CN114072665B - Solid reference substance and hydrogen sensor - Google Patents
Solid reference substance and hydrogen sensor Download PDFInfo
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- CN114072665B CN114072665B CN202080048796.1A CN202080048796A CN114072665B CN 114072665 B CN114072665 B CN 114072665B CN 202080048796 A CN202080048796 A CN 202080048796A CN 114072665 B CN114072665 B CN 114072665B
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 240
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 240
- 239000007787 solid Substances 0.000 title claims abstract description 85
- 239000013558 reference substance Substances 0.000 title claims abstract description 80
- 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 136
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 126
- 238000005259 measurement Methods 0.000 claims abstract description 113
- 239000007789 gas Substances 0.000 claims abstract description 102
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- 150000001875 compounds Chemical class 0.000 claims abstract description 27
- 239000012925 reference material Substances 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims description 44
- 239000002184 metal Substances 0.000 claims description 44
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 21
- 239000001301 oxygen Substances 0.000 claims description 21
- 229910052760 oxygen Inorganic materials 0.000 claims description 21
- 239000004020 conductor Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 229910016583 MnAl Inorganic materials 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 230000002093 peripheral effect Effects 0.000 description 41
- 239000003566 sealing material Substances 0.000 description 33
- 239000000463 material Substances 0.000 description 24
- 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
- 239000000126 substance Substances 0.000 description 11
- 239000000919 ceramic Substances 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 238000010304 firing Methods 0.000 description 5
- 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
- 238000009423 ventilation Methods 0.000 description 5
- 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
- 229910052742 iron Inorganic materials 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- 229910000629 Rh alloy Inorganic materials 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000009529 body temperature measurement Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- PXXKQOPKNFECSZ-UHFFFAOYSA-N platinum rhodium Chemical compound [Rh].[Pt] PXXKQOPKNFECSZ-UHFFFAOYSA-N 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 229910052706 scandium Inorganic materials 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 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
- 241001070941 Castanea Species 0.000 description 1
- 235000014036 Castanea Nutrition 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
- LIXXICXIKUPJBX-UHFFFAOYSA-N [Pt].[Rh].[Pt] Chemical compound [Pt].[Rh].[Pt] LIXXICXIKUPJBX-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
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- -1 stainless steel Chemical class 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
-
- 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 present invention provides a solid reference substance and a hydrogen sensor capable of measuring the hydrogen concentration in a short time with high accuracy. The present invention is made using a solid reference material comprising a non-stoichiometric compound catalyst that generates a specified gas upon exposure 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, and the hydrogen partial pressure in the vicinity of the solid reference substance is drastically reduced, so that a hydrogen concentration cell in which the generated voltage is uniquely determined only by the hydrogen concentration at the measurement electrode side is formed. By measuring the electromotive force of the concentration cell, the hydrogen concentration can be measured in a short time.
Description
Technical Field
The present 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. The hydrogen sensor is sometimes also referred to as a hydrogen sensor. The hydrogen sensor is described in, for example, non-patent documents 1 to 2. These documents describe electromotive hydrogen sensors 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 is a measuring electrode exposed to a hydrogen-containing substance (for example, a measuring gas or a 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 concentration of hydrogen gas (a difference in pressure of hydrogen gas, a difference in partial pressure) 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 so as to sandwich the sensor element. 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, a potential difference between a measurement electrode and the reference electrode is measured by electrodes provided at both electrodes, and the hydrogen concentration (hydrogen partial pressure) at the measurement electrode side is obtained (see non-patent document 1). In particular, when an α -alumina proton conductor is used as the sensor element, the hydrogen partial pressure of the reference electrode is greatly reduced, and thus the electromotive force can be uniquely determined only by the hydrogen partial pressure of the measurement electrode (see non-patent document 2). Conventionally, in order to obtain such conditions, a method of removing hydrogen as water vapor by flowing air on a reference pole side has been used. Therefore, there is a problem in that the structure of the electromotive force type hydrogen sensor becomes complicated.
Prior art literature
Non-patent literature
Non-patent document 1: hydrogen sensors using alpha-alumina Kurita et al Solid State Ionics 162-163, (2003) 135-145
Non-patent document 2: practical chestnut field etc. copper and copper alloy volume 53, no. 1 (2014) 171-176 of electromotive force type hydrogen sensor for molten copper
Disclosure of Invention
The conventional electromotive force type hydrogen sensor can continuously measure the hydrogen concentration. For example, continuous measurement can be performed for 24 hours. In the continuous measurement, the reference electrode is continuously supplied with the reference gas or air. Specifically, a predetermined reference gas or air is continuously supplied.
The conventional electromotive force type hydrogen sensor having such a configuration has a problem in that it takes time until the hydrogen concentration on the reference electrode side stabilizes and it takes time until the measurement of the substantial hydrogen concentration starts.
Specifically, the electromotive hydrogen sensor described in non-patent document 2 is used for continuously measuring the hydrogen concentration in molten metal at the time of casting, and the like. In casting, the time required from when the metal is dissolved to when the metal is solidified by casting in the step of pouring the molten metal into the mold to solidify the molten metal is often short. I.e. the holding time of the molten metal is mostly very short. As described above, it is difficult to measure the accurate hydrogen concentration in a short time using the conventional hydrogen sensor that continuously measures hydrogen.
In addition, there is no suitable reference substance that can be used for a sensor for measuring the hydrogen concentration in a short time, and in this regard, it is difficult to measure the hydrogen concentration.
The present invention has been made in view of the above-described circumstances, and an object of the present invention is to provide a solid reference substance and a hydrogen sensor that can measure the hydrogen concentration in a short time with high accuracy.
The solid reference substance of the present invention for solving the above-mentioned problems is characterized by comprising a non-stoichiometric compound type catalyst which generates a predetermined gas when exposed to a predetermined temperature.
The hydrogen sensor of the present invention is characterized by having the solid reference substance of the present invention.
The solid reference substance of the present invention is disposed on the reference electrode side to form a hydrogen sensor (hydrogen sensor of the present invention). In this hydrogen sensor, when the solid reference substance is exposed to a predetermined temperature (typically, a measurement temperature of the hydrogen concentration in the hydrogen sensor), a predetermined gas is immediately generated. The prescribed gas produced greatly reduces the partial pressure of hydrogen in the vicinity of the solid reference substance (i.e., in the vicinity of the reference electrode). Particularly, in the case where the generated predetermined gas is oxygen, the reaction with hydrogen in the vicinity of the solid reference substance (i.e., in the vicinity of the reference electrode) greatly reduces the hydrogen partial pressure. This allows the hydrogen sensor to obtain the same effect as in the case where air continuously flows into the reference electrode. In this hydrogen sensor, a great difference (great difference) occurs in hydrogen concentration between the solid reference substance (reference electrode) and the measurement object (measurement electrode). A hydrogen concentration cell whose generated voltage is uniquely determined only by the hydrogen concentration at the measurement electrode side was formed. The hydrogen sensor obtains the hydrogen concentration of a measuring electrode from the potential difference between the two electrodes of the concentration cell. In this way, 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 with high accuracy in a short time.
Further, according to the present invention, since there is no need to continuously flow air to the reference pole side, a sensor of a simple structure can be obtained.
Drawings
Fig. 1 is a cross-sectional view schematically showing the structure of a hydrogen sensor according to embodiment 1.
Fig. 2 is a cross-sectional view schematically showing the structure of the hydrogen sensor according to embodiment 2.
Fig. 3 is a cross-sectional view schematically showing the structure of the hydrogen sensor according to embodiment 3.
Fig. 4 is a cross-sectional view schematically showing the structure of the hydrogen sensor according to embodiment 4.
Fig. 5 is a cross-sectional view schematically showing the structure of the hydrogen sensor according to embodiment 5.
Fig. 6 is a cross-sectional view schematically showing the structure of the hydrogen sensor according to embodiment 6.
Fig. 7 is a cross-sectional view schematically showing the structure of the hydrogen sensor according to embodiment 7.
Fig. 8 is a cross-sectional view schematically showing the structure of the hydrogen sensor according to embodiment 8.
Fig. 9 is a cross-sectional view schematically showing the structure of the hydrogen sensor of the comparative example.
Fig. 10 is a graph showing measurement results of the hydrogen sensors of the examples and the comparative examples.
Detailed Description
Hereinafter, the solid reference material of the present invention and the hydrogen sensor using the same will be specifically described with reference to embodiments. It should be noted that these embodiments are one embodiment for embodying the present invention, and the present invention is not limited to these embodiments only. The configurations of the respective modes can be appropriately combined. In the present 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 catalyst that generates a specified gas when exposed to a predetermined temperature.
The non-stoichiometric compound catalyst produces a specified gas upon exposure to a predetermined temperature. The non-stoichiometric compound catalyst generates gas by crystal defect reaction, and when the temperature is raised to a predetermined temperature, gas (predetermined gas) is immediately generated. In the non-stoichiometric compound type catalyst, the compound does not generate a predetermined gas by generating another phase by thermal decomposition or the like, but reacts rapidly like a catalyst to generate a predetermined gas.
When a predetermined gas is generated in the non-stoichiometric compound catalyst, the relative amount of other gases (for example, the gas to be measured in the gas sensor, hydrogen gas in the hydrogen gas sensor) becomes small in the vicinity of the non-stoichiometric compound catalyst (solid reference substance). In addition, the reaction of the predetermined gas with the other gas by the non-stoichiometric compound catalyst (solid reference substance) consumes the other gas, and the absolute amount of the other gas is reduced. As a result, the partial pressure of the other gas decreases in the vicinity of the non-stoichiometric compound catalyst.
In this embodiment, when the nonstoichiometric compound catalyst is exposed to a predetermined temperature, a predetermined gas can be immediately generated. As a result, when a non-stoichiometric compound type catalyst is used as a solid reference material of the sensor, the gas partial pressure of other gas in the vicinity of the solid reference material immediately becomes low, and the gas concentration can be measured with high accuracy in a short time.
The solid reference substance according to 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 (a measured 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 ℃ (a temperature measured by the gas sensor to a temperature 50 ℃ lower than the measured temperature).
The type of the predetermined gas generated by the non-stoichiometric compound type catalyst of the solid reference substance according to the present embodiment is not limited. When used as a gas sensor, the gas sensor may be a gas of a type capable of reducing the partial pressure of other gases to be measured. The prescribed gas is preferably oxygen.
Oxygen readily reacts with other gases, particularly hydrogen. If the generated oxygen reacts with other gases (hydrogen), the other gases (hydrogen) are consumed. In this way, the partial pressure of the other gas (hydrogen) is greatly reduced and kept low. As a result, when the solid reference substance is used in a gas sensor, the condition that the voltage generated between the electrodes of the reference electrode and 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 compound catalyst of the solid reference substance according to the present embodiment is not limited. Preferably more gas is produced. 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 catalyst of the solid reference substance of the present embodiment is not limited as long as it is a substance capable of generating a predetermined gas (for example, oxygen reacting with hydrogen) at a predetermined temperature. The non-stoichiometric compound catalyst is one that can bring the partial pressure of hydrogen near the solid reference substance to a very low pressure when gas is generated (e.g., 101325×10 -7 Pa(10 -7 atm) or less.
Examples of the non-stoichiometric compound catalyst as the solid reference substance include catalysts selected from (Zr 1-x Ce x ) y M 1-y O 2 (0 < x < 1,0 < y < 1, M: any one of Sc, Y, la, pr, nd, gd, dy), la 1-x Sr x MnO 3 (0＜x＜1)、Ba 1-x K x MnAl 11 O 19 (0＜x＜1)、Ce x Nd 1-x O 2 (0 < x < 1) or a mixture of more than 2.
Ce in these compounds x Nd 1-x O 2 (0 < x < 1) oxygen is produced 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 substance 3, a reference electrode 4, a measurement electrode 5, a sealing material 6, and a potentiometer 7.
The sensor element 2 is a bottomed tubular member including a proton conductor. The sensor element 2 is a portion functioning as a sensor for detecting the hydrogen concentration, and is formed in a cylindrical shape having a U-shaped cross section and closed at the front end (a bottomed cylindrical shape having a closed bottom in the drawing) as shown in fig. 1. The sensor element 2 is formed so that a base end (upper end in the drawing) is open to allow ventilation.
The proton conductor forming the sensor element 2 may be made of the same material as that of the conventional hydrogen sensor. The sensor element 2 may be formed of a proton conductive solid electrolyte. In this embodiment, as the solid electrolyte, an α -alumina-based material containing alumina (Al 2 O 3 ) 99.5 mass% or more, 0.2 mass% or less of magnesium oxide (MgO), or 0.05 mass% or less of calcium oxide (CaO). The solid electrolyte used in this embodiment can measure the correct hydrogen concentration in a region of 526.85 to 1426.85 ℃ (800 to 1700K) without being affected by oxygen.
If α -alumina contains divalent alkaline earth metals (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 in contact with the measurement gas containing hydrogen, a concentration gradient of protons 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 was measured, and the hydrogen concentration of the measurement gas was obtained according to the theoretical formula described below. In the hydrogen sensor 1 of the present embodiment, the outer peripheral surface (in particular, the outer peripheral surface of the tip 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 small, the difference in temperature 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 in which the reference electrode 4 is closely adhered to the inner peripheral surface of the distal end side of the bottomed tubular shape.
The reference electrode 4 is an electrode for detecting the potential of the inner peripheral surface of the sensor element 2. The reference electrode 4 may be formed by applying an electrode material such as platinum paste to the inner peripheral surface of the sensor element 2 and firing (heat treatment) the electrode material under predetermined firing conditions. 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 tubular sensor element 2. That is, a concentration cell can be formed between the gas inside the sensor element 2 and the outside measurement gas.
The reference electrode 4 is connected to the potentiometer 7 by a first wire 80. The first lead 80 includes a material (a material excellent in resistance to reaction) that is stable in the use temperature range (measurement temperature range of the hydrogen concentration) of the hydrogen sensor 1. The first wire 80 is made of a material selected from iron, nickel, platinum, and platinum-rhodium alloy, for example. The first wire 80 of the present embodiment is a wire including iron.
The solid reference substance 3 is composed of the solid reference substance of the present embodiment described above, and is disposed in a state of being 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 tubular interior of the sensor element 2. The solid reference substance 3 of the present embodiment is disposed by filling and compressing a powdery corresponding substance in the sensor element 2.
The solid reference substance 3 is compressed by being put into the sensor element 2 and pressed in the direction of the front end (lower end in the drawing) by hand, and is arranged in a dense state. The compression of the substance may be performed by adding a powder and applying vibration. The solid reference substance 3 may be a corresponding substance in a powder form in a non-compressed state (after being put into the container).
The solid reference substance 3 is configured to completely cover the reference electrode 4. Specifically, the solid reference substance 3 is disposed such that the end face on the base end side is closer to the base end side (upper side in the figure) than the end of the reference electrode 4 on the base end side.
The particle size characteristics of the corresponding substances in powder form are not limited. Since the surface generating oxygen becomes large, the particle diameter (average particle diameter D50) is preferably small.
The solid reference substance 3 may be a molded body obtained by compressing a powdery corresponding substance. 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 that is in close contact with the inner peripheral surface of the sensor element 2. In the case where the solid reference substance 3 is a molded body of a powdery corresponding substance, the molded body is preferably a porous body.
The solid reference substance 3 is preferably formed of only the above-described substance, but may be mixed with other members or materials that do not inhibit the generation of the predetermined gas (oxygen). As other members and materials, there are mentioned binders for binding particles of the substance.
The sensor element 2 is provided in a state in which the measurement electrode 5 is in close contact with the outer peripheral surface of the distal end side of the bottomed tubular shape.
The measurement electrode 5 is an electrode for detecting the potential of the outer peripheral surface of the sensor element 2. The measurement electrode 5 is formed by applying an electrode material such as platinum paste to the outer peripheral surface of the front end side of the sensor element 2 and firing (heat treatment) the electrode under predetermined firing conditions, as in the case of the quasi-electrode 4. The measurement electrode 5 is also formed in a porous shape, and allows permeation of measurement gas.
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 surfaces of the sensor element 2 in the thickness direction. In this embodiment, the end face on the base end side of the measurement electrode 5 is disposed at the same height as the end on the base end side of the reference electrode 4.
The measuring electrode 5 is connected to the potentiometer 7 via a second wire 81. The second wire 81 contains a material (excellent-in-reactivity-resistance material) that is stable to the measurement gas (atmosphere containing hydrogen gas) in the use temperature range of the hydrogen sensor 1 (measurement temperature range of the hydrogen concentration). The second wire 81 is made of a material selected from iron, nickel, platinum, and platinum-rhodium alloy, for example. The second wire 81 of this embodiment is a wire containing iron, similarly to the first wire 80.
The sealing material 6 is disposed closer to the base end side (upper side in the drawing) 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 where the atmosphere inside the sensor element 2 can pass. Further, the sealing material 6 may be a constitution sealing 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.
The sealing material 6 is not limited in the constitution of the member forming the sealing material 6 in the case where the atmosphere inside the sensor element 2 is allowed to pass. Examples thereof include a mesh (or woven or non-woven) member containing a heat-resistant metal, a woven fabric of ceramic fibers, a non-woven 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 material 6 may be provided with two members 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 in a state of being spaced apart from each other.
The sealing material 6 may be in contact with the solid reference substance 3 or may be in a state of being spaced apart from the solid reference substance.
In the case where the sealing material 6 prevents the passage of the atmosphere inside the sensor element 2, the material forming the sealing material 6 is not limited. For example, heat-resistant ceramics, molten glass, and the like can be cited.
The potentiometer 7 is connected to the reference electrode 4 via a first wire 80, and is connected to the measurement electrode 5 via a second 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)
A method for measuring the hydrogen 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 ℃). The hydrogen gas sensor 1 is preferably preheated to a temperature lower than the measurement temperature by about 200 ℃ before being exposed to the high-temperature measurement gas. The preheating temperature is a temperature equal to or lower than the temperature at which the non-stoichiometric compound catalyst of the solid reference substance 3 generates gas, and the non-stoichiometric compound catalyst does not generate gas during the preheating.
In the hydrogen gas sensor 1 disposed in the measurement gas and exposed to the measurement temperature, the temperature of the sensor element 2 and the inside thereof increases to a predetermined temperature. Thus, the solid reference substance 3 immediately generates oxygen. The generated oxygen gas is filled into the sensor element 2, and the atmosphere existing before that is discharged from the opening at the base end. The inside of (the distal 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 contains almost no hydrogen. As a result, the hydrogen partial pressure inside the sensor element 2 decreases. In particular the partial pressure of hydrogen around the reference electrode 4 is reduced.
If the inside of (the front end portion of) the sensor element 2 is filled with oxygen, a difference is generated in hydrogen concentration between the inside and the outside of the sensor element 2, and a concentration cell is formed. The battery formula is shown in the following formula (1). In the formula (1), gas (1) represents the Gas of the reference electrode 4, P' O2 Represents the partial pressure of oxygen, P ', of reference electrode 4' H2 Indicating the hydrogen partial pressure of reference electrode 4, alpha-Al 2 O 3 (+MgO) represents the sensor element 2, gas (2) represents the gas of the measuring electrode 5, P' O2 Indicating the partial pressure of oxygen, P ", of the measuring electrode 5" H2 The partial pressure of hydrogen at the measurement electrode 5 is shown.
Gas(1)(P’ O2 ，P’ H2 )|α-Al 2 O 3 (+MgO)|Gas(2)(P” O2 ，P” H2 )…(1)
The electromotive force generated between the two poles of the concentration cell of formula (1) is represented by formula (2) below. In the formula (2), E represents an electromotive force (V), R represents a gas constant (8.3143J/K.mol), T represents an absolute temperature (K), and F represents a Faraday constant (9.64853 ×10) 4 C/mol)，P” H2 Indicating the partial pressure of hydrogen, P ', of the measurement electrode 5' H2 The hydrogen partial pressure of the reference electrode 4 is indicated, and a represents a constant.
As described above, the hydrogen partial pressure (P 'of the reference electrode 4' H2 ) Very small. Therefore, the formula (2) can be represented as formula (3).
As shown in the formula (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 oxygen is generated from the solid reference substance 3 of the present embodiment, the partial pressure of hydrogen in the sensor element 2 can be set to a very low pressure (for example, 101325×10 -7 Pa(10 -7 atm) below. As a result, the proton transfer number of α -alumina forming the inner peripheral surface of the sensor element 2 is almost 0, and therefore, the formula (3) can be used.
The hydrogen sensor 1 of the present embodiment can measure the potential difference by the potentiometer 7. Further, 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 according to the present embodiment measures the hydrogen concentration of the measurement gas.
(effects of the present embodiment)
In this embodiment, the solid reference substance 3 comprises a non-stoichiometric compound type catalyst that generates a specified gas when exposed to a predetermined temperature. The specified gas is oxygen. The non-stoichiometric compound catalyst is selected from (Zr 1-x Ce x ) y M 1-y O 2 (0 < x < 1,0 < y < 1, M: any one of Sc, Y, la, pr, nd, gd, dy), la 1-x Sr x MnO 3 (0＜x＜1)，Ba 1-x K x MnAl 11 O 19 (0＜x＜1)、Ce x Nd 1-x O 2 (0 < x < 1) or a mixture of more than 2.
According to these configurations, when the hydrogen concentration is measured by forming the hydrogen sensor 1, the solid reference substance 3 of the present embodiment is heated to a predetermined temperature and then immediately generates oxygen (predetermined gas). In this way, the partial pressure of hydrogen gas around the solid reference material 3 is reduced, and a great concentration difference of hydrogen gas is generated on both sides of the inner peripheral surface and the outer peripheral surface of the sensor element 2 of the hydrogen gas sensor 1, so that a concentration cell whose electromotive force is uniquely determined only by the partial pressure of hydrogen gas at the measuring electrode is formed. As described above, the concentration cell can be formed immediately by using the solid reference substance 3 of the present embodiment, and the hydrogen concentration can be measured (measurement is started) in the hydrogen sensor 1 with high accuracy in a short time.
In this embodiment, since it is not necessary to continuously flow air or reference gas on the reference electrode side, the hydrogen 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 sensor 1 according to the present embodiment can exhibit the above-described effect of the solid reference substance 3, and can measure the hydrogen concentration in a short time with high accuracy.
The hydrogen sensor 1 of the present embodiment includes: a sensor element 2 including a proton conductor, a solid reference substance 3 disposed in a state of being in close contact with an inner peripheral side (one end side) of the sensor element 2, a reference electrode 4 disposed in a state of being in close contact with an inner peripheral side (one end) of the sensor element 2, a measurement electrode 5 disposed 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 surface), and a potentiometer 7 for measuring a potential difference between the reference electrode 4 and the measurement electrode 5.
According to this configuration, a concentration cell whose electromotive force is uniquely determined only by the partial pressure of hydrogen on the measurement 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 measurement electrode 5 can be measured by the potentiometer 7. That is, the hydrogen sensor 1 that exhibits the above-described effects is obtained.
In the hydrogen sensor 1 of the present embodiment, the sensor element 2 is formed in a bottomed tubular shape, and the solid reference substance 3 is accommodated therein. That is, the sensor element 2 has a configuration in which a housing space for housing the solid reference substance 3 is provided therein.
According to this configuration, the solid reference substance 3 can be stored in the storage space provided in the sensor element 2, and the storage space can be filled with the generated oxygen gas when the hydrogen concentration is measured. That is, the storage space can be filled with oxygen more quickly. The remaining hydrogen gas reacts with the oxygen gas and is consumed as water vapor, and therefore, the sensor element 2 contains almost no hydrogen gas. As a result, the hydrogen partial pressure in the sensor element 2 is reduced, and the hydrogen concentration can be measured in a short time with high accuracy.
As described above, the hydrogen sensor 1 according to the present embodiment can measure the hydrogen concentration in a short time with high accuracy even when the hydrogen concentration in the gas phase is measured.
[ embodiment 2 ]
The present embodiment is the same as embodiment 1 except that the present embodiment further has a thermocouple 82.
As shown in the configuration of fig. 2, the hydrogen sensor 1 of the present embodiment 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 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 configuration as in embodiment 1.
The thermocouple 82 is housed in a space inside the bottomed cylindrical sensor element 2. The thermocouple 82 may have the same constitution and material as those of the conventional thermocouple. In this embodiment, a thermocouple of platinum-platinum rhodium alloy is used. In this embodiment, each wire is housed inside the sensor element 2 in a state of being housed in a 2-hole alumina protective tube 83.
The thermal contact 84 at the distal end of the thermocouple 82 is exposed from the protection tube 83. The thermal contact 84 is fixed to the reference electrode 4 provided on the inner peripheral surface of the sensor element 2, and is electrically connected thereto.
The thermocouple 82 is connected to the potentiometer 7. The potentiometer 7 measures (calculates) the hydrogen concentration with reference to the temperature measurement result of the thermocouple 82.
The thermocouple 82 is used in this embodiment, but a temperature measuring device other than the thermocouple 82 may be used.
(effects of the present embodiment)
The present embodiment has the same configuration as embodiment 1 except that the thermocouple 82 is provided, and the same effects as embodiment 1 are exhibited.
In this embodiment, a thermocouple 82 is provided. 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 concentration can be measured more accurately.
In this embodiment, the thermocouple 82 is housed in the sensor element 2. In this state, the thermocouple 82 is not exposed to the measurement gas, and therefore the thermocouple 82 is protected by the sensor element 2.
[ embodiment 3 ]
The present embodiment is the same as embodiment 1 except that the hydrogen sensor 1 further includes a conductive holding tube 85.
The hydrogen sensor 1 of the present embodiment is a gas sensor for measuring the concentration of hydrogen gas in a gas phase, and 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 a conductive holding tube 85, as shown in the configuration shown in fig. 3.
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 in embodiment 1.
The conductive holding tube 85 has a cylindrical shape. The sensor element 2 is fitted in the axial center portion. The sensor element 2 is disposed on 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 the tip (lower end in the drawing) 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 second 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 wire forming a conductive path.
The conductive holding tube 85 may be in a state where its inner peripheral surface is in close contact with the outer peripheral surface of the sensor element 2 (in a state of airtight contact and in a state where ventilation is impossible), or may be in a state where a gap is provided between its inner peripheral surface and the outer peripheral surface of the sensor element 2 (in a state where ventilation is possible). In addition, a sealing member (or a filler or a spacer) may be disposed between both surfaces.
The conductive holding tube 85 is not limited as long as it is made of a conductive material. Examples of the material include a conductive metal such as a heat resistant metal such as stainless steel and a conductive ceramic. The material of the conductive protection tube 85 of this embodiment is stainless steel.
The conductive holding tube 85 may be a combination of these, and specifically, may be a structure in which a conductive ceramic layer is formed on the surface of a base material of a conductive metal such as a heat-resistant metal such as stainless steel.
(effects of the present embodiment)
The present embodiment has the same configuration as embodiment 1 except that the conductive holding tube 85 is provided, and the same effects as embodiment 1 are exhibited.
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. Thus, the operation of the hydrogen sensor 1 can be facilitated by the conductive holding tube 85. Further, by providing the conductive holding pipe 85, it is not necessary to hold (support) the sensor element 2 when operating the hydrogen sensor 1, and damage to the sensor element 2 can be suppressed.
[ embodiment 4 ]
The present embodiment is the same as embodiment 3 except that the structure of the conductive holding tube 85 is different.
As shown in the configuration of fig. 4, the hydrogen sensor 1 of the present embodiment 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, 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 embodiment 3 (or embodiment 1).
The conductive holding tube 85 is a bottomed tubular member having a closed front 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 proximal end than the distal end, the through hole communicating 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 tube 85. The through hole 86 is not limited to this configuration, and may be formed in an end face of the tip (a lower end face in the drawing). 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 the same potential is set. In this embodiment, the conductive holding tube 85 is in contact with the measurement electrode 5 at the tip of the sensor element 2.
The conductive holding tube 85 supports and fixes the sensor element 2 to the inside of 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.
The support member 87 may be a cylindrical member in which the sensor element 2 is fitted, or a member that supports the outer peripheral surface of the sensor element 2. The support member 87 supports and fixes 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 (electrically connected state) in which a tip (lower end in the drawing) is in contact with the measurement electrode 5 formed on the surface of the sensor element 2.
As a material of the supporting member 87, a material having conductivity can be given. The material of the support member 87 of the present embodiment is a material having conductivity.
(effects of the present embodiment)
The present embodiment has the same configuration as embodiment 3 except that the shape of the conductive holding tube 85 is different, and the same effects as embodiment 3 are exhibited.
In this embodiment, the sensor element 2 is disposed inside the conductive holding tube 85 having a bottomed tubular shape 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.
[ embodiment 5 ]
The present embodiment is a hydrogen sensor 1 for measuring the hydrogen concentration in molten metal.
The hydrogen sensor 1 of the present embodiment is a gas sensor for measuring the hydrogen concentration in molten metal, and 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 a support tube 9, as shown in the configuration shown in fig. 5. The hydrogen sensor 1 of the present embodiment is configured to impregnate the sensor element 2 with 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 embodiment 1.
The measurement electrode 5 is a rod-shaped member having a tip immersed in molten metal, and is disposed in a state spaced apart from the sensor element 2. The measurement electrode 5 is electrically connected to the sensor element 2 via 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 called 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 measuring electrode 5 and the sensor element 2 is not limited as long as it is a length capable of forming a measuring circuit for measuring the potential difference of the concentration cell. That is, the present embodiment may be spaced from the outer peripheral surface of the sensor element 2, or may be in contact with the outer peripheral surface of the sensor element 2.
The measurement electrode 5 is connected to the potentiometer 7 via the second lead 81 similarly to embodiment 1.
The support tube 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 tube 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 a state of airtight contact). The support tube 9 is disposed in a state (i.e., a state in which ventilation is possible) in which a gap is provided between the inner peripheral surface of the support tube and the outer peripheral surface of the sensor element 2. 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 tube 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. The support pipe 9 has high strength, and thus prevents the hydrogen sensor 1 from being damaged (or broken) even when a stress due to the flow of the molten metal is applied.
The material of the support tube 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 tube 9 of this embodiment is stainless steel.
The support pipe 9 may be constituted by combining these, specifically, a ceramic layer is formed on the surface of a base material of heat-resistant metal such as stainless steel.
The support pipe 9 may be a member called a sleeve in a sensor for measuring the hydrogen concentration in the conventional molten metal.
The hydrogen sensor 1 of the present embodiment measures the hydrogen concentration contained in the molten metal. The hydrogen gas sensor 1 measures the hydrogen gas concentration at a measurement temperature (=the molten liquid temperature of the molten metal) 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 about 200 ℃ lower than the measurement temperature.
(measurement of Hydrogen)
The method of measuring the hydrogen concentration in the hydrogen sensor 1 according to the present embodiment may 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.
The hydrogen concentration in the hydrogen sensor 1 of the present embodiment can be measured by immersing the sensor element 2 and the measurement electrode 5 in molten metal. In this case, the level of the molten metal is preferably a position corresponding to the support pipe 9. The entire measuring electrode 5 is preferably immersed in the molten metal.
When foreign matter such as metal oxide or slag is present on the surface of the molten metal by the high-strength support pipe 9 being located at a position corresponding to the surface of the molten metal, the foreign matter is prevented from hitting the outer peripheral surface of the sensor element 2, and the sensor element 2 is prevented from being damaged.
(effects of the present embodiment)
This embodiment has the same configuration as embodiment 1 except that the measurement electrode 5 is spaced apart from the sensor element 2, and exhibits the same effects as embodiment 1.
That is, the hydrogen sensor 1 of the present embodiment can measure hydrogen gas contained in the molten metal.
[ embodiment 6 ]
The present embodiment is the same as embodiment 5 except that the constitution of the measurement electrode 5 and the support tube 9 is different.
As shown in the configuration of fig. 6, the hydrogen sensor 1 of the present embodiment includes a sensor element 2, a solid reference substance 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 embodiment 5.
The measurement electrode 5 has the same cylindrical shape as 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 thus 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.
(effects of the present embodiment)
The present embodiment has the same configuration as embodiment 5 except that the configuration of the measuring electrode 5 and the support tube 9 is different, and the same effects as embodiment 5 are exhibited.
[ embodiment 7 ]
The present embodiment is the same as embodiment 5 except for the configuration 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 substance 3, a reference electrode 4, a measurement electrode 5, a sealing material 6, a potentiometer 7, and a support
And a 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 configuration as in embodiment 5.
The support tube 9 is a cylindrical member in which the sensor element 2 and the measurement electrode 5 are disposed in the axial portion (cylindrical interior) in a state where the sensor element 2 and the measurement electrode 5 are exposed from the end face of the tip (the end face of the lower end in the drawing). The support pipe 9 of this embodiment has a cylindrical shape with 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 is a diameter that enables the sensor element 2 and the measurement electrode 5 to be disposed in the axial center portion.
The front end of the support tube 9 is sealed by a sealing material 90. The sealing material 90 forms an end face of the lower end of the cylindrical support pipe 9. The sealing material 90 is not limited as long as it is a material capable of preventing penetration of molten metal. Examples thereof include ceramics such as silica-based ceramics, alumina-based ceramics, and silica-alumina mixtures. The thickness of the sealing material 90 (the thickness in the vertical direction in fig. 7) is not limited.
(effects of the present embodiment)
The present embodiment has the same configuration as embodiment 5 except that the measurement electrode 5 is disposed inside the support tube 9 together with the sensor element 2, and the same effects as embodiment 5 are exhibited.
In the present embodiment, the sensor element 2 and the measurement electrode 5 are integrally housed and fixed in the support tube 9, and the operation of the hydrogen sensor 1 is facilitated.
[ embodiment 8 ]
The present embodiment is the same as embodiment 7 except that the present embodiment further includes a thermocouple 82.
As shown in the configuration of fig. 8, the hydrogen sensor 1 of the present embodiment 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, 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 configuration as in embodiment 7.
The support tube 9 is a cylindrical member in which the sensor element 2 and the measurement electrode 5 are disposed, and the thermocouple 82 is disposed in a state where the thermal contact portion 84 at the tip is exposed.
The thermocouple 82 has the same structure as the thermocouple 82 of embodiment 2. In the present embodiment, the thermal contact portion 84 of the thermocouple 82 is exposed, but the thermocouple 82 may be housed in the protective tube. That is, a conventional temperature detector may be used instead of the thermocouple 82.
(effects of the present embodiment)
The present embodiment has the same configuration as that of embodiment 7 except that the thermocouple 82 is also disposed inside the support tube 9, and the same effects as those of embodiment 7 are exhibited.
In this embodiment, the temperature of the molten metal is directly measured by the thermocouple 82, and the hydrogen concentration can be measured more accurately as in embodiment 2.
[ other forms ]
The hydrogen sensor 1 of each of the above-described embodiments is a sensor for detecting and measuring hydrogen. The hydrogen sensor 1 is a sensor that continuously measures the hydrogen concentration in a gas from a molten metal at the time of casting in a gas phase, or a sensor that continuously measures the hydrogen concentration in a molten metal by immersing the tip portion of the hydrogen sensor 1 in a molten metal.
The use of the hydrogen sensor 1 of each of the above-described embodiments is not limited to this use. 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 the gas phase.
The measurement temperature of hydrogen gas can be adjusted by changing the catalyst other than the stoichiometric compound of the solid reference material 3 to another catalyst.
Examples
Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples.
Example (example)
This example is the hydrogen sensor 1 of embodiment 7 described above.
In the hydrogen sensor 1 of this example, a commercially available Ce was used as the solid reference substance 3 0.8 Nd 0.2 O 2 (Ce x Nd 1-x O 2 Compound when x=0.8). The solid reference substance 3 generates oxygen at 1000 ℃.
The solid reference substance 3 was prepared by using a powder having an average particle diameter D50 of 100 μm, putting the powder into the sensor element 2, and lightly compressing the powder in the distal direction by hand.
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
In this example, a hydrogen sensor 1 using air (air) as a reference substance is provided. The gas sensor 1 of the present example corresponds to a conventional hydrogen sensor.
The hydrogen sensor 1 of the present example has the configuration shown in fig. 9. The configuration of the hydrogen sensor 1 of this example, which is not specifically mentioned, is the same as that of the embodiment.
The hydrogen sensor 1 of this example includes a sensor element 2, a reference electrode 4, a measurement electrode 5, a potentiometer 7, a blower tube 88, and a support tube 9.
The air supply pipe 88 is a ventilation pipe inserted into the sensor element 2 at a position near the tip end. The base end of the air supply pipe 88 is connected to an air supply device (not shown). The air supply duct 88 introduces air supplied from the air supply device to the vicinity of the front end portion of the inside of the sensor element 2.
The air supply device supplies air to the vicinity of the front end portion of the inside of the sensor element 2 via 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 into the sensor element 2, whereby the supply speed of the air and the discharge speed of the air discharged from the sensor element 2 are balanced with each other, and the composition of the atmosphere in the sensor element 2 is maintained at the composition of the air (the composition of the reference substance is stable).
[ evaluation ]
As an evaluation of the hydrogen sensor 1 of the example, measurement of the hydrogen concentration in the molten metal was performed. Specifically, the hydrogen concentration in molten copper as the molten metal was measured. The hydrogen concentration of the gas sensor 1 of the comparative example was measured, and the obtained measurement value of the hydrogen concentration was compared. Fig. 10 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 ℃ was immersed in molten copper (purity 99.99%) at 1150 ℃ to start measurement of the hydrogen concentration. Further, the stable value can be obtained. (in FIG. 10, a stable value was obtained at a time of 0.1 hour.)
After the output value of the hydrogen sensor of the comparative example was stabilized (in fig. 10, at a time of 0.1 hour), the hydrogen sensor 1 of the example preheated to 1000 ℃ was immersed in molten copper, and measurement of the hydrogen concentration was started.
Fig. 10 shows measurement results of the hydrogen concentration of the hydrogen sensor 1 of the example and the hydrogen sensor 1 of the comparative example. Fig. 10 is a graph showing the calculation result of calculating the hydrogen gas concentration from the potential difference between the measured reference electrode 4 and the measured electrode 5 and converting the calculated hydrogen gas concentration into the hydrogen gas concentration.
As shown in fig. 10, the measurement results in the hydrogen sensor 1 of the example were identical to those of the hydrogen sensor 1 of the comparative example after 4 minutes from the start of immersion in molten copper. The measurement results of the latter two were also identical.
From the agreement of the measurement results, it was confirmed that the hydrogen sensor 1 of the example could 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 concentration with high accuracy, similarly to the hydrogen sensor 1 of the comparative example (conventional hydrogen sensor).
Further, it was confirmed that the hydrogen sensor 1 of the example was able to measure the hydrogen concentration with high accuracy in a short time after 4 minutes from the start of immersion in molten copper. On the other hand, it took longer (0.1 hr) for the hydrogen sensor 1 of the comparative example to reach stable measurement value of the hydrogen concentration. That is, the hydrogen sensor 1 of the example can measure the hydrogen concentration more rapidly than the hydrogen sensor 1 of the comparative example (conventional hydrogen sensor). In other words, the hydrogen sensor 1 of the embodiment can perform measurement of the hydrogen concentration in a short time
Moreover, it was confirmed that these effects were brought about by the solid reference substance 3 of the hydrogen sensor 1 of the example.
As described above, it was confirmed that the hydrogen sensor 1 of the example was the hydrogen sensor 1 having the solid reference substance 3 capable of measuring the hydrogen concentration with high accuracy in a short time.
Symbol description
1: hydrogen sensor 2: sensor element 3: solid reference substance
4: reference electrode 5: measurement electrode 6: sealing material
7: potentiometer 82: thermocouple 9: and a support tube.
Claims (7)
1. A solid reference material comprising a non-stoichiometric compound catalyst which generates a specified gas upon exposure to a predetermined temperature,
the non-stoichiometric compound catalyst is selected from (Zr 1-x Ce x ) y M 1-y O 2 、La 1-x Sr x MnO 3 、Ba 1- x K x MnAl 11 O 19 、Ce x Nd 1-x O 2 In a mixture of 1 or more than 2 of the above (Zr 1-x Ce x ) y M 1-y O 2 Wherein x is more than 0 and less than 1, y is more than 0 and less than 1, M: sc, Y, la, pr, nd, gd, dy, in the La 1-x Sr x MnO 3 Wherein x is more than 0 and less than 1, in Ba 1- x K x MnAl 11 O 19 Wherein x is more than 0 and less than 1, in Ce x Nd 1-x O 2 Wherein x is more than 0 and less than 1.
2. The solid reference substance according to claim 1, wherein the prescribed gas is oxygen.
3. A hydrogen sensor characterized by having a solid reference substance according to claim 1 or 2.
4. The hydrogen sensor according to claim 3, comprising:
A sensor element comprising a proton conductor,
the solid reference substance is disposed in a state of being in close contact with one end side of the sensor element,
a reference electrode provided in a state of being in close contact with one end of the sensor element,
a measurement electrode provided in a state of having the same potential as the other end of the sensor element, and
a potentiometer for measuring a potential difference between the reference electrode and the measurement electrode.
5. The hydrogen sensor according to claim 4, wherein the sensor element has a receiving space that receives the solid reference substance.
6. The hydrogen sensor according to any one of claims 3 to 5, wherein a hydrogen concentration in a gas phase is measured.
7. The hydrogen sensor according to any one of claims 3 to 5, wherein a hydrogen concentration in the molten metal is measured.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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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 CN114072665A (en) | 2022-02-18 |
| CN114072665B true CN114072665B (en) | 2024-03-12 |
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| WO2021002199A1 (en) | 2021-01-07 |
| CN114072665A (en) | 2022-02-18 |
| JP7265007B2 (en) | 2023-04-25 |
| JPWO2021002199A1 (en) | 2021-01-07 |
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