WO2018055925A1 - Élément de détection d'hydrogène et capteur d'hydrogène - Google Patents

Élément de détection d'hydrogène et capteur d'hydrogène Download PDF

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WO2018055925A1
WO2018055925A1 PCT/JP2017/028109 JP2017028109W WO2018055925A1 WO 2018055925 A1 WO2018055925 A1 WO 2018055925A1 JP 2017028109 W JP2017028109 W JP 2017028109W WO 2018055925 A1 WO2018055925 A1 WO 2018055925A1
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hydrogen sensing
hydrogen
layer
state
sensing element
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PCT/JP2017/028109
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English (en)
Japanese (ja)
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山田　保誠
吉村　和記
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国立研究開発法人産業技術総合研究所
山田　保誠
吉村　和記
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Priority to JP2018540674A priority Critical patent/JP6697781B2/ja
Publication of WO2018055925A1 publication Critical patent/WO2018055925A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C28/00—Alloys based on a metal not provided for in groups C22C5/00 - C22C27/00
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/04—Alloys based on a platinum group metal
    • 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
    • G01N21/78—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 producing a change of colour
    • 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

Definitions

  • the present invention relates to a hydrogen sensing element and a hydrogen sensor.
  • Alloys based on rare earth metals such as yttrium (Y) and lanthanum (La) (for example, see Patent Document 4), alloys based on magnesium (Mg) (for example, see Patent Documents 5 and 6), tungsten oxide (See, for example, Patent Document 7) and the like are used for hydrogen sensing elements and hydrogen sensors because optical characteristics and electrical resistance characteristics change greatly when hydrogen is occluded or released.
  • a hydrogen sensing element a hydrogen storage layer such as an Mg—Ni alloy is formed on the surface of a transparent substrate such as a glass substrate or a plastic substrate, and palladium or the like is formed on the surface of the hydrogen storage layer.
  • the element in which the catalyst layer is formed is used (for example, refer to Patent Document 8).
  • the hydrogen sensing element can detect hydrogen leakage safely and quickly by detecting a change in light reflectance or light transmittance associated with the hydrogen occlusion layer occludes hydrogen at normal temperature and pressure. Can do.
  • such a hydrogen sensing element has two different types in which when hydrogen leaks, the optical characteristics change by occluding hydrogen, and when hydrogen does not leak, it releases hydrogen and returns to its original state. It has only optical properties. For this reason, when hydrogen is not leaking at the present time, it is not possible to leave a history of hydrogen leaking in the past. In addition, even if it is possible to maintain the state of storing hydrogen without releasing the stored hydrogen so that a history of hydrogen leakage in the past remains, it is not possible to determine whether hydrogen is leaking at this time. .
  • An object of the present invention is to provide a hydrogen sensing element capable of determining the state of being present.
  • a hydrogen sensing layer including a metal whose state changes reversibly between a transparent state by trihydride and a reflection state by dihydride on a transparent substrate; And a catalyst layer containing a metal or an alloy that promotes hydrogenation and dehydrogenation in the hydrogen sensing layer, and the metal contained in the hydrogen sensing layer has non-hydride, dihydride, and trihydrogen having different optical characteristics. Has the state of a compound.
  • a state in which no hydrogen has leaked, a state in which hydrogen has not leaked at the present time, a history of hydrogen leaks in the past, or a state in which hydrogen has leaked is determined.
  • a hydrogen sensing element that can be provided can be provided.
  • a hydrogen sensing element includes a hydrogen sensing layer including a metal whose state reversibly changes between a transparent state by trihydride and a reflection state by dihydride, and a hydrogen sensing layer.
  • stimulates hydrogenation and dehydrogenation in, and a transparent base material are provided.
  • the metal contained in the hydrogen sensing layer has a non-hydride, dihydride, and trihydride state with different optical properties.
  • FIG. 1 shows a configuration example of a hydrogen sensing element according to the first embodiment of the present invention.
  • the hydrogen sensing element 100 includes a hydrogen sensing layer 10 and a catalyst layer 20, and further includes a transparent substrate (transparent substrate) 40 on the opposite side of the hydrogen sensing layer 10 from the catalyst layer 20.
  • the metal contained in the hydrogen sensing layer 10 includes a non-hydrogenated (metal) state that has not been hydrogenated after film formation, and a trihydride state that has become transparent due to the hydrogenation of a non-hydride or dihydride. , Having a dihydride state that is in a reflective state by dehydrogenation of the trihydride.
  • the hydrogen sensing layer 10 preferably contains a rare earth metal, more preferably a rare earth metal or an alloy based on a rare earth metal.
  • the rare earth metal (X) is not particularly limited as long as it has a state of non-hydride (X), dihydride (XH 2 ) and trihydride (XH 3 ) having different optical characteristics. Absent.
  • the rare earth metal is preferably selected from the group consisting of Sc, Y, La, Gd, and Ce in view of availability, cost, and stability in the atmosphere.
  • the alloy based on rare earth metal preferably contains a Group 2 metal.
  • the rare earth metal or the alloy based on the rare earth metal is preferably yttrium, yttrium / magnesium alloy or yttrium / magnesium / scandium alloy.
  • the yttrium-magnesium alloy has a clear difference in optical properties between the hydride of yttrium (Y) and the yttrium dihydride (YH 2 ) dehydrogenated after yttrium is once hydrogenated, the general formula Y 1-x Mg x (0 ⁇ x ⁇ 0.4) (1) And a compound represented by the general formula Y 1-x Mg x (0 ⁇ x ⁇ 0.25) (2) It is more preferable that it is a compound represented by these.
  • the magnesium-yttrium alloy is preferably a compound represented by the general formula (1) in order to exhibit stable hydrogen sensing characteristics of 1000 times or more, that is, repeated durability.
  • the yttrium-magnesium-scandium alloy has the general formula Y 1-xy Mg x Sc y (0 ⁇ x ⁇ 0.4, 0 ⁇ y ⁇ 0.6, x + y ⁇ 1) for the same reason as above. ... (3) It is preferable that it is a compound represented by these.
  • the thickness of the hydrogen sensing layer 10 is selected in consideration of light transmittance, light reflectance, and the like, and is not particularly limited, but is preferably 10 nm or more and 1000 nm or less. When the thickness of the hydrogen sensing layer 10 is 10 nm or more, the light reflectance in the reflective state of the hydrogen sensing layer 10 can be improved. On the other hand, when the thickness of the hydrogen sensing layer 10 is 1000 nm or less, the light transmittance in the transparent state of the hydrogen sensing layer 10 can be improved.
  • the method for forming the hydrogen sensing layer 10 is not particularly limited. For example, general film formation such as sputtering, vacuum deposition, electron beam deposition, chemical vapor deposition (CVD), plating, and the like. The method can be used.
  • the catalyst layer 20 is formed on the hydrogen sensing layer 10 and has a function of promoting hydrogenation and dehydrogenation in the hydrogen sensing layer 10. For this reason, a sufficient switching speed from the transparent state to the reflective state of the hydrogen sensing layer 10 and a sufficient switching speed from the reflective state to the transparent state of the hydrogen sensing layer 10 are ensured.
  • the metal or alloy contained in the catalyst layer 20 is not particularly limited as long as it has a function of promoting hydrogenation and dehydrogenation in the hydrogen sensing layer 10.
  • the metal or alloy contained in the catalyst layer 20 is preferably at least one selected from the group consisting of palladium, palladium alloy, platinum and platinum alloy, and has high hydrogen permeability, so palladium or palladium-ruthenium alloy. More preferably.
  • the palladium-ruthenium alloy has a general formula Pd 1-x Ru x (0 ⁇ x ⁇ 0.7) (4) from the viewpoint of cost and dehydrogenation speed. It is preferable that it is a compound represented by these.
  • the thickness of the catalyst layer 20 is appropriately selected depending on the reactivity of the hydrogen sensing layer 10 and the catalytic ability of the metal or alloy contained in the catalyst layer 20, and is not particularly limited, but is 1 nm or more and 20 nm or less. It is preferable that The function of the catalyst layer 20 can be improved as the thickness of the catalyst layer 20 is 1 nm or more. On the other hand, when the thickness of the catalyst layer 20 is 20 nm or less, the light transmittance of the catalyst layer 20 can be improved.
  • the method for forming the catalyst layer 20 is not particularly limited.
  • a general film forming method such as a sputtering method, a vacuum evaporation method, an electron beam evaporation method, a chemical vapor deposition method (CVD), or a plating method is used.
  • CVD chemical vapor deposition method
  • a plating method is used.
  • the transparent substrate 40 has a function as a base of the hydrogen sensing element 100.
  • the transparent substrate 40 preferably has a function of preventing the hydrogen sensing layer 10 from being oxidized by water or oxygen.
  • the shape of the transparent substrate 40 may be, for example, a sheet shape or a film shape.
  • the shape of the transparent base material 40 is not specifically limited, You may have flexibility.
  • the material constituting the transparent substrate 40 is not limited as long as it has a light transmittance of 50% or more in the visible light region having a wavelength of 380 nm to 780 nm, but glass or plastic is used. preferable.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • nylon acrylic or the like
  • the hydrogen sensing element 200 may be formed by inserting a diffusion prevention layer 50 between the hydrogen sensing layer 10 and the catalyst layer 20 of the hydrogen sensing element 100.
  • the material constituting the catalyst layer 20 is prevented from diffusing into the hydrogen sensing layer 10, and the hydrogen permeated through the catalyst layer 20 can effectively diffuse into the hydrogen sensing layer 10.
  • the material constituting the catalyst layer 20 is prevented from diffusing into the hydrogen sensing layer 10, and the hydrogen permeated through the catalyst layer 20 can effectively diffuse into the hydrogen sensing layer 10.
  • it will not specifically limit if it has this, It is preferable to use niobium, vanadium, titanium, and a tantalum.
  • a method for forming the diffusion preventing layer 50 is not particularly limited, and for example, a general film formation such as a sputtering method, a vacuum evaporation method, an electron beam evaporation method, a chemical vapor deposition method (CVD), or a plating method. The method can be used.
  • the hydrogen sensing elements 100 and 200 are provided with the hydrogen sensing layer 10 so that, unlike the conventional hydrogen sensing elements, no hydrogen is leaking, or hydrogen is leaking at this time. However, it is possible to determine a state indicating a history of hydrogen leakage in the past and a state where hydrogen is leaking at the present time.
  • the hydrogen sensing element according to the second embodiment of the present invention is a stack of hydrogen sensing layers having two or more different composition ratios as the hydrogen sensing layer in the hydrogen sensing element according to the first embodiment of the present invention. Is provided.
  • FIG. 3 shows a configuration example of the hydrogen sensing element according to the second embodiment of the present invention.
  • the hydrogen sensing element 300 includes a stack of hydrogen sensing layers 12 and 14 having two different composition ratios instead of the hydrogen sensing layer 10 in the hydrogen sensing element 200.
  • the configuration of the hydrogen sensing element 300 other than the hydrogen sensing layers 12 and 14 is the same as that of the hydrogen sensing element 200, and thus the description of the configuration of the hydrogen sensing element 300 other than the hydrogen sensing layers 12 and 14 is omitted.
  • the hydrogen sensing layers 12 and 14 preferably include a rare earth metal, and more preferably include a rare earth metal or an alloy based on a rare earth metal.
  • the alloy based on rare earth metal preferably contains a second group metal.
  • the rare earth metal or rare earth metal based alloy contained in the hydrogen sensing layers 12 and 14 is preferably yttrium, yttrium / magnesium alloy or yttrium / magnesium / scandium alloy.
  • the metal or alloy contained in the hydrogen sensing layer 12 (or 14) is a rare earth metal or an alloy based on a rare earth metal
  • the metal or alloy contained in the hydrogen sensing layer 14 (or 12) is a rare earth metal. It may be a metal or alloy obtained by removing a rare earth metal from a base alloy.
  • the hydrogen sensing element 300 includes the hydrogen sensing layers 12 and 14 having different composition ratios, the optical characteristics of the metal non-hydride, dihydride, and trihydride states included in the hydrogen sensing layers 12 and 14 are different. .
  • the hydrogen sensing element 300 has a higher optical property in the state of metal non-hydride, dihydride, and trihydride than the hydrogen sensing element 100 including one type of hydrogen sensing layer 10 due to the interference effect. Large differences can be expressed. For this reason, the metal or alloy contained in each of the hydrogen sensing layers 12 and 14 is not particularly limited as long as an interference effect occurs, but it is preferable that the difference in the composition ratio is large.
  • magnesium, yttrium, or a magnesium yttrium alloy is used as the metal or alloy contained in each of the hydrogen sensing layers 12 and 14 will be described more specifically.
  • yttrium or yttrium-magnesium alloy contained in the hydrogen sensing layer 12 is represented by the general formula Y 1-x Mg x (0 ⁇ x ⁇ 0.25) (5)
  • the magnesium or yttrium-magnesium alloy contained in the hydrogen sensing layer 14 has the general formula Y 1-x Mg x (0.35 ⁇ x ⁇ 1) (6)
  • the general formula Y 1-x Mg x (0.35 ⁇ x ⁇ 0.5) It is more preferable that it is a compound represented by these.
  • the magnesium or yttrium-magnesium alloy contained in the hydrogen sensing layer 12 is represented by the general formula Y 1-x Mg x (0.5 ⁇ x ⁇ 1) (8)
  • the case where it is set as the compound represented by is demonstrated.
  • the yttrium or yttrium-magnesium alloy contained in the hydrogen sensing layer 14 has the general formula Y 1-x Mg x (0 ⁇ x ⁇ 0.5) (9)
  • the general formula Y 1-x Mg x (0 ⁇ x ⁇ 0.25) 10 It is more preferable that it is a compound represented by these.
  • the thickness of the hydrogen sensing layer 12 is selected in consideration of light transmittance, light reflectance, and the like, and is not particularly limited, but is preferably 1 nm to 100 nm.
  • the thickness of the hydrogen sensing layer 12 is 1 nm or more, compared with the hydrogen sensing element 100 including one type of hydrogen sensing layer 10, the optical characteristics of the metal non-hydride, dihydride, and trihydride states. Greater differences can be developed.
  • the thickness of the hydrogen sensing layer 12 is 100 nm or less, the light transmittance in the transparent state of the hydrogen sensing layer 12 can be improved.
  • the thickness of the hydrogen sensing layer 14 is selected in consideration of light transmittance, light reflectance, and the like, and is not particularly limited, but is preferably 10 nm to 1000 nm. When the thickness of the hydrogen sensing layer 14 is 10 nm or more, the light reflectance in the reflection state can be improved. On the other hand, when the thickness of the hydrogen sensing layer 14 is 1000 nm or less, the light transmittance in a transparent state can be improved.
  • the formation method of the hydrogen sensing layers 12 and 14 is the same as the formation method of the hydrogen sensing layer 10, the description of the formation method of the hydrogen sensing layers 12 and 14 is omitted.
  • diffusion prevention layer 50 may not be inserted between the hydrogen sensing layer 14 and the catalyst layer 20 in the same manner as the hydrogen sensing element 100.
  • the hydrogen sensing element according to the third embodiment of the present invention further includes one or more protective layers on the surface of the hydrogen sensing element according to the first embodiment of the present invention.
  • FIG. 4 shows a configuration example of the hydrogen sensing element according to the third embodiment of the present invention.
  • the hydrogen sensing element 400 further includes a protective layer 30 on the surface of the hydrogen sensing element 100.
  • the configuration of the hydrogen sensing element 400 other than the protective layer 30 is the same as that of the hydrogen sensing element 100, the description of the configuration other than the protective layer 30 of the hydrogen sensing element 400 is omitted.
  • the protective layer 30 is formed on the surface of the catalyst layer 20 opposite to the hydrogen sensing layer 10 and has hydrogen permeability and water repellency.
  • the protective layer 30 has a function of preventing oxidation of the catalyst layer 20 by water and oxygen and a function of preventing oxidation of the hydrogen sensing layer 10 by water and oxygen in cooperation with the catalyst layer 20.
  • the material constituting the catalyst layer 20 is usually a noble metal, it is difficult to oxidize.
  • the protective layer 30 having a function of preventing the oxidation of the catalyst layer 20, the catalytic ability can be maintained for a long time. It becomes possible.
  • the catalyst layer 20 also has a function of preventing the hydrogen sensing layer 10 from being oxidized.
  • the formation of the protective layer 30 can enhance the function of preventing the hydrogen sensing layer 10 from being oxidized.
  • the protective layer 30 has permeability to hydrogen (hydrogen ions) (hydrogen permeability) and non-permeability to water (water repellency).
  • the material constituting the protective layer 30 is not particularly limited as long as it has hydrogen permeability and water repellency.
  • fluororesin polyvinyl acetate, polyvinyl chloride, polystyrene, cellulose acetate, etc.
  • inorganic materials such as titanium oxide are used.
  • a general film forming method such as a method of applying a dispersion liquid in which a polymer is dispersed and then drying, a method of forming an inorganic thin film by a sputtering method, or a vacuum evaporation method, etc. Can be used.
  • oxidation of the catalyst layer 20 and the hydrogen sensing layer 10 by water or oxygen can be prevented. For this reason, deterioration of the catalyst layer 20 and the hydrogen sensing layer 10 can be prevented, and durability can be enhanced.
  • the hydrogen sensing element further including one or more protective layers on the surface of the hydrogen sensing element according to the first embodiment of the present invention has been described.
  • the hydrogen sensing element may further include one or more protective layers on the surface of the hydrogen sensing element. That is, as shown in FIG. 5, in the hydrogen sensing element 300, the hydrogen sensing element 500 in which the protective layer 30 is formed on the surface of the catalyst layer 20 opposite to the hydrogen sensing layer 14 may be used. In this case, as described in the hydrogen sensing element 400, the catalyst layer 20 and the hydrogen sensing layers 12 and 14 can be prevented from being deteriorated and the durability can be improved.
  • Example 1 In this embodiment, a hydrogen sensing layer 10 made of yttrium or an yttrium-magnesium alloy, a diffusion prevention layer 50 made of tantalum, and a catalyst layer 20 made of palladium are sequentially laminated on a glass substrate as the transparent substrate 40. A hydrogen sensing element 200 was produced.
  • a glass substrate transparent base material 40 having a thickness of 1 mm
  • an yttrium thin film with a changed film thickness or an yttrium-magnesium alloy thin film with a changed film thickness and composition ratio hydrogen sensing layer 10
  • a tantalum thin film (diffusion prevention layer 50) having a thickness of 2 nm
  • a palladium thin film (catalyst layer 20) having a thickness of 3 nm were formed.
  • the tantalum thin film of the diffusion preventing layer 50, and the palladium thin film of the catalyst layer 20 a magnetron sputtering apparatus capable of multi-element film formation was used.
  • metal yttrium, metal magnesium, metal tantalum, and metal palladium were set as targets on the four sputter guns, respectively.
  • the glass substrate was set in a vacuum apparatus, and the inside of the chamber was evacuated.
  • sputtering was performed by setting the argon gas pressure during sputtering to 0.3 Pa and applying a predetermined power to each target for a predetermined time by a direct current sputtering method.
  • composition ratio of the thin film (hydrogen sensing layer 10) to be formed can be controlled by the power applied to each target. Further, the film thickness of the thin film (hydrogen sensing layer 10) to be formed can be controlled by the time during which power is applied to the target.
  • An yttrium-magnesium alloy thin film represented by the following formula was formed as the hydrogen sensing layer 10 in the hydrogen sensing element 200 of Examples 1-1 to 1-18.
  • a calibration curve showing the relationship of the composition ratio of the yttrium-magnesium alloy thin film to the ratio of the power applied to the metal yttrium target and the metal magnesium target was created by Rutherford backscattering method.
  • the composition ratio of the formed yttrium-magnesium alloy thin film was estimated based on the calibration curve.
  • Table 1 shows the power applied to the target and the application time, the composition ratio and the film thickness of the hydrogen sensing layer 10 when forming the hydrogen sensing layer 10 in the hydrogen sensing elements 200 of Examples 1-1 to 1-18. Indicates.
  • a power of 20 W is applied to the metal tantalum target to form a tantalum thin film (diffusion prevention layer 50), and then a metal palladium target.
  • a hydrogen thin film (catalyst layer 20) was formed by applying a power of 30 W to the hydrogen sensing element 200.
  • the hydrogen sensing element 200 manufactured by the above procedure is in a reflective state with metallic luster, but the surface of the palladium thin film is diluted to 4% by volume with argon (hereinafter referred to as “hydrogen-containing gas”). ),
  • the yttrium thin film or the yttrium-magnesium alloy thin film was hydrogenated to produce yttrium trihydride (and magnesium dihydride), which changed to a transparent state.
  • yttrium trihydride and magnesium dihydride
  • yttrium dihydride and magnesium
  • the hydrogen sensing element 200 is in a state containing yttrium trihydride (hereinafter referred to as “trihydride state”) from a state containing yttrium that is not hydrogenated (hereinafter referred to as “non-hydride state”). ) And a state containing yttrium dihydride (hereinafter referred to as “dihydride state”).
  • trihydride state a state containing yttrium trihydride
  • dihydride state a state containing yttrium dihydride
  • the hydrogen sensing element 200 is then switched between a trihydride state and a dihydride state by hydrating the yttrium dihydride and dehydrogenating the yttrium trihydride. It was confirmed to change reversibly.
  • the optical characteristics of the hydrogen sensing element 200 were evaluated using a spectrophotometer. Specifically, each state of the hydrogen sensing element 200 in a non-hydride state (reflection state) (X), a dihydride state (reflection state) (XH 2 ), and a trihydride state (transparent state) (XH 3 ). The light transmittance (T) at a wavelength of 550 nm and the light reflectance (Rb) at a wavelength of 550 nm from the transparent substrate 40 side were measured.
  • Table 2 shows the evaluation results of the optical characteristics of the hydrogen sensing element 200.
  • the difference in reflectance ( ⁇ Rb) is also shown in Table 2.
  • the hydrogen sensing elements 200 of Examples 1-1 to 1-18 show the difference in light transmittance ( ⁇ T) and / or the difference in light reflectance ( ⁇ Rb) between the non-hydride state and the dihydride state. It can be seen that the difference in light transmittance ( ⁇ T) and / or the difference in light reflectance ( ⁇ Rb) between the dihydride state and the trihydride state is 5% or more, respectively. For this reason, the hydrogen sensing elements 200 of Examples 1-1 to 1-18 are in a state in which no hydrogen leaks, no hydrogen leaks at the present time, but a state indicating a history of hydrogen leaks in the past, Thus, it is possible to visually determine the state of hydrogen leakage.
  • Example 2 In this embodiment, instead of the hydrogen sensing layer 10 made of yttrium or yttrium-magnesium alloy, a laminate of a hydrogen sensing layer 12 made of magnesium (or yttrium) and a hydrogen sensing layer 14 made of yttrium (or yttrium-magnesium alloy).
  • a hydrogen sensing element 300 was fabricated in the same manner as in Example 1 except that was used. That is, a hydrogen sensing layer 12 made of magnesium (or yttrium), a hydrogen sensing layer 14 made of yttrium (or yttrium-magnesium alloy), a diffusion prevention layer 50 made of tantalum, and palladium on a glass substrate as a transparent substrate 40.
  • a hydrogen sensing element 300 in which the catalyst layers 20 made of the layers were sequentially stacked was manufactured.
  • a magnesium thin film (or yttrium thin film) (hydrogen sensing layer 12) whose thickness is changed sequentially on a glass substrate (transparent substrate 40) having a thickness of 1 mm, and an yttrium thin film whose thickness is changed.
  • a glass substrate transparent substrate 40
  • an yttrium thin film whose thickness is changed.
  • an yttrium / magnesium alloy thin film with a changed film thickness and composition ratio hydrogen sensing layer 14
  • a tantalum thin film with a thickness of 2 nm diiffusion prevention layer 50
  • a palladium thin film with a thickness of 3 nm catalyst layer 20.
  • the magnesium thin film (or yttrium thin film) of the hydrogen sensing layer 12 When forming the magnesium thin film (or yttrium thin film) of the hydrogen sensing layer 12, the yttrium thin film (or yttrium-magnesium alloy thin film) of the hydrogen sensing layer 14, the tantalum thin film of the diffusion preventing layer 50, and the palladium thin film of the catalyst layer 20.
  • a magnetron sputtering apparatus capable of multi-element film formation was used.
  • metal yttrium, metal magnesium, metal tantalum, and metal palladium were set as targets on the four sputter guns, respectively.
  • the glass substrate was set in a vacuum apparatus and the chamber was evacuated.
  • sputtering was performed by setting the argon gas pressure during sputtering to 0.3 Pa and applying a predetermined power to each target for a predetermined time by a direct current sputtering method.
  • composition ratio of the thin films (hydrogen sensing layers 12 and 14) to be formed can be controlled by the power applied to each target.
  • film thickness of the thin film (hydrogen sensing layers 12 and 14) to be formed can be controlled by the time during which power is applied to the target.
  • a magnesium thin film (or yttrium thin film) was formed so as to have a film thickness of 12 nm to 25 nm, and used as the hydrogen sensing layer 12 in the hydrogen sensing element 300 of Examples 2-1 to 2-5.
  • an yttrium thin film (or composition formula Y 0.55 Mg 0.45 is used so that the film thickness is 80 nm to 150 nm.
  • a calibration curve of the composition ratio of the yttrium-magnesium alloy to be formed with respect to the ratio of the power applied to the metal yttrium target and the metal magnesium target was created by Rutherford backscattering method.
  • the composition ratio of the formed yttrium-magnesium alloy thin film was estimated based on the calibration curve.
  • Table 3 shows the power applied to the target and the application time, the hydrogen sensing layer 12 and the hydrogen sensing layer 12 and the hydrogen sensing layer 14 in the hydrogen sensing elements 300 of Examples 2-1 to 2-5.
  • the composition ratio and film thickness of the hydrogen sensing layer 14 are shown.
  • a tantalum thin film (diffusion prevention layer 50) by applying a power of 20 W to a metal tantalum target under the same vacuum conditions as those for forming the hydrogen sensing layer 12 and the hydrogen sensing layer 14.
  • a hydrogen thin film (catalyst layer 20) was formed by applying a power of 30 W to a metallic palladium target, and a hydrogen sensing element 300 was produced.
  • the hydrogen sensing element 300 manufactured by the above procedure is in a metallic glossy reflecting state, but when the surface of the palladium thin film is exposed to a hydrogen-containing gas at 1 atm diluted to 4% by volume with argon, the yttrium thin film, magnesium When the thin film or the yttrium-magnesium alloy thin film was hydrogenated, yttrium trihydride and magnesium dihydride were produced and changed to a transparent state. When the surface of the palladium thin film was exposed to the atmosphere in this state, yttrium trihydride and magnesium dihydride were dehydrogenated to produce yttrium dihydride and magnesium, which returned to the reflective state. .
  • the hydrogen sensing element 300 changes from the non-hydride state to the trihydride state and the dihydride state.
  • the hydrogen sensing element 300 can then be switched between a trihydride state and a dihydride state by hydrogenating the yttrium dihydride and dehydrogenating the yttrium trihydride. It was confirmed to change reversibly.
  • Table 4 shows the evaluation results of the optical characteristics of the hydrogen sensing element 300.
  • the hydrogen sensing elements 300 of Examples 2-1 to 2-5 have the difference in light transmittance ( ⁇ T) and / or the difference in light reflectance ( ⁇ Rb) between the non-hydride state and the dihydride state. It can be seen that the difference in light transmittance ( ⁇ T) and / or the difference in light reflectance ( ⁇ Rb) between the dihydride state and the trihydride state is 5% or more, respectively. For this reason, the hydrogen sensing elements 300 of Examples 2-1 to 2-5 are in a state in which no hydrogen leaks, no hydrogen is leaking at the present time, but a state indicating a history of hydrogen leak in the past, Thus, it is possible to visually determine the state of hydrogen leakage.
  • Example 3 a hydrogen sensing element 200 was produced in the same manner as in Example 1 except that a palladium-ruthenium alloy thin film was used as the catalyst layer 20. That is, a hydrogen sensing layer in which a hydrogen sensing layer 10 made of yttrium / magnesium alloy, a diffusion prevention layer 50 made of tantalum, and a catalyst layer 20 made of palladium / ruthenium alloy are sequentially laminated on a glass substrate as a transparent substrate 40. Element 200 was produced.
  • a yttrium / magnesium alloy thin film (hydrogen sensing layer 10) having a thickness of 100 nm and a tantalum thin film having a thickness of 2 nm (diffusion prevention layer 50) are sequentially formed on a glass substrate (transparent substrate 40) having a thickness of 1 mm. Then, a palladium-ruthenium alloy thin film (catalyst layer 20) having a thickness of 3 nm with a changed composition ratio was formed.
  • the tantalum thin film of the diffusion preventing layer 50, and the palladium thin film of the catalyst layer 20 a magnetron sputtering apparatus capable of multi-element film formation was used.
  • metal magnesium, metal yttrium, metal tantalum, metal palladium, and metal ruthenium were set as targets on the five sputter guns, respectively.
  • the glass substrate was set in a vacuum apparatus and the chamber was evacuated.
  • a tantalum thin film (diffusion prevention layer 50) was formed by applying a power of 20 W to a metal tantalum target under the same vacuum conditions as those for forming the hydrogen sensing layer 10.
  • Table 5 shows the power applied to the target, the composition ratio and the film thickness of the catalyst layer 20 when forming the catalyst layer 20 in the hydrogen sensing elements 200 of Examples 3-1 to 3-3.
  • the hydrogen sensing element 200 manufactured by the above procedure is in a metallic glossy reflection state, but when the surface of the palladium-ruthenium alloy thin film is exposed to a hydrogen-containing gas at 1 atm diluted to 4% by volume with argon, it is yttrium.
  • a hydrogen-containing gas at 1 atm diluted to 4% by volume with argon
  • yttrium trihydride and magnesium dihydride were produced and changed to a transparent state. In this state, when the surface of the palladium-ruthenium alloy thin film is exposed to the atmosphere, yttrium trihydride and magnesium dihydride are dehydrogenated to produce yttrium dihydride and magnesium, which is in a reflective state. Returned to.
  • the hydrogen sensing element 200 changes from the non-hydride state to the trihydride state and the dihydride state.
  • the hydrogen sensing element 200 is then switched between a trihydride state and a dihydride state by hydrating the yttrium dihydride and dehydrogenating the yttrium trihydride. It was confirmed to change reversibly.
  • Table 6 shows the evaluation results of the optical characteristics of the hydrogen sensing element 200.
  • the hydrogen sensing elements 200 of Examples 3-1 to 3-3 have the difference in light transmittance ( ⁇ T) and / or the difference in light reflectance ( ⁇ Rb) between the non-hydride state and the dihydride state. It can be seen that the difference in light transmittance ( ⁇ T) and / or the difference in light reflectance ( ⁇ Rb) between the dihydride state and the trihydride state is 5% or more, respectively. For this reason, the hydrogen sensing elements 200 of Examples 3-1 to 3-3 are in a state in which no hydrogen is leaking, no hydrogen is leaking at the present time, but a state indicating a history of hydrogen leakage in the past, Thus, it is possible to visually determine the state of hydrogen leakage.

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Abstract

Dans un mode de réalisation de la présente invention, un élément de détection d'hydrogène est disposé sur un substrat transparent avec : une couche de détection d'hydrogène contenant un métal dont l'état change de façon réversible entre un état transparent résultant d'un trihydrure et un état réfléchissant résultant d'un dihydrure; et une couche de catalyseur contenant un métal ou un alliage qui favorise l'hydrogénation et la déshydrogénation dans la couche de détection d'hydrogène. Le métal contenu dans la couche de détection d'hydrogène possède un état d'anhydride, un état de dihydrure et un état de trihydrure, chacun ayant des caractéristiques optiques mutuellement différentes.
PCT/JP2017/028109 2016-09-23 2017-08-02 Élément de détection d'hydrogène et capteur d'hydrogène WO2018055925A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019089267A (ja) * 2017-11-15 2019-06-13 学校法人加計学園 希土類水素化物の製造方法、水素センサー及び薄膜トランジスター
CN111118330A (zh) * 2019-12-16 2020-05-08 北京凯恩特技术有限公司 钯基三元合金氢敏材料、薄膜、元件及制备方法，氢传感器
JP2022540875A (ja) * 2019-07-10 2022-09-20 デヒョンエスティー カンパニー リミテッド 水素センサ及びその製造方法

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5992350A (ja) * 1982-11-19 1984-05-28 Fuji Photo Film Co Ltd 分析要素
JP2005265590A (ja) * 2004-03-18 2005-09-29 Fujikura Ltd 水素センサ及びその利用
JP2007057233A (ja) * 2005-08-22 2007-03-08 Hitachi Cable Ltd 光学式ガスセンサ
US20070224081A1 (en) * 2005-04-29 2007-09-27 Gary Bokerman Gas permeable chemochromic compositions for hydrogen sensing
JP2008298724A (ja) * 2007-06-04 2008-12-11 Atsumi Tec:Kk 水素センサ
JP2010210243A (ja) * 2009-03-06 2010-09-24 Atsumi Tec:Kk 水素センサ
JP2011219841A (ja) * 2010-04-14 2011-11-04 Atsumi Tec:Kk 水素吸蔵合金及びこれを用いた水素センサ
WO2015152712A1 (fr) * 2014-03-31 2015-10-08 Technische Universiteit Delft Matériau de détection d'hydrogène à élément unique
WO2016091598A1 (fr) * 2014-12-09 2016-06-16 Abb Technology Ag Système de détection d'hydrogène ayant une faible complexité

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL1030299C2 (nl) * 2005-10-28 2007-05-03 Advanced Chem Tech Optische schakelinrichting.

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5992350A (ja) * 1982-11-19 1984-05-28 Fuji Photo Film Co Ltd 分析要素
JP2005265590A (ja) * 2004-03-18 2005-09-29 Fujikura Ltd 水素センサ及びその利用
US20070224081A1 (en) * 2005-04-29 2007-09-27 Gary Bokerman Gas permeable chemochromic compositions for hydrogen sensing
JP2007057233A (ja) * 2005-08-22 2007-03-08 Hitachi Cable Ltd 光学式ガスセンサ
JP2008298724A (ja) * 2007-06-04 2008-12-11 Atsumi Tec:Kk 水素センサ
JP2010210243A (ja) * 2009-03-06 2010-09-24 Atsumi Tec:Kk 水素センサ
JP2011219841A (ja) * 2010-04-14 2011-11-04 Atsumi Tec:Kk 水素吸蔵合金及びこれを用いた水素センサ
WO2015152712A1 (fr) * 2014-03-31 2015-10-08 Technische Universiteit Delft Matériau de détection d'hydrogène à élément unique
WO2016091598A1 (fr) * 2014-12-09 2016-06-16 Abb Technology Ag Système de détection d'hydrogène ayant une faible complexité

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
RADEVA TSVETA: "Highly sensitive and selective visual hydrogen detectors based on Y x Mgl-x thin films", SENS ACTUATORS B CHEM, vol. 203, November 2014 (2014-11-01), pages 745 - 751, XP055498744, DOI: doi:10.1016/j.snb.2014.06.134 *
YAMADA, YASUSEI: "A novel switchable mirror using gasochromic method", MATERIALS SCIENCE AND TECHNOLOGY, vol. 52, no. 3, 20 June 2015 (2015-06-20), pages 86 - 89, XP009513809 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019089267A (ja) * 2017-11-15 2019-06-13 学校法人加計学園 希土類水素化物の製造方法、水素センサー及び薄膜トランジスター
JP2022540875A (ja) * 2019-07-10 2022-09-20 デヒョンエスティー カンパニー リミテッド 水素センサ及びその製造方法
CN111118330A (zh) * 2019-12-16 2020-05-08 北京凯恩特技术有限公司 钯基三元合金氢敏材料、薄膜、元件及制备方法，氢传感器
CN111118330B (zh) * 2019-12-16 2021-05-04 北京凯恩特技术有限公司 钯基三元合金氢敏材料、薄膜、元件及制备方法，氢传感器

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