 0.001 mol / liter or more and 0.25 mol / liter or less, more preferably 0.08 mol / liter or more and 0.10 mol / liter. Or less, and particularly preferably 0.09 mol / liter.
  • the optical fiber 11 is immersed in this sol-gel solution, the optical fiber 11 is pulled up from the sol-gel solution, and the sol-gel solution is applied to the outer peripheral surface 11a of the optical fiber 11 (step B).
  • sol-gel solution As a method of applying the sol-gel solution to the surface of the substrate, in addition to the above dip coating method, spin coating method, roll coating method, spray coating method, bar coating method, meniscus coating method, wicking coating method, A normal wet coating method such as a flow coating method can be used.
  • optical fiber 11 coated with the sol-gel solution is dried at room temperature for 1 hour or longer (step C).
  • the optical fiber 11 is placed in a head space of a formaldehyde solution having a predetermined concentration, and the optical fiber 11 in the solution is irradiated with ultraviolet light having a wavelength of 254 nm, so that the outer peripheral surface 11a of the optical fiber 11 has a uniform thickness Pt / A WO 3 film 12 is formed (step D).
  • a reducing gas other than formaldehyde can be used.
  • the concentration of the formaldehyde solution is 10% or more and 36%. The following is preferable, and particularly preferably 36%.
  • the wavelength of ultraviolet rays applied to the coating film is preferably 250 nm to 400 nm, particularly preferably 254 nm.
  • the intensity of the ultraviolet light is preferably from 100 .mu.W / cm 2 or more, particularly preferably 600 ⁇ W / cm 2 or more.
  • the time for irradiating the coating film with ultraviolet rays is preferably 15 minutes or longer and 8 hours or shorter, more preferably 30 minutes or longer and 60 minutes or shorter. If the irradiation time of ultraviolet rays is within the range of 15 minutes or more and 8 hours or less, the obtained platinum / tungsten oxide-based hydrogen sensitive film is colored (colored) in dark blue as the reduction reaction with hydrogen proceeds. It can be used as a hydrogen sensor using color development.
  • the obtained platinum / tungsten oxide-based hydrogen sensitive film has a high response speed to hydrogen and, after reacting with hydrogen, It takes a short time to be used as a hydrogen sensor (high recovery speed).
  • the platinum / tungsten oxide molar ratio in the platinum / tungsten oxide-based hydrogen sensitive film is preferably in the range of 1/5 to 1/100, more preferably 1/10 to 1/25. Preferably it is 1/13.
  • a method for manufacturing a distributed optical fiber hydrogen sensor using a sol-gel method includes a step of manufacturing a platinum / tungsten oxide hydrogen sensitive film.
  • the hydrogen-sensitive film (Pt / WO 3 film 12) is produced by mixing a tungstic acid precursor and a platinum compound to prepare a sol-gel solution of tungstic acid, and a base material (optical fiber 11). ), Applying a sol-gel solution to the surface, drying the substrate coated with the sol-gel solution to form a coating film on the surface of the substrate, and reducing gas such as formaldehyde And a step D of irradiating the coating film with ultraviolet light in an atmosphere containing the same.
  • the platinum / tungsten oxide-based hydrogen sensitive film obtained through the above steps A to D is a thin film of about 10 nm to 1 ⁇ m. Therefore, when it is necessary to further increase the thickness of the platinum / tungsten oxide-based hydrogen sensitive film, the above steps A to D may be repeated.
  • a platinum / tungsten oxide-based hydrogen sensitive film can be formed without firing the coating film at a high temperature of 500 ° C. or higher as in the prior art. Therefore, platinum / tungsten oxide-based hydrogen can be used on the surface of a base material that is inferior in heat resistance, such as a bismuth oxide fiber (upper limit of use temperature of about 300 ° C.) or a thermoplastic resin, without damaging these base materials.
  • a sensitive film can be formed.
  • tungsten oxide powder and platinum powder placed in separate crucibles are placed in a vapor deposition source, and the chamber is decompressed to 4 ⁇ 10 ⁇ 4 Pa.
  • the tungsten oxide powder is heated by an electron beam and deposited on the outer periphery of the optical fiber to a predetermined film thickness (50 nm) at a rate of about 1.0 nm / s.
  • platinum is heated by an electron beam, and is laminated on the tungsten oxide film to a predetermined film thickness (5 nm) at a rate of about 0.1 nm / s.
  • the distance between the vapor deposition source and the sample optical fiber is, for example, 30 cm.
  • the distributed optical fiber hydrogen sensor 10 is provided with a Pt / WO 3 film 12 having a lower refractive index than the outer peripheral surface 11a of an optical fiber 11 made of a bismuth oxide fiber of a high refractive index material. ing.
  • a light hydrogen transmission loss is very low and a long hydrogen sensor can be realized.
  • the sensor length is in the centimeter order.
  • a distributed optical fiber hydrogen sensor having a sensor length on the order of several meters to several hundred meters can be realized.
  • the evanescent wave absorption in the Pt / WO 3 film 12 since the evanescent wave absorption in the Pt / WO 3 film 12 is used, it is possible to accurately identify the hydrogen leakage location. Furthermore, the reaction between the Pt / WO 3 film 12 and hydrogen causes the Pt / WO 3 film 12 not only to change the optical absorption coefficient but also to cause discoloration. Even if a problem occurs, the hydrogen detection can be performed visually, and a more reliable hydrogen sensor can be obtained.
  • FIG. 2 is a schematic configuration diagram showing an embodiment of a distributed optical fiber hydrogen sensor for multipoint observation according to the present invention.
  • the distributed optical fiber hydrogen sensor 20 for multipoint observation is provided on a long optical fiber 21 and an outer peripheral surface 21 a of the optical fiber 21, and is predetermined along the longitudinal direction of the optical fiber 21.
  • the sensor unit 22 (22A, 22B,..., 22J) composed of ten hydrogen-sensitive films provided at intervals of.
  • the refractive index of the optical fiber 21 n 1 if the refractive index of the hydrogen sensitive film constituting the sensor unit 22 was set to n 2, n 1> n 2 relationship Meet.
  • the same optical fiber 11 as described above is used.
  • the hydrogen sensitive film forming the sensor unit 22 the same one as the hydrogen sensitive film 12 described above is used.
  • a light source 31 is connected to one end of the optical fiber 21 via a communication multimode fiber 33, and the communication multimode fiber 33 is connected to the other end.
  • the light meter 32 is connected via Then, light enters the optical fiber 21 from the light source 31, and a change in the amount of light (light amount) in each sensor unit 22 (22 ⁇ / b> A, 22 ⁇ / b> B,..., 22 ⁇ / b> J) is measured by the light amount meter 32. Thereby, the leakage detection of hydrogen can be performed.
  • the Pt / WO 3 film 12 alone can be used as a hydrogen-sensitive film that is colored (colored) in a deep blue color when a reduction reaction with hydrogen proceeds.
  • This hydrogen-sensitive film is not limited to optical fibers as the base material, but is provided on the surface of base materials made of various metals, resins, glass, etc., various devices used for handling hydrogen, surfaces of gas tanks, etc. Can be used.
  • the bismuth oxide fiber is a single mode fiber having an outer diameter of 125 ⁇ m. Therefore, the evanescent wave region does not appear outside the cladding when light is simply incident on the core. Therefore, there is a method in which light is incident on the clad to obtain the effect.
  • a method of connecting a multimode fiber to both ends of a single mode fiber there is a method of connecting a multimode fiber to both ends of a single mode fiber.
  • a structure in which fibers having different core diameters are connected is called a hetero-core structure.
  • the hetero-core structure is an effective structure as a base for various sensors using evanescent waves because the evanescent wave region can be oozed out of the cladding.
  • This hetero-core structure was applied to a bismuth oxide fiber to produce an experimental distributed optical fiber hydrogen sensor as shown in FIG. 3B.
  • a transfer fiber an SI type multimode fiber having a core material of quartz, a cladding material of plastic, a core diameter of 125 ⁇ m, and a cladding diameter of 140 ⁇ m was used.
  • the SI type multimode fiber and the bismuth oxide fiber were axially aligned and fixed using a V-groove.
  • the bismuth oxide fiber has a low melting point and cannot be fused and connected to the quartz fiber, so a V-groove was used.
  • a Pt / WO 3 film was provided on the outer peripheral surface of the bismuth oxide fiber by the sol-gel method described above.
  • a sensor having a hetero-core structure in which a multi-mode fiber is fusion-bonded to both ends of a quartz single-mode fiber was also produced for the quartz single-mode fiber in the same manner as the hetero-core structure shown in FIG. 3B.
  • a Pt / WO 3 film was provided on the outer peripheral surface of the quartz single mode fiber by the sol-gel method described above. In the following evaluation, the propagation loss and hydrogen response behavior were evaluated using these sensors.
  • the quartz single-mode fiber attenuates the amount of light even if the coating is only a few millimeters. This is presumably because the hetero-core structure guides light to the clad, and if there is a coating (ultraviolet curable resin) having a higher refractive index than the clad on the outer side, loss occurs there.
  • the bismuth oxide fiber no change was observed in the amount of light with or without coating. This is presumably because the refractive index of the core of the bismuth oxide fiber is higher than the refractive index of the coating and is hardly affected by the coating. That is, when producing a multipoint sensor using a bismuth oxide fiber, it can be said that there is almost no influence even if the coating remains.
  • the quartz single-mode fiber has a loss of about ⁇ 9 dB (about ⁇ 90 dB / m) when the length of the hydrogen-sensitive film is 10 cm, whereas the bismuth oxide fiber has almost no loss.
  • the quartz single mode fiber was not attenuated when the length of the hydrogen sensitive film was 10 cm or more. This is considered to be because all the light related to the evanescent region is absorbed and only the light propagating through the core is detected in the light propagating through the cladding of the quartz single mode fiber.
  • a sensor part was produced in each part where the coating of the bismuth oxide fiber was removed by the sol-gel method described above.
  • the irradiation time of ultraviolet rays was 1 hour.
  • the produced sensor part was made into sensor (1), sensor (2), ..., sensor (10) in order from the light source.
  • a thermometer was installed on the light source and hot plate to record the temperature.
  • Table 1 and FIG. 14 show the results of stepwise exposure of hydrogen to the three sensor parts (6), (9), and (10).
  • each sensor unit showed a behavior dependent on the previous sensor unit, so even if hydrogen was exposed to multiple sensor units provided in the bismuth oxide fiber, hydrogen could be detected. It was confirmed that it also functions as a distributed optical fiber hydrogen sensor for multipoint observation.
  • the aspect according to the present invention is suitable for detecting a hydrogen leak in a fuel supply system such as a rocket and a space transport aircraft using liquid hydrogen fuel, or in a test facility for evaluating them, and for specifying a leak location. It can be used for measurement.
  • hydrogen becomes a popular alternative energy source in the future, hydrogen leakage monitoring and soundness assessment will be conducted in hydrogen-related infrastructure equipment (hydrogen storage facilities, hydrogen power generation facilities) and fuel cell vehicles. The application of is greatly expected.

Landscapes

  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Plasma & Fusion (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
  • Investigating Or Analysing Materials By Optical Means (AREA)
  • Catalysts (AREA)

Abstract

La présente invention concerne un capteur d’hydrogène à fibre optique réparti (10) comprenant : une fibre optique (11) ; et un film sensible à l’hydrogène (12) disposé sur la surface périphérique (11a) de la fibre optique (11). Le film (12) comprend un catalyseur au platine et un support composé d’oxyde de tungstène soutenant le catalyseur au platine sur celui-ci. Le capteur satisfait à la relation n1>n2, dans laquelle n1 est l’indice de réfraction de la fibre optique (11) et n2 est l’indice de réfraction du film sensible à l’hydrogène (12).
PCT/JP2009/061002 2008-06-20 2009-06-17 Capteur d’hydrogène à fibre optique réparti, capteur d’hydrogène à fibre optique réparti pour observation multipoint, film sensible à l’hydrogène, et procédé de fabrication de ceux-ci WO2009154216A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2010517938A JP5540248B2 (ja) 2008-06-20 2009-06-17 水素感応膜の製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2008-162364 2008-06-20
JP2008162364 2008-06-20

Publications (1)

Publication Number Publication Date
WO2009154216A1 true WO2009154216A1 (fr) 2009-12-23

Family

ID=41434133

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2009/061002 WO2009154216A1 (fr) 2008-06-20 2009-06-17 Capteur d’hydrogène à fibre optique réparti, capteur d’hydrogène à fibre optique réparti pour observation multipoint, film sensible à l’hydrogène, et procédé de fabrication de ceux-ci

Country Status (2)

Country Link
JP (1) JP5540248B2 (fr)
WO (1) WO2009154216A1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2584340A1 (fr) 2011-10-20 2013-04-24 Draka Comteq BV Fibre de détection d'hydrogène et capteur d'hydrogène
CN103308451A (zh) * 2013-05-20 2013-09-18 重庆科技学院 一种微型光纤氢气传感装置及测量方法
JP2014059300A (ja) * 2012-08-24 2014-04-03 Soka Univ 水素センサ、および、それを用いた検出装置
JP2016161507A (ja) * 2015-03-04 2016-09-05 国立研究開発法人産業技術総合研究所 水素ガス感応性膜及びその製造方法
CN106525776A (zh) * 2016-12-14 2017-03-22 中国计量大学 一种基于纤芯不匹配光纤的表面等离子体共振氢气传感器
CN107449757A (zh) * 2017-09-02 2017-12-08 重庆黄桷树光电科技有限公司 高灵敏度及稳定度的光纤消逝场氢浓度传感器及制备方法
WO2018150699A1 (fr) 2017-02-15 2018-08-23 株式会社フジクラ Capteur à fibre optique
CN112645386A (zh) * 2020-04-03 2021-04-13 苏州泛氢新材料科技有限公司 一种光纤氢敏传感器、制备方法及氢气泄漏检测装置
JP2021113764A (ja) * 2020-01-20 2021-08-05 国立大学法人東海国立大学機構 水素センサ及び演算装置

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004046084A (ja) * 2002-05-15 2004-02-12 National Institute Of Advanced Industrial & Technology 光伝送媒体
JP2004309636A (ja) * 2003-02-20 2004-11-04 Fujikura Ltd ガラス構造物の加工方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4524363B2 (ja) * 2004-06-08 2010-08-18 独立行政法人 宇宙航空研究開発機構 水素分布計測を可能とする光ファイバ水素センサ及びそれを用いた測定法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004046084A (ja) * 2002-05-15 2004-02-12 National Institute Of Advanced Industrial & Technology 光伝送媒体
JP2004309636A (ja) * 2003-02-20 2004-11-04 Fujikura Ltd ガラス構造物の加工方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
MACFARLANE D R ET AL.: "Heavy metal oxide glasses for application in remote sensing", PROCEEDINGS OF SPIE, vol. 3416, 1998, pages 166 - 176 *
SHINJI OKAZAKI ET AL.: "Hikari Fiber o Mochiita Suiso Sensor no Kaihatsu Doko", THE JOURNAL OF THE SURFACE FINISHING SOCIETY OF JAPAN, vol. 57, no. 4, 1 April 2006 (2006-04-01), pages 250 - 256 *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2584340A1 (fr) 2011-10-20 2013-04-24 Draka Comteq BV Fibre de détection d'hydrogène et capteur d'hydrogène
US9322969B2 (en) 2011-10-20 2016-04-26 Draka Comteq, B.V. Hydrogen-sensing optical fiber hydrogen-passivated to prevent irreversible reactions with hydrogen and hydrogen-induced attenuation losses
JP2014059300A (ja) * 2012-08-24 2014-04-03 Soka Univ 水素センサ、および、それを用いた検出装置
CN103308451A (zh) * 2013-05-20 2013-09-18 重庆科技学院 一种微型光纤氢气传感装置及测量方法
JP2016161507A (ja) * 2015-03-04 2016-09-05 国立研究開発法人産業技術総合研究所 水素ガス感応性膜及びその製造方法
CN106525776A (zh) * 2016-12-14 2017-03-22 中国计量大学 一种基于纤芯不匹配光纤的表面等离子体共振氢气传感器
WO2018150699A1 (fr) 2017-02-15 2018-08-23 株式会社フジクラ Capteur à fibre optique
CN107449757A (zh) * 2017-09-02 2017-12-08 重庆黄桷树光电科技有限公司 高灵敏度及稳定度的光纤消逝场氢浓度传感器及制备方法
JP2021113764A (ja) * 2020-01-20 2021-08-05 国立大学法人東海国立大学機構 水素センサ及び演算装置
JP7457317B2 (ja) 2020-01-20 2024-03-28 国立大学法人東海国立大学機構 水素センサ
CN112645386A (zh) * 2020-04-03 2021-04-13 苏州泛氢新材料科技有限公司 一种光纤氢敏传感器、制备方法及氢气泄漏检测装置

Also Published As

Publication number Publication date
JP5540248B2 (ja) 2014-07-02
JPWO2009154216A1 (ja) 2011-12-01

Similar Documents

Publication Publication Date Title
JP5540248B2 (ja) 水素感応膜の製造方法
Okazaki et al. Sensing characteristics of an optical fiber sensor for hydrogen leak
Caucheteur et al. Hybrid fiber gratings coated with a catalytic sensitive layer for hydrogen sensing in air
Li et al. Humidity sensor with a PVA-coated photonic crystal fiber interferometer
US6965708B2 (en) Devices, systems, and methods for sensing moisture
Tian et al. High-performance humidity sensor based on a micro-nano fiber Bragg grating coated with graphene oxide
US8547553B2 (en) Fiber optic hydrogen purity sensor and system
KR101327501B1 (ko) 그래핀 산화물 및 환원된 그래핀 산화물을 포함하는 광섬유, 및 이를 포함하는 가스 센서의 제조 방법
WO2008125686A1 (fr) Capteur de gaz
US7263246B1 (en) Oxygen detection using evanescent fields
JP4524363B2 (ja) 水素分布計測を可能とする光ファイバ水素センサ及びそれを用いた測定法
JP5152797B2 (ja) 白金／酸化タングステン系水素感応膜の製造方法
WO2003071251A2 (fr) Capteur a fibre optique a ame de fibre sol-gel et son procede de production
Eguchi Optical gas sensors
Dai et al. Ultra-high sensitive optical fiber hydrogen sensor using self-referenced demodulation method and WO 3-Pd 2 Pt-Pt composite film
Tong et al. Multimode interferometer based on no-core fiber with GQDs-PVA composite coating for relative humidity sensing
CN114235743A (zh) 基于相移光栅温度补偿技术的氢气检测装置
Elosua et al. Optical fiber sensors to detect volatile organic compound in sick building syndrome applications
CN100595572C (zh) 一种双峰谐振镀膜光纤光栅气敏传感器的制造方法
Sinchenko Fibre optic distributed corrosion sensor
JP2004309354A (ja) 光学式物質センサーおよびモニタリング方法
Yu et al. Water-durability and high-performance all-fiber humidity sensor using methyldiethanolamine-photopolymer-PDMS structure
Lv et al. Humidity sensor based on optical fiber Bragg grating with high sensitivity and fast response
Gao et al. (3-Aminopropyl) triethoxysilane-based immobilization of Pt/WO3 on a microfiber sensor for high sensitivity hydrogen sensing
Cusano et al. Fiber Bragg gratings evanescent wave sensors: A view back and recent advancements

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 09766664

Country of ref document: EP

Kind code of ref document: A1

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
WWE Wipo information: entry into national phase

Ref document number: 2010517938

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 09766664

Country of ref document: EP

Kind code of ref document: A1