CN114072665A - Solid reference substance and hydrogen sensor - Google Patents
Solid reference substance and hydrogen sensor Download PDFInfo
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- CN114072665A CN114072665A CN202080048796.1A CN202080048796A CN114072665A CN 114072665 A CN114072665 A CN 114072665A CN 202080048796 A CN202080048796 A CN 202080048796A CN 114072665 A CN114072665 A CN 114072665A
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 210
- 239000007787 solid Substances 0.000 title claims abstract description 88
- 239000013558 reference substance Substances 0.000 title claims abstract description 65
- 125000004435 hydrogen atom Chemical class [H]* 0.000 title 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 144
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 121
- 239000007789 gas Substances 0.000 claims abstract description 106
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- 239000012925 reference material Substances 0.000 claims abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims description 43
- 239000002184 metal Substances 0.000 claims description 43
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 20
- 239000001301 oxygen Substances 0.000 claims description 20
- 229910052760 oxygen Inorganic materials 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 9
- 239000004020 conductor Substances 0.000 claims description 7
- 229910002075 lanthanum strontium manganite Inorganic materials 0.000 claims description 4
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 229910052706 scandium Inorganic materials 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 238000005259 measurement Methods 0.000 abstract description 114
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 230000002093 peripheral effect Effects 0.000 description 39
- 239000003566 sealing material Substances 0.000 description 31
- 239000000463 material Substances 0.000 description 25
- 230000000694 effects Effects 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 12
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 239000007784 solid electrolyte Substances 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 239000000919 ceramic Substances 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000000395 magnesium oxide Substances 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000005266 casting Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910001882 dioxygen Inorganic materials 0.000 description 4
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
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- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/403—Cells and electrode assemblies
- G01N27/406—Cells and probes with solid electrolytes
- G01N27/411—Cells and probes with solid electrolytes for investigating or analysing of liquid metals
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/403—Cells and electrode assemblies
- G01N27/406—Cells and probes with solid electrolytes
- G01N27/407—Cells and probes with solid electrolytes for investigating or analysing gases
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Measuring Oxygen Concentration In Cells (AREA)
Abstract
The invention provides a solid reference substance and a hydrogen sensor capable of measuring the hydrogen concentration with high precision in a short time. The present invention is made using a solid reference material containing a non-stoichiometric compound type catalyst that generates a predetermined gas when exposed to a predetermined temperature. In the hydrogen sensor of the present invention, when the solid reference substance is exposed to a predetermined temperature, gas is immediately generated from the solid reference substance, and the hydrogen partial pressure in the vicinity of the solid reference substance is rapidly decreased, thereby forming a hydrogen concentration cell in which the generated voltage is uniquely determined only by the hydrogen concentration on the measurement electrode side. By measuring the electromotive force of the concentration cell, the hydrogen concentration can be measured in a short time.
Description
Technical Field
The invention relates to a solid reference substance and a hydrogen sensor.
Background
Conventionally, a hydrogen gas sensor has been used for measuring the concentration of hydrogen contained in a gas and the concentration of dissolved hydrogen in a molten metal. Hydrogen sensors are sometimes also referred to as hydrogen sensors. Hydrogen gas sensors are described in, for example, non-patent documents 1 to 2. These documents describe an electromotive force type hydrogen sensor using a proton conductor containing an α -alumina-based inorganic oxide as a sensor element.
In a conventional electromotive force type hydrogen sensor, one surface of a sensor element serves as a measurement electrode exposed to a hydrogen-containing substance (for example, a measurement gas or molten metal) to be measured. The other surface of the sensor element is exposed to a reference electrode of a reference substance, typically a reference gas such as a mixture of hydrogen and argon. When there is a difference in hydrogen gas concentration (difference in hydrogen gas pressure or partial pressure difference) between the measurement electrode on one surface side and the reference electrode on the other surface side of the sensor element, a hydrogen concentration cell is formed with the sensor element interposed therebetween. In a hydrogen concentration cell, a potential difference is generated between a measurement electrode and a reference electrode. In a general electromotive force type hydrogen sensor, the hydrogen concentration (hydrogen partial pressure) of a reference electrode is kept constant, and a potential difference between a measurement electrode and the reference electrode is measured by electrodes provided at both electrodes to obtain the hydrogen concentration (hydrogen partial pressure) on the measurement electrode side (see non-patent document 1). In particular, when an α -alumina-based proton conductor is used as the sensor element, the electromotive force can be uniquely determined only by the hydrogen partial pressure at the measurement electrode by greatly lowering the hydrogen partial pressure at the reference electrode (see non-patent document 2). Conventionally, in order to obtain such conditions, a method of removing hydrogen as water vapor by passing air through the reference electrode side has been used. Therefore, there is a problem that the structure of the electromotive force type hydrogen sensor becomes complicated.
Documents of the prior art
Non-patent document
Non-patent document 1: hydrogen sensor Kurita et al, Solid State Ionics 162-
Non-patent document 2: practical use of electromotive hydrogen sensor for molten copper in Tachi-field and other copper and copper alloy No. 53 Vol.1 (2014)171-
Disclosure of Invention
The conventional electromotive force type hydrogen sensor can continuously measure the hydrogen concentration. For example, a continuous measurement can be performed for 24 hours. In the continuous measurement, a reference gas or air is continuously supplied to the reference electrode. Specifically, a predetermined reference gas or air is continuously supplied.
The conventional electromotive force type hydrogen sensor having this structure has a problem that it takes time until the hydrogen concentration on the reference electrode side becomes stable and time until the measurement of the substantial hydrogen concentration is started.
Specifically, the electromotive force type hydrogen sensor described in non-patent document 2 is used for continuously measuring the hydrogen concentration in the molten metal during casting, and the like. In casting, the time required from the time of metal dissolution to the time of solidification by casting in the step of pouring a molten metal into a mold and solidifying the molten metal is often short. That is, the holding time of the molten metal is often short. As described above, it is difficult to measure an accurate hydrogen gas concentration in a short time by using a conventional hydrogen gas sensor that measures continuously.
Further, it is difficult to measure the hydrogen gas concentration from the viewpoint that there is no appropriate reference substance for a sensor that can measure the hydrogen gas concentration in a short time.
The present invention has been made in view of the above circumstances, and an object thereof is to provide a solid reference substance and a hydrogen sensor capable of measuring a hydrogen gas concentration with high accuracy in a short time.
The solid reference material of the present invention for solving the above problems is characterized by containing a non-stoichiometric compound type catalyst that generates a predetermined gas when exposed to a predetermined temperature.
In addition, the hydrogen sensor of the present invention is characterized by having the solid reference substance of the present invention.
The solid reference material of the present invention is disposed on the reference electrode side to form a hydrogen gas sensor (hydrogen gas sensor of the present invention). In this hydrogen sensor, when a solid reference substance is exposed to a predetermined temperature (generally, a measurement temperature of the hydrogen concentration in the hydrogen sensor), a predetermined gas is immediately generated. The generated regulated gas greatly reduces the partial pressure of hydrogen in the vicinity of the solid reference material (i.e., in the vicinity of the reference electrode). In particular, when the predetermined gas generated is oxygen, the hydrogen reacts with hydrogen in the vicinity of the solid reference substance (i.e., in the vicinity of the reference electrode), and the hydrogen partial pressure is greatly reduced. This hydrogen sensor can obtain the same effect as in the case where air is continuously supplied to the reference electrode. In addition, in this hydrogen sensor, a great difference (large difference) occurs in hydrogen gas concentration between the solid reference material (reference electrode) and the measurement target (measurement electrode). A hydrogen concentration cell is formed in which the generation voltage is uniquely determined only by the hydrogen concentration at the measurement electrode side. The hydrogen sensor determines the hydrogen concentration at the measurement electrode from the potential difference between the two electrodes of the formed concentration cell. As such, the solid reference substance of the present invention is able to immediately lower the partial pressure of hydrogen in its vicinity. Therefore, the hydrogen sensor using the solid reference substance of the present invention can measure the hydrogen concentration accurately in a short time.
Further, according to the present invention, since it is not necessary to continuously flow air to the reference electrode side, a sensor of a simple structure can be obtained.
Drawings
Fig. 1 is a cross-sectional view schematically showing the configuration of a hydrogen sensor according to embodiment 1.
Fig. 2 is a sectional view schematically showing the configuration of the hydrogen sensor according to embodiment 2.
Fig. 3 is a sectional view schematically showing the configuration of the hydrogen sensor according to embodiment 3.
Fig. 4 is a sectional view schematically showing the configuration of the hydrogen sensor according to embodiment 4.
Fig. 5 is a sectional view schematically showing the configuration of the hydrogen sensor according to embodiment 5.
Fig. 6 is a sectional view schematically showing the configuration of the hydrogen sensor according to embodiment 6.
Fig. 7 is a sectional view schematically showing the configuration of a hydrogen sensor according to embodiment 7.
Fig. 8 is a sectional view schematically showing the configuration of a hydrogen sensor according to embodiment 8.
Fig. 9 is a cross-sectional view schematically showing the structure of a hydrogen sensor of a comparative example.
Fig. 10 is a graph showing the measurement results of the hydrogen sensors of the examples and comparative examples.
Detailed Description
Hereinafter, the solid reference substance of the present invention and the hydrogen sensor using the same will be specifically described with reference to embodiments. These embodiments are specific embodiments for carrying out the present invention, and the present invention is not limited to these embodiments. The configurations of the respective modes can be appropriately combined. In this embodiment, the hydrogen sensor is a sensor for detecting and measuring hydrogen.
[ embodiment 1 ]
(solid reference substance)
The solid reference material of the present embodiment includes a non-stoichiometric compound type catalyst that generates a predetermined gas when exposed to a predetermined temperature.
The non-stoichiometric compound type catalyst generates a prescribed gas when exposed to a predetermined temperature. The non-stoichiometric compound type catalyst generates a gas by a crystal defect reaction, and when the temperature rises to reach a predetermined temperature, a gas (predetermined gas) is generated immediately. Here, in the non-stoichiometric compound type catalyst, the compound does not generate another phase due to thermal decomposition or the like to generate a predetermined gas, but rapidly reacts like a catalytic action to generate a predetermined gas.
When the non-stoichiometric catalyst generates a predetermined gas, the relative amount of another gas (for example, a gas to be measured in the gas sensor, or hydrogen gas in the hydrogen sensor) decreases in the vicinity of the non-stoichiometric catalyst (solid reference material). Further, the reaction between the predetermined gas generated by the non-stoichiometric compound type catalyst (solid reference material) and the other gas consumes the other gas, and the absolute amount of the other gas is also reduced. As a result, the gas partial pressure of the other gas is reduced in the vicinity of the non-stoichiometric compound type catalyst.
In the present embodiment, when the non-stoichiometric compound type catalyst is exposed to a predetermined temperature, a predetermined gas can be immediately generated. As a result, when the non-stoichiometric compound type catalyst is used as the solid reference substance of the sensor, the gas partial pressure of other gas in the vicinity of the solid reference substance is immediately lowered, and the gas concentration can be measured in a short time with high accuracy.
The solid reference substance of the present embodiment is a substance that can be used in a gas sensor for detecting and measuring a gas. The predetermined temperature is preferably a temperature to which the gas sensor is exposed when used (measurement temperature of the gas sensor). For example, a hydrogen sensor for measuring the concentration of hydrogen contained in a high-temperature gas measures the concentration of hydrogen at a measurement temperature of 600 to 1300 ℃. In this case, the predetermined temperature is preferably a temperature included in a temperature range of 550 to 1300 ℃ (the measurement temperature of the gas sensor is a temperature 50 ℃ lower than the measurement temperature).
The predetermined gas generated by the non-stoichiometric compound type catalyst of the solid reference substance of the present embodiment is not limited to its kind. When used as a gas sensor, the gas sensor may be a gas of a type capable of reducing the gas partial pressure of another gas to be measured. The prescribed gas is preferably oxygen.
Oxygen readily reacts with other gases, particularly hydrogen. If the generated oxygen reacts with other gas (hydrogen), the other gas (hydrogen) is consumed. In this way, the gas partial pressure of the other gas (hydrogen) is greatly reduced and kept low. As a result, when a solid reference substance is used in the gas sensor, the condition that the voltage generated between the reference electrode and the electrode of the measurement electrode can be uniquely measured only by the hydrogen partial pressure of the measurement electrode can be maintained.
The amount of gas generated by the non-stoichiometric catalyst of the solid reference substance of the present embodiment is not limited to the amount of gas generated. More gas is preferably generated. By generating a large amount of gas, the gas partial pressure (hydrogen partial pressure) of other gas can be reliably reduced.
The non-stoichiometric compound type catalyst of the solid reference substance of the present embodiment is a substance that can generate a predetermined gas (for example, oxygen that reacts with hydrogen) at a predetermined temperature,the material thereof is not limited. The non-stoichiometric compound type catalyst is a catalyst that can generate a gas at a pressure at which the partial pressure of hydrogen in the vicinity of the solid reference substance is very low (for example, 101325X 10)-7Pa(10-7atm) or less).
As the non-stoichiometric compound type catalyst of the solid reference substance, for example, there may be mentioned one selected from the group consisting of (Zr)1-xCex)yM1-yO2(x is more than 0 and less than 1, Y is more than 0 and less than 1, M is any one of Sc, Y, La, Pr, Nd, Gd and Dy), La1-xSrxMnO3(0＜x＜1)、Ba1-xKxMnAl11O19(0＜x＜1)、CexNd1-xO2(0 < x < 1) or a mixture of 1 or more than 2 thereof.
Ce in these compoundsxNd1-xO2(0 < x < 1) oxygen is generated at 1000 ℃.
(Hydrogen sensor)
The hydrogen sensor 1 of the present embodiment is a gas sensor for measuring the concentration of hydrogen in a gas phase. As shown in fig. 1, the hydrogen sensor 1 of the present embodiment includes a sensor element 2, a solid reference material 3, a reference electrode 4, a measurement electrode 5, a sealing material 6, and a potentiometer 7.
The sensor element 2 is a bottomed cylindrical member including a proton conductor. The sensor element 2 is a portion functioning as a sensor for detecting the hydrogen gas concentration, and is formed in a U-shaped cross-sectional shape and a tubular shape with a closed front end (a bottomed tubular shape with a closed lower end in the figure) as shown in fig. 1. The sensor element 2 is formed so that the base end (upper end in the drawing) is open and air can be passed.
The proton conductor forming the sensor element 2 may be made of the same material as that used in a conventional hydrogen sensor. The sensor element 2 may be formed from a proton-conducting solid electrolyte. In this embodiment, the solid electrolyte used is a solid electrolyte containing alumina (Al) and α -alumina as a base material2O3)99.5 mass% or more, 0.2 mass% or less of magnesium oxide (MgO), or 0.05 mass% or less of calcium oxide (CaO). Solid used in the present modeThe electrolyte is not affected by oxygen, and the hydrogen concentration can be accurately measured in a range of 526.85-1426.85 ℃ (800-1700K).
If the α -alumina contains a divalent alkaline earth metal (e.g., Mg, Ca), it functions as a solid electrolyte exhibiting proton conductivity at high temperatures. Therefore, if one surface of the solid electrolyte is brought into contact with a measurement gas containing hydrogen, a proton concentration gradient is generated in the solid electrolyte, and a potential gradient is generated in the solid electrolyte, thereby forming a concentration cell. The potential difference between one surface and the other surface of the solid electrolyte is measured, and the hydrogen gas concentration of the measurement gas is determined from the theoretical formula described later. In the hydrogen sensor 1 of the present embodiment, the outer peripheral surface (particularly, the outer peripheral surface of the distal end portion) of the sensor element 2 is in contact with the gas (hydrogen gas) to be measured.
When the heat capacity of the sensor element 2 is large and the thickness is thin, the temperature difference between the inside and the outside of the sensor element 2 is negligible. For example, the thickness of the sensor element 2 of the present embodiment is 0.75mm, and the difference between the internal and external temperatures is negligible.
The sensor element 2 is provided in a state where the reference electrode 4 is in close contact with the inner peripheral surface of the bottomed cylindrical distal end side.
The reference electrode 4 is an electrode for detecting the potential of the inner peripheral surface of the sensor element 2. As the reference electrode 4, an electrode formed by applying an electrode material such as platinum paste to the inner peripheral surface of the sensor element 2 and baking (heat treatment) the electrode material under predetermined baking conditions can be used. The platinum paste becomes porous (porous) after firing. Therefore, the reference electrode 4 allows gas to pass through the hole, and the inner peripheral surface of the sensor element 2 can be in contact with the gas (atmosphere) inside the bottomed cylindrical sensor element 2. That is, a concentration cell can be formed between the gas inside the sensor element 2 and the measurement gas outside.
The reference electrode 4 is connected to a potentiometer 7 by a lead wire 80. The lead wire 80 is made of a material (material having excellent reaction resistance) that is stable in the use temperature range (measurement temperature range of hydrogen gas concentration) of the hydrogen sensor 1. Examples of the wire 80 include wires made of a material selected from iron, nickel, platinum, and platinum-rhodium alloys. The wire 80 of this embodiment is a wire containing iron.
The solid reference material 3 is composed of the solid reference material of the present embodiment described above, and is disposed in close contact with the inner peripheral surface (the reference electrode 4 disposed in close contact with the inner peripheral surface) at the distal end portion of the bottomed cylindrical interior of the sensor element 2. The solid reference material 3 of the present embodiment is configured by filling and compressing a powdery corresponding material in the sensor element 2.
The solid reference substance 3 is placed in a dense state by being put into the sensor element 2 in a powdery form and pressed by a hand in the direction of the tip (lower end in the figure) to be compressed. The compression of the substance can be carried out by adding powder and applying vibration. The solid reference substance 3 may be a powdery corresponding substance disposed in an uncompressed state (a state after charging).
The solid reference substance 3 is arranged to completely cover the reference electrode 4. Specifically, the solid reference substance 3 is disposed such that the end face on the proximal end side is closer to the proximal end side (upper side in the figure) than the end portion on the proximal end side of the reference electrode 4.
The particle size characteristics of the corresponding substance in powder form are not limited. Since the surface on which oxygen is generated becomes large, the particle diameter (average particle diameter D50) is preferably small.
The solid reference substance 3 may be a molded body formed by compressing a corresponding substance in a powder form. The molded body preferably has an outer peripheral shape along the shape of the inner peripheral surface of the sensor element 2. The molded body preferably has an outer peripheral shape closely adhering to the inner peripheral surface of the sensor element 2. When the solid reference substance 3 is a molded body of a corresponding substance in powder form, the molded body is preferably a porous body.
The solid reference substance 3 is preferably formed only of the above-described substance, but may be mixed with other members or materials that do not inhibit the generation of the predetermined gas (oxygen). Examples of the other members and materials include a binder that binds particles of the substance.
The sensor element 2 is provided in a state where the measurement electrode 5 is in close contact with the outer peripheral surface of the closed-end cylindrical distal end side.
The measurement electrode 5 is an electrode for detecting the potential of the outer peripheral surface of the sensor element 2. As the measurement electrode 5, an electrode formed by applying an electrode material such as platinum paste to the outer peripheral surface of the sensor element 2 on the tip side and firing (heat treatment) under predetermined firing conditions is used, similarly to the quasi-electrode 4. The measurement electrode 5 is also formed in a porous shape to allow the measurement gas to permeate therethrough.
The measurement electrode 5 is also provided on the outer peripheral side of the reference electrode 4. Specifically, the reference electrode 4 and the measurement electrode 5 are formed on both sides of the sensor element 2 in the thickness direction. In this embodiment, the end face on the proximal end side of the measurement electrode 5 is arranged to be located at the same height as the end portion on the proximal end side of the reference electrode 4.
The measuring electrode 5 is connected to the potentiometer 7 by a lead wire 81. The lead wire 81 includes a material (material having excellent reaction resistance) that is stable to a measurement gas (atmosphere containing hydrogen gas) in a use temperature range (measurement temperature range of hydrogen gas concentration) of the hydrogen sensor 1. Examples of the wire 81 include wires made of a material selected from iron, nickel, platinum, and platinum-rhodium alloys. The lead wire 81 of the present embodiment is a lead wire containing iron, as in the case of the lead wire 80.
The sealing member 6 is disposed closer to the base end side (upper side in the figure) than the solid reference substance 3 of the sensor element 2, and seals the cylindrical portion of the sensor element 2. The sealing material 6 seals the base end (upper end) of the sensor element 2 in a state in which the atmosphere inside the sensor element 2 can pass through. Further, the sealing material 6 may be configured to seal the base end (upper end) of the sensor element 2 to prevent passage of the atmosphere inside the sensor element 2. That is, the sealing material 6 may block the base end (upper end) of the sensor element 2.
When the sealing material 6 is permeable to the atmosphere inside the sensor element 2, the structure of the member forming the sealing material 6 is not limited. Examples thereof include a net-like (or woven or nonwoven) member containing a heat-resistant metal, a woven or nonwoven ceramic fiber fabric, a nonwoven fabric, and a braid (ひも). The sealing material 6 may be formed by filling these components into the sensor element 2.
As shown in fig. 1, the sealing member 6 may be formed of two members arranged in the axial direction. The sealing material 6 may be provided with 3 or more members in the axial direction. When the sealing material 6 includes a plurality of members, the members may be in contact with each other or may be spaced apart from each other.
The sealing material 6 may be in contact with the solid reference substance 3, or may be spaced apart from the solid reference substance.
When the sealing material 6 prevents the atmosphere inside the sensor element 2 from passing through, the material forming the sealing material 6 is not limited. Examples thereof include heat-resistant ceramics and molten glass.
The potentiometer 7 is connected to the reference electrode 4 via a lead wire 80, and is connected to the measurement electrode 5 via a lead wire 81. The potentiometer 7 measures the potential difference between the reference electrode 4 and the measurement electrode 5. The potentiometer 7 calculates the hydrogen concentration from the measured potential difference.
(measurement of Hydrogen gas)
A method of measuring the hydrogen gas concentration in the hydrogen sensor 1 of the present embodiment will be described.
First, the hydrogen sensor 1 is disposed in a measurement gas containing hydrogen. At this time, the measurement gas is maintained at the above measurement temperature (600 to 1300 ℃). Before the hydrogen sensor 1 is exposed to the high-temperature measurement gas, it is preferably preheated to a temperature about 200 ℃. The preheating temperature is a temperature equal to or lower than the temperature at which the non-stoichiometric catalyst of the solid reference substance 3 generates gas, and the non-stoichiometric catalyst does not generate gas during preheating.
In the hydrogen sensor 1 disposed in the measurement gas and exposed to the measurement temperature, the temperature of the sensor element 2 and the inside thereof rises to reach a predetermined temperature. In this way, the solid reference substance 3 immediately generates oxygen. The generated oxygen gas is filled in the sensor element 2, and the atmosphere existing before this is discharged from the opening at the base end. Then, the inside of (the tip end portion of) the sensor element 2 is filled with oxygen, and the remaining hydrogen reacts with the oxygen to be consumed as water vapor, and almost no hydrogen is contained. As a result, the hydrogen partial pressure inside the sensor element 2 decreases. In particular, the partial pressure drop of hydrogen around the reference electrode 4 is low.
If the inside of (the front end portion of) the sensor element 2 is filled with oxygenGas, a difference in hydrogen concentration occurs between the inside and the outside of the sensor element 2, forming a concentration cell. The battery type is the following formula (1). In formula (1), Gas (1) represents Gas of reference electrode 4, P'O2Represents the oxygen partial pressure, P 'of the reference electrode 4'H2Represents the hydrogen partial pressure, alpha-Al, of the reference electrode 42O3(+ MgO) for the sensor element 2, Gas (2) for the Gas of the measuring electrode 5, P "O2Denotes the partial pressure of oxygen, P', at the measuring electrode 5 "H2The hydrogen partial pressure at the measurement electrode 5 is shown.
Gas(1)(P’O2，P’H2)|α-Al2O3(+MgO)|Gas(2)(P”O2，P”H2)···(1)
The electromotive force generated between the two electrodes of the concentration cell of formula (1) is represented by formula (2). In the formula (2), E represents electromotive force (V), R represents gas constant (8.3143J/K.mol), T represents absolute temperature (K), and F represents Faraday constant (9.64853X 10)4C/mol)，P”H2Represents the hydrogen partial pressure, P ', of the measurement electrode 5'H2The hydrogen partial pressure of the reference electrode 4 is shown, and A is a constant.
As described above, the hydrogen partial pressure (P ') of reference electrode 4'H2) Is very small. Therefore, formula (2) may be represented by formula (3).
As shown in equation (3), if the hydrogen concentration in the measurement gas changes, the potential difference between the reference electrode 4 and the measurement electrode 5 changes.
When the solid reference substance 3 of the present embodiment generates oxygen, the partial pressure of hydrogen in the sensor element 2 can be set to a very low pressure (for example, 101325 × 10)-7Pa(10-7atm) below). As a result, the number of protons transported by the α -alumina forming the inner peripheral surface of the sensor element 2 is almost equal to the number of protons transported by the α -alumina forming the inner peripheral surfaceIs 0, and therefore, formula (3) can be used.
The hydrogen sensor 1 of the present embodiment can measure this potential difference by the potentiometer 7. Then, the hydrogen partial pressure (i.e., hydrogen concentration) in the measurement gas is calculated from the measured potential difference.
As described above, the hydrogen sensor 1 of the present embodiment measures the hydrogen concentration of the measurement gas.
(Effect of the present embodiment)
In this embodiment, the solid reference substance 3 contains a non-stoichiometric compound type catalyst that generates a prescribed gas when exposed to a predetermined temperature. The specified gas is oxygen. The catalyst of the non-stoichiometric compound type is selected from (Zr)1-xCex)yM1-yO2(x is more than 0 and less than 1, Y is more than 0 and less than 1, M is any one of Sc, Y, La, Pr, Nd, Gd and Dy), La1-xSrxMnO3(0＜x＜1)，Ba1-xKxMnAl11O19(0＜x＜1)、CexNd1-xO2(0 < x < 1) or a mixture of 1 or more than 2 thereof.
According to these configurations, when the hydrogen sensor 1 is formed and the hydrogen concentration is measured, the solid reference substance 3 of the present embodiment generates oxygen (predetermined gas) immediately after the temperature is raised to a predetermined temperature. As a result, the hydrogen partial pressure around the solid reference substance 3 is reduced, and a large concentration difference of hydrogen is generated between the inner circumferential surface and the outer circumferential surface of the sensor element 2 of the hydrogen sensor 1, thereby forming a concentration cell in which the electromotive force is uniquely determined only by the hydrogen partial pressure at the measurement electrode. As described above, the concentration cell can be formed immediately by the solid reference material 3 of the present embodiment, and the hydrogen sensor 1 can measure the hydrogen concentration (start measurement) with high accuracy in a short time.
In this embodiment, it is not necessary to continuously flow air or reference gas to the reference electrode side, and therefore the hydrogen gas sensor 1 has a simple structure.
The hydrogen sensor 1 of the present embodiment has the solid reference substance 3 described above. With this configuration, the hydrogen gas sensor 1 of the present embodiment can exhibit the above-described effects of the solid reference substance 3, and can measure the hydrogen gas concentration with high accuracy in a short time.
The hydrogen sensor 1 of the present embodiment includes: a sensor element 2 including a proton conductor, a solid reference material 3 disposed in close contact with an inner peripheral side (one end side) of the sensor element 2, a reference electrode 4 provided in close contact with an inner peripheral side (one end) of the sensor element 2, a measurement electrode 5 provided in close contact with an outer peripheral side (the other end) of the sensor element 2 (i.e., in a state of having the same potential as the outer peripheral side), and a potentiometer 7 for measuring a potential difference between the reference electrode 4 and the measurement electrode 5.
With this configuration, a concentration cell having an electromotive force uniquely determined only by the partial pressure of hydrogen gas on the measuring electrode side can be formed between the inside and the outside of the sensor element 2, and the potential difference between the reference electrode 4 and the measuring electrode 5 can be measured by the potentiometer 7. That is, the hydrogen sensor 1 exhibits the above-described effects.
In the hydrogen sensor 1 of the present embodiment, the sensor element 2 is formed in a bottomed cylindrical shape, and the solid reference substance 3 is accommodated therein. That is, the sensor element 2 has a housing space for housing the solid reference substance 3 therein.
According to this configuration, the housing space provided in the sensor element 2 can be filled with the generated oxygen gas when the solid reference substance 3 is housed and the hydrogen gas concentration is measured. That is, the inside of the housing space can be filled with oxygen more quickly. Since the remaining hydrogen gas reacts with the oxygen gas and is consumed as water vapor, the hydrogen gas is hardly contained in the sensor element 2. As a result, the hydrogen partial pressure in the sensor element 2 is reduced and kept low, and the hydrogen concentration can be measured with high accuracy in a short time.
As described above, the hydrogen sensor 1 of the present embodiment can measure the hydrogen concentration with high accuracy in a short time even when the hydrogen concentration in the gas phase is measured.
[ 2 nd embodiment ]
This embodiment is the same hydrogen sensor 1 as embodiment 1 except that it further includes a thermocouple 82.
As shown in the configuration shown in fig. 2, the hydrogen sensor 1 of the present embodiment includes a sensor element 2, a solid reference material 3, a reference electrode 4, a measurement electrode 5, a sealing material 6, a potentiometer 7, and a thermocouple 82.
The sensor element 2, the solid reference substance 3, the reference electrode 4, the measurement electrode 5, the sealing material 6, and the potentiometer 7 have the same configurations as those of embodiment 1.
A thermal contact portion 84 at the tip of the thermocouple 82 is exposed from the protective tube 83. The thermal contact portion 84 is fixed to the reference electrode 4 provided on the inner peripheral surface of the sensor element 2, and is electrically connected thereto.
In this embodiment, the thermocouple 82 is used, but a temperature measuring device other than the thermocouple 82 may be used.
(Effect of the present embodiment)
This embodiment has the same configuration as embodiment 1 except that it further includes a thermocouple 82, and exhibits the same effects as embodiment 1.
In addition, the present embodiment includes a thermocouple 82. As shown in the above formula (3), the electromotive force of α -alumina (proton conductor) depends not only on the hydrogen concentration but also on the temperature. By integrally providing the thermocouple 82, the temperature of the sensor element 2 can be measured, and the hydrogen gas concentration can be measured more accurately.
In this embodiment, the thermocouple 82 is housed inside the sensor element 2. In this state, thermocouple 82 is not exposed to the measurement gas, and therefore thermocouple 82 is protected by sensor element 2.
[ embodiment 3 ]
This embodiment is the same hydrogen sensor 1 as embodiment 1 except that it further includes a conductive holding tube 85.
The hydrogen gas sensor 1 of the present embodiment is a gas sensor for measuring the concentration of hydrogen gas in a gas phase, and as shown in the configuration shown in fig. 3, includes a sensor element 2, a solid reference substance 3, a reference electrode 4, a measurement electrode 5, a sealing material 6, a potentiometer 7, and an electrically conductive holding tube 85.
The sensor element 2, the solid reference substance 3, the reference electrode 4, the measurement electrode 5, the sealing material 6, and the potentiometer 7 have the same configurations as those of embodiment 1.
The conductive holding tube 85 has a cylindrical shape. The sensor element 2 is embedded in the axial center portion. The sensor element 2 is disposed in the conductive holding tube 85 in a state where the tip of the sensor element 2 protrudes from the tip (lower end in the drawing) of the conductive holding tube 85. The conductive holding tube 85 holds the sensor element 2 in a state where a tip (lower end in the figure) thereof is in contact with the measurement electrode 5 formed on the surface of the sensor element 2 (electrically connected state).
The conductive holding tube 85 is connected to the potentiometer 7 via a lead wire 81. That is, the conductive holding tube 85 forms a path for transmitting the potential of the measurement electrode 5 to the potentiometer 7. In other words, the conductive holding tube 85 also functions as a lead wire forming a conductive path.
The conductive holding tube 85 may be in a state in which its inner peripheral surface is in close contact with the outer peripheral surface of the sensor element 2 (in a state in which it is in airtight contact with the outer peripheral surface of the sensor element 2 and in a state in which it is not able to allow air to flow therethrough), or may be in a state in which a gap is provided between its inner peripheral surface and the outer peripheral surface of the sensor element 2 (in a state in which it is able to allow air to flow therethrough). Further, a sealing member (or a filler or a spacer) may be disposed between both surfaces.
The material of the conductive holding tube 85 is not limited as long as it is a material having conductivity. Examples of the material include conductive metals such as heat-resistant metals such as stainless steel, and conductive ceramics. The conductive protection pipe 85 of the present embodiment is made of stainless steel.
The conductive holding pipe 85 may be configured by combining these components, and specifically, may be configured by forming a conductive ceramic layer on the surface of a conductive metal substrate such as a heat-resistant metal such as stainless steel.
(Effect of the present embodiment)
This embodiment has the same configuration as embodiment 1 except that it includes the conductive holding tube 85, and exhibits the same effects as embodiment 1.
In this embodiment, a member for holding the hydrogen sensor 1 may be attached to the base end (upper end in the drawing) of the conductive holding tube 85. This allows the operation to be performed through the conductive holding pipe 85, and the operation of the hydrogen sensor 1 is facilitated. Further, by providing the conductive holding pipe 85, it is not necessary to hold (support) the sensor element 2 when the hydrogen sensor 1 is operated, and damage to the sensor element 2 can be suppressed.
[ 4 th embodiment ]
This embodiment is the same hydrogen sensor 1 as embodiment 3, except that the configuration of the conductive holding tube 85 is different.
As shown in the configuration shown in fig. 4, the hydrogen sensor 1 of the present embodiment includes a sensor element 2, a solid reference material 3, a reference electrode 4, a measurement electrode 5, a sealing material 6, a potentiometer 7, a conductive holding tube 85, and a support member 87.
The sensor element 2, the solid reference substance 3, the reference electrode 4, the measurement electrode 5, the sealing material 6, and the potentiometer 7 have the same configuration as that of embodiment 3 (or embodiment 1).
The conductive holding tube 85 is a bottomed cylindrical member having a closed distal end (lower end in the drawing). The sensor element 2 is arranged inside. The conductive holding tube 85 has a through hole 86 formed in the outer peripheral surface of a portion slightly closer to the base end side than the tip end thereof to communicate the inside and the outside. The through hole 86 is opened at a position facing the measurement electrode 5 formed on the surface of the sensor element 2. In this embodiment, the through hole 86 has a plurality of openings in the circumferential direction on the outer circumferential surface of the conductive holding pipe 85. The through hole 86 is not limited to this form, and may be formed on an end surface (lower end surface in the drawing) of the tip. The opening area and shape of the through hole 86 are not limited.
The conductive holding tube 85 is in contact with the measurement electrode 5 provided on the outer surface of the sensor element 2 via the support member 87. By this contact, the conductive holding tube 85 is electrically connected to the measurement electrode 5 and has the same potential. In this embodiment, the conductive holding tube 85 is in contact with the measurement electrode 5 at the distal end of the sensor element 2.
The conductive holding tube 85 supports and fixes the sensor element 2 inside the conductive holding tube 85 via the support member 87. The support member 87 is not limited in its structure and material as long as it can support and fix the sensor element 2.
Examples of the support member 87 include a cylindrical member in which the sensor element 2 is fitted and a member that supports the outer peripheral surface of the sensor element 2. The support member 87 is a member for supporting and fixing the sensor element 2 to the conductive holding tube 85, and the support member 87 itself is also supported by the conductive holding tube 85.
The support member 87 holds the sensor element 2 in a state where the front end (lower end in the figure) is in contact with the measurement electrode 5 formed on the surface of the sensor element 2 (electrically connected state).
The material of the support member 87 may be a material having conductivity. The material of the support member 87 of this embodiment is a material having conductivity.
(Effect of the present embodiment)
This embodiment has the same configuration as embodiment 3 except that the shape of the conductive holding pipe 85 is different, and exhibits the same effects as embodiment 3.
In this embodiment, the sensor element 2 is disposed inside the conductive holding tube 85 having a cylindrical shape with a bottom so that the sensor element 2 is not exposed. In this configuration, when the hydrogen sensor 1 is operated, the sensor element 2 is prevented from being damaged by contact with an external member or the like.
[ 5 th embodiment ]
The present embodiment is a hydrogen sensor 1 for measuring the concentration of hydrogen in molten metal.
The hydrogen sensor 1 of the present embodiment is a gas sensor for measuring the concentration of hydrogen in molten metal, and as shown in the configuration shown in fig. 5, includes a sensor element 2, a solid reference material 3, a reference electrode 4, a measurement electrode 5, a sealing material 6, a potentiometer 7, and a support tube 9. The hydrogen sensor 1 of the present embodiment is configured to immerse the sensor element 2 in a molten metal and measure the hydrogen concentration in the molten metal.
The sensor element 2, the solid reference substance 3, the reference electrode 4, the sealing material 6, and the potentiometer 7 have the same configuration as in embodiment 1.
The measuring electrode 5 is a rod-shaped member having a tip end immersed in the molten metal, and is disposed at a distance from the sensor element 2. The measurement electrode 5 is electrically connected to the sensor element 2 via the molten metal. That is, the outer surface of the sensor element 2, the molten metal, and the measurement electrode 5 are at the same potential. The measurement electrode 5 is also referred to as an external electrode, and a conventional electrode rod including graphite (C), molybdenum (Mo), or the like can be used.
The measuring electrode 5 is immersed in the molten metal outside the sensor element 2. The distance between the measurement electrode 5 and the sensor element 2 is not limited as long as a measurement circuit for measuring the potential difference of the concentration cell can be formed. That is, the present embodiment may be in a state of being spaced apart from the outer peripheral surface of the sensor element 2, or may be in a state of being in contact with the outer peripheral surface of the sensor element 2.
The measuring electrode 5 is connected to the potentiometer 7 via a lead wire 81 as in embodiment 1.
The support pipe 9 is a cylindrical member in which the sensor element 2 is fitted into the axial center portion in a state where the sensor element 2 is exposed from the front end (lower end in the drawing).
The support pipe 9 is disposed in a state where its inner peripheral surface is in close contact with the outer peripheral surface of the sensor element 2 (in an airtight contact state). The support pipe 9 is disposed with a gap between its inner circumferential surface and the outer circumferential surface of the sensor element 2 (in a state in which ventilation is possible). Further, a sealing member (or a filler or a spacer) may be disposed between the outer peripheral surface of the sensor element 2 and the inner peripheral surface of the support pipe 9.
The support pipe 9 has high strength (rigidity). The hydrogen sensor 1 of the present embodiment is immersed in molten metal and measured. When the molten metal flows, stress due to the flow is applied to the hydrogen sensor 1. Since the support pipe 9 has high strength, even if stress due to the flow of the molten metal is applied, the hydrogen sensor 1 is prevented from being damaged (or broken).
The material of the support pipe 9 is not limited as long as it can support the sensor element 2. Examples thereof include heat-resistant metals such as stainless steel, conductive ceramics, and insulating ceramics. The material of the support pipe 9 of this embodiment is stainless steel.
The support pipe 9 may be configured by combining these components, specifically, a ceramic layer may be formed on the surface of a heat-resistant metal substrate such as stainless steel.
The support pipe 9 may be a member called a sleeve among conventional sensors for measuring the hydrogen gas concentration in the molten metal.
The hydrogen sensor 1 of the present embodiment measures the concentration of hydrogen gas contained in molten metal. The hydrogen sensor 1 measures the hydrogen concentration at a measurement temperature (i.e., the molten metal temperature) of 600 to 1300 ℃. In this case, the predetermined temperature is preferably a temperature included in a temperature range of 550 to 1300 ℃. The predetermined temperature is preferably a temperature lower than the measurement temperature by about 200 ℃.
(measurement of Hydrogen gas)
The method of measuring the hydrogen gas concentration in the hydrogen gas sensor 1 of the present embodiment can be performed in the same manner as in embodiment 1, except that the measurement target is changed from the measurement gas to the molten metal containing hydrogen gas.
The measurement of the hydrogen gas concentration in the hydrogen sensor 1 of the present embodiment can be performed by immersing the sensor element 2 and the measurement electrode 5 in molten metal. In this case, the surface of the molten metal is preferably at a position corresponding to the support pipe 9. The entire measuring electrode 5 is preferably immersed in the molten metal.
Since the high-strength support pipe 9 is positioned at a position corresponding to the liquid surface of the molten metal, when foreign matter such as metal oxide or slag is present on the liquid surface of the molten metal, the foreign matter is prevented from colliding with the outer peripheral surface of the sensor element 2 and damaging the sensor element 2.
(Effect of the present embodiment)
This embodiment has the same configuration as embodiment 1 except that the measurement electrode 5 and the sensor element 2 are spaced apart from each other, and exhibits the same effects as embodiment 1.
That is, the hydrogen sensor 1 of the present embodiment can measure hydrogen gas contained in molten metal.
[ 6 th embodiment ]
This embodiment is the same hydrogen sensor 1 as embodiment 5 except that the measurement electrode 5 and the support pipe 9 have different structures.
As shown in the configuration shown in fig. 6, the hydrogen sensor 1 of the present embodiment includes a sensor element 2, a solid reference material 3, a reference electrode 4, a measurement electrode 5, a sealing material 6, and a potentiometer 7.
The sensor element 2, the solid reference substance 3, the reference electrode 4, the sealing material 6, and the potentiometer 7 have the same configuration as in embodiment 5.
The measurement electrode 5 has a cylindrical shape similar to the support tube 9 of embodiment 5. That is, in this embodiment, the measurement electrode 5 is in close contact with the outer peripheral surface of the sensor element 2, and thereby has the same potential as the outer peripheral surface of the sensor element 2, and functions as an electrode. The measurement electrode 5 supports (holds) the sensor element 2 in the same manner as the support tube 9 of embodiment 5. That is, the measurement electrode 5 functions in the same manner as the support tube 9 of embodiment 5.
(Effect of the present embodiment)
This embodiment has the same configuration as embodiment 5 except that the measurement electrodes 5 and the support tube 9 have different configurations, and exhibits the same effects as embodiment 5.
[ 7 th embodiment ]
This embodiment is the same hydrogen sensor 1 as embodiment 5 except for the structure of the support pipe 9.
As shown in the configuration shown in fig. 7, the hydrogen sensor 1 of the present embodiment includes a sensor element 2, a solid reference material 3, a reference electrode 4, a measurement electrode 5, a sealing material 6, a potentiometer 7, and a support tube 9.
The sensor element 2, the solid reference substance 3, the reference electrode 4, the measurement electrode 5, the sealing material 6, and the potentiometer 7 have the same configurations as those of embodiment 5.
The support tube 9 is a cylindrical member in which the sensor element 2 and the measurement electrode 5 are disposed in an axial center portion (inside of a cylinder) in a state in which the sensor element 2 and the measurement electrode 5 are exposed from an end face at the front end (an end face at the lower end in the drawing). The support pipe 9 of the present embodiment has a cylindrical shape having a larger diameter than the support pipe of embodiment 5. The support tube 9 of the present embodiment is not limited to a specific diameter as long as it has a diameter that allows the sensor element 2 and the measurement electrode 5 to be disposed in the axial center portion.
The front end of the support pipe 9 is sealed with a sealing material 90. The sealing material 90 forms an end face of the lower end of the cylindrical support pipe 9. The material of the sealing material 90 is not limited as long as it can prevent penetration of molten metal. For example, ceramics such as silica-based, alumina-based, and silica-alumina mixtures are cited. The thickness of the sealing material 90 (the thickness in the vertical direction in fig. 7) is also not limited.
(Effect of the present embodiment)
This embodiment has the same configuration as embodiment 5 except for the configuration in which the measurement electrode 5 is disposed inside the support tube 9 together with the sensor element 2, and exhibits the same effects as embodiment 5.
In this embodiment, the sensor element 2 and the measurement electrode 5 are integrally housed and fixed in the support pipe 9, and the operation of the hydrogen sensor 1 is facilitated.
[ 8 th embodiment ]
This embodiment is the same hydrogen sensor 1 as embodiment 7 except that a thermocouple 82 is further provided.
As shown in the configuration shown in fig. 8, the hydrogen sensor 1 of the present embodiment includes a sensor element 2, a solid reference material 3, a reference electrode 4, a measurement electrode 5, a sealing material 6, a potentiometer 7, a support tube 9, and a thermocouple 82.
The sensor element 2, the solid reference substance 3, the reference electrode 4, the measurement electrode 5, the sealing material 6, the potentiometer 7, and the support tube 9 have the same configurations as those of embodiment 7.
The support tube 9 is a cylindrical member in which the thermocouple 82 is disposed in a state in which the thermal contact portion 84 at the distal end is exposed, in addition to the sensor element 2 and the measurement electrode 5 disposed inside.
(Effect of the present embodiment)
This embodiment has the same configuration as embodiment 7 except that the thermocouple 82 is also disposed inside the support pipe 9, and exhibits the same effects as embodiment 7.
In this embodiment, the thermocouple 82 directly measures the temperature of the molten metal, and the hydrogen gas concentration can be measured more accurately as in embodiment 2.
[ other forms ]
The hydrogen sensor 1 of each of the above embodiments is a sensor for detecting and measuring hydrogen. The hydrogen concentration in the gas from the molten metal during casting is continuously measured in the gas phase, or the hydrogen concentration in the molten metal is continuously measured by immersing the tip of the hydrogen sensor 1 in the molten metal.
The application of the hydrogen sensor 1 of each of the above embodiments is not limited to this application. For example, the hydrogen concentration in the exhaust gas from an internal combustion engine, an external combustion engine, or the like may be continuously measured in a gas phase.
Further, the measurement temperature of the hydrogen gas can be adjusted by changing the non-stoichiometric compound type catalyst of the solid reference substance 3 to another catalyst.
Examples
Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples.
(examples)
This example is the hydrogen sensor 1 according to embodiment 7 described above.
In the hydrogen sensor 1 of this example, commercially available Ce was used as the solid reference material 30.8Nd0.2O2(CexNd1-xO2Compounds where x is 0.8). The solid reference substance 3 generates oxygen at 1000 ℃.
The solid reference material 3 was placed in the sensor element 2 in a state of being lightly pressed toward the distal end by hand using a powder having an average particle diameter D50 of 100 μm.
The sensor element 2 uses a solid electrolyte containing 99.5 mass% or more of α -alumina and 0.2 mass% or less of MgO.
Comparative example
This example is a hydrogen sensor 1 using air (air) as a reference substance. The gas sensor 1 of the present example corresponds to a conventional hydrogen gas sensor.
The hydrogen sensor 1 of this example has the configuration shown in fig. 9. The configuration of the hydrogen sensor 1 of the present example, which is not particularly mentioned, is the same as that of the embodiment.
The hydrogen sensor 1 of the present example includes a sensor element 2, a reference electrode 4, a measurement electrode 5, a potentiometer 7, a blast pipe 88, and a support pipe 9.
The blower pipe 88 is a duct inserted into the sensor element 2 at a position near the distal end thereof. The proximal end of the air supply duct 88 is connected to an air supply device (not shown). The blower pipe 88 guides the air supplied from the air supply device to the vicinity of the front end portion inside the sensor element 2.
The air supply device supplies air to the vicinity of the front end portion inside the sensor element 2 through the air supply pipe 88. The air supplied to the inside of the sensor element 2 is discharged from the open end of the base end of the sensor element 2. The air supply device continuously supplies air to the inside of the sensor element 2, so that the supply rate of air and the discharge rate of air discharged from the sensor element 2 are balanced with each other, and the composition of the atmosphere inside the sensor element 2 is maintained at the composition of air (the composition of the reference substance is stable).
[ evaluation ]
As an evaluation of the hydrogen sensor 1 of the example, the hydrogen concentration in the molten metal was measured. Specifically, the hydrogen gas concentration in molten copper as a molten metal was measured. Meanwhile, the gas sensor 1 of the comparative example also measured the hydrogen gas concentration, and the obtained measured values of the hydrogen gas concentration were compared. Fig. 10 also shows the measurement results of the hydrogen sensor 1 of the example and the comparative example.
(measurement of Hydrogen concentration)
First, the hydrogen sensor of the comparative example preheated to 1000 ℃ in advance was immersed in molten copper (purity 99.99%) at 1150 ℃ to start the measurement of the hydrogen concentration. Then, the temperature is maintained until a stable value is obtained. (in FIG. 10, a stable value was obtained at 0.1 hour)
After the output value of the hydrogen sensor of the comparative example stabilized (in fig. 10, when the time was 0.1 hour), the hydrogen sensor 1 of the example preheated to 1000 ℃.
Fig. 10 shows the measurement results of the hydrogen gas concentrations of the hydrogen gas sensor 1 of the example and the hydrogen gas sensor 1 of the comparative example. Fig. 10 is a graph showing the calculation results of calculating the hydrogen gas concentration from the measured potential difference between the reference electrode 4 and the measurement electrode 5 and converting the hydrogen gas concentration into the hydrogen gas concentration.
As shown in fig. 10, the measurement results of the hydrogen sensor 1 of the example were consistent with the measurement results of the hydrogen sensor 1 of the comparative example 4 minutes after the start of immersion in molten copper. The results of the subsequent measurements were also identical.
From the agreement of the measurement results, it was confirmed that the hydrogen sensor 1 of the example can obtain the same measurement results as the hydrogen sensor 1 of the comparative example (conventional hydrogen sensor). That is, it was confirmed that the hydrogen sensor 1 of the example can measure the hydrogen gas concentration with high accuracy as in the hydrogen sensor 1 of the comparative example (conventional hydrogen sensor).
It was also confirmed that the hydrogen sensor 1 of the example can measure the hydrogen gas concentration with high accuracy in a short time after 4 minutes from the start of immersion in molten copper. On the other hand, it takes a longer time (0.1hr) for the hydrogen sensor 1 of the comparative example to stabilize the measured value of the hydrogen concentration. That is, the hydrogen sensor 1 of the example can measure the hydrogen gas concentration more quickly than the hydrogen sensor 1 of the comparative example (conventional hydrogen sensor). In other words, the hydrogen sensor 1 of the embodiment can measure the hydrogen concentration in a short time
Further, it was confirmed that these effects are brought about by the solid reference substance 3 of the hydrogen sensor 1 of the embodiment.
As described above, it was confirmed that the hydrogen sensor 1 of the embodiment is a hydrogen sensor 1 having the solid reference substance 3 capable of measuring the hydrogen concentration with high accuracy in a short time.
Description of the symbols
1: hydrogen sensor 2: the sensor element 3: solid reference material
4: reference electrode 5: measurement electrode 6: sealing material
7: the potentiometer 82: thermocouple 9: a support tube.
Claims (8)
1. A solid reference material comprising a non-stoichiometric compound type catalyst that produces a specified gas when exposed to a predetermined temperature.
2. The solid reference substance according to claim 1, wherein the prescribed gas is oxygen.
3. The solid reference substance according to claim 2, wherein the non-stoichiometric compound-type catalyst is selected from (Zr)1-xCex)yM1-yO2、La1-xSrxMnO3、Ba1-xKxMnAl11O19、CexNd1-xO21 or a mixture of 2 or more thereof in the presence of (Zr)1-xCex)yM1-yO2Wherein x is more than 0 and less than 1, y is more than 0 and less than 1, M: any one of Sc, Y, La, Pr, Nd, Gd, and Dy in the La1-xSrxMnO3Where 0 < x < 1, in Ba1-xKxMnAl11O19Where 0 < x < 1, in CexNd1-xO2Wherein x is more than 0 and less than 1.
4. A hydrogen gas sensor comprising the solid reference substance according to any one of claims 1 to 3.
5. The hydrogen sensor according to claim 4, comprising:
a sensor element comprising a proton conductor,
the solid reference material disposed in close contact with one end side of the sensor element,
a reference electrode provided in close contact with one end of the sensor element,
a measuring electrode provided in a state of being at the same potential as the other end of the sensor element, and
a potentiometer for measuring the potential difference between the reference electrode and the measuring electrode.
6. The hydrogen sensor according to claim 5, wherein the sensor element has a housing space that houses the solid reference substance.
7. The hydrogen sensor according to any one of claims 4 to 6, wherein the hydrogen concentration in the gas phase is measured.
8. A hydrogen sensor according to any one of claims 4 to 6, wherein the concentration of hydrogen in the molten metal is measured.
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| JP2019123271 | 2019-07-01 | ||
| JP2019-123271 | 2019-07-01 | ||
| PCT/JP2020/023775 WO2021002199A1 (en) | 2019-07-01 | 2020-06-17 | Solid reference material and hydrogen gas sensor |
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| CN114072665A true CN114072665A (en) | 2022-02-18 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2021002199A1 (en) | 2021-01-07 |
| JP7265007B2 (en) | 2023-04-25 |
| CN114072665B (en) | 2024-03-12 |
| JPWO2021002199A1 (en) | 2021-01-07 |
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