WO2017080005A1 - 一种测量金属熔体中氢含量的传感器及测量方法 - Google Patents

一种测量金属熔体中氢含量的传感器及测量方法 Download PDF

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WO2017080005A1
WO2017080005A1 PCT/CN2015/096049 CN2015096049W WO2017080005A1 WO 2017080005 A1 WO2017080005 A1 WO 2017080005A1 CN 2015096049 W CN2015096049 W CN 2015096049W WO 2017080005 A1 WO2017080005 A1 WO 2017080005A1
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electrode
sensor
metal melt
hydrogen content
measuring
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French (fr)
Chinese (zh)
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厉英
丁玉石
周旭东
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Northeastern University China
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Northeastern University China
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Priority to EP15908135.5A priority Critical patent/EP3372998B1/en
Priority to JP2018517620A priority patent/JP6775012B2/ja
Priority to US15/774,205 priority patent/US10598629B2/en
Publication of WO2017080005A1 publication Critical patent/WO2017080005A1/zh
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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
    • G01N27/4112—Composition or fabrication of the solid electrolyte
    • G01N27/4114—Composition or fabrication of the solid electrolyte for detection of gases other than oxygen
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/0004—Gaseous mixtures, e.g. polluted air
    • G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
    • G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector
    • G01N33/0036—General constructional details of gas analysers, e.g. portable test equipment concerning the detector specially adapted to detect a particular component
    • G01N33/005—H2
    • 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
    • G01N27/28—Electrolytic cell components
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • 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
    • G01N27/28—Electrolytic cell components
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G01N27/301—Reference electrodes
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/20—Metals
    • G01N33/202—Constituents thereof
    • G01N33/2022—Non-metallic constituents
    • G01N33/2025—Gaseous constituents

Definitions

  • the invention relates to a hydrogen sensing technology, in particular to a sensor and a measuring method for measuring hydrogen content in a metal melt.
  • hydrogen is a harmful element in metal materials, which can cause defects such as hydrogen embrittlement, looseness, and pinholes in metal materials.
  • Timely measurement of the hydrogen content in the metal, and appropriate dehydrogenation treatment after feedback, can avoid various hydrogen-induced defects in the metal material.
  • EP0544281 The Tokyo kiln industry of Japan discloses a device for measuring the hydrogen content in an aluminum melt by a solid proton conductor, which can measure the hydrogen content in a metal melt such as an aluminum melt below 1000 °C.
  • the reference pole and the electrode to be tested of the solid proton conductor sensor are both externally applied porous electrodes, and the reference electrode is filled with a reference substance having a certain hydrogen partial pressure, or A gas having a certain partial pressure of hydrogen is introduced, and the electrode to be tested is brought into contact with the atmosphere to be tested to form a concentration battery.
  • the battery response is:
  • the potentiometer is used to measure the electromotive force of the concentration battery. It is known that the reference pole (hydrogen partial pressure can be higher than the pole to be measured or lower than the pole to be tested) hydrogen partial pressure, and the hydrogen partial pressure in the atmosphere to be tested can be calculated. The hydrogen content was calculated.
  • the probe and method for measuring hydrogen content disclosed by the Tokyo kiln industry in Japan use a solid proton conductor as the sensor probe body, which is separated by a ceramic sleeve, a ceramic cover or a porous material between the solid proton conductor and the metal melt, resulting in proton conductor and metal fusion. Establish a gas chamber between the bodies.
  • the method for measuring the hydrogen content in the metal melt is to establish an equilibrium hydrogen partial pressure between the metal melt and the gas chamber atmosphere in the sensor probe, and measure the hydrogen partial pressure according to Sievert's law:
  • S is the hydrogen content of the metal melt
  • k is a constant. It is the equilibrium hydrogen partial pressure of the metal melt.
  • the hydrogen partial pressure of the atmosphere in the porous material is the equilibrium partial hydrogen partial pressure of the metal melt, and the hydrogen content in the aluminum melt is calculated.
  • US2005/0252789 proposes the use of chemically stable ⁇ Ti- ⁇ Ti, ⁇ Zr- ⁇ Zr, ⁇ Hf- ⁇ Hf metal-hydrogen materials as reference for the sensor, the interface between the reference and the solid electrode can maintain chemistry at higher temperatures Stability, reducing the effect of oxygen on solid proton conductors and providing a stable hydrogen partial pressure.
  • this patent does not mention in detail the method of determining the hydrogen content.
  • US 2009/0139876 discloses a device for measuring the hydrogen content of a metal melt using a solid proton conductor, and proposes to utilize A method for recovering a proton conductor solid electrolyte from an AlN, BN water absorbing material.
  • the above device and method use a solid proton conductor hydrogen concentration cell to measure the equilibrium hydrogen partial pressure established between the metal melt and the gas chamber in the probe.
  • This method has the following disadvantages: (1) the metal melt is balanced with the gas chamber for a longer period of time, resulting in a lower response speed of the sensor; (2) the material for establishing the gas chamber in the sensor is mostly a ceramic cover or a fiber material. The surface of the material is easy to adhere to water. During the measurement process, water reacts with the metal melt to generate a large amount of hydrogen, which affects the accuracy of the measurement results. (3) During the multiple measurement process, the metal and metal oxide attached to the surface of the probe easily block the gas. The room leads to a slower balance, slower response, and even measurement accuracy.
  • the present invention provides a sensor and a measuring method for measuring a hydrogen content in a metal melt, wherein a proton conductor in the sensor is directly in contact with a molten metal to form an electrode to be tested, and the electrode to be tested is not required.
  • the equilibrium of hydrogen dissolution is established by the gas and the metal melt, and the electrochemical balance of the reference material and the hydrogen in the metal melt is directly established by the proton conductor.
  • a sensor for measuring hydrogen content in a metal melt comprising a solid proton conductor component, a reference electrode, a quasi-test electrode, a reference, a via, an insulating ceramic binder; wherein the pass tube and the solid proton conductor element are between Connected by an insulating ceramic adhesive and forming an inner space, the surface of the solid proton conductor element in the space is an inner surface, the surface exposed to the outside is an outer surface, and the reference porous electrode is coated on the inner surface of the solid proton conductor element,
  • the quasi-test electrode is an outer surface of the solid proton conductor element;
  • the reference is a gas, a liquid or a solid, placed in the inner space and in contact with the reference porous electrode.
  • the quasi-test electrode is in contact with the metal melt during the hydrogen measurement process, and the contact surface constitutes the electrode to be tested.
  • the sensor for measuring the hydrogen content in the metal melt may further include an air guiding tube and a three-way fixture.
  • the reference material is gas
  • the three-way fixture and the upper part of the tube Connecting, the air guiding tube is connected to the reference porous electrode through the tee fixture inserted into the inner space formed by the through tube, the insulating ceramic binder and the solid proton conductor element; when the bottom end of the air guiding tube is facing the reference porous electrode and the solid proton conductor
  • the bottom end of the air guiding tube is a blind end, and the side opening is used as an air outlet.
  • the function of the air inlet is to avoid the change of the air pressure caused by the gas reference material rushing toward the reference porous electrode or the proton conductor element, thereby improving the measurement precision.
  • the sensor for measuring the hydrogen content in the metal melt may further include a reference electrode wire.
  • the reference electrode wire When the reference material is a gas, the reference electrode wire is inserted into the through tube through the tee clamp, connected to the reference porous electrode, and externally connected To the measuring circuit; when the reference material is liquid or solid, the reference electrode wire is connected to the reference porous electrode through the insulating ceramic adhesive and externally connected to the measuring circuit.
  • the air guiding tube material is corundum, quartz, zirconia, stainless steel, nickel-chromium alloy or iron-chromium aluminum alloy.
  • the sensor structure further comprises a reference pole wire.
  • the three-way fixture material is stainless steel, copper, polytetrafluoroethylene, nylon or polyurethane.
  • the reference electrode material is metal platinum, gold, silver, nickel chromium alloy, iron chromium aluminum alloy or stainless steel.
  • the sensor for measuring the hydrogen content in the metal melt when the reference material is a liquid or a solid, the sensor structure comprises an inert material made of Al 2 O 3 , YSZ or Y 2 O 3 ; the inert material is filled in the reference material and Between insulating ceramic binders.
  • the solid proton conductor element may be tubular, spherical, sheet, disc, square or columnar, and is made of perovskite or composite perovskite structural material.
  • the reference electrode material is silver, platinum or gold.
  • the insulating ceramic binder is an alumina-based material.
  • the reference substance is a gas, a liquid or a solid, wherein the gas comprises Ar-H 2 , N 2 -H 2 , He-H 2 , O 2 -H 2 O doped with one or more or no inert gases.
  • N 2 -NH 3 gas liquid includes Li-LiH
  • solid includes YH, Ti-H, Zr-H or Sc-H.
  • the reference material is made of insulating ceramic binder. Sealed to the reference electrode side.
  • the material of the pipe is corundum, quartz, graphite, stainless steel, sialon, SiC or LaCrO 3 , which functions as a support body and a gas path.
  • the method for measuring the hydrogen content in the metal melt by using the sensor is carried out according to the following process steps: 1 inserting the sensor and the corrosion-resistant electrode into the metal melt, and ensuring that the solid proton conductor element is completely immersed in the metal melt, and the quasi-measured pole Direct contact with the metal melt, the contact surface is the electrode to be tested; 2 connect the potentiometer and the reference pole wire or the metal air pipe and the corrosion resistant electrode, measure the potential difference between the reference pole and the pole to be tested; The potential difference, the metal melt temperature, the saturation solubility of hydrogen in the metal melt, and the hydrogen content S of the metal melt are calculated.
  • the battery reaction equation and the calculation formula are as shown in (4) and (5):
  • ⁇ G is the Gibbs free energy, J/mol
  • ⁇ G ⁇ is the standard Gibbs free energy, J/mol
  • R is the gas constant, J/(K ⁇ mol)
  • T is the thermodynamic temperature, K
  • a [ H] is the hydrogen activity
  • p ⁇ is the standard pressure, Pa
  • E is the electromotive force, V
  • F is the Faraday constant, C / mol.
  • Equation (6) Is the equilibrium hydrogen partial pressure in the atmosphere
  • f [H] is the activity coefficient of hydrogen in the metal melt
  • w [H] is the mass percentage of hydrogen in the metal melt.
  • the equilibrium hydrogen partial pressure is 1 standard atmospheric pressure.
  • w [H] Due to hydrogen saturation in the metal melt, w [H] can be converted into units by the saturation solubility conversion of hydrogen;
  • S 0 is a hydrogen-saturated solubility, ml/100 g, and K is a constant generated by a conversion unit. Since the saturation solubility S 0 of most metals is known thermodynamic data or thermodynamic data that can be calculated, the calculation can obtain the standard Gibbs free energy ⁇ G ⁇ of hydrogen dissolved in the metal melt.
  • the standard Gibbs free energy ⁇ G ⁇ due to hydrogen dissolved in the metal melt is only related to the type and temperature of the metal melt, and does not change with the change of the hydrogen content in the metal melt. Therefore, when hydrogen is saturated in the metal melt, hydrogen is dissolved.
  • the standard Gibbs free energy ⁇ G ⁇ of the metal melt is the same as in the case of unsaturated;
  • the metal melt hydrogen content S is obtained by calculation. According to the nature of the selected solid proton conductor and the molten metal to be tested, the formula (14) can be corrected according to the experimental results.
  • the hydrogen content measuring sensor of the present invention wherein the proton conductor can directly contact the metal melt, and quickly establish an atmosphere in which the reference material and the hydrogen in the metal melt are balanced, the measuring speed is faster, the result is more precise, and the hydrogen detecting sensor
  • the simplification is simpler and the hydrogen content of the metal melt at a temperature below 1000 ° C can be determined.
  • the hydrogen content determination method of the present invention directly calculates the hydrogen content in the metal melt by the potential difference between the reference material and the hydrogen in the metal melt, and the method is more intuitive and more accurate, and avoids the gas chamber of the original sensor. The effect of instability on the measurement results.
  • Figure 1 is a schematic illustration of the process for measuring the hydrogen content of a metal melt using the sensor of the present invention.
  • FIG. 2 is a schematic structural view of a hydrogen content measuring sensor according to Embodiment 1 of the present invention.
  • FIG. 3 is a schematic structural view of a hydrogen content measuring sensor according to Embodiment 2 of the present invention.
  • FIG. 4 is a schematic structural view of a hydrogen content measuring sensor according to Embodiment 3 of the present invention.
  • Fig. 5 is a structural schematic view showing a hydrogen content measuring sensor according to a fourth embodiment of the present invention.
  • Fig. 6 is a structural schematic view of a hydrogen content measuring sensor according to a fifth embodiment of the present invention.
  • Fig. 7 is a structural schematic view of a hydrogen content measuring sensor according to a sixth embodiment of the present invention.
  • Figure 8 is a schematic view showing the structure of a hydrogen content measuring sensor according to Embodiment 7 of the present invention.
  • Figure 9 is a schematic view showing the structure of a hydrogen content measuring sensor according to Embodiment 8 of the present invention.
  • a sensor for measuring the hydrogen content in an aluminum melt comprising a CaZr 0.9 In 0.1 O 3- ⁇ solid proton conductor element 1, a reference porous electrode 2, a quasi-measurement electrode 6, and a reference Ar -H 2 , stainless steel air pipe 3, corundum pipe 5, alumina-based insulating ceramic binder 4 and polytetrafluoroethylene tee clamp 104; wherein the solid proton conductor component 1 is a tubular structure, the material is perovskite One end is sealed with an alumina-based ceramic adhesive 4, and the through-tube 5 and the solid proton conductor element 1 are connected by an insulating ceramic adhesive 4 to form an inner space, and the surface of the solid proton conductor element 1 is located inside the space.
  • the surface, the surface exposed to the outside is the outer surface; the reference porous electrode 2 is applied to the inner surfaces of the solid proton conductor element 1 and the alumina-based ceramic binder 4, and the quasi-to-be-tested electrode 6 is the outer surface of the solid proton conductor element 1.
  • the upper part of the through pipe 5 is connected by a Teflon tee clamp 104, and the Teflon three-way clamp has a gas outlet 105 on one side; the reference Ar-H 2 is introduced into the inner space, and The reference porous electrode 2 is in contact; the air guiding tube 3 is inserted through the PTFE tee device 104 To the inner space, and a porous electrode in contact with the reference 2.
  • the reference porous electrode is made of porous platinum.
  • the reference material Ar-H 2 had a molar hydrogen content of 1.00%.
  • the method for measuring the hydrogen content in the aluminum melt by using the sensor is carried out according to the following process steps: 1 inserting the sensor and the graphite corrosion-resistant electrode into the aluminum melt at 750 ° C, and ensuring that the solid proton conductor element is completely immersed in the metal melt, The quasi-measured pole is in direct contact with the metal melt, and the contact surface is the electrode to be tested; 2 the stainless steel wire is used to connect the potentiometer and the air guiding tube and the graphite corrosion-resistant electrode, and the potential difference between the reference pole and the pole to be tested is measured as 17.3. mV; 3 using the measured potential difference, metal melt temperature, hydrogen saturation in the metal melt to calculate the metal melt hydrogen content S, battery reaction equation and calculation formula (4) and (5):
  • S 0 is a hydrogen-saturated solubility, ml/100 g, and K is a constant generated by a conversion unit. Since the saturation solubility S 0 of most metals is known thermodynamic data or thermodynamic data that can be calculated, the calculation can obtain the standard Gibbs free energy ⁇ G ⁇ of hydrogen dissolved in the metal melt.
  • the standard Gibbs free energy ⁇ G ⁇ due to hydrogen dissolved in the metal melt is only related to the type and temperature of the metal melt, and does not change with the change of the hydrogen content in the metal melt. Therefore, when hydrogen is saturated in the metal melt, hydrogen is dissolved.
  • the standard free energy ⁇ G ⁇ of the metal melt is the same as in the case of unsaturation.
  • the sensor for measuring the hydrogen content in the aluminum melt is the same as that of Embodiment 1, as shown in FIG. 3, except that the sensor structure further includes a reference electrode wire 7 made of metal platinum, which is inserted through the copper tee clamp 104.
  • the quartz tube 5 is connected to the gold reference porous electrode 2 and externally connected to the measuring circuit; the air guiding material is corundum; the solid proton conductor element 1 is CaZr 0.9 Sc 0.1 O 3- ⁇ ; the three-way clamp 104 material It is copper; the material of the tube is quartz; the reference porous electrode is made of porous gold.
  • the method for measuring the hydrogen content in the metal melt by using the sensor is carried out according to the following process steps: 1 Inserting the sensor and the graphite corrosion-resistant electrode into the aluminum melt at 750 ° C, and ensuring that the solid proton conductor element is completely immersed therein, and the quasi-test
  • the pole is in direct contact with the metal melt, and the contact surface is the electrode to be tested; 2 the platinum pole is used to connect the potentiometer and the reference pole wire and the graphite corrosion electrode, and the potential difference between the reference pole and the pole to be tested is measured;
  • the sensor for measuring the hydrogen content in the aluminum melt is the same as that of the first embodiment, as shown in FIG. 4, except that the solid proton conductor element 1 used in the sensor structure is a sheet-like structure; the material of the through-tube 5 is stainless steel; One end of the air guiding tube 3 in contact with the proton conductor 1 is a blind end, and the side opening is used as an air outlet, and the vertical distance between the air outlet and the uppermost end of the solid proton conductor is 2 to 5 mm; the air guiding material is nickel-chromium alloy; the reference gas is He -H 2 , the molar hydrogen content is 1.00%.
  • the method for measuring the hydrogen content in the metal melt using the sensor is carried out according to the following process steps: 1
  • the graphite corrosion-resistant electrode is inserted into the aluminum melt at 750 ° C, and the solid proton conductor component is completely immersed in the metal melt, the quasi-measurement pole is in direct contact with the metal melt, the contact surface is the electrode to be tested; 2 using the nickel-chromium wire
  • the potentiometer and the nickel-chromium gas pipe are connected with the graphite corrosion-resistant electrode to measure the potential difference between the reference electrode and the electrode to be tested; 3 using the measured potential difference, the metal melt temperature, and the saturation solubility of hydrogen in the metal melt
  • S 0.109 ml / 100 g of Al.
  • the sensor for measuring the hydrogen content in the aluminum melt is the same as that of the third embodiment, as shown in FIG. 5, except that the sensor structure further includes a reference electrode wire 7 made of metallic silver, which is inserted into the pipe through the stainless steel clamp 104. 5, connected to the porous silver reference porous electrode 2, externally connected to the measuring circuit; the material of the through tube 5 is quartz; the material of the air guiding tube is corundum; the reference porous electrode is made of porous silver; the reference gas is N 2 -H 2 The molar hydrogen content is 1.00%.
  • the sensor for measuring the hydrogen content in the aluminum melt is the same as that of the third embodiment, as shown in Fig. 6, except that the solid proton conductor member 1 employed in the sensor structure has a spherical structure.
  • the sensor for measuring the hydrogen content in the aluminum melt is the same as that of the embodiment 5, as shown in FIG. 7, except that the sensor structure further includes a reference electrode wire 7 made of stainless steel and a Teflon tee clamp. 104 is inserted into the through tube 5, connected to the reference porous electrode 2, and externally connected to the measuring circuit; the air guiding tube material is corundum.
  • a sensor for measuring the hydrogen content in the aluminum melt includes a solid proton conductor element 1, a reference porous electrode 2, an electrode to be tested, a platinum wire 7, a solid reference 8, a corundum tube 5, and an oxidation Aluminum-based ceramic binder 4 and Al 2 O 3 inert material 9; wherein the solid proton conductor element 1 is a tube-packed structure, the material is CaZr 0.9 In 0.1 O 3- ⁇ , and one end thereof is sealed with an alumina-based ceramic binder 4 The through tube 5 and the solid proton conductor element 1 are connected by an insulating ceramic adhesive 4 and form an inner space.
  • the surface of the solid proton conductor element 1 in the inner space is an inner surface, and the surface exposed to the outside is an outer surface;
  • the reference porous electrode 2 is coated on the inner surface of the solid proton conductor element 1, and the quasi-to-be-measured electrode 6 is the outer surface of the solid proton conductor element 1;
  • the bottom of the solid proton conductor element 1 is filled with the Al 2 O 3 inert material 9, and the upper portion is filled
  • the YH system solid reference material 8, the reference material 8 is in contact with the reference electrode 2 and the platinum wire lead 7, and the reference material 8 is filled with the Al 2 O 3 inert material 9 and then sealed with the alumina-based ceramic binder 4 .
  • An adhesive 42 is connected to the reference electrode is porous, and to an external measuring circuit.
  • the reference porous electrode is made of a platinum material.
  • the reference material was a Y-H system solid, and the equilibrium atmosphere molar hydrogen content in the 750 ⁇ Y-H system solid was 0.11%.
  • the method for measuring the hydrogen content in the metal melt using the sensor is carried out according to the following process steps: 1 Inserting the sensor and the graphite corrosion-resistant electrode into the aluminum melt at 750 ° C, and ensuring that the solid proton conductor element 1 is completely immersed in the metal melt.
  • the quasi-measurement pole is in direct contact with the metal melt, and the contact surface is the electrode to be tested; 2 the platinum potential is connected to the platinum wire and the graphite corrosion-resistant electrode by using a platinum wire, and the potential difference between the reference electrode and the electrode to be measured is measured.
  • the sensor for measuring the hydrogen content in the aluminum melt is the same as that of the embodiment 7, as shown in FIG. 9, except that the solid proton conductor element 1 used in the sensor structure is a sheet-like structure and the material is CaZr 0.9 Sc 0.1 O 3- ⁇ .
  • the inert material is Y 2 O 3 ; the reference is a solid of Sc-H system, and the equilibrium atmosphere has a molar hydrogen content of 0.25% in the 750 ⁇ Sc-H system.

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PCT/CN2015/096049 2015-11-12 2015-11-30 一种测量金属熔体中氢含量的传感器及测量方法 Ceased WO2017080005A1 (zh)

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EP15908135.5A EP3372998B1 (en) 2015-11-12 2015-11-30 Sensor and method for measuring content of hydrogen in metal melt
JP2018517620A JP6775012B2 (ja) 2015-11-12 2015-11-30 アルミニウム溶融体中の水素含有量測定用センサー及び測定方法
US15/774,205 US10598629B2 (en) 2015-11-12 2015-11-30 Sensor and measurement method for measuring hydrogen content in metal melt

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0544281B1 (en) * 1991-11-26 1998-06-03 Tokyo Yogyo Kabushiki Kaisha Sensor probe for measuring hydrogen concentration in molten metal and method for measuring hydrogen concentration
US20050252789A1 (en) * 2002-09-14 2005-11-17 Fray Derek J Hydrogen sensing apparatus and method
CN101071119A (zh) * 2007-06-15 2007-11-14 东北大学 一种测氢传感器及固体电解质的制备方法
US20090139876A1 (en) * 2005-10-12 2009-06-04 Enviromental Monitoring And Control Limited Apparatus and Method for Measuring Hydrogen Concentration

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63269053A (ja) * 1987-04-25 1988-11-07 Tottori Univ 溶融金属またはガス中に含有されている水素または水蒸気の濃度の測定装置用基準物質
JP2578542B2 (ja) * 1991-12-27 1997-02-05 東京窯業株式会社 溶融金属中の水素溶解量測定用センサプローブ
US5490965A (en) * 1994-01-24 1996-02-13 Hewlett-Packard Company Method for closing holes in ceramic substrates
JPH0829375A (ja) * 1994-07-12 1996-02-02 Tokyo Yogyo Co Ltd 溶融金属中の水素溶解量測定用センサ
JP3878875B2 (ja) * 2002-03-29 2007-02-07 三井造船株式会社 酸素濃度計
JP3095929U (ja) * 2003-02-17 2003-08-29 株式会社エバニユー 運動用ボール空気入れ
US7396443B2 (en) * 2003-02-17 2008-07-08 Dongsub Park Solid-state electrochemical hydrogen probe for the measurement of hydrogen content in the molten aluminum
DE102004022763B3 (de) * 2004-05-05 2005-09-15 Heraeus Electro-Nite International N.V. Messeinrichtung zur Bestimmung der Sauerstoffaktivität in Metall- oder Schlackeschmelzen
JP4433489B2 (ja) * 2007-08-10 2010-03-17 昭和ホールディングス株式会社 ソフトテニスボール用空気入れポンプ
KR101325508B1 (ko) * 2012-03-14 2013-11-07 한국과학기술원 고체 산소이온 전도체와 고체 수소이온 전도체의 접합구조를 가진 용융금속 내 수소 측정 센서
JP2014160006A (ja) * 2013-02-19 2014-09-04 Tokyo Yogyo Co Ltd センサプローブ
JP2015086093A (ja) * 2013-10-29 2015-05-07 株式会社ノリタケカンパニーリミテド セラミック積層体およびその製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0544281B1 (en) * 1991-11-26 1998-06-03 Tokyo Yogyo Kabushiki Kaisha Sensor probe for measuring hydrogen concentration in molten metal and method for measuring hydrogen concentration
US20050252789A1 (en) * 2002-09-14 2005-11-17 Fray Derek J Hydrogen sensing apparatus and method
US20090139876A1 (en) * 2005-10-12 2009-06-04 Enviromental Monitoring And Control Limited Apparatus and Method for Measuring Hydrogen Concentration
CN101071119A (zh) * 2007-06-15 2007-11-14 东北大学 一种测氢传感器及固体电解质的制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3372998A4 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111289405A (zh) * 2020-03-02 2020-06-16 哈尔滨理工大学 铝合金熔体氢分压惰性气体循环在线连续检测装置及其检测方法
CN111289405B (zh) * 2020-03-02 2022-07-01 哈尔滨理工大学 铝合金熔体氢分压惰性气体循环在线连续检测装置及其检测方法

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